Amine-functionalized poly(arylene sulfide) polymers

Abstract

The present invention relates to certain amine-functionalized polyarylsulfide polymers that offer a compromise of advantageous properties, namely, molecular weight to ensure sufficient mechanical properties, sufficient amine functionalization for suitable reactivity towards epoxies, and melting points not exceeding about 260° C. to allow reaction in the molten state in liquid epoxies during cure, methods for their preparation, and their use in coating applications.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 335,254, filed April 27, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to amine-functionalized poly(arylene sulfide) polymers, their preparation process, and compositions containing said polymers and the use of said compositions for coatings, in particular for heat and chemical resistant coatings for use in chemical process piping or in the oil and gas sector. [Background technology]

[0003] Poly(arylene sulfide) (PAS) polymers, including polyphenylene sulfide (PPS) polymers, are well-known polymers that have excellent properties that make them suitable for engineering plastics, such as heat resistance, chemical resistance, electrical insulation, moldability, and mechanical properties.

[0004] PPS, a typical PAS, has a T of 85℃~100℃. g and a melting temperature (T m ) in a polar solvent. 2 It is formed by the reaction of sodium hydrosulfide (NaSH) with p-dichlorobenzene.

[0005] Amine-functionalized PAS polymers, i.e., PAS containing at least one amine as an end group on the backbone or as a side group, are also known and have been promoted for a variety of functionalities and advantageous properties, particularly related to their ability to bind impact modifiers, adhesives, or fillers.

[0006] Methods for introducing amine groups into PAS copolymers by copolymerizing dihaloaromatic compounds with dichloroanilines are known, inter alia, from JP 3,599,124 and JP 3,779,336.

[0007] These documents teach that the dihaloaromatic compound is preferably p-dichlorobenzene, thus resulting in a PPS-type poly(arylene sulfide), although small amounts (up to 20 mol %) of additional dihaloaromatic compounds, including particularly m-dichlorobenzene and o-dichlorobenzene, are sometimes tolerated.

[0008] PAS have heat and chemical resistance which may make them particularly desirable for use in applications where they are exposed to high temperature hydrocarbon fluids, such as the transport of corrosive fluids in chemical processing piping, and the transport of oil and gas in deep reservoir drilling.

[0009] Certain classes of coatings used in the chemical industry and / or oil and gas recovery, such as coatings based on fusion-bonded epoxies, have cure temperatures not exceeding 260° C. As previously mentioned, PASs can provide beneficial properties to such coatings, but in order to be incorporated into such cured coatings, the PAS requires both reactive functional groups (such as amines) and a melting temperature below 260° C. A PAS possessing both of these advantageous characteristics will be in a molten state at the cure temperature, i.e., prone to intermingling and blending, and possibly reacting to form an interpenetrating network that is chemically bonded with the host polymer matrix of the coating.

[0010] Thus, there is a need in the art for a PAS polymer that has a compromise of such properties, namely, molecular weight to ensure sufficient mechanical properties, sufficient amine functionalization for adequate reactivity towards the epoxy, and a melting point not exceeding about 260° C. to allow reaction in the molten state in the liquid epoxy during cure.

[0011] Additionally, there is a need in the art for a method to prepare such PAS polymers in an effective and simple manner that results in a fully amine-functionalized polymer while avoiding tedious post-functionalization procedures. Summary of the Invention

[0012] In a first aspect, the present invention provides a poly(arylene sulfide) polymer [polymer (PAS)] having a weight average molecular weight of at least 24,000 as determined by gel permeation chromatography, from 85.0 to 97.0 mol % of [-Ar p -S-] (R PASp ) (In the formula, -Ar p -teeth [ka] is) The repeating unit (R PASp )and, from 2.5 to 10.0 mol % of the formula: [-Ar o / m -S-] (R PASo / m ) (In the formula, -Ar p / m -teeth [ka] (either The repeating unit (R PASo / m )and, from 0.5 to 5.0 mol % of the formula: [-Ar n -S-] (R PASn ) (In the formula, -Ar n -teeth [ka] is) The repeating unit (R PASn )and, Including, · The mole % is determined relative to the total moles of repeat units of the polymer (PAS); R, in each case, C 1 ~C 12 Alkyl group, C 7 ~C 24 Alkylaryl group, C 7 ~C 24 Aralkyl group, C 6 ~C 24 Arylene groups, and C 6 ~C 18 aryloxy groups; i, at each occurrence, is an independently selected integer from 0 to 4; j, in each occurrence, is an independently selected integer from 0 to 3; Regarding polymers (PAS).

[0013] In all of the above formulas (a1) to (a4), the dashed bond symbol ( [ka] ) is used to represent the bond to the sulfur atom attached to the adjacent repeat unit.

[0014] The polymers (PAS) of the present invention advantageously have a combination of properties suitable for use in combination with fusion-bonded epoxies, namely, excellent mechanical properties, high reactivity, and low melting points, particularly the cure temperatures of fusion-bonded epoxies (T less than about 260° C.). m ) has the ability to reach a molten state.

[0015] In a second aspect, the present invention relates to a process for the preparation of a poly(arylene sulfide) polymer, in particular a polymer (PAS) as detailed above, comprising the steps of: 85.0 to 97.0 mol % of at least one first dihalo compound of the following formula: X-Ar p -X'(in the formula, -Ar p -teeth [ka] ) and 2.5 to 10.0 mol % of at least one second dihalo compound of the following formula: X″-Ar o / m -X"' (in the formula, -Ar o / m -teeth [ka] ) and 2.5 to 5.0 mol % of at least one third dihalo compound of the following formula: X' v -Ar n -X v (In the formula, -Ar n -teeth [ka] ) and reacting a monomer mixture containing X, X', X”, X”', X' v , and X v each of is an independently selected halogen, preferably chlorine or bromine, more preferably chlorine; R, in each case, C 1 ~C 12 Alkyl group, C 7 ~C 24 Alkylaryl group, C 7 ~C 24 Aralkyl group, C 6 ~C 24 Arylene groups, and C 6 ~C 18 aryloxy groups; i, at each occurrence, is an independently selected integer from 0 to 4; j, in each occurrence, is an independently selected integer from 0 to 3; It concerns the method.

[0016] In a third aspect, the present invention provides a method for producing a composition comprising the steps of: The above-mentioned polymer (PAS), at least one epoxy resin, The present invention relates to a composition (C) comprising:

[0017] The applicant has disclosed that in the polymer (PAS) described above, the repeating unit (R PASp ), repeating unit (R PASo / m ), and repeating units (R PASn It has been found that by combining these two components in the amounts specified above, an optimum balance of performance can be achieved, including proper functionalization, an acceptable molecular weight range, and a moderate melting point, to facilitate the penetration of the polymer (PAS) in a variety of curable coating applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] In this application, any description is described in relation to a particular embodiment, but is applicable and interchangeable with other embodiments of the present disclosure.

[0019] Where in this application an element or component is said to be included in and / or selected from a list of enumerated elements or components, in the relevant embodiments expressly contemplated herein, the element or component can also be any one of the individual enumerated elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; it should be understood that any element or component enumerated in a list of elements or components may be omitted from such list.

[0020] In this application, any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range, and equivalents thereof.

[0021] Poly(arylene sulfide) polymer [Polymer (PAS)] As mentioned above, poly(arylene sulfide) polymer [polymer (PAS)] is Repeating units (RPASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Including, The mole percentages herein are determined relative to the total moles of repeat units in the polymer (PAS).

[0022] Repeating unit (R PASo / m If the amount of .alpha.-phenylene ether is less than 2.5 mole percent, the polymer (PAS) will not be optimized, and in particular the melting point will be too high for the polymer (PAS) to be useful in certain curable coating compositions, such as molten epoxy solutions.

[0023] On the other hand, the amount of repeating units (R PASo / m When the carboxylate ester (C) exceeds 10.0 mole %, the ability to achieve the proper molecular weight of the polymer (PAS) is adversely affected, which generally impedes mechanical property performance.

[0024] The polymer (PAS) is a repeating unit of the following formula (R PASt ) may further include: [-Ar t -S-] (R PASt ) (In the formula, -Ar t -teeth, [ka] and R, in each case, C 1 ~C 12 Alkyl group, C 7 ~C 24 Alkylaryl group, C 7 ~C 24 Aralkyl group, C 6 ~C 24 Arylene groups, and C 6 ~C 18 aryloxy groups; k, at each occurrence, is an independently selected integer from 0 to 3; m is 1 or 0 in each case).

[0025] In formula a5), the bond symbol [ka] is the repeating unit (R PASp ), (R PASo / m ), and / or (R PASn ) is intended to denote a polymer chain comprising a sequence of

[0026] Thus, the polymer (PAS) of the present invention is Repeating units (R PASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Optionally, the repeat unit (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0027] Preferably, the polymer (PAS) of the present invention is Repeating units (R PASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Optionally, the repeat unit (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0028] More preferably, the polymer (PAS) of the present invention is Repeating units (RPASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Optionally, the repeat unit (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0029] According to a particular embodiment, the polymer (PAS) is in fact a repeating unit (R PASt ).

[0030] According to these embodiments, the polymer (PAS) of the present invention comprises: Repeating units (R PASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Repeating units (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0031] Preferably, the polymer (PAS) of the present invention is Repeating units (R PASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Repeating units (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0032] More preferably, the polymer (PAS) of the present invention is Repeating units (R PASp )and, Repeating units (R PASo / m )and, Repeating units (R PASn )and, Repeating units (R PASt )and, where mole % is determined relative to the total moles of repeat units in the polymer (PAS).

[0033] According to one embodiment of the present invention, the polymer (PAS) comprises a repeating unit (R PASp ), (R PASo / m ), (R PASn ), and optionally (R PASt As mentioned above, according to another particular embodiment, the polymer (PAS) consists or essentially consists of repeating units (R PASp ), (R PASo / m ), (R PASn ), and (R PASt The term "consisting essentially of" when used in relation to the repeat units of a polymer (PAS) is intended to mean that small amounts of erroneous repeat units can be tolerated without significantly altering the advantageous properties of the polymer (PAS). Amounts less than 1 mole percent are generally not expected to significantly affect the properties of the polymer (PAS).

[0034] Repeating unit (R PASp ) is preferably a repeating unit of the following formula (R PPSp ): [ka] It is.

[0035] Similarly, the repeating unit (R PASo / m) is preferably a repeating unit of the following formula (R PPSo ) and (R PPSm ): [ka] is selected from the group consisting of:

[0036] Furthermore, the repeating unit (R PASn ) is preferably represented by the following formula (R PPSn,o ), (R PPSn,m ), (R PPSn,p ): [ka] Any repeating unit (R PPSn ).

[0037] The repeating units detailed above are units derived from the polycondensation reaction of dihaloanilines, particularly dichloroanilines.

[0038] Most preferably, the repeating unit (R PASn ) is expressed by the formula (R PPS_TCA ) repeating unit: [ka] It is.

[0039] Furthermore, the repeating unit (R PASt ) is preferably of the following formula: [ka] Repeating units (R PPSt ) and m is 0 or 1, and preferably m is zero.

[0040] Thus, the polymer (PAS) of the present invention is preferably a polyphenylene sulfide polymer [polymer (PPS)], which is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Optionally, the repeat unit (R PPSt )and, where mole % is determined relative to the total moles of repeat units of the polymer (PPS).

[0041] Preferably, the polymer of the present invention (PPS) is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Optionally, the repeat unit (R PASt ), where mole percent is determined relative to the total moles of repeat units of the polymer (PPS).

[0042] More preferably, the polymer (PAS) of the present invention is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Optionally, the repeat unit (R PPSt )and, where mole percent is determined relative to the total moles of repeat units of the polymer (PPS).

[0043] According to a particular embodiment, the polymer (PAS) is preferably a polyphenylene sulfide polymer [polymer (PPS)], which is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Repeating units (R PPSt )and, where mole percent is determined relative to the total moles of repeat units of the polymer (PPS).

[0044] Preferably, the polymer (PPS) of these embodiments is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Repeating units (R PASt )and, where mole percent is determined relative to the total moles of repeat units of the polymer (PPS).

[0045] More preferably, the polymer (PAS) of these embodiments is Repeating units (R PPSp )and, The repeating units (R PPSo ) and / or repeating units (R PPSm )and, Repeating units (R PPSn )and, Repeating units (R PPSt )and, where mole percent is determined relative to the total moles of repeat units of the polymer (PPS).

[0046] Most preferably, in all the above listed preferred polymers (PPS), the repeating unit (R PPSn ) is expressed by the formula (R PPS_TCA ) is a unit of mass.

[0047] Preferably, the polymer (PAS) has a weight average molecular weight (Mw) as determined by gel permeation chromatography of at least 25,000 g / mol, more preferably at least 26,000 g / mol, and even more preferably at least 27,000 g / mol.

[0048] Preferably, the polymer (PAS) has a weight average molecular weight (Mw) determined by gel permeation chromatography of at most 120,000 g / mol, more preferably at most 110,000 g / mol, even more preferably at most 100,000 g / mol, even more preferably at most 90,000 g / mol.

[0049] Preferably, the polymer (PAS) has a melting point (T) of at least 230° C., more preferably at least 235° C., and even more preferably at least 240° C., as determined by a second heat scan in a differential scanning calorimetry (DSC) according to ASTM D3418 using a heating and cooling rate of 20° C. / min. m ).

[0050] Preferably, the polymer (PAS) has a melting point (T) of at most 265°C, more preferably at most 264°C, and even more preferably at most 263°C, as determined by a second heat scan in Differential Scanning Calorimetry (DSC) according to ASTM D3418 using a heating and cooling rate of 20°C / min. m ).

[0051] The polymer (PAS) may advantageously include at least one functional group at at least one of its chain ends, for example the polymer (PAS) may have a functional group at each end of its chain.

[0052] When present, the functional group has formula (I) below: [ka] wherein Z is selected from the group consisting of halogen atoms (e.g., chlorine), carboxyl groups, amino groups, hydroxyl groups, thiol groups, acid anhydride groups, isocyanate groups, amide groups, and derivatives thereof, such as the sodium, lithium, potassium, calcium, magnesium, and zinc salts. Follow.

[0053] Preferably, the functional groups, if present, are selected from the group consisting of amino groups, hydroxyl groups, thiol groups, hydroxylates, and thiolates.

[0054] Such end groups can be suitably introduced into the polymer (PAS) of the present invention by using suitable monohalogenated functional compounds during the preparation of the polymer (PAS) itself and / or by suitable chemical reactions at the end groups.

[0055] Method for producing poly(arylene sulfide) polymers As mentioned above, in a second aspect, the present invention relates to a method for the preparation of a poly(arylene sulfide) polymer, in particular the polymer (PAS) as detailed above, which comprises reacting a dihalo compound X-Ar as defined above in the presence of at least one sulfur compound [compound (SC)]. p -X' and X"-Ar o / m -X”' and X' v -Ar n -X v and reacting a mixture containing

[0056] Optionally, the mixture further comprises at least one trihalo compound of formula (II): [ka] (In the formula, R, in each case, C 1 ~C 12 Alkyl group, C 7 ~C 24 Alkylaryl group, C 7 ~C 24 Aralkyl group, C 6 ~C 24 Arylene groups, and C 6 ~C 18 aryloxy groups; k, at each occurrence, is an independently selected integer from 0 to 3; m, in each occurrence, is either 1 or 0, preferably m is 0; X 1 , X 2 , and X 3 each of which is an independently selected halogen, preferably chlorine or bromine, more preferably chlorine.

[0057] The dihalo compounds X-Ar p -X', X"-Ar o / m -X”' and X' v -Ar n -X v The amount of the trihalo compound of formula (II), as well as the amount of the corresponding repeat unit (R PASp ), (R PASo / m ), (R PASn ), and where appropriate (R PASt ) target amount.

[0058] Thus, as previously mentioned, the monomer mixture is 85.0-97.0 mol % of dihalo compounds X-Ar p -X' and 2.5 to 10.0 mol % of the dihalo compound X″-Ar o / m -X”' and 0.5 to 5.0 mol % of dihalo compound X' v -Ar n -X v and, where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0059] In particular, the monomer mixture may be 85.0-97.0 mol % of dihalo compounds X-Ar p -X' and 2.5 to 10.0 mol % of the dihalo compound X″-Ar o / m -X”' and 0.5 to 5.0 mol % of a dihalo compound X' v -Ar n -X v and, optionally, a trihalo compound of formula (II) in an amount of 0 to 3.0 mol %, where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0060] Preferably, the monomer mixture comprises: 88.0-96.0 mol % of dihalo compounds X-Ar p -X' and 3.0-8.0 mol % of the dihalo compound X″-Ar o / m -X”' and A dihalo compound X' in an amount of 1.0 to 4.0 mol % v -Ar n -X v and, optionally, a trihalo compound of formula (II) in an amount of 0 to 2.0 mol %, where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0061] More preferably, the monomer mixture comprises 89.0-94.5 mol % of dihalo compounds X-Ar p -X' and 4.0-7.5 mol % of the dihalo compound X”-Ar o / m -X”' and Dihalo compound X' in an amount of 1.5 to 3.5 mol % v -Ar n -X v and, optionally, a trihalo compound of formula (II) in an amount of 0 to 1.5 mol %, where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0062] The polymer (PAS) is actually a repeating unit (R PASt In embodiments comprising the monomer mixture, 85.0-96.8 mol % of dihalo compounds X-Ar p -X' and 2.5 to 10.0 mol % of the dihalo compound X″-Ar o / m -X”' and 0.5 to 5.0 mol % of a dihalo compound X' v -Ar n -X v and, a trihalo compound of formula (II) in an amount of 0.2 to 3.0 mol %; where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0063] Preferably, the monomer mixture according to these embodiments comprises: Dihalo compounds X-Ar in an amount of 88.0-95.7 mol % p -X' and 3.0-8.0 mol % of the dihalo compound X″-Ar o / m -X”' and A dihalo compound X' in an amount of 1.0 to 4.0 mol % v -Ar n -X v and, a trihalo compound of formula (II) in an amount of 0.3 to 2.0 mol %; where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0064] More preferably, the monomer mixture according to these embodiments comprises: 89.0-94.0 mol % of dihalo compounds X-Ar p -X' and 4.0-8.0 mol % of the dihalo compound X″-Ar o / m -X”' and Dihalo compound X' in an amount of 1.5 to 4.0 mol % v -Ar n -X v and, a trihalo compound of formula (II) in an amount of 0.5 to 1.5 mol %; where mole percent is determined relative to the total moles of compounds in the monomer mixture.

[0065] In all of the above embodiments, the formula X-Ar p The first dihalo compound of -X' is preferably para-dihalobenzene, more preferably para-dichlorobenzene.

[0066] In all of the above embodiments, the formula X″-Ar o / m The second dihalo compound of -X"' is preferably selected from the group consisting of ortho-dihalobenzenes and meta-dihalobenzenes, more preferably selected from the group consisting of ortho-dichlorobenzenes and meta-dichlorobenzenes.

[0067] In all of the above embodiments, the formula: X' v -Ar n -X v The third dihalo compound is preferably a dihaloaniline, preferably selected from the group consisting of 3,5-dichloroaniline, 2,5-dichloroaniline, and 2,6-dichloroaniline, with 3,5-dichloroaniline being preferred.

[0068] In all the above embodiments, the trihalo compound of formula (II) is preferably a trihalobenzene, more preferably 1,2,4-trichlorobenzene.

[0069] The sulfur compounds (SC) used in the process of the present invention are selected from the group consisting of thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides, and hydrogen sulfide. Preferably, the sulfur compounds are alkali metal sulfides. In some embodiments, the alkali metal sulfides are generated in situ from alkali metal hydrosulfides and alkali metal hydroxides. For example, Na 2 S is a particularly preferred alkali metal sulfide that can be advantageously used as the sulfur compound (SC). 2 S can be generated in situ from NaSH and NaOH.

[0070] The polymerization solvent is selected to be a solvent for the reactants at the reaction temperature (described below). In some embodiments, the polymerization solvent is a polar aprotic solvent. Examples of desirable polar aprotic solvents include, but are not limited to, hexamethylphosphoramide, tetramethylurea, n,n-ethylenedipyrrolidone, N-methyl-2-pyrrolidone ("NMP"), pyrrolidone, caprolactam, n-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. Preferably, the polymerization solvent is NMP. In embodiments in which the polymerization solvent comprises NMP, NMP can be reacted with NaOH to form N-methyl-1,4-aminobutanoate ("SMAB").

[0071] In some embodiments, the reaction components further comprise a molecular weight modifier. The molecular weight modifier may contribute to increasing the molecular weight of the polymer (PAS) compared to a synthesis scheme that does not include a molecular weight modifier. Preferably, the molecular weight modifier is an alkali metal carboxylate. The alkali metal carboxylate has the formula: R'CO 2 M', where R' is C 1 ~C 20 Hydrocarbyl group, C 1 ~C 20 Hydrocarbyl groups, and C 1 ~C5 and M' is selected from the group consisting of lithium, sodium, potassium, rubidium, or cesium. Preferably, M' is sodium or potassium, and most preferably sodium. Preferably, the alkali metal carboxylate is sodium acetate.

[0072] The process of the invention advantageously comprises the step of reacting a dihalo compound X-Ar p -X', X"-Ar o / m -X”' and X' v -Ar n -X v and optionally the trihalo compound of formula (II) as described above, p -X', X"-Ar o / m -X”' and X' v -Ar n -X v and an optional trihalo compound of formula (II) and reacting the SC at a reaction temperature selected to polymerize to form a polymer (PAS). In some embodiments, the temperature at which the monomer mixture is reacted ranges from 170° C. to 450° C., or from 200° C. to 285° C. The reaction time (i.e., duration of the polymerization reaction) can be from 10 minutes to 3 days, or from 1 hour to 8 hours. In the method of the present invention, the pressure (reaction pressure) is advantageously selected to maintain the monomer mixture and solvent (if used) in the liquid phase during the reaction. 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.

[0073] The process of reacting the monomer mixture can be stopped by cooling the product mixture to a temperature at which the polymerization reaction is stopped. "Product mixture" refers to the mixture formed during the reaction, including any remaining unreacted monomer mixture components, the polymer (PAS) formed, and any reaction by-products. Cooling can be accomplished using a variety of techniques known in the art. In some embodiments, cooling can be accomplished by rapidly flashing the reaction mixture. In some embodiments, cooling can include liquid quenching. In liquid quenching, a quenching liquid is added to the reaction mixture to cool the product mixture. In some embodiments, the quenching liquid is selected from the group consisting of the polymerization solvent, water, and combinations thereof. In some embodiments, the quenching liquid can have a temperature of about 15°C to 99°C. In some embodiments, the quenching liquid can have a temperature of 54°C to 100°C (e.g., in embodiments where the quenching liquid is a solvent) or 15°C to 32°C (e.g., in embodiments where the quenching liquid is water). Cooling can be further facilitated by cooling the reaction vessel in which the polymerization reaction is carried out ("polymerization reactor") using a reactor jacket or coils. For clarity, termination of a polymerization reaction does not mean complete reaction of the reactants. Generally, termination is initiated when the polymerization reaction is substantially complete or reaches a target yield, or when further reaction of the reactants does not result in a significant increase in the average molecular weight of the polymer (PAS).

[0074] After the reaction is complete, the polymer (PAS) is usually present in a mixed state in the product mixture. The product mixture usually further includes water, solvent, reaction by-products such as salts (e.g., sodium chloride and sodium acetate), oligomers, and any unreacted reaction components (collectively "post-reaction compounds"). After the reaction is complete, the product mixture containing the polymer (PAS) is usually present as a slurry (precipitated from the solvent during liquid quenching or flashing) having a liquid phase and a solid phase containing the polymer (PAS). In some embodiments, the product mixture containing the polymer (PAS) can be obtained as the polymer (PAS) in a wet state, for example, by filtering the slurry after the stoppage.

[0075] Following quenching, a recovery process can be performed that includes one or more washes, each wash including contacting the polymer (PAS) formed during the polymerization reaction with a liquid, each wash liquid being independently selected from water, an aqueous acid solution, and an aqueous metal cation solution.

[0076] Following the recovery process, the polymer (PAS) can be dried. Drying can be carried out at any temperature that can substantially dry the polymer (PAS) to obtain a dried polymer (PAS). Desirably, the drying process is selected to help prevent oxidative hardening of the polymer (PAS). For example, if the drying process is carried out at a temperature of at least 100°C, the drying can be carried out in a substantially non-oxidizing atmosphere (e.g., a substantially oxygen-free atmosphere or at a pressure lower than atmospheric pressure, e.g., under vacuum). If the drying process is carried out at a temperature below 100°C, the drying process can be accelerated by carrying out the drying at a pressure lower than atmospheric pressure, which can result in vaporization of liquid components from the polymer (PAS). If the drying is carried out at a temperature below 100°C, the presence of a gaseous oxidizing atmosphere (e.g., air) usually does not result in detectable hardening of the polymer (PAS).

[0077] Composition (C) and its manufacturing method As mentioned above, the present invention also relates to a composition (C) containing the above polymer (PAS) and at least one epoxy resin.

[0078] Suitable epoxy resin compositions for use in composition (C) include, but are not limited to, epoxy ethers formed by the reaction of epihalohydrins, such as epichlorohydrin, with polyphenols, typically in the presence of an alkali. Suitable polyphenols include, for example, catechol, hydroquinone, resorcinol, bis(4-hydroxyphenyl)-2,2-propane (bisphenol A), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyphenyl)-1,1-ethane, bis(2-hydroxyphenyl)-methane, 4,4-dihydroxybenzophenone, 1,5-hydroxynaphthalene, and the like. Bisphenol A and diglycidyl ethers of bisphenol A are preferred.

[0079] Suitable epoxy resins also include polyglycidyl ethers of polyhydric alcohols. These compounds can be derived from polyhydric alcohols, such as, for example, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and the like. Other suitable epoxides or polyepoxides include polyglycidyl esters of polycarboxylic acids formed by the reaction of epihalohydrins or other epoxy compositions with aliphatic or aromatic polycarboxylic acids, such as, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, and the like. In one embodiment, polyglycidyl esters of polycarboxylic acids can also be produced by reacting dimerized unsaturated fatty acids with polymeric polycarboxylic acids.

[0080] In one embodiment, epoxy resins suitable for use in composition (C) can be derived by oxidation of an ethylenically unsaturated alicyclic compound which is epoxidized by reaction with oxygen, perbenzoic acid, acid-aldehyde monoperacetate, peracetic acid, and the like. Polyepoxides produced by such reactions are known to those skilled in the art and include, but are not limited to, epoxy alicyclic ethers and esters.

[0081] In one embodiment, the epoxy resin includes epoxy novolac resins obtained by the reaction of condensation products of aldehydes with monohydric or polyhydric phenols with epihalohydrin. Examples include, but are not limited to, the reaction products of condensation products of formaldehyde with various phenols (e.g., phenol, cresol, xylenol, butylmethylphenol, phenylphenol, biphenol, naphthol, bisphenol A, bisphenol F, etc.) with epichlorohydrin.

[0082] In one embodiment, composition (C) is a curable composition further comprising at least one curing agent. In one embodiment, the curing agents described herein are useful for achieving composition (C) with a curing time on the order of about 3 minutes or less. The curing agent is typically selected to be compatible with composition (C) and to function to cure composition (C) only when melted at the temperature used to cure composition (C).

[0083] Suitable hardeners include dihydrazides prepared by reacting carboxylic acid esters with hydrazine hydrate. Such reactions are known to those skilled in the art and produce, for example, carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, ethylmalonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, isophthalic acid dihydrazide, icosane diacid dihydrazide, valine dihydrazide, and mixtures thereof. Among these, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, icosane diacid dihydrazide, valine dihydrazide are preferred, and sebacic acid dihydrazide is particularly preferred.

[0084] Composition (C) may also contain at least one additive, for example in an amount of less than 10 weight percent, selected from the group consisting of colorants, dyes, pigments, lubricants, plasticizers, flame retardants, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof, where weight percent is based on the total weight of composition (C).

[0085] Composition (C) may also contain at least one filler different from the above additives. When present, said filler may be present in composition (C) in an amount of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, based on the total weight of composition (C).

[0086] According to various embodiments of the present invention, said at least one filler may be present in composition (C) in an amount of up to 60% by weight, up to 55% by weight, up to 50% by weight, up to 45% by weight, based on the total weight of polymer composition (C).

[0087] According to various embodiments of the present invention, the at least one additional additive described above may be present in composition (C) 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 composition (C).

[0088] The at least one filler may be selected from the group consisting of reinforcing agents and reinforcing agents.

[0089] The toughening agent is preferably selected from elastomers. In a preferred embodiment, the toughening agent is present in composition (C) in an amount of not more than 30% by weight, for example not more than 25% by weight, based on the total weight of composition (C).

[0090] The reinforcing agent may be selected from the group consisting of fibrous reinforcing fillers, particulate reinforcing fillers, and mixtures thereof. Fibrous reinforcing fillers are herein considered to be materials having a length, width, and thickness, the average length being significantly greater than both the width and thickness. Generally, fibrous reinforcing fillers have an aspect ratio, defined as the average ratio between the length and the maximum width and thickness, of at least 5, at least 10, at least 20, or at least 50.

[0091] Fibrous reinforcing fillers include glass fibers, carbon or graphite fibers, and fibers formed from silicon carbide, alumina, titania, boron, etc., and can include mixtures containing two or more such fibers. Non-fibrous reinforcing fillers include talc, mica, titanium dioxide, calcium carbonate, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, etc., among others.

[0092] Preferably, said at least one filler is a fibrous reinforcing filler. Among the fibrous reinforcing fillers, glass fibers and carbon fibers are preferred. According to a preferred embodiment of the present invention, said composition (C) comprises 60% by weight or less, for example 30-40% by weight of glass fibers and / or carbon fibers, based on the total weight of composition (C).

[0093] According to a particular embodiment, composition (C) can be used to formulate a composite solution.

[0094] According to a particular embodiment, composition (C) is a powder coating composition. Powder coating compositions are fusible compositions made from loose particles that melt upon application of heat to form a coating film. The powder can be applied using methods known to those skilled in the art, such as electrostatic spraying, and cured to a dry film thickness of about 200 to about 500 microns, preferably 300 to 400 microns.

[0095] Articles and uses In one embodiment, the present invention provides a method of coating a substrate using composition (C) as detailed above.

[0096] The use of composition (C) makes it possible to combine the advantageous properties of the epoxy resin and the polymer (PAS), while still achieving a homogeneous interpenetrating coating network by curing the epoxy resin at a temperature at which the polymer (PAS) can react in the molten state.

[0097] In particular, powder coatings of the type described herein are used on oil and natural gas pipelines, i.e. large diameter pipes made from high grade steel.

[0098] In one embodiment, the powder composition is preferably applied to the surface of a substrate, preferably a metal substrate, more preferably a high performance steel substrate. The powder composition is applied using methods known to those skilled in the art, such as, for example, electrostatic spraying. Prior to applying the powder coating, the substrate is typically preferably degreased and shot blasted, preferably to a depth of about 50-70 μm.

[0099] In one embodiment, the method described herein includes applying the powder composition to a substrate and curing the composition on the substrate. In one aspect, the powder composition is applied to the substrate by conventional methods, such as, for example, electrostatic spraying. The coated substrate is then heated until the powder particles melt and fuse together, followed by curing of the coating at the same temperature.

[0100] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements in this application to the extent that any term may be unclear, the statements in this application shall control.

[0101] The present invention will now be described with reference to the following examples, the purposes of which are illustrative only and are not intended to limit the scope of the invention. EXAMPLES

[0102] Experimental section raw materials 1-Methyl-2-pyrrolidone ("NMP") (>99.0%): available from TCI Sodium hydrogen sulfide ("NaSH") (55-60% by weight): available from AkzoNobel 1,4-Dichlorobenzene ("DCB") (≧99): obtained from Alfa Aesar 1,3-Dichlorobenzene ("mDCB") (≧99): Obtained from Alfa Aesar Sodium hydroxide (≥97.0%): obtained from Fisher Chemical Sodium acetate (≥99%): available from VWR Chemicals 3,5-Dichloroaniline ("DCA") (98%): obtained from Alfa Aesar 1,2,4-Trichlorobenzene ("TCB") (99%): Obtained from Alfa Aesar 3,3',4,4'-biphenyltetracarboxylic dianhydride ("BPDA") (97%): obtained from Sigma

[0103] Characterization The extrusion rate, referred to as "1270ER", was measured by the method of ASTM D1238-86, Procedure B - Automatic Time Controlled Flow Procedure, Condition 316 / 5.0. The orifice diameter was 0.0825 + / - 0.002 inches, the length was 1.25 inches, the total drive weight including piston was 1270 grams, the operating temperature was 316°C, and a 5 minute preheat period was allowed before the measurement. The 1270ER value is expressed in grams per 10 minutes (g / 10 min). The extrusion rate, referred to as "MFR", was measured using a die with an orifice of 0.0825 + / - 0.002 inches and a length of 0.315 inches, using a total drive weight of 5000 g.

[0104] Molecular weights were determined by gel permeation chromatography from amorphous pressed film samples at 210° C. using an Agilent PL220 HT-GPC with 1-chloronaphthalene mobile phase and polystyrene standards.

[0105] The melting points were determined by DSC according to the ASTM D3418 standard. The samples were heated to 350°C, held for 5 minutes to erase the thermal history, cooled to 30°C, and heated again to 350°C, all at a rate of 20°C / min.

[0106] synthesis Example 1: (2.5 mol% DCA / 5 mol% mDCB terpolymer) Resin synthesis: A 1 L autoclave reactor was charged with 34.50 g sodium hydroxide (0.863 mol), 22.89 g sodium acetate (0.279 mol), 79.78 g NaSH (59.43 wt%, 0.846 mol), and 234 g NMP. The reactor was purged and pressurized to 10 psig with nitrogen and set for continuous stirring at 400 rpm. A separate addition vessel was charged with 115.00 g DCB (0.782 mol), 3.43 g DCA (0.021 mol), 6.22 g mDCB (0.042 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 from room temperature at 1.5° C. / min. After reaching 150°C, the reactor was vented through the condenser and approximately 46 mL of clear condensate was collected under a small nitrogen flow (60 mL / min) until the reactor reached 200°C. At this point, the condenser was removed, the nitrogen flow was stopped, and the DCB / DCA / mDCB / NMP mixture in the addition vessel was quickly added to the reactor. The addition vessel was charged with an additional 30 mL of NMP, purged and pressurized to 90 psig with nitrogen, and the contents were immediately added to the reactor. Heating of the sealed reactor was continued to 240°C, then held at 240°C for 2 hours, heated at 1.5°C / min to 265°C, and held at 265°C for 2 hours. At this point, a mixture of 15.8 g water and 7.5 g NMP was added to the reactor under 250 psig pressure. The reactor contents were then cooled to 200°C at 1.0°C / min, and finally allowed to cool to room temperature. The resulting slurry was diluted with 200 mL of NMP, removed from the reactor, heated to 80 °C, and sieved through a No. 120 sieve (125 μm mesh size). The solids were rinsed with an additional 100 mL of warm NMP (60 °C). The solids were then transferred to a separate container, stirred in 300 mL of heated DI water (70 °C) for 15 minutes, and sieved through a No. 120 sieve. This process was repeated a total of five times. The rinsed solids were dried in a vacuum oven under nitrogen at 100 °C overnight to give 60.49 g of white granular resin. 1270ER = 102 g (10 min) -1 M W = 27,000 g / mol. T m =263℃.

[0107] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer obtained as detailed above was mixed with 407 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder at a screw speed of 100 rpm and a barrel temperature of 335° C. for 10 minutes. The resulting tan colored extrudate had an MFR of 0 indicating a large amount of crosslinking. This was further evidence of the presence of bound amine groups in the polymer.

[0108] Thus, BPDA, 3,3',4,4'-biphenyltetracarboxylic dianhydride, has been shown to form imide bridges between amine sites in the resulting polymer, significantly reducing the measured melt flow rate (MFR) of the polymer.

[0109] Example 2: (2.5 mol% DCA / 7.5 mol% mDCB terpolymer) Synthesis of resin: The synthesis was carried out according to the procedure of Example 1, but in a 400 L reactor, 31.23 kg of sodium hydroxide solution (50.40 wt%, 394 mol), 12.13 kg of sodium acetate (148 mol), 41.56 kg of NaSH (56.62 wt%, 420 mol), 53.18 kg of DCB (362 mol), 1.63 kg of DCA (10 mol), 4.43 kg of mDCB (30 mol), and a total of 123.47 kg of NMP were used. The reaction yielded 25.17 kg of white powdery resin. 1270ER=54 g (10 min) -1 M W = 34,000 g / mol. T m =258℃.

[0110] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer obtained as shown above was mixed with 407 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder at a screw speed of 100 rpm and a barrel temperature of 335° C. for 10 minutes. The resulting tan extrudate had an MFR of 21 indicating significant crosslinking. This was further evidence of the presence of bound amine groups in the polymer.

[0111] Example 3: (2.5 mol% DCA / 10 mol% mDCB terpolymer) Synthesis of resin: Following the procedure of Example 1, 33.69 g of sodium hydroxide (0.842 mol), 22.36 g of sodium acetate (0.273 mol), 77.91 g of NaSH (59.43 wt%, 0.826 mol), 106.23 g of DCB (0.723 mol), 3.35 g of DCA (0.021 mol), 12.14 g of mDCB (0.083 mol), and a total of 307 g of NMP were used to synthesize the resin. The reaction yielded 42.78 g of white granular resin. 1270ER = 183 g (10 min) -1 M W = 25,000 g / mol. T m =248℃.

[0112] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer shown above was mixed with 407 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder at a screw speed of 100 rpm and a barrel temperature of 335° C. for 10 minutes. The resulting tan extrudate had an MFR of 0.66 indicating a large amount of crosslinking. This was further evidence that bound amine groups were present in the polymer.

[0113] Example 4: (2.5 mol% DCA / 7.5 mol% mDCB / 0.8% TCB tetrapolymer) Synthesis of resin: Following the procedure of Example 1, 31.82 g (0.796 mol) sodium hydroxide, 21.11 g sodium acetate (0.257 mol), 76.78 g NaSH (56.95 wt%, 0.780 mol), 103.19 g DCB (0.702 mol), 3.16 g DCA (0.019 mol), 8.60 g mDCB (0.058 mol), 1.132 g TCB (0.006 mol), and a total of 290 g NMP were used to synthesize the resin. The reaction yielded 77.17 g of white granular resin. 1270ER = 20 g (10 min) -1 M W = 42,000 g / mol. T m=248℃.

[0114] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer shown above was mixed with 407 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder at a screw speed of 100 rpm and a barrel temperature of 335° C. for 10 minutes. The resulting tan extrudate had an MFR of 0 indicating a large amount of crosslinking. This was further evidence that bound amine groups were present in the polymer.

[0115] Comparative Example 1: (2.5 mol% DCA copolymer) Synthesis of resin: Following the procedure of Example 1 (except that the polymer was isolated in a medium porosity fritted funnel instead of a sieve), 33.40 g sodium hydroxide (0.835 mol), 22.17 g sodium acetate (0.270 mol), 80.35 g NaSH (57.13 wt%, 0.819 mol), 117.35 g DCB (0.798 mol), 3.32 g DCA (0.020 mol), and a total of 304 g NMP were used to synthesize the resin. The reaction yielded 81.9 g of white powdery resin. 1270ER = 147 g (10 min) -1 M W = 23,000 g / mol. T m =280℃.

[0116] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer shown above was mixed with 407 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder for 10 minutes at a screw speed of 100 rpm and a barrel temperature of 335° C. The resulting tan extrudate had an MFR of 0.41 indicating a large amount of crosslinking. This was further evidence that bound amine groups were present in the polymer.

[0117] Comparative Example 2: (5 mol% DCA copolymer) Synthesis of resin: Following the procedure of Example 1 (except that the polymer was isolated through a medium porosity fritted funnel instead of a sieve), 32.16 g sodium hydroxide (0.804 mol), 21.34 g sodium acetate (0.260 mol), 77.35 g NaSH (57.13 wt%, 0.788 mol), 110.08 g DCB (0.749 mol), 6.38 g DCA (0.039 mol), and a total of 293 g NMP were used to synthesize the resin. The reaction yielded 79.21 g of white powdery resin. 1270ER=793 g (10 min) -1 M W = 16,000 g / mol. T m =276℃.

[0118] Reactive extrusion with BPDA to test amine reactivity: 12 g of resin was mixed with 810 mg of BPDA in a DSM Xplore 15 cc twin screw microcompounder for 10 minutes at a screw speed of 100 rpm and a barrel temperature of 335° C. The resulting tan colored extrudate had an MFR of 0 indicating a large amount of crosslinking. This was further evidence that bound amine groups were present in the polymer.

[0119] Comparative Example 3: (10 mol% DCA copolymer) Resin synthesis: The procedure of Example 1 was followed (except the polymer was isolated in a medium porosity fritted funnel instead of a sieve) with 32.29 g sodium hydroxide (0.807 mol), 21.43 g sodium acetate (0.261 mol), 77.67 g NaSH (57.13 wt%, 0.792 mol), 104.71 g DCB (0.712 mol), 12.82 g DCA (0.079 mol), and a total of 294 g NMP. The reaction yielded 82.73 g of white powdery resin. The 1270ER could not be determined, it was >10,000. M W = 7,000 g / mol. T m =256℃.

[0120] Reactive extrusion with BPDA to test amine reactivity: 12 g of the polymer obtained as shown above was mixed with 1.61 g of BPDA in a DSM Xplore 15 cc twin screw microcompounder for 10 minutes at a screw speed of 100 rpm and a barrel temperature of 335° C. The resulting tan colored extrudate had an MFR of 0 indicating a large amount of crosslinking. This was additional evidence of the presence of bound amine groups in the polymer.

[0121] DSC data was obtained from amorphous film samples by heating to 350°C, holding for 5 minutes, cooling to 30°C, and heating again to 350°C (all at 20°C per minute). The MFR melt flow index was measured in an extrusion plastometer at 315.6°C using a 5.00 kg load and a 0.0825 in. x 0.315 in. die. The 1270ER melt flow index was measured in an extrusion plastometer at 315.6°C using a 1.27 kg load and a 0.0825 in. x 1.25 in. die.

Claims

1. A poly(arylene sulfide) polymer [polymer (PAS)] having a weight average molecular weight of at least 24,000 as determined by gel permeation chromatography, said polymer (PAS) comprising: an amount of 85.0 to 97.0 mol % of the following formula: [-Ar ｐ -S-] (R ＰＡＳｐ ) (In the formula, -Ar ｐ -teeth 【Chemistry 1】 is) The repeating unit (R ＰＡＳｐ )and, in an amount of 2.5 to 10.0 mol % of the following formula: [-Ar ｏ／ｍ -S-] (R ＰＡＳｏ／ｍ ) (In the formula, -Ar ｐ／ｍ -teeth 【Chemistry 2】 (either The repeating unit (R ＰＡＳｏ／ｍ )and, in an amount of 0.5 to 5.0 mol % of the following formula: [-Ar ｎ -S-] (R ＰＡＳｎ ) (In the formula, -Ar ｎ -teeth 【Transformation 3】 is) The repeating unit (R ＰＡＳｎ )and, Including, The mole % is determined relative to the total number of moles of repeat units of the polymer (PAS); R is, in each case, C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ an arylene group, and C ６ ~C １８ aryloxy groups; i, at each occurrence, is an independently selected integer from 0 to 4; j, at each occurrence, is an independently selected integer from 0 to 3; Polymer (PAS).

2. The polymer (PAS) Repeating units (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Optional repeat units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); The polymer (PAS) is preferably A repeating unit (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Optional repeat units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); The polymer (PAS) is more preferably Repeating units (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Optional repeat units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); The polymer (PAS) according to claim 1.

3. The polymer (PAS) contains a repeating unit (R ＰＡＳｔ ): [-Ar ｔ -S-] (R ＰＡＳｔ ) (In the formula, -Ar ｔ -teeth, 【Chemistry 4】 and R is, in each case, C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ an arylene group, and C ６ ~C １８ aryloxy groups; k, at each occurrence, is an independently selected integer from 0 to 3; m is 1 or 0 in each case The polymer (PAS) according to claim 1, further comprising:

4. The polymer (PAS) Repeating units (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Repeating units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); Preferably, the polymer (PAS) is Repeating units (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Repeating units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); More preferably, the polymer (PAS) is A repeating unit (R ＰＡＳｐ )and, Repeating units (R ＰＡＳｏ／ｍ )and, Repeating units (R ＰＡＳｎ )and, Repeating units (R ＰＡＳｔ )and, wherein the mole percent is determined relative to the total moles of repeat units of the polymer (PAS); The polymer (PAS) according to claim 3.

5. The polymer (PAS) has a repeating unit (R ＰＡＳｐ ), (R ＰＡＳｏ／ｍ ), (R ＰＡＳｎ ), and optional (R ＰＡＳｔ ), or the polymer (PAS) consists of or essentially consists of repeating units (R ＰＡＳｐ ), (R ＰＡＳｏ／ｍ ), (R ＰＡＳｎ ), and (R ＰＡＳｔ 2. The polymer (PAS) according to claim 1, which consists of or consists essentially of:

6. Repeating unit (R ＰＡＳｐ ) is a repeating unit of the following formula (R ＰＰＳｐ ): 【Transformation 5】 and and / or Repeating unit (R ＰＡＳｏ／ｍ ) is a repeating unit of the following formula (R ＰＰＳｏ ) and (R ＰＰＳｍ ): 【Transformation 6】 selected from the group consisting of: and / or Repeating unit (R ＰＡＳｎ ) is expressed by the following formula (R ＰＰＳｎ，ｏ ), (R ＰＰＳｎ，ｍ ), (R ＰＰＳｎ，ｐ ): 【Transformation 7】 Any repeating unit (R ＰＰＳｎ ) and and / or Repeating unit (R ＰＡＳｎ ) is represented by the following formula (R ＰＰＳ＿ＴＣＡ ): 【Transformation 8】 is a repeating unit of If present, repeating units (R ＰＡＳｔ ) is of the following formula: 【Chemistry 9】 Repeating units (R ＰＰＳｔ ) and m is 0 or 1, preferably m is zero; The polymer (PAS) according to claim 1.

7. The polymer (PAS) has a weight average molecular weight (M ｗ ) and / or said polymer (PAS) has a weight average molecular weight (M) of at most 120,000 g / mol, more preferably at most 110,000 g / mol, even more preferably at most 100,000 g / mol, even more preferably at most 90,000 g / mol. ｗ ) and the M ｗ is determined by gel permeation chromatography; and / or The polymer (PAS) has a melting point (T ｍ ) and / or said polymer (PAS) has a melting point (T ｍ ) and the T ｍ is determined in the second heating scan by differential scanning calorimetry (DSC) according to ASTM D3418 using a heating and cooling rate of 20°C / min; The polymer (PAS) according to claim 1.

8. A process for the preparation of a poly(arylene sulfide) polymer, in particular a polymer (PAS) according to any one of claims 1 to 7, comprising the steps of: 85.0 to 97.0 mol % of at least one first dihalo compound of the following formula: X-Ar ｐ -X' (in the formula, -Ar ｐ -teeth 【Chemistry 10】 ) and 2.5 to 10.0 mol % of at least one second dihalo compound of the following formula: X″—Ar ｏ／ｍ -X"' (in the formula, -Ar ｏ／ｍ -teeth 【Chemistry 11】 ) and 2.5 to 5.0 mol % of at least one third dihalo compound of the following formula: X' ｖ -Ar ｎ -X ｖ (In the formula, -Ar ｎ -teeth 【Chemistry 12】 ) and reacting a monomer mixture containing During the ceremony, ・X, X', X", X"', X' ｖ , and X ｖ each is an independently selected halogen, preferably chlorine or bromine, more preferably chlorine; R is, in each case, C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ an arylene group, and C ６ ~C １８ aryloxy groups; i, at each occurrence, is an independently selected integer from 0 to 4; j, at each occurrence, is an independently selected integer from 0 to 3; method.

9. The formula X-Ar ｐ the first dihalo compound of —X′ is a para-dihalobenzene, preferably para-dichlorobenzene; and / or The formula X″-Ar ｏ／ｍ the second dihalo compound of -X"' is selected from the group consisting of ortho-dihalobenzenes and meta-dihalobenzenes; preferably selected from the group consisting of ortho-dichlorobenzenes and meta-dichlorobenzenes; and / or The formula: X' ｖ -Ar ｎ -X ｖ the third dihalo compound is a dihaloaniline, preferably selected from the group consisting of 3,5-dichloroaniline, 2,5-dichloroaniline, and 2,6-dichloroaniline, with 3,5-dichloroaniline being more preferred; and / or the trihalo compound of formula (II) is a trihalobenzene, more preferably 1,2,4-trichlorobenzene; The method of claim 8.

10. The compound (SC) is selected from the group consisting of thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and hydrosulfides, and hydrogen sulfide; the compound (SC) is preferably an alkali metal sulfide, particularly an alkali metal hydrosulfide and an alkali metal sulfide generated in situ from an alkali metal hydroxide; the compound (SC) is most preferably an NaOH-based compound generated in situ from NaSH and NaOH. ２ The method of claim 8, wherein S is

11. 9. The method of claim 8, wherein the reaction of compound (SC) with the monomer mixture is carried out in a polar aprotic solvent, preferably a polar aprotic solvent selected from the group consisting of hexamethylphosphoramide, tetramethylurea, n,n-ethylenedipyrrolidone, N-methyl-2-pyrrolidone ("NMP"), pyrrolidone, caprolactam, n-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone.

12. A composition (C) comprising the polymer (PAS) according to any one of claims 1 to 7 and at least one epoxy resin.

13. The epoxy resin is epoxy ethers formed by the reaction of epihalohydrins, such as epichlorohydrin, with polyphenols, typically in the presence of alkali, where the polyphenols include catechol, hydroquinone, resorcinol, bis(4-hydroxyphenyl)-2,2-propane (bisphenol A), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyphenyl)-1,1-ethane, bis(2-hydroxyphenyl)-methane, 4,4-dihydroxybenzophenone, 1,5-hydroxynaphthalene; polyglycidyl ethers of polyhydric alcohols derived from polyhydric alcohols including ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and polyglycidyl esters of polycarboxylic acids formed by the reaction of epihalohydrins or other epoxy compositions with aliphatic or aromatic polycarboxylic acids including succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid; epoxy resins derived from the oxidation of ethylenically unsaturated alicyclic compounds; epoxy novolac resins obtained by reacting epihalohydrins with condensation products of aldehydes and monohydric or polyhydric phenols; The composition (C) of claim 12, selected from the group consisting of:

14. 13. The composition of claim 12, wherein said composition (C) further comprises at least one curing agent, said curing agent being preferably selected from the group consisting of dihydrazides prepared by the reaction of a carboxylic acid ester with hydrazine hydrate, preferably carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, ethylmalonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, isophthalic acid dihydrazide, icosandioic acid dihydrazide, valine dihydrazide, and mixtures thereof.

15. A method of coating a substrate using the composition (C) of claim 12.

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