Poly(arylene sulfide) Composition

Cross-Reference to Related Application

[0001 ] This application claims priority to US Provisional Application filed on 24 August 2021 with Nr 63/236510, the whole content of this application being incorporated herein by reference for all purposes.

Technical Field

[0002] The present invention relates to a poly(arylene sulfide) polymer composition, a process for preparing it, a composition comprising the polymer composition and a filler, an article, part or composite material comprising said polymer composition or composition, and to the use of the polymer composition or composition for the manufacture of 3D objects.

Background

[0003] Poly(arylene sulfide) polymers are semi-crystalline thermoplastic polymers having notable mechanical properties, such as high tensile modulus and high tensile strength, and stability towards thermal degradation. They are also characterized by excellent melt processing.

[0004] This broad range of properties makes PAS polymers suitable for a large number of applications, for example in the automotive, electrical, electronic, aerospace and appliance markets.

[0005] Despite their advantageous properties, PAS polymers may be too inflexible or stiff for applications in which a high degree of flexibility, resilience, toughness, and/or impact resistance is/are desired. Modification of PAS polymers with macromers having a low glass transition temperature (i.e., less than 0 °C) and/or linear impact resistance modifiers/tougheners has proven to be useful to be an effective way to extend their utility into additional applications.

[0006] However, a need yet remains for polymer compositions that exhibit the advantageous properties of poly(arylene sulfide) polymers, with improved flexibility, toughness and impact resistance.

Summary SSPU 2021/023

[0007] Polymer compositions addressing the aforementioned need are provided. Advantageously, the polymer compositions, comprising at least one poly(arylene sulfide) polymer and at least one epoxy-functional ized aromatic macromer, exhibit substantially increased ductility, toughness and impact resistance as compared to analogous polymer compositions not comprising the epoxy-functionalized aromatic macromer. The thermal properties, elastic modulus and tensile strength of the polymer compositions are substantially maintained relative to the analogous polymer compositions not comprising the epoxy-functionalized aromatic macromer. These results are surprising and unexpected, given that many known impact resistance modifiers/tougheners have linear backbones and thus lower melting, softening and/or glass transition temperatures than the epoxy-functionalized aromatic macromer. The results are even more surprising and unexpected in light of the low amounts, i.e. , less than 5 wt.%, of epoxy-functionalized aromatic macromer used.

[0008] In one aspect, a polymer composition is provided. The polymer composition comprises:

- at least one poly(arylene sulfide) polymer; and

- at most 5 wt.% of at least one epoxy-functionalized aromatic macromer (EFAM) based upon the total weight of the polymer composition, wherein the epoxy-functionalized aromatic macromer has a number average molecular weight of at most 5000 g/mol.

[0009] In an additional aspect, a process for preparing the polymer composition is provided, comprising: blending at a temperature of at least T _m +10°C a reaction mixture comprising:

- at least one poly(arylene sulfide) polymer; and

- at most 5 wt.% of at least one epoxy-functionalized aromatic macromer; Wherein

- T _m is the melting point of the component of the reaction mixture with the highest melting point;

- wt. % is based upon the total weight of the polymer composition;

- the epoxy-functionalized aromatic macromer has a number average molecular weight of at most 5000 g/mol; and SSPU 2021/023 the process is carried out in the presence of less than 2 wt.% added solvent based on the total weight of the reaction mixture.

[0010] In a further aspect, a composition is provided and comprises the polymer composition and up to 60 wt. % of at least one filler, based on the total weight of the composition.

[0011] In another aspect, an article, part or composite material is provided comprising the polymer composition, or composition. The article, part or composite material may be extruded, injection molded or compression molded. Exemplary articles, parts or composite materials include a cable coating, a cable tie, a metal pipe coating, a molded article, an extruded article or a three- dimensional (3D) object.

[0012] In yet another aspect, use of the polymer composition, or composition, for the manufacture of a three-dimensional (3D) object using additive manufacturing, preferably fused deposition modelling (FDM), selective laser sintering (SLS) or multi jet fusion (MJF) is provided.

Description of the Drawings

[0013] FIG. 1 is graph showing the data from tensile testing of annealed bars of comparative example C1 and inventive examples E1 , E4, E5 and E6; and

[0014] FIG. 2 is a graph showing the capillary viscosity data for pellets of comparative example C2 and inventive examples E9-E12. Melt flow rate (MFR) data is shown in the legend of FIG. 2.

Detailed description

[0015] There are provided polymer compositions comprising poly(arylene sulfide) and up to 5 wt.% of at least one epoxy-functionalized aromatic macromer (EFAM). The at least one epoxy-functionalized aromatic macromer has a number average molecular weight (“Mn”) of at most 5000 g/mol.

[0016] It has been surprisingly and unexpectedly discovered that the present polymer composition provides a significant increase in the elongation at break of the polymer composition as compared to an analogous polymer composition without the epoxy-functionalized aromatic macromer. Achieving this result SSPU 2021/023 with such a small amount of any macromer would be surprising and unexpected, but even more so when the macromer utilized is so different from any previously used for this purpose. One of ordinary skill in the art would not expect that an aromatic macromer would provide the same or similar improvements, or even a greater improvement, in the same mechanical property(ies) as provided by conventional impact resistance modifiers/tougheners, which are typically linear.

[0017] Further surprising and unexpected is that the improvements in ductility and toughness do not come at the expense of the strength and stiffness, or even the thermal properties, of the polymer composition. That is to say, the polymer composition provided shows greater ductility and toughness, while substantially maintaining the Tg, Tm, strength and stiffness, as compared to an analogous polymer composition without the epoxy-functionalized aromatic macromer. Advantageously, epoxy-functionalized aromatic macromers are readily commercially available at reasonable cost, and do not require shipping, handling, storage or manufacturing conditions unusual in the art of polymer manufacture or processing. Cost and time efficiencies are thus also provided.

[0018] As used herein, the term “chain” is intended to denote the longest series of covalently bonded atoms that together create a continuous chain in a molecule.

[0019] As used herein, “substantially maintained” is meant to indicate that a property has changed no more than 15%, no more than 10%, no more than 5%, or no more than 1 %, relative to the same property measured in an analogous polymer composition without an epoxy-functionalized aromatic macromer.

[0020] As used herein, the phrase “analogous polymer composition” indicates a polymer composition comprising the same poly(arylene sulfide) and any additives or fillers, but not comprising any epoxy-functionalized aromatic macromer. For example, comparative examples 1 and 2 (C1), below, are each analogous polymer compositions to each of the inventive polymer compositions of Examples 1-12 (E1-E12).

[0021] As used herein, a divalent radical of a bisphenol is the radical resulting from the dehydroxylation of both hydroxyl groups of the bisphenol. SSPU 2021/023

[0022] Any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Further, any element or component recited in a list of elements or components may be omitted from such list.

[0023] Any recitation of numerical ranges by endpoints includes all numbers and subranges subsumed within the recited ranges as well as the endpoints of the range.

[0024] As used herein, the mol% of a particular recurring unit is determined relative to the total number of recurring units in the indicated polymer, unless explicitly indicated otherwise.

[0025] All concentrations expressed as parts per million (“ppm”) are by weight. As used herein, wt.% is relative to the total weight of the polymer composition, unless explicitly stated otherwise.

[0026] The amount of energy in the form of heat required to bring about a change of state of a thermoplastic polymer from the solid to the liquid form is the heat of fusion (“AHf”), and the temperature at which this change of state occurs is called the melting temperature (“T _m ”). AHf and T _m can be measured according to ASTM D3418.

[0027] The glass transition temperature (“T _g ”) is the temperature at which an amorphous material (or an amorphous region within a semicrystalline material) transitions from a hard and relatively brittle state into a viscous or rubbery state. T _g can be measured according to ASTM E1356, “Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry.”

[0028] Values of AHf , T _m and T _g reported herein are determined on the 2 ^nd heat scan in differential scanning calorimetry (“DSC”) using heating and cooling rates of 20°C/min.

[0029] The terms “halogen” or “halo” include fluorine, chlorine, bromine and iodine.

[0030] 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 cyclopropyl. SSPU 2021/023

[0031] Similarly, unless specifically stated otherwise, the term “aryl” is inclusive of both mono- and polynuclear aryl groups. The term “aryl” thus refers to a phenyl, indanyl or naphthyl group. Furthermore, an aryl group may comprise one or more heteroatoms, e.g., N, O, or S, and in such instances may appropriately be referred to as a “heteroaryl” group. Such heteroaromatic rings may also be fused to other aromatic systems. Examples of heteroaromatic rings include, but are not limited to, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothazolyl, pyridyl, pyridazyl, pryimidyl, pyrazinyl and triazinyl ring structures.

[0032] Unless specifically stated otherwise, each alkyl, aryl and heteroaryl group may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, 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.

[0033] For example, an aryl group may comprise one or more alkyl groups, and if this is the case, may be referred to as “alkylaryl.” An aromatic group, for example, may be substituted with one or more C1-C6 alkyl groups, such as methyl or ethyl.

[0034] THE POLY(ARYLENE SULFIDE) POLYMER COMPOSITION

[0035] The polymer composition comprises at least one poly(arylene sulfide) polymer (PAS) and at least one epoxy-functionalized aromatic macromer (“EFAM”).

[0036] In some embodiments, the polymer composition comprises at least 95.0 wt.%, at least 95.5 wt.%, at least 96.0 wt.%, or at least 96.5 wt.% of the poly(arylene sulfide) polymer. In some embodiments, the polymer composition comprises no more than 99.9 wt.%, no more than 99.5 wt.%, no more than 99.0 wt.%, or no more than 98.5 wt.% of the poly(arylene sulfide) polymer. The polymer composition, in some embodiments, comprises from 95 wt.% to 99.9 wt.%, or from 95.5 wt.% to 99.5 wt.%, or from 96.0 wt.% to 99.0 wt.%, or from 96.5 wt.% to 98.5 wt.% of the poly(arylene sulfide) polymer.

[0037] In some embodiments, the polymer composition comprises at least 0.1 wt.%, at least 0.5 wt.%, at least 1.0 wt.%, or at least 1.5 wt.% of the epoxyfunctionalized aromatic macromer. In some embodiments, the polymer SSPU 2021/023 composition comprises no more than 5.0 wt.%, no more than 4.5 wt.%, no more than 4.0 wt.%, or no more than 3.5 wt.% of the epoxy-functionalized aromatic macromer. The polymer composition, in some embodiments, comprises from 0.1 wt.% to 5.0 wt.%, or from 0.5 wt.% to 4.5 wt.%, or from 1 .0 wt.% to 4.0 wt.%, or from 1.5 wt.% to 3.5 wt.% of the epoxy-functionalized aromatic macromer.

[0038] In some embodiments, the weight ratio of the poly(arylene sulfide) polymer to the epoxy-functionalized aromatic macromer in the polymer composition ranges from 95:5 to 99.9:0.1 , from 95.5:4.5 to 99.5:0.5, from 96:4 to 99.0:1.0, from 96.5:3.5 to 98.5:1.5.

[0039] In some embodiments, the polymer compositions exhibit an elongation at break of at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11 %, at least 12%, at least 13%, at least 14%, or least 15%, when measured according to ASTM D638 on a universal testing machine at ambient temperature. Stated another way, and in some embodiments, the polymer compositions exhibit an elongation at break of at least 115%, at least 120%, at least 125%, at least 130%, at least 135%, at least 140%, at least 150%, at least 175%, at least 200%, at least 225%, at least 250%, or at least 275% of the elongation at break of an analogous polymer composition not comprising the epoxy-functionalized aromatic macromer.

[0040] This increase in elongation at break does not come at the expense of elastic modulus and tensile strength, both of which are substantially maintained relative to an analogous polymer composition not comprising the epoxy- functionalized aromatic macromer.

[0041] More specifically, the tensile strength of the present polymer composition is within 10%, within 9%, within 8%, within 7%, within 6%, within 5%, within 4%, within 3%, within 2%, or within 1 % of the tensile strength of an analogous polymer composition not comprising the epoxy-functionalized aromatic macromer when measured according to ASTM D638 on a universal testing machine at ambient temperature.

[0042] Similarly, the elastic modulus of the present polymer composition is within 10%, within 9%, within 8%, within 7%, within 6%, within 5%, within 4%, within 3%, within 2%, or within 1 % of the elastic modulus of an analogous polymer SSPU 2021/023 composition not comprising the epoxy-functionalized aromatic macromer when measured according to ASTM D638 on a universal testing machine at ambient temperature.

[0043] In some embodiments, the polymer composition has a Tm of at least 230 °C, at least 240 °C, at least 250 °C, or at least 260 °C. In some embodiments, the polymer composition has a Tm of no more than 320 °C, no more than 310 °C, no more than 300 °C, or no more than 290 °C. In some embodiments, the polymer composition has a T _m of from 230 °C to 320 °C, from 240 °C to 310 °C, from 250 °C to 300 °C, or from 260 °C to 290 °C.

[0044] In some embodiments, the polymer composition has a Tg of at least 60°C, more preferably of at least 70°C, even more preferably of at least 80°C. In some embodiments, the polymer composition has a Tg of at most 150°C, more preferably of at most 140°C, even more preferably of at most 130°C. In some embodiments, the polymer composition has a Tg of from 60 °C to 150 °C, from 70 °C to 140 °C, from 80 °C to 130 °C.

[0045] In some embodiments, the polymer composition has at least 1 ppm, at least 100 ppm, at least 200 ppm, or at least 300 ppm content of polymer-bonded chlorine.

[0046] In some embodiments, the polymer composition has no more than 2,000 ppm, no more than 1 ,800 ppm, no more than 1 ,500 ppm, or no more than 1 ,200 ppm content of polymer-bonded chlorine.

[0047] In some embodiments, the polymer composition has a content of polymer- bonded chlorine ranging from 1 to 2,000 ppm, from 100 to 1 ,800 ppm, from 200 to 1 ,500 ppm or from 300 to 1200 ppm.

[0048] The content of polymer-bonded chlorine indicates the content of chloro- end groups and is determined according to BS EN 14582.

[0049] Poly(arylene sulfide)

[0050] As used herein, a poly(arylene sulfide) (“PAS”) refers to any polymer including at least 50 mol% of a recurring unit (RPAS) of formula (I):

-[-Ar-S-]- (I)

[0051] wherein Ar is an arylene. SSPU 2021/023

[0052] In some embodiments, recurring unit (RPAS) is represented by a formula selected from the following group of formulae:

[0053] wherein

- Each R is independently selected from the group consisting of a halogen, a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, a C1-C12 alkoxy group and a Ce-Cis aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, -C(CF3)2-, phenyl and -CH2-;

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

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

[0054] In recurring units (RPAS), respective phenylene moieties may independently have 1 ,2-, 1 ,3- or 1 ,4-linkages to moieties other than R. In some embodiments, the total concentration of recurring units (RPAS) wherein the SSPU 2021/023 phenylene moieties have 1 ,2- and/or 1 ,3- linkages is at most 10 mol%, at most 5 mol%, at most 3 mol%, or at most 1 mol%. In some embodiments, the phenylene moieties each independently have 1 ,3 or 1 ,4-linkages to moieties other than R. Preferably, the phenylene moieties have 1 ,4-linkages to moieties other than R.

[0055] In some embodiments, -Ar- of formula (I) is a phenyl group, so that the recurring unit (RPAS) is represented by formula (II). In some such embodiments, the phenyl group is unsubstituted, i.e., i is 0. Preferably, -Ar- of formula (I) is represented by Formula (II) wherein i is 0 and the phenylene moieties have 1 ,4-linkages to moieties other than R so that recurring unit (RPAS) is represented by the following formula (II’):

[0056] In such embodiments, the poly(arylene sulfide) is polyphenylene sulfide.

[0057] In some embodiments, the concentration of recurring unit (RPAS) of formulae

(II), (II’), (III) and/or (IV) in the poly(arylene sulfide) is 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%. In such embodiments, the poly(arylene sulfide) consists essentially of recurring unit (RPAS). In other embodiments, the concentration of recurring unit (RPAS) of formulae (II), (II’),

(III) and/or (IV) in the poly(arylene sulfide) is 100 mol% and in these embodiments, the poly(arylene sulfide) consists of recurring unit (RPAS).

[0058] In some embodiments, the poly(arylene sulfide) comprises at least one functional group at at least one of its chain ends. According to some embodiments, the poly(arylene sulfide) has functional groups at each end of its chain.

[0059] When present, the functional groups of the poly(arylene sulfide) are according to formula (V) below, wherein the dashed bond indicates the bond to the chain end: SSPU 2021/023 wherein Z is selected from the group consisting of a halogen, a carboxyl group, an amino group, a hydroxyl group, a thiol group, an acid anhydride group, an isocyanate group, an amide group, and derivatives thereof such as salts of sodium, lithium, potassium, calcium, magnesium or zinc. Preferably, Z is selected from the group consisting of a hydroxyl group, a thiol group, a hydroxylate and a thiolate.

[0060] In some embodiments, the poly(arylene sulfide) has a weight average molecular weight (“M _w ”) of at least 15,000 g/mol, at least 25,000 g/mol, at least 35,000 g/mol, or at least 45,000 g/mol. In some embodiments, the poly(arylene sulfide) has an M _w of no more than 120,000 g/mol, no more than 110,000 g/mol, no more than 100,000 g/mol, or no more than 90,000 g/mol. In some embodiments, the poly(arylene sulfide) has an M _w of from 15,000 g/mol to 120,000 g/mol, from 25,000 g/mol to 110,000 g/mol, from 35,000 g/mol to 100,000 g/mol, or from 45,000 g/mol to 90,000 g/mol. The M _w of poly(arylene sulfide) can be measured with gel permeation chromatography (“GPC”) using a 4-chloronapthalene standard.

[0061] In some embodiments, the melt flow rate of the poly(arylene sulfide) is at most 1500 g/10 min, 1000 g/10 min, or at most 500 g/10min. In some embodiments, the melt flow rate of the poly(arylene sulfide) is at least 30 g/10 min, at least 40 g/10 min or at least 50 g/10 min. In some embodiments, the melt flow rate of the poly(arylene sulfide) is from 30 to 1500 g/10 min, from 40 to 1000 g/10 min, or from 50 to 500 g/10 min. Melt flow rate can be measured according to ASTM D1238, procedure B, at 315°C under a weight of 5 kg.

[0062] The poly(arylene sulfide) can be amorphous or semi-crystalline. Amorphous polymers lack a detectable T _m , and as such, are typically characterized by heat of fusion, which for amorphous polymers is no more than 5 Joules/g (“J/g”). SSPU 2021/023

[0063] In some embodiments, the poly(arylene sulfide) is semi-crystalline. In such embodiments, the poly(arylene sulfide) has a AHf of at least 10 J/g, at least 20 J/g, at least, or at least 25 J/g. In some of these embodiments, the poly(arylene sulfide) has a AHf of no more than 90 J/g, no more than 70 J/g or no more than 60 J/g. In some embodiments, the poly(arylene sulfide) has a AHf of from 10 J/g to 90 J/g, from 20 J/g to 70 J/g or from 25 J/g to 60 J/g.

[0064] In some embodiments, the poly(arylene sulfide) has a T _m of at least 230 °C, at least 240 °C, or at least 250 °C. In some embodiments, the poly(arylene sulfide) has a T _m of no more 320 °C, no more than 310 °C, or no more than 300 °C. In some embodiments, the poly(arylene sulfide) has a T _m of from 230 °C to 320 °C, from 240 °C to 310 °C, from 250 °C to 300 °C.

[0065] In some embodiments, the poly(arylene sulfide) exhibits a calcium content of less than 200 ppm, as measured according to ASTM LIOP714 - 07.

[0066] Poly(arylene sulfide) can be prepared by known methods. Exemplary poly(arylene sulfides) are commercially available as RYTON® PPS from Solvay Specialty Polymers USA, L.L.C.

[0067] Epoxy-functionalized aromatic macromer

[0068] The epoxy-functionalized aromatic macromer comprises at least one epoxy group. The epoxy group may be either an end group, or a pendant group in a recurring unit. In some embodiments, the epoxy-functionalized aromatic macromer comprises at least one epoxy end group, and preferably, comprises two epoxy end groups.

[0069] As used herein, the phrase “epoxy group” designates a functional group including an oxygen atom joined by single bonds to two adjacent carbon atoms, thus forming a three-membered epoxide ring. In particular, the epoxy group encompasses groups of formulae (VI) and (VII), wherein the dashed bond is the bond to the macromer: SSPU 2021/023

[0070] Wherein R is selected from H and CH3.

[0071] In some embodiments, the epoxy-functionalized aromatic macromer is represented by the following formula (VIII):

[0072] wherein

- Q is an epoxy group;

- Each R1 is independently selected from the group consisting of a C6-C30 aryl group, a C6-C30 alkaryl group, and a C6-C30 aryloxy group;

- R2 is selected from the group consisting of a C1-C10 alkyl group and a C1- C10 alkoxy group; SSPU 2021/023

- Each R3 is independently selected from a C1-C10 alkyl group and a C1-C10 alkoxy group;

- n is any number between 1 and 20, between 1 and 15, between 1 and 10 or between 1 and 5.

[0073] With respect to n, those of ordinary skill in the art understand that a sample of the epoxy functionalized macromer may include a distribution of molecules according to formula VIII having different numbers of repeating units n. In such embodiments, n may be expressed as the average number of repeat units of the distribution of molecules within the sample of epoxy-functionalized macromer.

[0074] In some embodiments, at least one R1 is a compound according to formula (IX):

[0075] Wherein

- Each R4 is independently selected from the group consisting of a halogen, an alkyl, an aryl, and an ether;

- i, for each R4, is independently an integer from 0 to 4, and

- T is selected from the group consisting of a bond, a sulfone group [-S(=O)2-], and a group of formula (X)

-C(R ₅ )(R ₅ )- (X)

[0076] Wherein

- Each R5 is independently selected from a hydrogen, a halogen, an alkyl, an aryl, alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium. SSPU 2021/023

[0077] In some embodiments, each Ri is a divalent radical of a bisphenol, the bisphenol being independently selected from the group consisting of bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z.

[0078] In some embodiments, at least one Ri is a divalent radical of bisphenol A, i.e. , i of formula (IX) is zero and T is a group according to formula (X) wherein each Rs is a methyl group. Preferably, both Ri’s are a divalent radical of bisphenol A.

[0079] In some embodiments, the epoxy-functionalized aromatic macromer has a number average molecular weight (“Mn”) of at most 5,000 g/mol, at most 4,000 g/mol, at most 3,000 g/mol, or at most 2,500 g/mol, as determined by gel permeation chromatography. In some embodiments, the Mn of the epoxyfunctionalized aromatic macromer is at least 500 g/mol, at least 600 g/mol, at least 700 g/mol, or at least 800 g/mol. In some embodiments, the Mn of the epoxy-functionalized aromatic macromer ranges from 500 to 5000 g/mol, from 500 to 4000 g/mol, from 500 to 3000 g/mol or from 500 to 2500 g/mol.

[0080] In some embodiments, the polymer composition comprises at least 0.1 wt.%, at least 0.5 wt.%, at least 1.0 wt.%, or at least 1.5 wt.% of the epoxy- functionalized aromatic macromer. In some embodiments, the polymer composition comprises no more than 5.0 wt.%, no more than 4.5 wt.%, no more than 4.0 wt.%, or no more than 3.5 wt.% of the epoxy-functionalized aromatic macromer. The polymer composition, in some embodiments, comprises from 0.1 wt.% to 5.0 wt.%, or from 0.5 wt.% to 4.5 wt.%, or from 1 .0 wt.% to 4.0 wt.%, or from 1.5 wt.% to 3.5 wt.% of the epoxy-functionalized aromatic macromer.

[0081] In some embodiments, the epoxy-functionalized aromatic macromer has Tg of at least 50°C, more preferably of at least 60°C, even more preferably of at least 70°C. In some embodiments, the epoxy-functionalized aromatic macromer has a Tg of at most 150°C, more preferably of at most 140°C, even more preferably of at most 130°C. In some embodiments, the epoxy- functionalized aromatic macromer has a Tg of from 50 °C to 150 °C, from 60 °C to 140 °C, from 70 °C to 130 °C. SSPU 2021/023

[0082] Additives

[0083] The polymer composition may also comprise one or more additives commonly used in the art including plasticizers, colorants, pigments, (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, heat stabilizers, processing aides, fusing agents, electromagnetic absorbers, flame retardants, nucleating agents, tougheners and antioxidants.

[0084] In embodiments including additives, the total additive concentration is less than 5 wt.%, or less than 4 wt.%, or less than 3 wt.%, or less than 2 wt.%, or less than 1 wt.%.

[0085] PROCESSES OF PREPARING THE POLYMER COMPOSITIONS

[0086] Processes of preparing the polymer composition are also provided. The processes generally comprise blending a reaction mixture comprising the poly(arylene sulfide) polymer and the epoxy-functionalized aromatic macromer at a temperature greater than the T _m of the component with the highest T _m , typically, at least 10°C greater than the T _m of the component with the highest T _m .

[0087] In some embodiments, the process is carried out in the absence of added solvent. As used herein, the absence of added solvent means the added solvent concentration is less than 2 wt.%, less than 1 wt.%, less than 0.05 wt.% or less the 0.001 wt.%. In some such embodiments, the added solvent concentration is not detectable. The absence of solvent is an advantage, as no solvent stripping or recovery process is required, and product contamination by solvent or solvent impurities is avoided.

[0088] When the process is carried out in the presence of added solvent, the solvent is preferably an organic amide solvent. Examples thereof include N-alkyl pyrrolidones, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N- cyclohexyl-2-pyrrolidone, caprolactams, such as N-methyl-s-caprolactam, 1 ,3- dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, diphenyl sulfone and mixtures thereof. Among these, N-methyl-2-pyrrolidone and 1 ,3-dimethyl-2-imidazolidinone are preferred, with N-methyl-2-pyrrolidone being more preferred. SSPU 2021/023

[0089] In some embodiments, the polymer composition is obtained by reactive extrusion (“REX”). Reactive extrusion includes several operations that take place inside the extruder, such as melting, compounding, homogenization and pumping of the reactive materials. The reactive materials and any additives (poly(arylene sulfide) polymer and epoxy-functionalized aromatic macromer) can be introduced at various points along the extruder, or, two or more can be dry blended and introduced simultaneously. In some embodiments, the extruder is a horizontal reactor with one or several internal screws for conveying the reactive materials in the form of a solid or slurry, melt or liquid. The poly(arylene sulfide) polymer may be introduced into the extruder in the form of powder, granules or pellets. The epoxy-functionalized aromatic macromer may be introduced into the extruder in a solid format, such as a powder.

[0090] COMPOSITIONS AND METHODS OF MAKING

[0091] Also provided are compositions comprising the polymer compositions and at least one filler in an amount up to 60 wt.%, based on the total weight of the composition.

[0092] According to various embodiments, said at least one filler is present in the composition in an amount of at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, or at least 20 wt.%, based on the total weight of the composition. In some embodiments, said at least one filler is present in the composition in an amount of at most 60 wt.%, at most 55 wt.%, at most 50 wt.%, or at most 45 wt.%, based on the total weight of the polymer composition. In some embodiments, the composition may comprise from 5 wt.% to 60 wt.%, from 10 wt.% to 55 wt.%, from 15 wt.% to 50 wt.%, or from 20 wt.% to 45 wt.% of the at least one filler, based on the total weight of the composition.

[0093] The at least one filler may be selected from the group consisting of toughening agents, such as elastomers, and reinforcing agents.

[0094] Suitable reinforcing agents are selected from the group consisting of fibrous reinforcing agents, particulate reinforcing agents and mixtures thereof. A fibrous reinforcing agent is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and the thickness. Generally, a fibrous reinforcing agent has an SSPU 2021/023 aspect ratio, defined as the average ratio between the length and the largest of the width and the thickness of at least 5, at least 10, at least 20 or at least 50.

[0095] Fibrous reinforcing agents include glass fibers, carbon or graphite fibers, and fibers formed of silicon carbide, alumina, titania, basalt, boron and the like, and may include mixtures comprising two or more such fibers. Non-fibrous reinforcing agents include but are not limited to talc, mica, titanium dioxide, calcium carbonate, potassium titanate, silica, kaolin, chalk, alumina, and mineral fillers.

[0096] Preferably, the at least one filler is a fibrous reinforcing agent. Among fibrous reinforcing agents, glass fibers and carbon fibers are preferred.

[0097] In addition to the filler, the composition may also comprise at least one additive, or in the event that the polymer composition comprises an additive, an additional amount of at least one additive. Suitable additives include, but are not limited to colorants, dyes, pigments, lubricants, plasticizers, flame retardants, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fusing agents, electromagnetic absorbers and combinations thereof.

[0098] In some embodiments, any additive(s), including any incorporated into the polymer composition, are present in the composition in an amount of less than 5 wt. % , less than 4 wt. % , less than 3 wt. % , less than 2 wt. % , less than 1 wt. % , based on the total weight of the composition.

[0099] The composition can be manufactured by a method comprising mixing the polymer composition, the at least one filler and, optionally, the at least one additional additive. The mixing may occur by dry blending and/or melt compounding, in continuous or batch devices. Such devices are well known to those skilled in the art.

[00100] One example of a class of suitable devices to continuously melt compound the composition are screw extruders. Preferably, melt compounding is carried out in a twin-screw extruder.

[00101] If the composition comprises a fibrous reinforcing agent having a long physical shape (e.g. a long glass fiber), drawing extrusion molding may be used to prepare the composition. SSPU 2021/023

[00102] SHAPED ARTICLES AND APPLICATIONS

[00103] The present invention also relates to an article, part or composite material, comprising the polymer composition or composition as described above. The article, part or composite material of the present invention finds is suitable for use in automotive applications, electric and electronic applications, and consumer goods.

[00104] In some embodiments, the article, part or composite material is molded from the polymer composition or composition by various molding methods such as injection molding, extrusion molding, compression molding, blow molding, and injection compression molding. Preferably, the article, part or composite material is formed via injection molding, compression molding or extrusion molding.

[00105] Furthermore, the article, part or composite material can be molded by a process of extrusion molding requiring a relatively high molding temperature and a long melt residence time, due to the flexibility, extremely high tensile elongation at break and high heat aging resistance of the polymer composition.

[00106] Examples of articles produced by extrusion molding include round bars, square bars, sheets, films, tubes, and pipes. Applications include electrical insulating materials for motors such as water heater motors, air-conditioner motors, and drive motors, film capacitors, speaker diaphragms, recording magnetic tapes, printed board materials, printed board peripherals, semiconductor packages, trays for conveying semiconductors, process/release films, protection films, film sensors for automobiles, insulating tapes for wire cables, insulating washers in lithium ion batteries, tubes for hot water, cooling water, and chemicals, fuel tubes for automobiles, pipes for hot water, pipes for chemicals in chemical plants, pipes for ultrapure water and ultrapure solvents, pipes for automobiles, pipes for chlorofluorocarbons and supercritical carbon dioxide refrigerants, and workpiece-holding rings for polishers. Other examples include molded articles for coating motor coil wires in hybrid vehicles, electric vehicles, railways, and power plants; and molded articles for coating heat-resistant electric wires and cables for household electrical appliances, wire harnesses and control wires such as flat cables SSPU 2021/023 used for the wiring in automobiles, and winding wires of signal transformers and car-mounted transformers for communication, transmission, high frequencies, audios, and measurements.

[00107] Applications of molded articles obtained by injection molding include electrical equipment components such as generators, electric motors, potential transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, multipole rods, and electrical component cabinets; electronic components such as sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, radiators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related components; domestic and office electric appliance components such as VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, acoustic components, audio equipment components for audios, laserdiscs (registered trademark), and compact discs, illumination components, refrigerator components, air conditioner components, typewriter components, and word processor components; machine-related components such as office computer-related components, telephone set-related components, facsimile-related components, copier-related components, cleaning jigs, motor components, lighters, and typewriters: components of optical and precision instruments such as microscopes, binoculars, cameras, and watches; automobile and vehicle-related components such as alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, various valves including exhaust gas valves, various pipes for fuels, exhaust systems, and air intake systems, ducts, turboducts, air intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, thermostat bases for air-conditioners, warming hot air flow control valves, SSPU 2021/023 brush holders for radiator motors, water pump impellers, turbine vanes, windshield wiper motor-related components, distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, airconditioner panel switch boards, coils for fuel solenoid valves, fuse connectors, horn terminals, electric component insulators, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition cases; and gaskets for primary batteries and secondary batteries in cellular phones, notebook computers, video cameras, hybrid vehicles, and electric vehicles.

[00108] The polymer composition and the composition provided herein are suitable for manufacturing cable coatings, cable ties and metal pipe coatings. Particularly, the polymer composition and the composition provided herein are suitable for making molded articles for coating motor coil wires in hybrid vehicles, electric vehicles, railways, and power plants; and various pipes for fuels, exhaust systems, and air intake systems and ducts. The present compositions and polymer compositions are particularly useful in turboducts in automobiles, which are routinely exposed to high-temperatures.

[00109] In some embodiments, the articles are 3D printed from the polymer composition or composition provided herein. Such a 3D process may comprise a step of extrusion of the material, e.g., into the form of a filament, or may comprise a step of selectively sintering the material in powder form.

[00110] The polymer composition or composition can therefore be in the form of a thread or a filament to be used in a process of 3D printing, e.g. Fused Filament Fabrication, also known as Fused Deposition Modelling (FDM), or continuous fiber printing (CF), or in the form of a powder to be used in a process of 3D printing, e.g. Selective Laser Sintering (SLS) and Multi Jet Fusion (MJF).

[00111] Accordingly, the polymer composition and composition provided herein can advantageously be used in 3D printing applications. As such, a process for manufacturing a three-dimensional (3D) article, part or composite material is provided and comprises depositing successive layers of the polymer composition or composition provided herein. SSPU 2021/023

[00112] If the polymer composition or composition is in the form of a powder, the process for manufacturing a 3D object may comprise selective sintering by means of an electromagnetic radiation of the powder.

[00113] If the polymer composition or composition is in the form of a filament, the process for manufacturing a 3D object may comprise the extrusion of the filament.

[00114] 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.

[00115] Exemplary embodiments will now be described in the following non-limiting examples.

[00116] EXAMPLES

[00117] Materials

[00118] RYTON® QA200N PPS is a poly(phenylene sulfide) commercially available from Solvay Specialty Polymers USA, LLC.

[00119] Fortegra 310 (hereinafter “310”) a toughened epoxy resin commercially available from Olin Corporation.

[00120] DER 6224 (hereinafter “6224”) a bisphenol A epoxy resin commercially available from Olin Corporation.

[00121] EPON 2002 (hereinafter “2002”) a bisphenol A epoxy resin commercially available from Hexion.

[00122] EPON 2003 (hereinafter “2003”) a bisphenol A epoxy resin commercially available from Hexion.

[00123] EPON 2004 (hereinafter “2004”) a bisphenol A epoxy resin commercially available from Hexion.

[00124] Fortegra 304 (hereinafter “304”) a toughened epoxy resin commercially available from Olin Corporation.

[00125] EPON 2005 (hereinafter “2005”) a bisphenol A epoxy resin commercially available from Hexion.

[00126] DER 6155 (hereinafter “6155”) a bisphenol A epoxy resin commercially available from Olin Corporation.

[00127] Each of the above epoxy resins are epoxy-functional ized aromatic macromers according to formula (VIII), above, wherein R1 is bisphenol A-derived moiety, SSPU 2021/023

R2 is a C3 alkoxy, R3 is methyl, and Q is an epoxy according to formula (VI) wherein R is H. Number average molecular weight, the n value in Formula (VIII), and Examples in which each macromer were used are provided below in Table 1 . Each macromer sample includes a distribution of molecules having different numbers of repeating units. As shown in Table 1 , n is the average number of repeat units reflected in the distribution of molecules comprising the macromer sample.

SSPU 2021/023

[00128] Table 1

* https://olinepoxy.com/products/toughening-agents-and-toughen ed-epoxy-resins/

** https://www.hexion.com/en-US/chemistry/epoxy-resins-curing-a gents- modifiers/semi-solid-solid-and-powder-grade-resins/powders/

[00129] Methods

[00130] DSC/Heat of fusion

DSC analyses were carried out on a TA Q20 Differential Scanning Calorimeter according to ASTM D3418 and data was collected through a two heat - one cool method. The protocol used is the following: 1 ^st heat cycle from 30.00°C to 350.00°C at 20.00°C/min; isothermal for 5 minutes; 1 ^st cool cycle from 350.00°C to 100.00°C at 20.00°C/min; 2^ heat cycle from 100.00°C to 350.00°C at 20.00°C/min.

[00131] Melt Rheology

Melt rheology studies were carried out on a Dynisco LCR 7000 Capillary Rheometer according to ASTM D3835 at 316 C. Melt flow rate was determined using a Tinius Olsen MP600 Extrusion Plastometer according to ASTM D1238 (Procedure B, 316 C / 5 kg). SSPU 2021/023

[00132] Sample preparation

[00133] Test specimens according to Examples 1 to 8 (E1 - E8) and Control 1 (no epoxy-functionalized aromatic macromer, C1) were injection molded into Type V tensile bars according to ASTM D3641 (using a barrel temperature set at T _m +30°C in a mold regulated at 130°C) and annealed for 8 hours at 150°C.

[00134] Test specimens according to Examples 9 to 12 (E9-E12) and Control 2 (no epoxy-functionalized aromatic macromer, C2) were injection molded into ISO bars on a Toshiba ISG 150 Injection Molder. Additional bars of Control C2 and Examples 11 and 12 were injection molded in the same way and annealed for 8 hours at 150°C prior to testing (Examples C2A, E11A and E12A).

[00135] Tensile Testing

[00136] Annealed bars E1-E8 and C1 were tested at ambient temperature according to ASTM D638 at a speed of 0.05 in/min.

[00137] Bars E9, E10, E11A, E12A and C2A were tested at ambient temperature according to ISO 527-2 at a speed of 1 mm/min

[00138] Impact Testing

[00139] Notched and unnotched bars of unannealed bars C2 and E9-E12 were tested according to ISO 180.

[00140] Example 1

[00141] The compositions shown in Table 2, below were made in a DSM Xplore Microcompounder equipped with a Micro Injection Molding Machine 10cc. The processing conditions used for making the compositions are the following: Recirculation time = 15 minutes;

Screw speed = 200 rpm;

Temperature = 310 °C. SSPU 2021/023

Table 2

[00142] Results

[00143] Table 3 shows the DSC values obtained for the inventive poly(phenylene sulfide) polymer compositions (E1-E8) in comparison to those of poly(phenylene sulfide) polymers not comprising an amount of epoxyfunctionalized aromatic macromer (C1).

[00144] Table 3

[00145] The data reported in Table 3 show that the glass, melt and crystallization transitions for all inventive examples (E1-E8) are substantially unaltered in SSPU 2021/023 comparison to the control (C1). The calculated percent crystallization was 95% or greater for all samples. The heat of fusion values further indicate a similar of crystallinity for all samples.

[00146] Table 4 reports the mechanical properties of the inventive poly(phenylene sulfide) polymer compositions (E1-E8) in comparison to those of poly(phenylene sulfide) polymers not comprising an amount of epoxyfunctionalized aromatic macromer (C1).

[00147] Table 4

[00148] The data reported in Table 4 show that all inventive bars (E1-E8) had greater elongation at break, with bars E1 , E4, E5 and E6 bars exhibiting increases of SSPU 2021/023 up to 160% relative to that of the comparative example (C1). Therefore, the poly(arylene sulfides) of the present invention are much more ductile than the comparative poly(arylene sulfide). This improvement in ductility is provided without significant alteration to the other mechanical properties of the samples, or in the instance of tensile stress and elastic modulus, a slight improvement.

[00149] Example 2

[00150] The compositions shown in Table 5 were made by blending the components in a Coperion ZSK-26 twin screw extruder.

[00151] Table 5

Epoxy-Functionalized Aromatic Macromer (wt. %)

[00152] The components were initially mixed in a plastic bucket and sealed. The bucket was placed on a vibratory shaker for 2-3 minutes to assure homogeneity. The so obtained mixture was then placed in a K-TronT-35 gravimetric feeder and fed into the Coperion ZSK-26 twin screw extruder, melted, and mixed with screws designed to achieve a homogeneous melt composition. The melt stream was cooled and fed into a Maag Primo 60E pelletizer. The pellets were collected and kept in sealed plastic buckets until used for injection molding.

[00153] Results

[00154] Data from the melt rheology studies conducted on pellets of Comparative Example C2 and Examples E9-E12 are shown in FIG. 2. As shown, increasing amounts or lower molecular weight of the epoxy-functionalized aromatic macromer result in increases in viscosity and decreases in melt flow rate of the polymer composition. These data may indicate an increase in molecular weight of the polymer composition. SSPU 2021/023

[00155] Table 6 shows the DSC values obtained for the inventive polymer compositions (E9-E12) in comparison to those of polymer compositions not comprising an amount of epoxy-functionalized aromatic macromer (C2).

[00156] Table 6

[00157] The data reported in Table 6 show that the glass, melt and crystallization transitions for all inventive examples (E9-E12) are substantially unaltered in comparison to the control (C2). The calculated percent crystallization was 100% for all samples. The heat of fusion values further indicate a similar of crystallinity for all samples.

[00158] Table 7 reports the results of tensile testing of the inventive polymer compositions (E9, E10, E11A and E12A) in comparison to those of polymer compositions not comprising an amount of epoxy-functionalized aromatic macromer (C2A).

SSPU 2021/023

Table 7

[00159] As shown in Table 7, all inventive bars (E9, E10, E11A and E12A) had greater elongation at break than the comparative example (C2A), exhibiting increases of 215% or more in elongation at break relative to the comparative example C2A. This improvement in ductility is provided while tensile strength at yield and modulus remain close to parity with the comparative example. Therefore, the inventive polymer compositions are much more ductile than the comparative polymer composition, while retaining similar mechanical and thermal properties.

[00160] Tables 8 and 9 report the results of impact testing of notched (Table 8) and unnotched (Table 9) bars of the inventive polymer compositions (E9-E12) in comparison to those of a polymer composition not comprising an amount of epoxy-functionalized aromatic macromer (C2). SSPU 2021/023

[00161] Table 8

[00162] Table 9

[00163] As reported in Table 9, unnotched bars prepared from the inventive polymer composition showed such great impact resistance and toughness that a break energy could not be determined for these samples. Further, unnotched bars of inventive examples E9-E12 show a number of partial breaks, and samples E10 and E11 show 2 and 9 non-breaks, respectively. These results indicate SSPU 2021/023 enhanced resistance to impact and toughness as compared to the comparative example C2.