KR20220084273A - Poly(arylene sulfide) polymers and corresponding polymer compositions and articles - Google Patents

Abstract

Described herein are poly(arylene sulfide) (“PAS”) polymers (PASPs) comprising repeat units formed from dihalocarbazole containing monomers. Surprisingly, it has been found that such monomers can be incorporated into the PAS polymer at concentrations desired to provide improved amine content. Additionally, surprisingly, it was found that the PAS polymers (PASPs) described herein increase the glass transition temperature (“T _g ”) compared to PAS homopolymers and PAS polymers incorporating repeat units with primary amines. PAS polymers (PASPs) and PAS polymer compositions can be advantageously incorporated into a wide variety of articles including, but not limited to, automotive articles and oil and gas articles.

Description

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

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No. 62/915,155, filed on October 15, 2019, and European Patent Application No. 19206825.2, filed on November 4, 2019, the entire contents of each of these applications It is incorporated herein by reference for this purpose.

technical field

The present invention relates to poly(arylene sulfide) (“PAS”) polymers having excellent thermal and mechanical properties. The present invention also relates to PAS polymer compositions, to PAS polymers and to methods of making PAS compositions, and to articles incorporating the PAS polymers and PAS polymer compositions.

Poly(arylene sulfide) ("PAS") polymers having pendant amines are at least such that the amine is a carboxylic acid, carboxylate, anhydride, epoxide, urethane, amide, ketone, isocyanate, urea, halogen, activated ether, It is preferred because it can react with many types of functional groups including, but not limited to, esters, and acid chlorides. The ability of pendant amines to react with a wide variety of functional groups increases the compatibility between the PAS polymers and other polymers in the PAS polymer blend as compared to similar PAS polymers without pendant amine groups.

In a first aspect, the present invention relates to a poly(arylene sulfide) ("PAS") polymer (PASP) comprising a repeating unit R _PAS1 and a repeating unit R _PAS2 each represented by the formula:

[Formula 1]

[-Ar ₁ -S-],

[Formula 2]

[-Ar ₂ -S-],

(In the above formula,

- -Ar ₁ - is selected from the group of the formula consisting of:

[Formula 3]

,

,

[Formula 4]

, 및

, and

[Formula 5]

;

;

-Ar ₂ - is represented by the formula:

[Formula 6]

,

,

- R and R' at each occurrence are independently a C ₁ -C ₁₂ alkyl group, a C ₇ -C ₂₄ alkylaryl group, a C ₇ -C ₂₄ aralkyl group, a C ₆ -C ₂₄ arylene group, and a C ₆ is selected from the group consisting of a -C ₁₈ aryloxy group;

- T is selected from the group consisting of a bond, -CO-, -SO ₂ -, -O-, -C(CH ₃ ) ₂ , phenyl and -CH ₂ -;

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

- j and k at each occurrence are independently selected integers from 0 to 3).

In some embodiments, the PAS polymer (PASP) comprises a T _g of at least 95 °C. Additionally or alternatively, in some embodiments, the PAS polymer (PASP) comprises a T _m of at least 200 °C. In yet another additional or alternative embodiment, the PAS polymer (PASP) comprises an impact strength of at least 30 J/g as determined according to ASTM D256.

In a second aspect, the present invention relates to a PAS polymer (PASP) comprising: a carboxylic acid, a carboxylate, an anhydride, an epoxide, a urethane, an amide, a ketone, an isocyanate, a urea, a halogen, an activated ether, an ester, and an acid chloride. a polymer composition (PC) comprising a further polymer comprising a functional group selected from the group consisting of: In some embodiments, the additional polymer is a thermoplastic polymer. In some embodiments, the additional polymer is a thermoset polymer or a thermoset precursor. In some embodiments, additionally or alternatively, the polymer composition (PC) comprises a fibrous reinforcing filler or a toughening agent, preferably a fibrous reinforcing filler.

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

In yet a further aspect, the present invention relates to a process for preparing a PAS polymer (PASP), said process comprising: a dihaloaromatic compound having the formula X ₁ -Ar ₁ -X ₂ ; dihalocarbazole containing a monomer having the formula X ₃ -Ar ₂ -X ₄ ; and reacting a sulfur compound in a reaction mixture, wherein X ₁ to X ₄ are independently selected halogen, and the sulfur compound is thiosulfate, thiourea, thioamide, elemental sulfur, thiocarbamate, metal selected from the group consisting of disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides, and hydrogen sulfide; Preferably the sulfur compound is an alkali metal sulfide; Most preferably the sulfur compound is Na ₂ S.

Described herein are poly(arylene sulfide) (“PAS”) polymers (PASPs) comprising repeat units formed from dihalocarbazole containing monomers. Surprisingly, it has been found that such monomers can be incorporated into the PAS polymer at desirable concentrations to provide improved amine content while maintaining high molecular weight. Additionally, surprisingly, it was found that the glass transition temperature ("T _g ") was increased in the PAS polymers (PASP) described herein compared to PAS homopolymers, and PAS polymers incorporating repeat units with primary amines. PAS polymers (PASPs) and PAS polymer compositions can be advantageously incorporated into a wide variety of articles including, but not limited to, automotive articles, aerospace articles, aircraft articles, and oil and gas articles.

As described above, surprisingly, the dihalocarbazole containing monomer can be incorporated into the PAS polymer at a desired concentration to provide improved amine content while maintaining high molecular weight. The traditional method of introducing amine content into PAS polymers involves copolymerization with dichloroaniline (“DCA”) (eg, 3,5-DCA). Surprisingly, however, it was found that, at relatively low comonomer concentrations, high molecular weight PAS polymers could not be formed using 3,5-DCA, as demonstrated in the examples below. Moreover, it was also surprisingly found that for PAS polymers with the desired dihalocarbazole comonomer concentration, high molecular weight PAS polymers are obtained only when the dihalocarbazole containing monomer has a halogen in the 2,7-position.

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

In this application, any description, even if set forth in relation to specific embodiments, is applicable to and interchangeable with other embodiments of the present disclosure. Moreover, where an element or component is intended to be included within and/or selected from a list of recited elements or components, in related embodiments expressly contemplated herein, the element or component is also individually recited may be any one of the specified elements or components, or may also be selected from the group consisting of any two or more of the explicitly recited elements or components; It should be understood that any element or component listed in a list of elements or components may be omitted from such list. Additionally, any reference herein to a numerical range by an endpoint includes all numbers subsumed within the stated range, as well as the endpoints of such range and equivalent expressions.

Unless specifically limited otherwise, as used herein, the term “alkyl” as well as derivative terms such as “alkoxy,” “acyl,” and “alkylthio” refer to straight-chain, branched-chain and cyclic moieties. ) are included within their scope. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclo-propyl. Unless specifically stated otherwise, each alkyl and aryl group is halogen, hydroxy, sulfo, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl, cyano, C It may be unsubstituted or substituted with one or more substituents selected from, but not limited to, ₆ -C ₁₅ aryloxy or C ₆ -C ₁₅ aryl, provided that these substituents are sterically compatible, and the chemical bond and strain energy of The rules must be satisfied. The term “halogen” or “halo” includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.

The term “aryl” refers to a phenyl, indanyl or naphthyl group. An aryl group may include one or more alkyl groups, sometimes in this case referred to as "alkylaryl"; For example, it may consist of an aromatic group and two C ₁ -C ₆ groups (eg, methyl or ethyl). Aryl groups may also contain one or more heteroatoms, such as N, O or S, sometimes in this case referred to as a “heteroaryl” group; These heteroaromatic rings may be fused to other aromatic systems. Such heteroaromatic rings include furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl and triazinyl ring structures. Aryl or heteroaryl substituents are halogen, hydroxy, C ₁ -C ₆ alkoxy, sulfo, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl, cyano, C ₆ -C ₁₅ aryloxy or C It may be unsubstituted or substituted with one or more substituents selected from, but not limited to, ₆ -C ₁₅ aryl, provided that these substituents are sterically compatible and the rules of chemical bond and strain energy are satisfied.

PAS Polymer (PASP)

The PAS polymer (PASP) comprises a repeating unit (R _PAS1 ) and a repeating unit (R _PAS2 ) each represented by the formula:

[Formula 1]

[-Ar ₁ -S-], and

[Formula 2]

[-Ar ₁ -S-].

-Ar ₁ - is represented by a formula selected from the group of the following formulas:

[Formula 3]

,

,

[Formula 4]

, 및

, and

[Formula 5]

,

,

wherein R at each occurrence is independently a C ₁ -C ₁₂ alkyl group, a C ₇ -C ₂₄ alkylaryl group, a C ₇ -C ₂₄ aralkyl group, a C ₆ -C ₂₄ arylene group, and a C ₆ - selected from the group consisting of a C ₁₈ aryloxy group; T is selected from the group consisting of a bond, -CO-, -SO ₂ -, -O-, -C(CH ₃ ) ₂ , phenyl and -CH ₂ -; i at each occurrence is an independently selected integer from 0 to 4; j is an independently selected integer from 0 to 3 at each occurrence. For clarity, each benzyl ring in the above formula has either 4-i hydrogens (Formula 3 and Formula 4) or 3-j hydrogens (Formula 5). Thus, when i or j is 0, the corresponding benzyl ring is unsubstituted. Similar notations are used throughout this specification. Additionally, each of Formulas 3 through 5 contains two dashed bonds, wherein one bond is to a specified sulfur atom within the repeating unit (R _PAS1 ) and the other is outside the repeating unit (R _PAS1 ) (e.g. For example, it is a bond to an atom in an adjacent repeating unit). Similar notations are used throughout.

In a preferred embodiment, i and j are in each case 0. Preferably, -Ar ₁ - is represented by any one of Formula 3 or Formula 4, more preferably Formula 3 ([-Ar ₁ -S-] corresponds to a repeating unit of polyphenylene sulfide), and even more Preferably, -Ar ₁ - is represented by the formula:

[Formula 6]

.

.

Most preferably, -Ar ₁ - is represented by the formula (6), wherein i is 0.

-Ar ₂ - is represented by any one of the following formulas:

[Formula 7]

,

,

wherein R' at each occurrence is independently a C ₁ -C ₁₂ alkyl group, a C ₇ -C ₂₄ alkylaryl group, a C ₇ -C ₂₄ aralkyl group, a C ₆ -C ₂₄ arylene group, and a C ₆ is selected from the group consisting of a -C ₁₈ aryloxy group; k is an independently selected integer from 0 to 3 at each occurrence. Preferably, k is 0 in each occurrence (eg -Ar ₂ - is formed from 2,7-dihalocarbazole).

In some embodiments, the total concentration of repeat units (R _PAS1 ) and repeat units (R _PAS2 ) in the PAS polymer is at least 50 mole %, at least 60 mole %, at least 70 mole %, at least 80 mole %, at least 90 mole %, at least 95 mole %, at least 98 mole %, at least 99 mole % or at least 99.9 mole %. As used herein, the molar concentration of repeating units in a polymer is relative to the total number of repeating units in that polymer, unless expressly stated otherwise. In some embodiments, the concentration of repeating units (R _PAS1 ) is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 85 mol%, at least 88 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 98.5 mol%, or at least 99 mol%.

In some embodiments, the concentration of repeating units (R _PAS2 ) is at least 0.5 mol%, at least 1 mol%, at least 1.5 mol%, at least 2 mol%, or at least 2.5 mol%. In some embodiments, the concentration of repeating units (R _PAS2 ) is 15 mole % or less, 12 mole % or less, 10 mole % or less, or 8 mole % or less. In some embodiments, the number of moles of the repeating unit (R _PAS2 ) is from 0.5 mol% to 15 mol%, from 0.5 mol% to 12 mol%, from 0.5 mol% to 10 mol%, from 0.5 mol% to 8 mol%, from 1 mol% to 15 mol%, 1 mol% to 12 mol%, 1 mol% to 10 mol%, 1 mol% to 8 mol%, 2 mol% to 8 mol% or 2.5 mol% to 8 mol%. In some embodiments, the ratio of the number of repeating units (R _PAS2 ) to the total number of repeating units (R _PAS1 ) and repeating units (R _PAS2 ) is at least 1 mol%, at least 1.5 mol%, at least 2 mol%, or at least 2.5 is mole %. In some embodiments, the ratio of the number of repeating units (R _PAS2 ) to the total number of repeating units (R _PAS1 ) and repeating units (R _PAS2 ) is 15 mol% or less, 12 mol% or less, 10 mol% or less, or 8 mol% or less. In some embodiments, the ratio of the number of repeating units (R _PAS2 ) to the total number of moles of repeating units (R _PAS1 ) and repeating units (R _PAS2 ) is from 1 mol% to 15 mol%, from 1 mol% to 12 mol%, 1 mol% to 10 mol%, 1 mol% to 8 mol%, 2 mol% to 8 mol% or 2.5 mol% to 8 mol%. Nevertheless, in some embodiments, the PAS polymer (PASP) has a higher concentration of repeat units (R _PAS2 ). In some such embodiments, the concentration of repeating unit (R _PAS2 ) is from 0.5 mol% to 99 mol%, 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol% or less or 20 mol% or less.

Of course, in some embodiments, the PAS polymer may have additional repeating units, each different from one another and distinct from the repeating unit (R _PAS1 ) and the repeating unit (R _PAS2 ). In one such embodiment, the PAS polymer comprises at least one further repeating unit according to formula (1) or at least one further repeating unit according to formula (2). In some embodiments comprising additional repeating units according to Formulas 1 and 2, the total concentration of repeating units according to Formulas 1 and 2 is given above for the repeating unit (R _PAS1 ) and the repeating unit (R _PAS2 ) is within the range, and the ratio of the total number of repeating units according to Formula 1 to the total number of repeating units according to Formulas 1 and 2 is within the ranges given above for the repeating unit (R _PAS1 ) and the repeating unit (R _PAS2 ). Of course, in other embodiments, the concentration of additional repeating units according to formulas 1 and 2, as well as the number of additional repeating units according to formula 1 relative to the total number of repeating units according to formulas 1 and 2, is the repeating unit ( different from the ranges given above for R _PAS1 ) and repeat units (R _PAS2 ).

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

The PAS polymer may be amorphous or semi-crystalline. As used herein, an amorphous polymer has an enthalpy of fusion (“ΔH _f ”) of 5 joules/g (“J/g”) or less. Those skilled in the art will recognize that when PAS is amorphous, it lacks a detectable T _m . Accordingly, when a PAS polymer has a T _m , one of ordinary skill in the art will recognize that the PAS polymer refers to a semi-crystalline polymer. Preferably, the PAS polymer is semi-crystalline. In some embodiments, the PAS polymer has a ΔH _f of at least 10 J/g, at least 20 J/g, or at least 25 J/g. In some embodiments, the PAS polymer has a ΔH _f of 90 J/g or less, 70 J/g or 60 J/g or less. In some embodiments, the PAS polymer has a ΔH _f of from 10 J/g to 90 J/g or from 20 J/g to 70 J/g. ΔH _f can be measured as described in the Examples below.

In some embodiments, the PAS polymer has a T _g of at least 95°C or at least 99°C. In some embodiments, the PAS polymer has a T _g of 200°C or less or 150°C or less. In some embodiments, the PAS polymer has a T _g of from 95°C to 200°C, from 99°C to 150°C, from 95°C to 200°C, or from 99°C to 150°C. In some embodiments, the PAS polymer has a melting temperature (“T _m ”) of at least 200°C, at least 220°C, at least 240°C, or at least 250°C. In some embodiments, the PAS polymer has a T _m of 350 °C or less, 320 °C or less, 300 °C or less, or 285 °C or less. In some embodiments, the PAS polymer has a T _m of 200°C to 350°C, 220°C to 320°C, 240°C to 300°C, or 250°C to 285°C. In some embodiments, the PAS polymer has a crystallization temperature (“T _c ”) of at least 140° C. or at least 150° C. In some embodiments, the PAS polymer has a T _c of 250 °C or less, or 220 °C or less. In some embodiments, the PAS polymer has a T _c from 140°C to 250°C or from 150°C to 220°C. T _g , T _m and T _c can be determined as described in the Examples below. In some embodiments, the PAS polymer (PASP) is amorphous and has a T _g of at least 90°C, at least 95°C, or at least 100°C.

In some embodiments, the PAS polymer (PASP) has an impact strength of at least 30 joules/gram (“J/g”), or at least 35 J/g. In some embodiments, the PAS polymer (PASP) has an impact strength of 150 J/g or less or 125 J/g or less. In some embodiments, the PAS polymer has an impact strength of 30 J/g to 150 J/g, 35 J/g to 150 J/g, 30 J/g to 125 J/g, 35 J/g to 125 J/g to be. Unless explicitly stated otherwise, as used herein, impact strength refers to the notched-Izod impact strength measured as described in the Examples below.

Synthesis of PAS Polymers

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

The polymerization reaction is carried out according to the following scheme, wherein the dihaloaromatic compound having the formula X ₁ -Ar ₁ -X ₂ in a polymerization solvent; dihalocarbazole containing a monomer having the formula X ₃ -Ar ₂ -X ₄ ; and reacting the sulfur compound (collectively referred to as "reaction component") in the state of the reaction mixture:

[Reaction Scheme S1]

wherein X ₁ to X ₄ are independently selected halogen, -Ar ₁ - and -Ar ₂ - are as provided above, and SC is a sulfur compound described below. Preferably, X ₁ and X ₂ are the same halogen and X ₃ and X ₄ are the same halogen. More preferably, X ₁ and X ₂ are both chlorine or X ₃ and X ₄ are both bromine. In some embodiments, X ₁ and X ₂ are both chlorine and X ₃ and X ₄ are both bromine. Preferably, X ₁ -Ar ₁ -X ₂ is para-dihalobenzene, most preferably para-dichlorobenzene. Preferably, X ₃ -Ar ₂ -X ₄ is 2,7-dibromocarbazole. The skilled person knows that -Ar ₁ - and -Ar ₂ - in Scheme S1 are introduced into the repeating unit (R _PAS1 ) and the repeating unit (R _PAS2 ), respectively, as detailed above and as shown in Scheme S1. will recognize Thus, the preferences and embodiments for the -Ar ₁ - and -Ar ₂ - described above for the repeating unit (R _PAS1 ) and the repeating unit (R _PAS2 ) are -Ar ₁ - and -Ar ₂ - in Scheme S1 is also applicable to For example, in some embodiments, X ₃ -Ar ₂ -X ₄ is 2,7-dihalocarbazole, where k is 0 at each occurrence. In some embodiments, the reaction component may further comprise a molecular weight modifier.

Sulfur compounds (SC) are thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides. cargo, and hydrogen sulfide. Preferably, the sulfur compound is an alkali metal sulfide. In some embodiments, alkali metal sulfides are generated in situ from alkali metal hydrogen sulfide salts and alkali metal hydroxides. For example, Na ₂ S is a particularly preferred alkali metal sulfide. Na ₂ S can be formed in situ from NaSH and NaOH.

The polymerization solvent is selected to be a solvent for the reaction components at the reaction temperature (discussed below). In some embodiments, the polymerization solvent is a polar aprotic solvent. Examples of preferred polar aprotic solvents include hexamethylphosphoramide, tetramethylurea, n,n-ethylenedipyrrolidone, n-methyl-2-pyrrolidone (“NMP”), pyrrolidone, caprolactam, n-ethylcaprolactam, sulfolane, n,n'-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. Preferably, the polymerization solvent is NMP. In embodiments where the polymerization solvent comprises NMP, the NMP can react with NaOH to form n-methyl-1,4-aminobutanoate (“SMAB”).

As described above, in some embodiments, the reaction component further comprises a molecular weight modifier. The molecular weight modifier increases the molecular weight of the PAS polymer compared to a synthetic scheme that does not include the molecular weight modifier. Preferably, the molecular weight modifier is an alkali metal carboxylate. Alkali metal carboxylates are represented by the formula R'CO ₂ M', wherein R' is a C ₁ to C ₂₀ hydrocarbyl group, a C ₁ to C ₂₀ hydrocarbyl group and a C ₁ to C ₅ hydrocarbyl group. selected from the group consisting of; M' is selected from the group consisting of lithium, sodium, potassium, rubidium or cesium. Preferably M' is sodium or potassium, most preferably sodium. Preferably, the alkali metal carboxylate is sodium acetate.

The polymerization reaction is carried out by contacting the reaction components at a reaction temperature selected such that X ₁ -Ar ₁ -X ₂ , X ₃ -Ar ₂ -X ₄ and SC polymerize to form a PAS polymer. In some embodiments, the reaction temperature is between 170°C and 450°C, or between 200°C and 285°C. The reaction time (duration of polymerization reaction) may be from 10 minutes to 3 days or from 1 hour to 8 hours. During the polymerization reaction, the pressure (reaction pressure) is selected to keep the reaction components in the liquid phase. In some embodiments, the reaction pressure can be from 0 pounds per square inch gauge (“psig”) to 400 psig, 30 psig to 300 psig, or 100 psig to 250 psig.

The polymerization reaction may be terminated by cooling the reaction mixture to a temperature at which the polymerization reaction ceases. "Reaction mixture" refers to the mixture formed during a polymerization reaction and contains any remaining reaction components, the PPS polymer formed, and reaction byproducts. Cooling can be accomplished using a variety of techniques known in the art. In some embodiments, cooling can be done by rapidly flashing the reaction mixture. In some embodiments, cooling may include liquid quenching. In liquid quenching, a quenching liquid is added to the reaction mixture to cool the reaction mixture. In some embodiments, the quenching liquid is selected from the group consisting of a polymerization solvent, water, and combinations thereof. In some embodiments, the temperature of the quenching liquid may be between about 15°C and 99°C. In some embodiments, the temperature of the quenching liquid is between 54°C and 100°C (eg, in embodiments where the quenching liquid is a solvent), or between 15°C and 32°C (eg, in embodiments where the quenching liquid is water). can Cooling may be further facilitated by the use of reactor jackets or coils to cool the reaction vessel in which the polymerization reaction is carried out (“polymerization reactor”). For the sake of clarity, termination of the polymerization reaction does not imply completion of the reaction of the reaction components. In general, termination is initiated when the polymerization reaction is substantially complete or a target yield is reached, or when further reaction of the reaction components does not result in a significant increase in the average molecular weight of the PAS polymer.

After termination, the PAS polymer is present as a PAS polymer mixture. The PAS polymer mixture may contain water, polymerization solvents, reaction by-products including salts (eg, sodium chloride and sodium acetate); PAS oligomers, and any unreacted reaction components (collectively referred to as “post-reaction compounds”). Generally, after termination, the PAS polymer mixture is present as a slurry having a solid phase and a liquid phase containing the PAS polymer (precipitation from the solvent during liquid quenching or during flashing). In some embodiments, the PAS polymer mixture can exist as a wet PAS polymer, for example by filtration of the slurry after termination. PAS polymer synthesis, including polymerization and termination, and recovery (including water treatment), acid treatment, and metal cation treatment, is described in US Patent Application Publication No. 2015/0175748, filed December 19, 2013 (Fodor et al. ) ("'748 Patent"), which is incorporated herein by reference in its entirety.

Following termination, a recovery process is implemented. The recovery process includes one or more washes, each wash comprising contacting the PAS polymer formed during polymerization with a liquid. The liquid for each wash is independently selected from water, an aqueous acid solution, and an aqueous metal cation solution. An example of a post-reaction recovery process is discussed in the '748 patent. Based on the disclosure herein, those skilled in the art will know how to select a recovery process to obtain the PAS polymers described herein.

Following the recovery process, the PAS polymer mixture may be dried. Drying can be carried out at any temperature that can substantially dry the PAS polymer mixture to produce a dried PAS polymer. Preferably, the drying process is selected to help prevent oxidative curing of the PAS polymer. For example, if the drying process is carried out at a temperature of at least 100° C., the drying may be carried out in a substantially non-oxidizing atmosphere (eg, in a substantially oxygen-free atmosphere or at a pressure lower than atmospheric pressure, such as under vacuum). can be performed. If the drying process is carried out at a temperature below 100° C., the drying process may be facilitated by carrying out the drying at a pressure lower than atmospheric pressure so that the liquid component can be vaporized from the PAS polymer mixture. When drying is performed at a temperature below 100° C., the presence of a gaseous oxidizing atmosphere (eg, air) generally does not result in detectable curing of the PAS polymer.

PAS polymer composition

The polymer composition (PC) comprises a PAS polymer and additional polymers, thermosetting precursors (eg epoxy resins), curing agents (eg aliphatic, cycloaliphatic and aromatic monoamines and polyamines), reinforcing agents, toughening agents, plasticizers, at least one other component selected from the group consisting of colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants (including but not limited to halogen-free flame retardants), nucleating agents and antioxidants do.

In some embodiments, the concentration of PAS polymer in the polymer composition (PC) is at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt% or at least 40 wt%. In some embodiments, the concentration of PAS polymer in the polymer composition (PC) is 99.95 wt% or less, 99 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 70 wt% or less or 60% by weight or less. In some embodiments, the concentration of PAS polymer in the polymer composition (PC) is 20 wt% to 99.95 wt%, 20 wt% to 95 wt%, 20 wt% to 85 wt%, 20 wt% to 80 wt%, 20 wt% % to 70% by weight, or from 20% to 60% by weight. As used herein, the concentrations of components in a polymer composition are relative to the total weight of the polymer composition (PC) unless explicitly stated otherwise.

As described above, the PAS polymer (PASP) can preferably be incorporated into a polymer blend wherein the polymer composition (PC) comprises the PAS polymer (PASP) and further polymers as described below. Pendant amines of PAS polymers (PASPs) (derived from dihalocarbazole containing monomers) are carboxylic acids, carboxylates, anhydrides, epoxides, urethanes, amides, ketones, isocyanates, ureas, halogens, activated ethers, esters, and a wide variety of functional groups including, but not limited to, acid chlorides. In some embodiments, the polymer composition (PC) comprises a PAS polymer (PASP) with a carboxylic acid, carboxylate, anhydride, epoxide, urethane, amide, ketone, isocyanate, urea, halogen, activated ether, ester, and additional polymers containing functional groups selected from the group consisting of acid chlorides. Functional groups may be present at the chain ends of the polymer or on the backbone of the polymer (ie, in repeat units that do not terminate the polymer chain). In some embodiments, the additional polymer is a thermoplastic polymer. In some such embodiments, the additional polymer is poly(aryl ether sulfone), polyamide, polyamideimide, liquid crystalline polymer, polyimide, polyetherimide, poly(aryl ether ketone), polyurethane, polyester, and polycarramide. is selected from the group consisting of bonates. In some embodiments, the additional polymer is a thermoset polymer or a thermoset precursor. In some such embodiments, the additional polymer is composed of an epoxy resin, an epoxy novolac resin, a benzoxazine, a bismaleimide, a polyacid amic solution, a polyester thermosetting resin, a vinyl ester, a cyanate ester, and a urea-formaldehyde resin. is selected from the group being Of course, in some embodiments, the polymer composition (PC) may comprise a plurality of further polymers as described above, which may be any thermoplastic polymer, any thermoset polymer, or mixtures thereof.

In some embodiments, the polymer composition (PC) further comprises a reinforcing agent (also referred to as reinforcing fibers or fillers). They may be selected from fibrous and particulate reinforcement. As used herein, a fibrous reinforcing filler is considered to be a material having a length, a width and a thickness, wherein the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio of at least 5, at least 10, at least 20 or at least 50, defined as the average ratio between length and width and thickness, whichever is greater. In some embodiments, the reinforcing fibers (eg, glass fibers or carbon fibers) have an average length of 3 mm to 50 mm. In some such embodiments, the reinforcing fibers have an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the reinforcing fibers have an average length between 10 mm and 50 mm, between 10 mm and 45 mm, between 10 mm and 35 mm, between 10 mm and 30 mm, between 10 mm and 25 mm or between 15 mm and 25 mm. The average length of the reinforcing fibers may be taken as the average length of the reinforcing fibers prior to introduction into the polymer composition (PC), or may be taken as the average length of the reinforcing fibers in the polymer composition (PC). Glass fibers may be round (circular cross-section) or flat (non-circular cross-section, including, but not limited to, oval, oval or rectangular cross-section).

Reinforcing fillers include mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, It may be selected from rock wool fibers, steel fibers and wollastonite.

Among the fibrous fillers, glass fibers are preferred; These include chopped strands A-, E-, C-, D-, S- and R-glass fibers, which are chapter 5.2.3 of Additives for Plastics Handbook, 2nd edition, John Murphy. As described on pages 43-48 of Preferably, the filler is selected from fibrous fillers. More preferred are reinforcing fibers capable of withstanding high temperature applications.

In some embodiments, the concentration of the reinforcing agent (eg, glass fiber or carbon fiber) in the polymer composition (PC) is at least 5% by weight, at least 10% by weight, at least 15% by weight or at least 20% by weight. In some embodiments, the concentration of the reinforcing agent in the polymer composition (PC) is 70 wt% or less, 65 wt% or less, or 60 wt% or less. In some embodiments, the concentration of the reinforcing agent in the polymer composition (PC) is 5 wt% to 70 wt%, 10 wt% to 70 wt%, 10 wt% to 65 wt%, 10 wt% to 60 wt%, 15 wt% to 60% by weight, or from 20% to 60% by weight.

In some embodiments, the polymer composition (PC) further comprises a flame retardant. The flame retardant may be a halogen-free flame retardant or a halogenated flame retardant. Preferably, the flame retardant is a halogen-free flame retardant. Halogen-free flame retardants include, but are not limited to, organophosphorus compounds selected from the group consisting of phosphinic acid salts (“phosphinates”), diphosphinic acid salts (“diphosphinates”), and condensation products thereof. Phosphinates are preferred organophosphorus compounds. Suitable phosphinates include, but are not limited to, those described in US Pat. No. 6,365,071 (Jenewein et al. ), issued Apr. 2, 2002 and incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate, and zinc phosphinate. Among the aluminum phosphinates, aluminum ethylmethylphosphinate and aluminum diethylphosphinate and combinations thereof are preferred. Halogenated flame retardants include 1,2-bis(tribromophenoxy)ethane, brominated epoxy oligomer, brominated polystyrene, chlorinated acid anhydride, chlorinated paraffin, decabromobiphenyl, decabromodiphenylethane, decabromodiphenyloxide, decabromodiphenyloxide, dechlorane plus, dibromoneopentyl glycol, ethylene-bis(5,6-dibromonorbornane-2,30dicarboximide), ethylene-bis(tetrabromophthalimide) , halogenated polyether polyol, hexabromocyclododecane, octabromodiphenyl oxide, octabromotrimethylphenylindane, pentabromodiphenyloxide, poly(dibromostyrene), poly(pentabromobenzylacrylate), tetra bromo-bisphenol-A, tetrabromo-bisphenol-A, bis(2,3-dibromopropyl ether), tetrabromophthalate diol and tetrabromophthalic anhydride. Preferably, the halogenated flame retardant is a brominated or chlorinated compound or polymer.

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

The polymer composition (PC) may also include a toughening agent. Toughening agents are generally low T _g polymers having a T _g below, for example, room temperature, below 0°C or even below -25°C. As a result of the low T _g , toughening agents are typically elastomeric at room temperature. The toughening agent may be a functionalized polymer backbone.

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

When the toughening agent is functionalized, the functionalization of the backbone may result from copolymerization of monomers comprising functional groups or from grafting the polymer backbone with additional components.

Specific examples of functionalized tougheners include, inter alia, terpolymers of ethylene, acrylic esters and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylates; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymer; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymer grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; It is an ABS copolymer grafted with maleic anhydride. Further specific examples of functionalized toughening agents also include copolymers of ethylene and glycidyl methacrylate as well as copolymers of ethylene and methacrylic acid.

The toughening agent may be present in the composition (C) in a total amount greater than 1%, greater than 2% or greater than 3% by weight, based on the total weight of the composition (C). The toughening agent may be present in the composition (C) in a total amount of less than 30%, less than 20%, less than 15% or less than 10% by weight, based on the total weight of the polymer composition (PC).

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

In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP) and glass fibers. In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP) and a toughening agent. In some embodiments, the polymer composition (PC) consists essentially of a PAS polymer (PASP), glass fibers and a toughening agent. As used herein in reference to a polymer composition (PC), "consisting essentially of" means that the concentration of components other than those explicitly recited is less than 5%, less than 2%, less than 1%, by weight; less than 0.5 wt%, less than 0.1 wt%, less than 0.05 wt%, or less than 0.01 wt%.

The polymer composition (PC) may also comprise at least one further polymer, preferably a further PAS polymer (PASP). For example, in some embodiments, the polymer composition (PC) may comprise a plurality of PAS polymers (PASP), each distinct from the other, each being a repeating unit (R _PAS1 ), a repeating unit (R _PAS2 ), or combinations thereof.

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

Preparation of polymer composition (PC)

The polymer composition (PC) can be prepared using methods well known in the art. In one approach, a polymer composition (PC) can be prepared by melt-blending a PAS polymer with certain ingredients (eg, reinforcing fillers, flame retardants, stabilizers, and any other ingredients).

Any melt-blending method may be used to mix the polymeric and non-polymeric components in the context of the present invention. For example, the polymer component and the non-polymer component may be fed into a melt mixer such as a single screw or twin screw extruder, stirrer, single or twin screw kneader, or Banbury mixer, wherein the addition step is to add all components at once or It may be added gradually in batches. When the polymer component and the non-polymer component are added gradually in batches, the polymer component and/or a portion of the non-polymer component are added first and then the remaining polymer added subsequently until an appropriately mixed composition is obtained. It is melt-mixed with the components and non-polymeric components. Where the reinforcing agent exhibits an elongated physical shape (eg, elongated glass fibers), pultrusion extrusion may be used to prepare the reinforced composition.

When the polymer composition (PC) contains a thermosetting polymer or thermosetting precursor as detailed above, (D50 of 1 micrometer to 500 micrometers, preferably 2 micrometers to 200 micrometers, most preferably 5 micrometers A PAS polymer (“PASP”) in powder form (characterized in meters to 100 microns) is a thermoset polymer, along with any other additives, using any equipment known in the art for dispersing additives in thermosetting precursors. or blended with a thermosetting precursor.

Goods and supplies

The PAS polymer and polymer composition (PC) can preferably be incorporated into the article.

Articles include, inter alia, portable electronics, LED packaging, components for oil and gas, food contact components (including but not limited to food films and casings), electrical and electronic components (computing, data-systems and office equipment). power device components, including but not limited to, surface mount technology compatible connectors and contacts for components; gas system pipes and fittings; and electrical protection devices for mini-circuit breakers, contactors, switches and sockets; industrial components; plumbing components (pipes, valves, fittings); , manifolds, shower taps and shower valves), automotive components, and aerospace components (including but not limited to interior cabin components).

The article may be, for example, a portable electronic device component. As used herein, "portable electronic device" refers to an electronic device that is conveniently transported and intended for use in a variety of places. Portable electronic devices include cell phones, personal digital assistants (“PDAs”), laptop computers, tablet computers, wearable computing devices (eg, smart watches, smart glasses, etc.), cameras, portable audio players, portable radios, satellite positioning. system receivers, and handheld game consoles. The portable electronic device component may comprise, for example, a radio antenna and composition (C). In this case, the radio antenna may be a WiFi antenna or an RFID antenna. The portable electronic device component may also be an antenna housing.

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

Examples of electrical and electronic devices include, but are not limited to, connectors, contactors, switches, flexible and inflexible printed circuit boards.

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

Examples of automotive components include, but are not limited to, components within thermal management systems (thermostat housings, water inlet/outlet valves, water pumps, water pump impellers, and heater cores and end caps), air management system components (including but not limited to turbocharger actuators, turbocharger bypass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronically controlled throttle valves, and hot air ducts), transmission components and launch devices Components (including but not limited to dual clutch transmission, automated manual transmission, continuously variable transmission, automatic transmission, torque converter, dual mass flywheel, power takeoff, clutch cylinder, seal ring, thrust washer, thrust bearing, needle bearing, and check ball (including but not limited to), automotive electronic components, automotive lighting components (including motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection/relays, actuator housings, Li-ion battery systems, and fuse boxes) ), traction motors and power electronic components (including but not limited to battery packs), fuels and selective catalytic reduction (“SCR”) systems (SCR module housings and connectors, SCR module housings and connectors; including but not limited to fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel delivery modules, fuel hoses, fuel pumps, fuel injector o-rings, and fuel hoses; fluid system components (such as For example, fuel system components) (including but not limited to inlet and outlet valves and fluid pump components), interior components (eg, dashboard components, display components, and seat components), and structural and lightweight components (eg, gears and bearings, sunroofs, brackets and mounts, electric battery housings, thermal management components, braking system components, and pumps and EGR systems).

The article may be molded from the PAS polymer (PASP) or polymer composition (PC) by any process adapted for the thermoplastic, for example extrusion, injection moulding, blow moulding, rotomolding or compression moulding.

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

In some embodiments, the PAS polymer (PASP) or polymer composition (PC) may be preferably incorporated into a three-dimensional printing article. One application relates to a method of manufacturing three-dimensional (“3D”) objects using an additive manufacturing system, comprising the steps of providing a part material comprising a PAS polymer (PASP) or polymer composition (PC) of the present invention; , and printing a layer of the three-dimensional object from the part material.

Thus, a PAS polymer (PASP) or polymer composition (PC) is a thread or filament used in a 3D printing process, for example, Fused Filament Fabrication, also known as Fused Deposition Modeling (“FDM”). may be in the form of

The PAS polymer (PASP) or polymer composition (PC) may also be in powder form, such as a substantially spherical powder, used in 3D printing processes, such as Selective Laser Sintering (SLS).

A PAS polymer (PASP) or a polymer composition (PC) may be incorporated into the composite. The composite includes continuous reinforcing fibers embedded within a thermoplastic matrix. In some embodiments, the continuous reinforcing fibers are glass fibers, carbon fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, aramid fibers, natural fibers (e.g., cotton, linen and wood) and any combination of one or more thereof. Preferably, the continuous reinforcing fibers are glass fibers or carbon fibers. As used herein, a continuous reinforcing fiber is a reinforcing fiber having an average length in its longest dimension of at least 5 millimeters (“mm”), at least 10 mm, at least 25 mm, or at least 50 mm. The thermoplastic matrix comprises a PAS polymer (PASP) or a polymer composition (PC). The composite may be a unidirectional composite (eg, a tape) or a multidirectional composite (eg, a woven fabric, mat, or laminated fabric).

The present invention relates to the use or article of a PAS polymer (PASP) and a polymer composition (PC) for preparing an article as described above. The invention also relates to the use of the above-described PAS polymer (PASP) or polymer composition (C) for 3D printing an object.

Example

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

Raw material

1-Methyl-2-pyrrolidone ("NMP") (>99.0%): obtained from TCI

Sodium hydrosulfide (“NaSH”) (55-60 wt %): obtained from AkzoNobel

1,4-Dichlorobenzene (“DCB”) (≥99): obtained from Alfa Aesar

Sodium hydroxide (≥97.0%): obtained from Fisher Chemical

Sodium Acetate (≥99%): obtained from VWR Chemicals

3,5-dichloroaniline ("3,5-DCA") (≥98%): obtained from Alfa Aesar

3,6-dibromocarbazole ("3,6-DBC") (≥98.0%): obtained from TCI

2,7-dibromocarbazole ("2,7-DBC") (≥97%): obtained from AccelaChemBio

Synthesis of PAS Polymers

Example 1 : (2.5 mol% 2,7-DBC co-PPS) 31.25 g sodium hydroxide (0.781 mol), 20.74 g sodium acetate (0.253 mol), 74.05 g NaSH (58.00 wt.) in a 1 L autoclave reactor %, 0.766 mol), 6.22 g of 2,7-DBC (0.019 mol), and 205 mL of NMP. The reactor was purged with nitrogen, pressurized to 10 psig, and set to stir continuously at 400 rpm. A separate addition vessel was charged with 109.80 g of DCB (0.747 mol) and 50 g of NMP. The addition vessel was purged with nitrogen, pressurized to 90 psig, and heated to 100°C. The reactor was heated to 240° C. at 1.5° C./min. When 150°C was reached, the reactor was vented through the condenser and about 40 mL of clear condensate was collected under a small stream of nitrogen (60 mL/min) until the reactor reached 200°C. At this point, the condenser was removed, the nitrogen flow was stopped, and the DCB/NMP mixture in the addition vessel was immediately added to the reactor. The addition vessel was charged with an additional 30 mL of NMP, purged with nitrogen and pressurized to 90 psig, and the contents were immediately added to the reactor. The sealed reactor was held at 240° C. for 2 hours, heated to 265° C. at 1.5° C./min, held at 265° C. for 2 hours, cooled to 200° C. at 1.0° C./min, and finally cooled to room temperature. did The resulting slurry was diluted with 200 mL of NMP, removed from the reactor, heated to 80° C. and filtered through a medium porosity sintered glass filter. The filter cake was washed once with 100 mL of warm NMP (60° C.). The solid was stirred in 300 mL of heated DI water (70° C.) for 15 min, filtered over a medium porosity glass filter, and this process was repeated a total of 5 times. The rinsed solid was dried in a vacuum oven overnight at 100° C. under nitrogen to give 77.15 g of a white granular solid. GPC, DSC, ASTM Type V Tensile, and ASTM Notched Izod data for this and below examples are provided in the table below.

Example 2 : (5 mol % 2,7-DBC co-PPS) 31.52 g sodium hydroxide (0.788 mol), 20.92 g sodium acetate (0.255 mol), 74.68 g NaSH (58.00 wt %, 0.773 mol), It was synthesized according to the procedure from Example 1 using 12.55 g of 2,7-DBC (0.039 mol), 107.89 g of DCB (0.734 mol), and 287 mL of total NMP. 83.30 g of fine white granular solid were obtained.

Example 3 : (10 mol% 2,7-DBC co-PPS) 31.35 g sodium hydroxide (0.784 mol), 20.80 g sodium acetate (0.254 mol), 72.76 g NaSH (59.21 wt%, 0.768 mol), It was synthesized according to the procedure from Example 1 using 24.97 g of 2,7-DBC (0.077 mol), 101.66 g of DCB (0.692 mol), and 286 mL of total NMP. 82.60 g of a white powder were obtained.

Control Example 1 : (PPS homopolymer) 45.89 g sodium hydroxide (1.147 mol), 30.45 g sodium acetate (0.371 mol), 106.95 g NaSH (58.96% by weight, 1.125 mol), 165.34 g DCB (1.125 mol) , and 418 mL of total NMP, synthesized according to the procedure from Example 1 (except that 2,7-DBC was not used). 112.60 g of a granular white solid were obtained.

Control Example 2 : (10 mol% 3,5-DCA co-PPS) 37.30 g of sodium hydroxide (0.932 mol), 24.75 g of sodium acetate (0.302 mol), 86.56 g of NaSH (59.21% by weight, 0.914 mol), Using 14.81 g of 3,5-DCA (0.091 mol), 120.95 g of DCB (0.823 mol), and 340 mL of total NMP, (except that 3,5-DCA was used instead of 2,7-DBC) ) was synthesized according to the procedure from Example 1. Polymerization resulted in higher than typical maximum pressures (170 psig vs. typical 150 psig). The reaction mixture was a brown sludge with a strong odor of thiophenols and other decomposing species. A portion was rinsed according to the procedure to yield a light brown powder.

Control Example 3 : (10 mol% 3,6-DBC co-PPS) 31.17 g of sodium hydroxide (0.779 mol), 20.69 g of sodium acetate (0.252 mol), 72.35 g of NaSH (59.21% by weight, 0.764 mol), Using 24.83 g of 3,6-DBC (0.076 mol), 101.09 g of DCB (0.688 mol), and 204 mL of total NMP, (except that 3,6-DBC was used instead of 2,7-DBC) ) was synthesized according to the procedure from Example 1. Polymerization resulted in higher than typical maximum pressures (170 psig vs. typical 150 psig). The reaction mixture was a brown sludge with a strong odor of thiophenols and other decomposing species. A portion was rinsed according to the procedure to yield a light brown powder.

Test Methods

Thermal Performance : T _g , T _m , and ΔH _f were determined using differential scanning calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20° C./min. Three scans were used for each DSC test: first heating to 350°C, then first cooling to 30°C, then second heating to 350°C. T _g , T _m , and ΔH _f were determined from the second heating.

Molecular Weight: M _w was determined by gel permeation chromatography (GPC) at 210° C. using PL 220 hot GPC with 1-chloronaphthalene mobile phase and polystyrene standards.

Impact Performance : Notched Izod values were determined according to ASTM D256 using a 0.125 inch flex bar at room temperature.

Thermal performance and impact performance

The test results are shown in Table 1. In the table, "E" represents an Example, and "CE" represents a control example.

Yes comonomer
(mole%) M _w
(g/mol) T _m
(℃) Δ H _f (J/g) T _g (℃) notch
Izod
(J/g) E1 2,7-DBC
(2.5) 268 44 104 36 E2 2,7-DBC
(5) 256 33 102 - E3 2,7-DBC(10) 40,900 not observed
0 105 - CE1 doesn't exist 52,100 280 42 98 28 CE2 3,5-DCA(10) 4,300 240 50 not observed
CE3 3,6-DBC(10) 3,600 256 44 not observed

Referring to Table 1, a comparison of E3 and CE2 shows that the traditional approach to introducing amine content into PAS polymers does not provide adequate molecular weight at the desired monomer concentration. For example, CE2 with 10 mol % of repeating units formed from 3,5-DCA had a molecular weight of 4,300 g/mol. On the other hand, E3 with 10 mol% of repeating units formed from 2,7-DBC had a molecular weight of 40,900 g/mol, which corresponds to a high molecular weight PPS. Similarly, a comparison of E3 and CE3 shows that a high molecular weight PAS polymer can be obtained only when the halogen of the dihalocarbazole containing monomer is in the 2,7-position. CE3 with 10 mol % of repeating units formed from 3,6-DBC had a molecular weight of only 3,600 g/mol. On the other hand, E3 with 10 mol% of repeating units formed from 2,7-DBC had a molecular weight of 40,900 g/mol. Surprisingly, we also observe that PPS containing only 2.5 mole % of 2,7-DCB of E1 has improved impact strength compared to PPS homopolymer (“CE1”). Note that with respect to CE2 and CE3, M _w was too low (not observed) to achieve T _g measurements.

The above embodiments are intended to be illustrative and non-limiting. Additional embodiments are within the concept of the present invention. Moreover, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. The incorporation of any of these documents by reference is limited so as not to include subject matter that is inconsistent with the express disclosure herein.

Claims (15)

A poly(arylene sulfide) ("PAS") polymer (PASP) comprising a repeating unit R _PAS1 and a repeating unit R _PAS2 each represented by the formula:
[Formula 1]
[-Ar ₁ -S-],
[Formula 2]
[-Ar ₂ -S-]
(In the above formula,
- -Ar ₁ - is selected from the group of the formula consisting of:
[Formula 3]

,
[Formula 4]

, and
[Formula 5]

;
-Ar ₂ - is represented by the formula:
[Formula 6]

,
- R and R' at each occurrence are independently a C ₁ -C ₁₂ alkyl group, a C ₇ -C ₂₄ alkylaryl group, a C ₇ -C ₂₄ aralkyl group, a C ₆ -C ₂₄ arylene group, and a C ₆ is selected from the group consisting of a -C ₁₈ aryloxy group;
- T is selected from the group consisting of a bond, -CO-, -SO ₂ -, -O-, -C(CH ₃ ) ₂ , phenyl and -CH ₂ -;
- i at each occurrence is an independently selected integer from 0 to 4;
- j and k at each occurrence are independently selected integers from 0 to 3). The PAS polymer (PASP) according to claim 1, wherein -Ar ₁ - is represented by the following formula:
[Formula 7]

. The PAS polymer (PASP) according to claim 1 or 2, wherein k is 0 at each position. 4. The method according to any one of claims 1 to 3, wherein the ratio of the number of repeating units (R _PAS2 ) to the total number of repeating units (R _PAS1 ) and repeating units (R _PAS2 ) is from 0.5 mol% to 15 mol%. , PAS polymer (PASP). 5. The method according to any one of claims 1 to 4, wherein the ratio of the number of repeating units (R _PAS2 ) to the total number of repeating units (R _PAS1 ) and repeating units (R _PAS2 ) is from 0.5 mol% to 8 mol%. , PAS polymer (PASP). The PAS polymer (PASP) according to any one of the preceding claims, comprising a T _g of at least 95°C. The PAS polymer (PASP) according to any one of the preceding claims, comprising a T _m of at least 200°C. 8. The PAS polymer (PASP) according to any one of claims 1 to 7, comprising an impact strength of at least 30 J/g as determined according to ASTM D256. 9. The PAS polymer (PASP) of any one of claims 1 to 8 with carboxylic acids, carboxylates, anhydrides, epoxides, urethanes, amides, ketones, isocyanates, ureas, halogens, activated ethers, esters, and A polymer composition (PC) comprising a further polymer comprising a functional group selected from the group consisting of acid chlorides. 10. Polymer composition (PC) according to claim 9, wherein the further polymer is a thermoplastic polymer. Polymer composition (PC) according to claim 9, wherein the further polymer is a thermosetting polymer or a thermosetting precursor. 12. The method of claim 11, wherein the additional polymer is an epoxy resin, an epoxy novolac resin, a benzoxazine, a bismaleimide, a polyacid amic solution, a polyester thermosetting resin, a vinyl ester, a cyanate ester, and a urea-formaldehyde A polymer composition (PC) selected from the group consisting of resins. The polymer composition (PC) according to any one of claims 10 to 12, comprising a fibrous reinforcing filler or a toughening agent, preferably a fibrous reinforcing filler. An automotive component, aerospace component, or oil and gas comprising the PAS polymer (PASP) of any one of claims 1-8 or the polymer composition (PC) of any one of claims 9-13 component for use. A process for the preparation of the PAS polymer (PASP) according to any one of claims 1 to 8, comprising:
a dihaloaromatic compound having the formula X ₁ -Ar ₁ -X ₂ ; dihalocarbazole containing a monomer having the formula X ₃ -Ar ₂ -X ₄ ; and reacting the sulfur compound in a reaction mixture state,
- X ₁ to X ₄ are independently selected halogen,
- sulfur compounds include thiosulfates, thioureas, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides, and hydrogen sulfide; Preferably the sulfur compound is an alkali metal sulfide; Most preferably the sulfur compound is Na ₂ S.