WO2021245155A1 - High molecular weight poly(arylene sulfide) polymer - Google Patents

Abstract

The present invention relates to poly(arylene sulfide) ("PAS") polymers having outstanding mechanical properties. The invention also relates to methods of making PAS polymers and articles incorporating the PAS polymer.

Description

High molecular weight poly(arylene sulfide) polymer Cross Reference to Related Applications

[0001] This application claims priority to US provisional patent application no.

63/033,766, filed on 02 June 2020, and to European patent application no. 20185866.9, filed on 15 July 2020, the whole content of each of these applications being incorporated herein by reference for all purposes.

Technical Field

[0002] The present invention relates to poly(arylene sulfide) (“PAS”) polymers having outstanding mechanical properties. The invention also relates to methods of making PAS polymers and articles incorporating the PAS polymer.

Background Art

[0003] Poly(arylene sulfide) (“PAS”) polymers generally have high temperature resistance, corrosion resistance, excellent electrical properties. This broad range of properties makes PAS polymers suitable for a large number of applications, for example in the automotive, electrical, electronic, aerospace and appliances markets.

[0004] PAS homopolymers and copolymers are generally prepared by a process that includes reacting an alkali metal sulfide and at least a polyhalo aromatic compound having at least two halogen substituents per molecule in a suitable polar organic solvent to form PAS polymers having a relatively low molecular weight.

[0005] For certain applications high molecular weight PAS polymers would be very desirable.

[0006] The molecular weight of PAS polymers can be increased by curing.

[0007] DE3339538 suggests to improve the molecular weight of PAS polymer by branching the polymer thanks to the inclusion of branching comonomers such as 1,2,4-trichlorobenzene to obtain PAS having molecular weight in the range of 25,000 to 30,000 g/mol. [0008] Historically, a key advance in PAS polymerizations was the inclusion of sodium acetate as a modifier to promote molecular weight.

[0009] In a different approach, higher molecular weight PAS can be achieved by lowering the ratio of polyhalo aromatic compound/alkali metal sulfide closer to 1 :1 in PAS polymerizations; however, this runs the risk of a sulfur excess which leads to polymer decomposition, thiophenol generation, and high reactor pressures.

[0010] Alternatively, one can use increasingly long polymerization times, which is however not convenient from an industrial point of view.

[0011] Despite modest increase in molecular weight, the processes known in the state of the art have limitation to obtain PAS polymers with improved mechanical properties.

[0012] There is therefore a need for a PAS polymer that has improved molecular weight and improved mechanical properties.

Summary of invention

[0013] In a first aspect, the present invention relates to a poly(arylene sulfide) (“PAS”) polymer (PASP) comprising recurring units (RPASI) and (RPAS2), represented by the following formulae, respectively:

[-An-S-] (RPASI)

[-Ar2-S-] (RPAS2) wherein

-An- is selected from the group of formulae consisting of:

and

wherein:

- R, at each instance, is independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6- C24 arylene group, and a C6-C18 aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO2-, -0-, - C(CH3)2, phenyl and -CH2-;

- i, at each instance, is an independently selected integer from 0 to 4;

- j, at each instance, is an independently selected integer from 0 to 3;

-AG2- is represented by the following formula:

wherein Ri is a Ci to C10 linear or branched alkyl group, preferably Ri is - CH₃; wherein said PAS polymer has a molecular weight determined by gel permeation chromatography (GPC) at 210°C of at least 50,000 g/mol, preferably at least 55,000 g/mol. [0014] 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:

C1-AG1-C2;

- a dihalotoluene monomer having the following formula:

X₃-Ar₂-X₄; wherein Xi to X₄ are independently selected halogens, and

- an alkali metalsulfide (S); preferably the alkali metal sulfide is NaSH. [0015] According to another aspect, the present invention relates to an article, part or composite material comprising the PAS polymer as described herein, and to the use of said article, part or composite material in oil and gas applications, automotive applications, electric and electronic applications, or aerospace and consumer goods.

Disclosure of the invention

[0016] 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, 1-methylethyl, propyl, 1,1 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, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6 C15 aryloxy or C6-C15 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. [0017] 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 C₁-C₆ 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, C₁-C₆ alkoxy, sulfo, C₁-C6 alkylthio, C₁-C6 acyl, formyl, cyano, C6 C₁₅ aryloxy or C₆-C₁₅ aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. The powdered material (M) of the present invention can have a regular shape such as a spherical shape, or a complex shape obtained by grinding/milling of the polymeric component (P), i.e. at least the PAS polymer, in the form of pellets or coarse powder.

[0018] 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;

- 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; and - any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents.

[0019] The PAS Polymer (PASP)

[0020] The PAS polymer (PASP) includes recurring unit (RPASI) and recurring unit (RPAS2) represented by the following formulae, respectively:

[-AT1-S-] (RPASI)

[-AT2-S-] (RPAS2) wherein -An- is selected from the group of formulae consisting of:

wherein:

- R, at each instance, is independently selected from the group consisting of a C₁-C₁₂ alkyl group, a C7-C₂₄ alkylaryl group, a C7-C₂₄ aralkyl group, a C6- C₂₄ arylene group, and a C6-C₁₈ aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO₂-, -0-, - C(CH3)2, phenyl and -CH2-;

- i, at each instance, is an independently selected integer from 0 to 4; j, at each instance, is an independently selected integer from 0 to 3;

-AG2- is represented by the following formula:

wherein Ri is a Ci to C10 linear or branched alkyl group, preferably Ri is - CH₃; wherein said PAS polymer has a molecular weight determined by gel permeation chromatography (GPC) at 210°C of at least 50,000 g/mol, preferably at least 55,000 g/mol.

[0021] In formulae (a), (b) and (c), when i or j is zero, the corresponding benzyl rings are unsubstituted. Similar notation is used throughout the present description. Additionally, each formula (a) to (c) contains two dashed bonds, where one bond is to the explicit sulfur atom in the recurring unit (RPASI) and the other is a bond to an atom outside the recurring unit (RPASI) (e.g. an adjacent recurring unit). Analogous notation is used throughout.

[0022] In formula (d), the dashed bond having a “^*” indicates the bond to the explicit sulfur atom in recurring unit (RPAS2) and the dashed bond without the “^*” indicates a bond to an atom outside the recurring unit (RPAS2).

[0023] In preferred embodiments, i and j, at each instance, is zero.

[0024] Preferably, -An- is represented by either formula (a) or (b), more preferably by formula (a) ([-An-S-] corresponding to recurring units of polyphenylene sulfide).

[0025] More preferably, -An- is represented by the following formula:

[0026] Still more preferably, -An- is represented by formula (a-1), where i is zero.

[0027] In some embodiments, the total concentration of recurring units (RPASI) and (RPAS2) in the PAS polymer 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%.

[0028] 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.

[0029] In some embodiments, the concentration of recurring unit (RPASI) in the PAS polymer 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%.

[0030] In some embodiments, the concentration of recurring unit (RPAS2) in the PAS polymer 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 recurring unit (RPAS2) is no more than 15 mol%, no more than 12 mol%, no more than 10 mol%, or no more than 8 mol%.

[0031] In some embodiments, the number of moles of recurring unit (RPAS2) in the PAS polymer is from 0.5 mol% to 15 mol%, from 0.5 mol% to 12 mol%, from 0.5 mol% to 10 mol%, from 0.5 mol% to 8 mol%, from 1 mol% to 15 mol%, from 1 mol% to 12 mol%, from 1 mol% to 10 mol%, from 1 mol% to 8 mol%, from 2 mol% to 8 mol% or from 2.5 mol% to 8 mol%.

[0032] In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPASI) and (RPAS2) in the PAS polymer is at least 1 mol%, at least 1.5 mol%, at least 2 mol% or at least 2.5 mol%.

[0033] In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPASI) and (RPAS2) is no more than 15 mol%, no more than 12 mol%, no more than 10 mol%, or no more than 8 mol%.

[0034] In some embodiments, the ratio of the number of recurring unit (RPAS2) to the total number of moles of recurring units (RPASI) and (RPAS2) is from 1 mol% to 15 mol%, from 1 mol% to 12 mol%, from 1 mol% to 10 mol%, from 1 mol% to 8 mol%, from 2 mol% to 8 mol% or from 2.5 mol% to 8 mol%.

[0035] It was surprisingly found that at relatively low concentration of recurring unit (RPAS2), the PAS polymers (PASP) had significantly increased molecular weight while maintaining or improving tensile strength and elongation.

[0036] The Applicant has surprisingly found that said advantage in the improvement of the molecular weight while maintaining or improving tensile strength and elongation can be achieved by PAS polymers including recurring units (RPAS₂) as above defined, but not by PAS polymers including different isomers of recurring units (RPAS2).

[0037] Of course, in some embodiments, the PAS polymer can have additional recurring units, each distinct from each other and distinct from recurring units (RPASI) and (RPAS2).

[0038] The PAS polymer has a weight average molecular weight (“M_w”) of at least 50,000 g/mol, preferably more than 55,000 g/mol, still more preferably at least 60,000 g/mol.

[0039] In some embodiments, the PAS polymer has an M_w of no more than

150,000 g/mol, no more than 100,000 g/mol, no more than 90,000 g/mol, no more than 85,000 g/mol, or no more than 80,000 g/mol.

[0040] M_w can be measured as described in the Examples below.

[0041] The PAS polymer can be amorphous or semi-crystalline. As used herein, an amorphous polymer has an enthalpy of fusion (“AH_f”) of no more than 5 Joules/g (“J/g”). The person of ordinary skill in the art will recognize that when the PAS is amorphous, it lacks a detectable T_m. 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 AH_f of at least 10 J/g, at least 20 J/g, at least, or at least 25 J/g. In some embodiments, the PAS polymer has a AH_f of no more than 90 J/g, no more than 70 J/g or no more than 60 J/g. In some embodiments, the PAS polymer has a AH_f of from 10 J/g to 90 J/g or from 20 J/g to 70 J/g. AH_f can be measured as described in the Examples below. [0042] Preferably, the PASP has a melt flow rate (at 315.6°C under a weight of 5 kg measured as described in the Examples below) of at most 700 g/10 min, more preferably of at most 500 g/10 min.

[0043] Preferably, the PASP has a melt flow rate (at 315.6°C under a weight of 5 kg measured as described in the Examples below) of at least 5 g/10 min, more preferably of at least 30 g/10 min, even more preferably at least 50 g/mol.

[0044] Synthesis of the PAS Polymer

[0045] In another aspect, the invention relates to a method of making the PAS polymer (PASP), the method including

-a polymerization reaction in which at least a dihaloaromatic monomer, a dihalotoluene monomer (distinct from the first dihaloaromatic monomer) and an alkali metal sulfide (S) are polymerized in a solvent to form the PAS polymer, and

- a termination, in which the polymerization reaction is stopped.

[0046] The polymerization reaction involves reacting in a reaction mixture a dihaloaromatic compound having the following formula: C1-AG1-C2; a dihalotoluene monomer having the following formula: C3-AG2-C4; and an alkali metal sulfide (collectively, “reaction components”) in a polymerization solvent according to the following scheme:

where Xi to X4 are independently selected halogens, -An- and -An- are as given above, and an alkali metal sulfide compound described below.

[0047] Preferably, X^ and X2 are the same halogen. More preferably, Xi and X2 are both chlorine.

[0048] Preferably, Xi-An-X2 is a para-dihalobenzene, most preferably para- dichlorobenzene.

[0049] X3 and X4 can be the same or different halogen.

[0050] According to a preferred embodiment, X3 and X4 are the same halogen. [0051] Preferred dihalotoluene monomers of formula C3-AG2-C4 are notably 2,5- dichlorotoluene, 2,5-dibromotoluene, 2,5-difluorotoluene, 2-bromo-5- chlorotoluene, 5-bromo-2-chlorotoluene, 2-bromo-5-fluorotoluene, 5- bromo-2-fluorotoluene, 2-chloro-5-fluorotoluene, and 5-chloro- 2-fluorotoluene.

[0052] The person of ordinary skill in the art will recognize that -An- and -An- in the reaction scheme above are incorporated into recurring units (RPASI) and (RPAS2), respectively, as described in detail above and shown in the reaction scheme. Accordingly, the preferences and embodiments for -An- and —An— described above for recurring units (RPASI) and (RPAS2) are also applicable for -An- and -An- in the reaction scheme.

[0053] Thean alkali metal sulfide (S) is preferably NaSH.

[0054] The Applicant has surprisingly found that, when the polymerization of a dihaloaromatic compound of formula Xi-An-X2 as above defined with a dihalotoluene monomer of formula X3-An-X4 as above defined is carried out in the presence of a hydrogen sulfide, the PAS polymers (PASP) thereby obtained has a significantly increased molecular weight in comparison to the polymerization processes of the prior art, which make use of Na2S as sulfide source in the polymerization.

[0055] 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-2-pyrrolidone (“NMP”), pyrrolidone, caprolactam, n- ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, and 1 ,3-dimethyl-2- imidazolidinone. Preferably, the polymerization solvent is NMP.

[0056] In embodiments, in which the polymerization solvent includes NMP, NMP can react with NaOH to form sodium N-methyl-1 ,4-aminobutanoate (“SMAB”).

[0057] 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: ROO₂M', where R' is selected from the group consisting of a Ci to C₂₀ hydrocarbyl group, a Ci to C₂₀ hydrocarbyl group and a Ci to C₅ 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.

[0058] The polymerization reaction is performed by contacting the reaction components at a reaction temperature selected such that Xi-An-X2, X3- AG2-C4 and the alkali metal sulfide (S) polymerize to form the PAS polymer.

[0059] The alkali metal sulfide (S) is suitably supplied as a water solution including NaSH in an amount of about 60% by weight.

[0060] Before adding the same to the reaction vessel in which the polymerization reaction is performed (“polymerization reactor”), the solution of NaSH must be dehydrated by a dehydration step carried out at a temperature in the range comprised from 150°C and 200°C to remove water. During this dehydration process, some of the sulfur is lost in the form of H2S. This means that the ratio of dihaloaromatic compound of formula Xi-An-X2 to NaSH varies unpredictably from batch-to-batch, resulting in significant variation in the melt flow index (MFR), often by as much as ±30%. The MFR is measured on a extrusion plastometer at 315.6 °C using a weight of 5 kg and a 0.0825 inch ^c 0.315 inch die after a 5 minute equilibration period (with units of g · (10 min)^-1), and is an indirect measure of molecular weight.

[0061] The Applicant has surprisingly found that the MFR responds less to stoichiometry variations when the comonomer of formula C3-AG2-C4 is present in polymerization. As such, addition of a small percentage of the comonomer of formula C3-AG2-C4 as above defined to the polymerization process of PPS would reduce the variations in MFR and result in a more consistent product.

[0062] In some embodiments, the reaction temperature is from 170°C to 450°C, or from 200°C to 285°C. The reaction time (time duration of the polymerization reaction) can be from 10 minutes to 3 days or from 1 hour to 8 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 0 pounds per square inch gauge (“psig”) to 400 psig, from 30 psig to 300 psig, or from 100 psig to 250 psig.

[0063] 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 15°C to 99°C. In some embodiments, the temperature of the quench liquid can be from 54°C to 100°C ( e.g . in embodiments in which the quench liquid is the solvent) or from 15°C to 32°C (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 polymerization reactor. For clarity, termination of the polymerization reaction does not imply 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.

[0064] 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 (such as calcium), is discussed in US patent application publication number, 2015/0175748 to Fodor etal., filed December 19, 2013 (“the 748 patent”) and incorporated by reference herein in its entirety.

[0065] 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 748 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.

[0066] 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 100°C, 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 100°C, 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 100°C, the presence of a gaseous oxidizing atmosphere ( e.g . air) generally does not result in significant curing of the PAS polymer.

[0067] The present invention also relates to an article, part or composite material comprising the PAS polymer as described herein, and to the use of said article, part or composite material in oil and gas applications, automotive applications, electric and electronic applications, or aerospace and consumer goods.

[0068] The invention will now be described with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

Experimental section

[0069] Materials

1-methyl-2-pyrollidone (“NMP”) (>99.0%) commercially available from TCI Sodium hydrosulfide (“NaSH”) (55 - 60 wt.%) commercially available from AkzoNobel

1.4-dichlorobenzene (“DCB”) (³99) commercially available from Alfa Aesar Sodium hydroxide (>97.0%) commercially available from Fisher Chemical Sodium acetate (>99%) commercially available from VWR Chemicals

2.5-dichlorotoluene (“2,5-DCT”) (>98.0%) commercially available from TCI

3.5-dichlorotoluene (>97%) commercially available from AOBChem

2.3-dichlorotoluene (>98.0%) commercially available from TCI

2.5-dichloro-p-xylene (>97.0%) commercially available from TCI

3.4-dichlorotoluene (>98.0%) commercially available from TCI

2.4-dichlorotoluene (99%) : obtained from Acres [0070] Testing methods

[0071] Thermal Performance: T_g, T_mc, T_m, and AH_f were determined using differential scanning calorimetry (“DSC”), according to ASTM D3418 employing a heating and cooling rate of 20°C/min. Three scans were used for each DSC test: a first heat up to 350°C, followed by a first cool down to 30°C, followed by a second heat up to 350°C. T_g, T_m, and AH_f were determined from the second heat. [0072] Molecular Weight: The weight-averaged molecular weight M_w was determined by gel permeation chromatography (GPC) at 210 °C using a PL 220 high temperature GPC with a 1-chloronaphtalene mobile phase and polystyrene standards.

[0073] Tensile properties: Tensile strength and elongation were determined with Type V ASTM tensile bars according to ASTM D638 with a testing speed of 0.05 in per min at room temperature.

[0074] Impact Performance: Notched Izod values were determined according to ASTM D256 using 0.125 inch flex bars at room temperature.

[0075] Melt Flow Rate: The MFR is measured on a extrusion plastometer at 315.6 °C using a weight of 5 kg and a 0.0825 inch ^c 0.315 inch die after a 5 minute equilibration period (with units of g · (10 min)^-1).

[0076] Example 1 : (10 mol% 2,5-DCT co-PPS) A 1-L autoclave reactor was charged with 36.72 g sodium hydroxide (0.918 mol), 24.36 g sodium acetate (0.297 mol), 84.83 g NaSH (59.38 wt%, 0.900 mol), and 255 mL NMP. The reactor was purged and pressurized to 10 psig with nitrogen and set to stir continuously at 400 rpm. A separate addition vessel was charged with 119.07 g DCB (0.810 mol), 14.49 g 2,5-DCT (0.090 mol), and 50 g NMP. The addition vessel was purged and pressurized to 90 psig with nitrogen, and heated to 100 °C. The reactor was heated to 240 °C at 1.5 °C/min. Upon reaching 150 °C, the reactor was vented through a condenser and ~42 mL of a clear condensate was collected under a small stream of nitrogen (60 mL/min) until the reactor reached 200 °C. At this point, the condenser was removed, the nitrogen flow was stopped, and the DCB/2,5-DCT/NMP mixture in the addition vessel was promptly added to the reactor. The addition vessel was charged with an additional 30 mL 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 washed according to Rinse procedure A, affording 90.10 g of a white, granular solid. The T_m, H_m,T_g, Tmc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0077] Rinse Procedure A: The slurry is diluted with 200 ml_ NMP, removed from the reactor, heated to 80 °C, and filtered through a medium porosity sintered glass filter. The filter cake is washed once with 100 mL warm NMP (60 °C). The solids are stirred for 15 minutes in 300 mL heated Dl water (70 °C) and subjected to filtration on the medium porosity glass filter, a process that is repeated five times in total. The rinsed solids are dried in a vacuum oven overnight at 100 °C under nitrogen.

[0078] Rinse Procedure B: The slurry is diluted with 200 mL NMP, removed from the reactor, heated to 80 °C, and screened on a No. 120 sieve. Next, the solids are washed once with 100 mL warm NMP (60 °C) and screened again on the No. 120 sieve. Then, the solids are stirred for 15 minutes in 300 mL heated Dl water (70 °C) and filtered on the No. 120 sieve, a process that is repeated five times in total. The solids are then stirred in a solution of 300 mL Dl water and 6 mL glacial acetic acid at 70 °C for 30 minutes. This mixture is then subject to filtration on a medium porosity glass filter and the solids are rinsed three times with heated Dl water (70 °C). The rinsed solids are dried in a vacuum oven overnight at 100 °C under nitrogen.

[0079] Comparative Example 1 : PPS homopolymer

[0080] Synthesized according to procedure from Example 1 with Rinse Procedure A using 35.44 g sodium hydroxide (0.886 mol), 23.51 g sodium acetate (0.287 mol), 82.59 g NaSH (58.96 wt%, 0.869 mol), 127.68 g DCB (0.869 mol), and 323 mL total NMP. Afforded 88.41 g of a white granular solid. The Tm, Hm,Tg, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0081] Comparative Example 2: (10 mol% 3,5-dichlorotoluene co-PPS)

Synthesized according to procedure from Example 1 with Rinse Procedure A using 31.90 g sodium hydroxide (0.798 mol), 21.17 g sodium acetate (0.258 mol), 73.92 g NaSH (59.31 wt%, 0.782 mol), 103.46 g DCB (0.704 mol), 12.59 g 3,5-dichlorotoluene (0.078 mol), and 291 mL total NMP. Afforded 77.75 g of a white granular solid. [0082] The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0083] Comparative Example 3: (10 mol% 2,3-dichlorotoluene co-PPS)

Synthesized according to procedure from Example 1 with Rinse Procedure A using 40.68 g sodium hydroxide (1.017 mol), 27.00 g sodium acetate (0.329 mol), 93.99 g NaSH (59.48 wt%, 0.997 mol), 131.93 g DCB (0.897 mol), 16.06 g 2,3-dichlorotoluene (0.100 mol), and 371 ml_ total NMP. Afforded 95.92 g of a white powdery solid.

[0084] The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0085] Comparative Example 4: (10 mol% 2,5-dichloro-p-xylene co-PPS)

Synthesized according to procedure from Example 1 with Rinse Procedure A using 37.34 g sodium hydroxide (0.933 mol), 24.77 g sodium acetate (0.302 mol), 87.02 g NaSH (58.96 wt%, 0.915 mol), 121.08 g DCB (0.824 mol), 16.02 g 2,5-dichloro-p-xylene (0.092 mol), and 340 ml_ total NMP. Afforded 110.70 g of a white fine granular solid.

[0086] The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0087] Comparative Example 5: (10 mol% 3,4-dichlorotoluene co-PPS)

Synthesized according to procedure from Example 1 with Rinse Procedure A using 34.72 g sodium hydroxide (0.868 mol), 23.04 g sodium acetate (0.281 mol), 80.44 g NaSH (59.31 wt%, 0.851 mol), 112.59 g DCB (0.766 mol), 13.70 g 3,4-dichlorotoluene (0.085 mol), and 316 ml_ total NMP. Afforded 85.70 g of a white powdery solid.

[0088] The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

[0089] Comparative Example 6: (10 mol% 2,4-dichlorotoluene co-PPS)

Synthesized according to procedure from Example 1 with Rinse Procedure A using 35.64 g sodium hydroxide (0.891 mol), 23.65 g sodium acetate (0.288 mol), 81.93 g NaSH (59.78 wt%, 0.874 mol), 115.59 g DCB (0.786 mol), 14.07 g 2,4-dichlorotoluene (0.087 mol), and 325 ml_ total NMP. Afforded 89.73 g of a white powdery solid. [0090] The T_m, AH_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 1.

Table 1

^*Bars too fragile to test

[0091] As shown in Table 1, the copolymerization with 10 mol% 2,5-DCT (Example 1) results in a surprisingly high Mw compared with PPS homopolymer (Comparative Example 1) and with the other dichlorotoluene isomers (Comparative Examples 2 - 6).

[0092] Furthermore, the 2,5-DCT copolymer in Example 1 displays a tensile strength of 75 MPa (equivalent to PPS homopolymer). In contrast, the isomer copolymers in examples 2 and 3 have low tensile strengths of 32 - 49 MPa, and the copolymer tensile bars in examples 4 - 6 were too fragile to test.

[0093] Example 2: (2.5 mol% 2,5-dichlorotoluene co-PPS) Synthesized according to procedure from Example 1 with Rinse Procedure B using 32.73 g sodium hydroxide (0.818 mol), 21.72 g sodium acetate (0.265 mol), 78.57 g NaSH (57.24 wt%, 0.802 mol), 114.97 g DCB (0.782 mol), 3.23 g 2,5- dichlorotoluene (0.020 mol), and 298 ml_ total NMP. Afforded 73.90 g of a white granular solid. The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 2.

[0094] Example 3: (5 mol% 2,5-dichlorotoluene co-PPS) Synthesized according to procedure from Example 1 with Rinse Procedure B using 31.38 g sodium hydroxide (0.784 mol), 20.82 g sodium acetate (0.254 mol), 75.33 g NaSH (57.24 wt%, 0.769 mol), 107.41 g DCB (0.731 mol), 6.19 g 2,5- dichlorotoluene (0.038 mol), and 286 ml_ total NMP. Afforded 70.40 g of a white granular solid. The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 2.

[0095] Example 4: (10 mol% 2-bromo-5-chlorotoluene co-PPS) Synthesized according to procedure from Example 1 with Rinse Procedure A using 35.27 g sodium hydroxide (0.882 mol), 23.41 g sodium acetate (0.285 mol), 82.07 g NaSH (59.06 wt%, 0.865 mol), 114.38 g DCB (0.778 mol), 17.77 g 2-bromo-5-chlorotoluene (0.086 mol), and 321 ml_ total NMP. Afforded 86.80 g of a white granular solid.

[0096] The T_m, H_m,T_g, T_mc, and M_w and mechanical properties of the obtained polymer are specified in Table 2.

Table 2

[0097] As shown in Table 2, 2,5-dichlorotoluene comonomer enhances mechanical properties when incorporated between 2.5 - 5 mol% loading. The tensile strength increases from 79 to 88 MPa, the notched Izod impact increases from 28 J/m to 39 J/m, and most remarkably, the elongation at yield increases from 3.8% to as high as 4.4%.

[0098] Effect on Melt flow rate

[0099] Comparative Example 7: (PPS homopolymer, 1.00:1 monomer to sulfur ratio) Synthesized according to procedure from Example 1 with Rinse Procedure B using 35.33 g sodium hydroxide (0.883 mol), 23.44 g sodium acetate (0.286 mol), 84.97 g NaSH (57.14 wt%, 0.866 mol), 127.31 g DCB (0.866 mol), and 322 ml_ total NMP. Afforded 82.01 g of a white granular solid. T_m = 283 °C. AH_m = 55 J/g. T_g = 92 °C. T_mc = 230 °C. MFR = 223 g · (10 min)^-1.

[00100] Comparative Example 8: (PPS homopolymer, 1.02:1 monomer to sulfur ratio) Synthesized according to procedure from Example 1 with Rinse Procedure B using 34.25 g sodium hydroxide (0.856 mol), 22.73 g sodium acetate (0.277 mol), 82.30 g NaSH (57.19 wt%, 0.840 mol), 125.88 g DCB (0.856 mol), and 312 mL total NMP. Afforded 79.58 g of a white granular solid. T_m = 281 °C. AH_m = 58 J/g. T_g = 94 °C. T_mc = 230 °C. MFR = 285 g · (10 min)^-1.

[00101] Example 5 (2.5 mol% 2,5-dichlorotoluene co-PPS, 1.00:1 monomer to sulfur ratio) Synthesized according to procedure from Example 1 with Rinse Procedure B using 32.94 g sodium hydroxide (0.824 mol), 21.86 g sodium acetate (0.266 mol), 79.23 g NaSH (57.14 wt%, 0.808 mol),

115.74 g DCB (0.787 mol), 3.25 g 2,5-dichlorotoluene (0.020 mol), and 300 mL total NMP. Afforded 73.21 g of a white granular solid. T_m = 275 °C. AH_m = 48 J/g. T_g = 96 °C. T_mc = 213 °C. MFR = 233 g · (10 min)-¹.

[00102] Example 6: (2.5 mol% 2,5-dichlorotoluene co-PPS, 1.02:1 monomer to sulfur ratio) Synthesized according to procedure from Example 1 with Rinse Procedure B using 34.39 g sodium hydroxide (0.860 mol), 22.82 g sodium acetate (0.278 mol), 82.71 g NaSH (57.14 wt%, 0.843 mol),

123.24 g DCB (0.838 mol), 3.46 g 2,5-dichlorotoluene (0.021 mol), and 313 mL total NMP. Afforded 76.36 g of a white granular solid. T_m = 276 °C. AH_m = 51 J/g. T_g = 93 °C. T_mc = 221 °C. MFR = 251 g · (10 min)-¹. Table 3

[00103] In Table 3, is shown that an increase in the dichloroarene:sulfur ratio from 1.00:1 to 1.02:1 in the PPS homopolymer polymerization caused the MFR to increase by 62 units, with a 28% increase. In contrast, the polymerization in the presence of 2.5 mol% 2,5-DCT copolymer only increased by 18 units, a variation of just 8%.

[00104] Thus, the comonomer 2, 5-dichlorotoluene has the additional benefit of reducing batch-to-batch variations in melt flow rate (MFR). As such, addition of a small percentage of 2,5-DCT to the PPS polymerization process results in lower variations in melt flow and result in a more consistent product.

[00105] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

Claims

Claims

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

[-An-S-] (RPASI)

[-Ar2-S-] (RPAS2) wherein

-An- is selected from the group of formulae consisting of:

and wherein:

- R, at each instance, is independently selected from the group consisting of a C₁-C₁₂ alkyl group, a C7-C₂₄ alkylaryl group, a C7-C₂₄ aralkyl group, a C6-C24 arylene group, and a C6-C18 aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO2-, -0-, - C(CH3)2, phenyl and -CH2-;

- i, at each instance, is an independently selected integer from 0 to 4;

- j, at each instance, is an independently selected integer from 0 to 3;

-Ar2- is represented by the following formula:

wherein Ri is a Ci to C10 linear or branched alkyl group, preferably Ri is -Chh; wherein said PAS polymer has a molecular weight determined by gel permeation chromatography (GPC) at 210°C of at least 50,000 g/mol, preferably of at least 55,000 g/mol.

Claim 2. The PAS polymer (PASP) according to claim 1 , wherein said PAS polymer has a molecular weight determined by gel permeation chromatography (GPC) at 210°C of at least 60,000 g/mol.

Claim 3. The PAS polymer (PASP) according to anyone of claims 1 or 2, wherein -An- is represented by either formula (a) or (b), more preferably by formula (a).

Claim 4. The PAS polymer (PASP) according to anyone of the preceding claims, wherein -An- is represented by formula (a-1):

Claim 5. The PAS polymer (PASP) according to anyone of the preceding claims, wherein -An- is represented by formula (a-1) where i is zero.

Claim 6. The PAS polymer (PASP) according to anyone of the preceding claims, wherein the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPASI) and (RPAS2) is at least 1 mol%, at least 1.5 mol%, at least 2 mol% or at least 2.5 mol%.

Claim 7. The PAS polymer (PASP) according to anyone of the preceding claims, wherein the ratio of the number of recurring unit (RPAS2) to the total number of recurring units (RPASI) and (RPAS2) is no more than 15 mol%, no more than 12 mol%, no more than 10 mol%, or no more than 8 mol%.

Claim 8. A method of making the PAS polymer (PASP) according to anyone of claimsl to 7, said method including reacting in a reaction mixture:

- a dihaloaromatic compound having the following formula:

C1-AG1-C2;

- a dihalotoluene monomer having the following formula: X₃-Ar₂-X ; wherein Xi to X₄ are independently selected halogens, wherein

-An- is selected from the group of formulae consisting of:

wherein:

- R, at each instance, is independently selected from the group consisting of a C₁-C₁₂ alkyl group, a C7-C₂₄ alkylaryl group, a C7-C₂₄ aralkyl group, a C6-C₂₄ arylene group, and a C6-C₁₈ aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO₂-, -0-, - C(CH3)2, phenyl and -CH2-;

- i, at each instance, is an independently selected integer from 0 to 4;

- j, at each instance, is an independently selected integer from 0 to 3; -Ar2- is represented by the following formula:

wherein Ri is a Ci to C10 linear or branched alkyl group, preferably Ri is -Chh; and

- a alkali metal sulfide (S).

Claim 9. The method of making the PAS polymer (PASP) according to claim 8, wherein in the dihalotoluene monomer of formula C3-AG2-C4 Ar2 is 2,5- dichlorotoluene.

Claim 10. The method of making the PAS polymer (PASP) according to claim 8, wherein in the dihalotoluene monomer of formula C3-AG2-C4 Ar2is 2-bromo-5- chlorotoluene.

Claim 11. The method of making the PAS polymer (PASP) according to anyone of claims 8 to 10, wherein the alkali metal sulfide is NaSH.

Claim 12. An article, part or composite material comprising the PAS according to anyone of claims 1 to 7.

Claim 13. The use of the article, part or composite material according to claim 12 in oil and gas applications, automotive applications, electric and electronic applications, or aerospace and consumer goods.