WO2016102277A1

WO2016102277A1 - Methods for making polyarylene ether sulfone (paes) polymers with silylated terphenyl compounds

Info

Publication number: WO2016102277A1
Application number: PCT/EP2015/080032
Authority: WO
Inventors: Chantal Louis
Original assignee: Solvay Specialty Polymers Usa, Llc
Priority date: 2014-12-22
Filing date: 2015-12-16
Publication date: 2016-06-30

Abstract

A method for making a poly(arylether sulfone) polymer [(t-PAES)polymer] includes reacting in a polar aprotic solvent and optionally in the presence of a small amount of potassium carbonate, a monomer mixture including at least one silylated terphenyl compound of Formula (SiTSi); at last one dihaloaryl compound, and at least one alkali metal fluoride, where R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* in Formula (SiTSi) are independently selected from a C₁-C₅ alkyl or an arylgroup, each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium, and u' is zero or an integer ranging from 1 to 4.

Description

Methods for Making Polyarylene ether sulfone (PAES) Polymers

With Silylated Terphenyl Compounds

Cross-Reference to Related Applications

This application claims priority to U.S. Provisional Application

No. 62/095,546, filed December 22, 2014, which is incorporated by reference herein in its entirety.

Field of the Invention

The present invention relates methods for making polyarylene ether sulfone (PAES) polymers with silylated terphenyl compounds.

Background

The selection of polymeric material in more demanding, corrosive, harsh chemical, high-pressure and high-temperature (HP/HT) environments, such as notably in oil and gas downhole applications, in particular in deep see oil wells, is of ultimate importance as it implies that said polymeric materials need to possess some critical properties in order to resist the extreme conditions associated with said environments.

It should be mentioned that in these extreme conditions the polymeric materials are exposed in a prolonged fashion to high pressure, e.g. pressures higher than 30,000 psi, high temperatures, e.g. temperatures up to 260°C, and to harsh chemicals including acids, bases, superheated water/steam, and of course a wide variety of aliphatic and aromatic organics. For example, enhanced oil recovery techniques involve injecting of fluids such as notably water, steam, hydrogen sulfide (H₂S) or supercritical carbon dioxide (sC0₂) into the well. In particular, sC0₂ having a solvating effect similar to n-heptane, can cause swelling of materials in for instance seals, which affect consequently their performance. Polymeric materials having glass transition temperatures (Tg) too low relative to the high temperature in HP/HT applications will suffer from being weak and susceptible to high creep in these HP/HT applications. This creep can cause the seal material made of said polymeric material to no longer effectively seal after prolonged exposure at temperature which are 20 or more°C above their Tg. Thus, properties such as maintaining mechanical rigidity and integrity (e.g. tensile strength and modulus, hardness and impact toughness) at high pressure and temperatures of at least 250°C, good chemical resistance, in particular when exposed to C0₂, H₂S, amines and other chemicals at said high pressure and temperature, swelling and shrinking by gas and by liquid absorption, decompression resistance in high pressure oil/gas systems, gas and liquid diffusion and long term thermal stability need to be considered in the selection of appropriate polymeric materials for HP/HT applications.

Thus, there is a need for polymeric materials that possess, for example, high melt stability and resistance to swelling in HP/HT applications and which exhibit excellent mechanical properties.

Summary of the Invention

It has surprisingly and unexpectedly been discovered that certain

poly(arylether sulfone) polymers exhibiting a high melt stability and excellent mechanical properties can be prepared by using certain silylated terphenyl compounds, optionally a small amount of an alkali metal fluoride, and optionally a minimal amount of potassium carbonate in the polymerization reaction.

Polymers made by the methods of the invention have unexpectedly been found to exhibit one or more of :

· For a given molecular weight, increased degree of crystallinity and higher melting temperature (Tm);

• A stable melt viscosity as measured by dynamic rheology (parallel plates) at 420°C, 10 rad/s for 40 minutes (no swelling of sample, viscosity ratio VR40 < 1.50);

· The absence of any signal in ^!H NMR at about 8.2 ppm (relative integration result < 0.1), and

• Good mechanical properties, for example, elongation at yield as measured according to ASTM D638 of greater than or equal to 5.0 %.

Without being bound by the theory, it is believed that the methods of the invention produce a particular polymer architecture/mi crostructure which give the polymer a high melt stability and excellent mechanical properties. Although the particular microstructure/architecture has not yet been determined, it has unexpectedly been observed that the intensity of the ^!H NMR at about 8.2 ppm, which is otherwise present in H NMR spectra of similar polymers prepared by comparative methods, is significantly reduced or absent in polymers prepared according the methods of the invention.

Exemplary embodiments are directed to a method for making a poly(arylether sulfone) polymer [(t-PAES) polymer], including :

step i. reacting a monomer mixture including :

a) at least one silylated terphenyl compound of Formula (SiTSi) :

(SiTSi) where :

- R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* are independently selected from a Ci-C₅ alkyl or an aryl group;

- each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and

- u' is zero or an integer ranging from 1 to 4;

b) o tionally, at least one dihydroxyaryl compound [diol (AA)] of Formula (T) :

where :

- j' is zero or an integer ranging from 1 to 4; c) optionally, at least one dihydroxyaryl compound [diol (ΑΆ')] different from diol (AA);

d) at least one dihaloaryl compound [dihalo(BB)] of Formula (S) :

X-Ar¹-S02-[Ai^?-Cr-Ai^)„-S02]m-Ar⁴-X' (S) where :

- n and m, equal to or different from each other, are independently zero or an integer ranging from 1 to 5 ;

- X and X' are independently selected from F, CI, Br, and I;

- each of Ar¹, Ar², Ar³ and Ar⁴' equal to or different from each other, is an

aromatic moiety; and

- T in Formula (S) is selected from a bond, -CH₂-, -C(O)-, -C(CH3)₂-,

-C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)( )-, and a group of formula :

e) optionally, at least one dihaloaryl compound [dihalo (B'B')] different from dihalo (BB);

f) at least one alkali metal fluoride; and

g) at least one polar aprotic solvent.

According to exemplary embodiments, the method may further include a step ii of further reacting the monomer mixture in the presence of at least one alkali metal carbonate selected from potassium carbonate (K₂C0₃), rubidium

carbonate (Rb₂C0₃), and caesium carbonate (Cs₂C0₃), in an amount less than or equal to 1 mol % of a total mol % of component a) and optional components b) and c).

Preferably, step ii further includes reacting the monomer mixture in the presence of sodium carbonate ( a₂C0₃).

At least 50 % of a total amount of alkali metal carbonates may be sodium carbonate ( a₂C0₃).

Preferably, the at least one alkali metal fluoride includes potassium fluoride.

According to exemplary embodiments, the method further includes heating the monomer mixture to a temperature ranging from 150°C to 320°C prior to step ii. In some embodiments, the method further includes a step iii including adding an additional amount of component d) to the monomer mixture, such that an overall amount of halo-groups and a sum of hydroxyl-groups and siloxy groups in the monomer mixture is substantially equimolecular.

In some embodiments, the method further includes a step iv of end-capping the (t-PAES) polymer by adding an additional amount of at least one of

component d) and component e) in molecular excess.

According to exemplary embodiments, the diol (ΑΆ') is present in the monomer mixture and is selected from compounds of Formula (D) :

HO-Ar⁹-(T'-Ar¹⁰)_n-O-H (D) where :

- n is zero or an integer ranging from 1 to 5;

- each of Ar⁹ and Ar¹⁰, equal to or different from each other, is an aromatic moiety of formula :

where :

- each R_s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;

- k is zero or an integer ranging from 1 to 4;

- k' is zero or an integer ranging from 1 to 3; and

- T' is selected from a bond, -S0₂-, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-,

-C(=CC1₂)-, -C(CH₃)(CH₂CH₂C roup of formula :

In some embodiments the dihalo (Β'Β') is present in the monomer mixture and is a compound of Formula (K) :

X-Ar⁵-CO-[Ar⁶-(T-Ar⁷)_n-CO]_m-Ar⁸-X' (K) where :

- n and m, equal to or different from each other, are independently zero or an integer ranging from 1 to 5 ,

- each of Ar⁵, Ar⁶, Ar⁷ and Ar⁸, equal to or different from each other, is an

aromatic moiety,

- T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, an :

X and X' are independently selected from F, CI, Br, or I.

Component a) preferably comprises :

The (t-PAES) polymer preferably has a number average molecular weight (M_n) of at least 41 ,000 g/mol, preferably the (t-PAES) polymer has a number average molecular weight (M_n) ranging from 41 ,000 to 90,000 g/mol

The (t-PAES) polymer may have a NMR signal from about 8.1 ppm to about 8.3 ppm of < 1 , and preferably the (t-PAES) polymer does not exhibit an 'PI NMR signal at from about 8.1 ppm to about 8.3 ppm.

The (t-PAES) polymer may exhibit at least one of an elongation at yield measured according to ASTM D638 that is greater than 5.0 %, and an elongation at break measured according to ASTM D638 that is greater than or equal to 5.0 %.

Component a) is preferably at least 10 % by mole of the sum of the moles of component a), optional component b), and optional component c).

Exemplary embodiments include a (t-PAES) polymer made by the methods described herein. Exemplary embodiments also include a shaped article including the (t-PAES) polymer made by the methods described herein.

Exemplary embodiments include a method for making a shaped article including injection moulding, extrusion moulding, or compression molding the (t-PAES) polymer made by the methods described herein.

Exemplary embodiments also include a composition comprising the (t-PAES) polymer made by the methods described herein.

Brief Description of the Figures

Fig. 1 A illustrates a IH NMR spectrum for the (t-PAES) polymer of Example CI . Fig. IB illustrates a IH NMR spectrum for the (t-PAES) polymer of Example C3. Fig. 1 C illustrates a IH NMR spectrum for the (t-PAES) polymer of Example 4. Fig. ID illustrates a IH NMR spectrum for the (t-PAES) polymer of Example 5. Detailed Description of Preferred Embodiments

Exemplary methods for making the polyarylene ether sulfone (PAES) polymers and the resulting (PAES) polymers will now be described in detail.

Method for Making (t-PAES) Polymers

step i. reacting a monomer mixture including :

a) at least one silylated terphenyl compound of Formula (SiTSi) :

(SiTSi) where :

- R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* are independently selected from a C₁-C5 alkyl or an aryl group;

- u' is zero or an integer ranging from 1 to 4; b) o tionally, at least one dihydroxyaryl compound [diol (AA)] of Formula (T) :

where :

- j' is zero or an integer ranging from 1 to 4;

c) optionally, at least one dihydroxyaryl compound [diol (ΑΆ')] different from diol (AA);

d) at least one dihaloaryl compound [dihalo(BB)] of Formula (S) :

X-Ar¹-S02-[Ai^?-Cr-Ai^)„-S02]m-Ar⁴-X' (S) where :

- n and m, equal to or different from each other, are independently zero or an integer ranging from 1 to 5;

- X and X' are independently selected from F, CI, Br, and I;

- each of Ar¹, Ar², Ar³ and Ar⁴' equal to or different from each other, is an aromatic moiety; and

- T in Formula (S) is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-,

-C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃) H)-, and a group of formula :

f) at least one alkali metal fluoride; and

g) at least one polar aprotic solvent. According to exemplary embodiments, the method may further include a step ii of further reacting the monomer mixture in the presence of at least one alkali metal carbonate selected from potassium carbonate (K₂CO₃₎, rubidium

carbonate (Rb₂C03), and caesium carbonate (CS₂CO₃), in an amount less than or equal to 1 mol % of a total mol % of component a) and optional components b) and c).

In some embodiments, step ii further includes reacting the monomer mixture in the presence of sodium carbonate ( a₂C03).

Component A : Silylated Terphenyl Compound

The silylated terphenyl compound is selected from compounds of

Formula (SiTSi) :

(SiTSi)

R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* are can be the same or different and are independently selected from a C1-C5 alkyl or an aryl group.

Preferably, at least one of R^1*, R^2*, and R^3*, and at least one of R^4*, R^5*, and R^6* is a linear C1-C5 alkyl, preferably a methyl or ethyl n-propyl group, most preferably a methyl group. More preferably, at least two of R^1*, R^2*, and R^3*, and at least two of R^4*, R^5*, and R^6* is a linear C1-C5 alkyl, preferably a methyl or ethyl n-propyl group, most preferably a methyl group. Most preferably, all of R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* is a linear C1-C5 alkyl, preferably a methyl or ethyl n-propyl group, most preferably a methyl group.

Preferably, R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* are the same.

Each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.

u' is zero or an integer ranging from 1 to 4.

According to exemplary embodiments, the silylated terphenyl compound is a compound of formula :

The silylated terphenyl compound of Formula (SiTSi) can be prepared by methods known in the art from the unsilylated terphenyl diol. More particularly, the silylated terphenyl compound can be prepared by reaction between

l,r:4',l"-terphenyl-4,4"-diol and a silylating agent, such as hexamethyldisilazane, trimethylsilyl chloride or trimethylsilyl iodide. Most preferably, the silylated terphenyl compound is prepared by reaction between l,r:4',l"-terphenyl-4,4"-diol and hexamethyldisilazane.

Optional Component B : Dihydrox aryl Compound [Diol (AA)]

The monomer mixture optionally may optionally include at least one dih droxyaryl compound [diol (AA)] of Formula (T) :

where :

- j' is zero or an integer ranging from 1 to 4.

Optional Component C : Dihydroxyatyl Compound [Diol (A Ά ')]

Among dihydroxyl compounds [diols (ΑΆ')] different from diol (AA), as above detailed, mention can be of compounds of formula (D) :

HO-Ar⁹-(T'-Ar¹⁰)_n-O-H (D) wherein :

- n is zero or an integer ranging from 1 to 5;

- each of Ar⁹ and Ar¹⁰, equal to or different from each other, is an aromatic moiety of the formula :

wherein :

- each R_s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and

- k is zero or an integer ranging from 1 to 4; k' is zero or an integer ranging from 1 to 3;

- T ' is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond, -S0₂-, -CH₂-, -C(O)-,

-C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

Preferably, dihydroxyl compounds [diols (ΑΆ')] are selected from compounds of the following formulae :

Component D : Dihaloaryl Compound [Dihalo (BB)J

Dihaloaryl compounds [dihalo(BB)] are selected from compounds of Formula (S) :

X-Ar¹-S0₂-[Ar²-(T-Ar³)_n-S0₂]_m-Ar⁴-X' (S) wherein :

- X and X' are independently selected from F, CI, Br, and I, preferably CI or F, most preferably F.

- each of Ar¹, Ar², Ar³ and Ar⁴' equal to or different from each other, is an aromatic moiety;

- T in Formula (S) is a bond or a divalent group optionally including one or more than one heteroatom; preferably T is selected from a bond, -CH₂-,

-C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

The aromatic moiety in each of Ar¹, Ar², Ar³ and Ar⁴ equal to or different from each other and at each occurrence preferably complies with following formulae :

wherein :

- k is zero or an integer ranging from 1 to 4; k' is zero or an integer ranging from 1 to 3.

Preferred dihalo (BB) are those of formulae (S'-l) to (S'-4), as shown below :

wherein :

- each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;

- j' is zero or an integer ranging from 1 to 4,

- T is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-,

-C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

- X and X', equal to or different from each other, are independently a halogen atom, preferably CI or F.

More preferred dihalo (BB) compounds are those complying with following

where X and X', equal to or different from each other, are preferably CI or F. More preferably X and X' are F.

Preferred dihaloaryl compounds [dihalo (BB)] are 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS),

4,4'-chlorofluorodiphenyl sulfone or a mixture thereof. Most preferred dihalo (BB) is 4,4'-difiuorodiphenyl sulfone (DFDPS) or a mixture of DCDPS and DFDPS. Optional Component E : Dihaloaryl Compound [Dihalo (B'B')J

Among dihaloaryl compound [dihalo (B'B')] different from dihalo (BB) mention can be notably made of dihalo (Β'Β') of formula (K) :

X-Ar⁵-CO-[Ar⁶-(T-Ar⁷)_n-CO]_m-Ar⁸-X' (K) wherein :

- each of Ar⁵, Ar⁶, Ar⁷ and Ar⁸ equal to or different from each other, is an aromatic moiety,

- T is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

- X and Χ', equal to or different from each other, are independently a halogen atom, preferably CI or F.

More preferred dihalo (Β'Β') compounds are those complying with the following formulae :

wherein :

- j' is zero or an integer ranging from 1 to 4;

wherein X and X', equal to or different from each other, are preferably CI or F. More preferably X and X' are F.

Preferred dihalo (Β'Β') are 4,4'-difluorobenzophenone,

4,4'-dichlorobenzophenone and 4-chloro-4'-fluorobenzophenone, with

4,4'-difluorobenzophenone being particularly preferred. Component F : Alkali Metal Fluoride

The alkali metal fluoride may be potassium fluoride or caesium fluoride. Potassium fluoride is preferred. The alkali metal fluoride is preferably present in an amount ranging from 0.05 to 25 mol % of the total [silylated terphenyl

compound (Si-T-Si) + Dihydroxyaryl Compound (AA) + Dihydroxyaryl

Compound (ΑΆ')], more preferably 0.1 to 5 mol %.

Component G : Polar Apr otic Solvent

As polar aprotic solvents, mention can be made of sulfur-containing solvents such as notably aromatic sulfones and aromatic sulfoxides and more specifically diaromatic sulfones and diaromatic sulfoxides according to the general formulae below :

R'-S0₂ -R" or R'-SO-R"

wherein R' and R", equal to or different from each other, are independently aryl, alkaryl and araryl groups.

More preferred polar aprotic solvents are those complying with following formulae shown below :

wherein Y and Y', equal to or different from each other, are independently selected from halogen, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl; Z is a bond, oxygen or two hydrogens (one attached to each benzene ring).

Specifically, among the sulfur-containing solvents that may be suitable for the purposes of this invention are diphenyl sulfone, phenyl tolyl sulfone, ditolyl sulfone, xylyl tolyl sulfone, dixylyl sulfone, tolyl paracymyl sulfone, phenyl biphenyl sulfone, tolyl biphenyl sulfone, xylyl biphenyl sulfone, phenyl naphthyl sulfone, tolyl naphthyl sulfone, xylyl naphthyl sulfone, diphenyl sulfoxide, phenyl tolyl sulfoxide, ditolyl sulfoxide, xylyl tolyl sulfoxide, dixylyl sulfoxide,

dibenzothiophene dioxide, and mixtures thereof.

Very good results have been obtained with diphenyl sulfone.

Other carbonyl containing polar aprotic solvents, including benzophenone may be used in exemplary embodiments. If desired, an additional solvent can be used together with the polar aprotic solvent which forms an azeotrope with water, whereby water formed as a byproduct during the polymerization may be removed by continuous azeotropic distillation throughout the polymerization.

The by-product water and carbon dioxide possibly formed during the polymerization can alternatively be removed using a controlled stream of an inter gas such as nitrogen or argon over and/or in to the reaction mixture in addition to or advantageously in the absence of an azeotrope-forming solvent as described above.

For the purpose of the present invention, the term "additional solvent" is understood to denote a solvent different from the polar aprotic solvent and the reactants and the products of said reaction.

The additional solvent that forms an azeotrope with water will generally be selected to be inert with respect to the monomer components and polar aprotic solvent. Suitable azeotrope-forming solvents for use in such polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like.

The azeotrope-forming solvent and polar aprotic solvent are typically employed in a weight ratio of from about 1 : 10 to about 1 : 1, preferably from about 1 : 5 to about 1 : 3.

Alkali Metal Carbonates

In exemplary embodiments, the potassium carbonate (K₂CO₃₎, rubidium carbonate (Rb₂C03₎, caesium carbonate (CS₂CO₃), or mixture thereof (most preferably K₂CO₃) in step ii is present in an amount less than or equal to 1 mol %, preferably less than 0.75 %, preferably less than 0.5 %, preferably less than 0.25 % of the total amount by mol of component a) and optional components b) and c).

Preferably, the potassium carbonate (K₂CO₃₎, rubidium carbonate (Rb₂C03₎, and/or caesium carbonate (CS₂CO₃) is not used in step ii.

Optionally, step ii includes reacting the monomer mixture in the presence of sodium carbonate ( a₂C03).

Preferably, step ii is not performed (i.e. no alkali metal carbonates are added).

If sodium carbonate (Na₂C03) is added, it is preferably added in an amount of at least 50 %, preferably at least 60 %, preferably at least 70 %, preferably at least 80 %, preferably at least 90 %, preferably at least 95 %, preferably at least 99 %, preferably more than 99 %, preferably more than 99.5 %, preferably 100 % by weight of the sum by weight of the potassium carbonate (K₂CO₃), rubidium carbonate (Rb₂C03), caesium carbonate (CS₂CO₃), and sodium

carbonate ( a₂C03).

A person of ordinary skill in the art will recognize additional ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure.

It has surprisingly been found that the use of an optimum amount of alkali metal carbonate, for example potassium carbonate, allows reducing significantly the reaction times of the process of the present invention while avoiding using excessive amounts of alkali metal carbonate which leads to higher costs and more difficult polymer purifications.

The use of an alkali metal carbonate having an average particle size of less than or equal to about 200 μηι, preferably of less than or equal to about 150 μηι preferably of less than or equal to about 75 μηι, more preferably < 45 μηι is especially advantageous. The use of an alkali metal carbonate having such a particle size advantageously permits the synthesis of the polymers with desirable molecular weights.

According to exemplary embodiments, the method includes reacting the monomer mixture at a temperature ranging from 150°C to 320°C prior to step ii, which may result in the formation of fiuorosilane. Preferably, after an initial heat up period, the temperature of the reaction mixture will be maintained in a range of advantageously from 250 to 350°C, preferably from 300 to 340°C. Good results were obtained at a temperature of about 320°C.

Preferably the monomer mixture of step i is heated in stages of increasing temperature. For example, the monomer mixture may be heated to a temperature of about 150°C and held for about 30 minutes then heated up to about 200°C and held for about 30 minutes, then heated up to about 250°C and held for about 30 minutes, then heated up to about 320°C prior to the addition of any alkali metal carbonate.

A person of ordinary skill in the art will recognize that additional temperatures within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure. In exemplary embodiments the method further includes a step iii, including adding an additional amount of component d) to the monomer mixture, such that an overall amount of halo-groups and a sum of hydroxyl-groups and siloxy groups in the monomer mixture is substantially equimolecular.

As used herein, the term "siloxy groups" means groups of the following formulae :

where R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* correspond to R^1*, R^2*, R^3*, R^4*, R^5*, and R^6* in Formula (SiTSi), respectively.

In exemplary embodiments, a total % monomer mixture concentration

[total % monomers, herein after] is equal to or more than 22 % and less than or equal to 50 % with respect to the combined weight of monomer mixture and solvent mixture.

For the purpose of the present invention, the term" total % monomers" is defined as the sum of the weight of all monomers initially present at the start of the reaction in the monomer mixture in grams, designated as Mwt, divided by the combined weight of all monomers initially present in the monomer mixture and of the solvent mixture, wherein the weight of the solvent mixture in grams is designated as Swt.

The total % monomers is thus equal to the formula :

l OO x Mwt wt + Swt).

The total % monomers is preferably equal to or more than 24 %, more preferably equal to or more than 25 %.

The total % monomers is in general less than or equal to 60 %, preferably less than or equal to 50 %, more preferably less than or equal to 45 %.

Very good results have been obtained at a total % monomers in a range from 25 % - 45 %.

For the purpose of the present invention, the expression "substantially equimolecular" used with reference to the overall amount of halo-groups and the sum of hydroxyl-groups and siloxy groups of the monomers initially present at the start of the reaction of the monomer mixture, as above detailed, is to be understood that the molar ratio of the overall amount of the sum of hydro xyl-groups and siloxy groups of the monomers of the monomer mixture to the overall amount of halo groups of the monomers of the monomer mixture is greater than or equal to 0.910, more preferably greater than or equal to 0.930, even more preferably greater than or equal to 0.950. It is further understood that the molar ratio of the overall amount of sum of hydroxyl-groups and siloxy groups of the monomers of the monomer mixture to the overall amount of halo groups of the monomers of the monomer mixture is less than or equal to 1.100, preferably less than or equal to 1.080, more preferably less than or equal to 1.050. Good results were obtained when the molar ratio of the overall amount of hydroxyl groups and siloxy groups of the monomers in the monomer mixture to the overall amount of halo groups of the monomers in the monomer mixture is in the range 1.010 to 1.050.

Preferably, component a) (the silylated terphenyl compound) is at least 10 %, preferably 20 %, preferably 30 %, preferably 40 %, preferably 50 %, preferably 60 %, preferably 70 %, preferably 80 %, preferably 90 %, preferably 95 %, preferably 99 %, preferably 100 % by mol of the sum of the moles of component a), optional component b), and optional component c).

If desired, an additional amount of the dihalo(BB), as described above, and/or dihalo (Β'Β'), as described above, can be added to the reaction mixture when the reaction is essentially complete to end-cap the (t-PAES) polymer. Accordingly, in exemplary embodiments the method may include an additional step iv of end- capping the (t-PAES) polymer by adding an additional amount of the dihaloaryl compound [dihalo(BB)] and/or the dihalo (Β'Β') in molecular excess.

For the purpose of the present invention, the expression "essentially complete" used with reference to the reaction is to be understood that the amount of all monomers which were initially present at the start of the reaction in the monomer mixture is less than or equal to 1.5 % mol, preferably less than or equal to 1 % mol, relative to the total amount of all monomers which were initially present at the start of the reaction.

Said additional amount, expressed in a molar amount with respect to the total amount of moles of the diol (AA) and silylated terphenyl compound (Si-T-Si), as detailed above and optionally the diol (ΑΆ'), as detailed above, is typically in the range from about 0.1 to 15 % mol, with respect to the total amount of moles of the diol (AA), as detailed above, optionally of the diol (Α'Α'), and the silylated terphenyl compound, preferably from 0.2 to 10 % mol, more preferably from 0.5 to 6 % mol.

If desired, the solvent mixture can further comprise any end-capping agent [agent (E)]. Said agent (E) is in general selected from a halo compound comprising only one reactive halo group [agent (MX)] and a hydroxyl compound comprising only one reactive hydroxy group [agent (MOH)].

The expression 'halo compound comprising only one reactive halo group [agent (MX)] ' is intended to encompass not only monohalogenated compounds but also halogenated compounds comprising more than one halo group, but wherein only one of said halo group is reactive.

It is nevertheless generally preferred that said agent (MX) comprises only one halo group.

Thus, agent (MX) is preferably selected from 4-monochlorodiphenylsulfone, 4-monofiuorodiphenylsulfone, 4-monofiuorobenzophenone, 4- monochlorobenzophenone, alkylchlorides such as methylchloride and the like.

Similarly, the expression 'hydroxyl compound comprising only one reactive hydroxy group [agent (MOH)] ' is intended to encompass not only

monohydroxylated compounds but also hydroxylated compounds comprising more than one hydroxy group, but wherein only one of said hydroxy group is reactive.

It is nevertheless generally preferred that said agent (MOH) comprises only one hydroxy group.

Thus, agent (MOH) is preferably selected from terphenol, phenol,

4-phenylphenol, 4-phenoxyphenol, 4-monohydroxydiphenylsulfone,

4-monohydroxybenzophenone.

In the process of the present invention, the total amount of agent (E), computed as

moles of agent (MOH) 100 agent (E) (%moles) ^:

total moles of (diol (AA) + diol (Α'Α')

+ silylated terphenyl compound (Si-T-Si¾l is comprised between 0.05 and 20 % moles, being understood that the agent (E) might advantageously be agent (MX) alone, agent (MOH) alone or a combination thereof. In other words, in above mentioned formula, the amount of agent (MX) with respect to the total moles of dihalo(BB), as detailed above, optionally of dihalo (Β'Β'), as detailed above, can be from 0.05 to 20 % moles, the amount of agent (MOH) with respect to the total moles of diol (AA), as detailed above, optionally of the diol (ΑΆ'), and the silylated terphenyl compound can be from 0.05 to 20 % moles, with the additional provision that their sum is 0.05 to 20 % moles.

The amount of agent (E), as above described, is of at most 10 % moles, preferably at most 8 % moles, more preferably at most 6 % moles.

The amount of agent (E), as above described, is of at least 1 % moles, preferably at least 2 % moles.

The agent (E) can be present at the start of the reaction in the monomer mixture or/and can be added to the reaction mixture when the reaction is essentially complete.

The agent (E) can be added with the aim to control the upper limit of the number average molecular weight (M_n) of the (t-PAES) polymer, as detailed below.

In general, the end-capping agent, as described above, may be added to the reaction mixture, as described above, at a temperature from 250 to 350°C, preferably from 300 to 340°C.

If desired, at least one salt (SI) different from a fluoride salt and able to react with a fluoride salt (S2) can be added to the reaction mixture. Said fluoride salt (S2) can be formed as one of the by-products during the polymerization reaction when X or/and X' in dihalo (BB) and/or dihalo (Β'Β') is F. Examples of such fluoride salt (S2) are notably sodium fluoride and potassium fluoride. Suitable salts (SI) for use in such polymerization processes include lithium chloride, calcium chloride and magnesium chloride. Lithium chloride is most preferred.

The process according to exemplary embodiments is advantageously pursued while taking care to avoid the presence of any reactive gases in the reactor. These reactive gases may be notably oxygen, water and carbon dioxide. 0₂ is the most reactive and should therefore be avoided.

In a particular embodiment, the reactor should be evacuated under pressure or under vacuum and filled with an inert gas including less than 20 ppm of reactive gases, and in particular less than 10 ppm of 0₂. Preferably, the reactor is under an inert atmosphere during forming of the premix. Preferably, the reaction in step b) of the method described above is performed under an inert atmosphere. Preferably, the reactor is under an inert atmosphere prior to any heating step. The inert gas is any gas that is not reactive under normal circumstances. It may be chosen from nitrogen, argon or helium. The inert gas contains preferably less than or equal to 10 ppm oxygen, 20 ppm water and 20 ppm carbon dioxide.

The (t-PAES) Polymer

Exemplary (t-PAES) polymers made by the methods described above are (t-PAES) polymers including recurring units (R_t) of formula (S_t) :

-E-Ar¹-S0₂-[Ar²-(T-Ar³)_n-S0₂]_m-Ar⁴- (S_t) wherein :

- each of Ar¹, Ar², Ar³ and Ar⁴ equal to or different from each other, is an aromatic moiety,

- T is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)( )-, and a group of formula :

- E is of formula (E_t) :

wherein :

- j' is zero or an integer ranging from 1 to 4.

Preferably the (t-PAES) polymer includes more than 50 % moles of the recurring units (R_t). The (t-PAES) polymer may exhibit a ^!H NMR signal in the range

about 8.1 ppm to about 8.3 ppm, preferably, about 8.1 ppm to about 8.25 ppm, preferably about 8.1 ppm to about 8.2 ppm. The intensity of this signal can be estimated by integrating the NMR signal from the baseline between 8.1

and 8.3 ppm. The relative intensity can be calculated using the formula :

% relative signal 8.2ppm = [Integral (signal at 8.2 ppm) x 24(=∑H⁺ OMCTS) x weight (OMCTS)]/[ Integral (OMCTS at 0.2 ppm) x weight (sample) x concentration (polymer % weight in pentafluorophenol) x MW(OMCTS)]*1000 The intensity of the of the ^!H NMR signal is preferably < 1 , preferably < 0.9, preferably < 0.8, preferably < 0.7, preferably < 0.6, preferably < 0.5,

preferably < 0.4, preferably < 0.3, preferably < 0.2, preferably < 0.1 , preferably zero or substantially zero.

A person of ordinary skill in the art will recognize that additional chemical shift ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure as necessary to define a given ^!H NMR signal.

The (t-PAES) polymer preferably also possesses one or more of a high Tg, high stiffness and strength, high toughness, high percent crystallization, high melt stability and good chemical resistance.

The aromatic moiety in each of Ar¹, Ar², Ar³ and Ar⁴ equal to or different from each other and at each occurrence is preferably at least one group of following formula

each R_s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and - k is zero or an integer ranging from 1 to 4; k' is zero or an integer ranging from 1 to 3.

In recurring unit (R_t), the respective phenylene moieties may independently have 1 ,2-, 1 ,4- or 1 ,3 -linkages to the other moieties different from R or R' in the recurring unit. Preferably, said phenylene moieties have 1 ,3- or 1 ,4- linkages, more preferably they have a 1 ,4-linkage.

Still, in recurring units (R_t), j ', k' and k are at each occurrence zero, that is to say that the phenylene moieties have no other substituents than those enabling linkage in the main chain of the polymer.

Preferred recurring units (R_t) are selected from those of formula (S_t-1) to (S_t-4) herein below :

- j' is zero or an integer ranging from 1 to 4,

- T is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond,

-CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

The above recurring units of preferred embodiments (R_t-1) to (R_t-4) can be each present alone or in admixture.

More preferred recurring units (R_t) are selected from those of formula (S _t-l) -3) herein below :

Preferably, recurring unit (R_t) is of formula (S _t-l), as shown above.

According to certain embodiments, the (t-PAES) polymer, as detailed above, comprises in addition to recurring units (R_t), as detailed above, recurring units (R_a) of formula (K_a) :

-E-Ar⁵-CO-[Ar⁶-(T-Ar⁷)_n-CO]_m-Ar⁸- (formula IQ wherein :

- each of Ar⁵, Ar⁶, Ar⁷ and Ar⁸ equal to or different from each other, is an aromatic moiety, T is a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-,

- E is of formula (E_t), as detailed above.

Recurring units (R_a) can notably be selected from those of formulae (K_a-1) o (K_a-2) herein below :

wherein :

- j' is zero or an integer ranging from 1 to 4.

More preferred recurring units (R_a) are selected from those of formula (K'_a-1) o '_a-2) herein below :

(K'_a-2) According to certain embodiments, the (t-PAES) polymer, as detailed above, comprises in addition to recurring units (R_t), as detailed above, recurring units (Rb) comprising a Ar-S0₂-Ar' group, with Ar and Ar', equal to or different from each other, being aromatic groups, said recurring units (Rb) generally complying with formulae (SI) :

(S I) : -Ar⁹-(T'-Ar^li))„-0-Ar¹¹-S02-[Ar¹²-Cr-Ar¹³)„-S02]m-Ar¹⁴-0- wherein :

Ar⁹, Ar¹⁰, Ar¹¹, Ar¹², Ar¹³ and Ar¹⁴, equal to or different from each other and at each occurrence, are independently an aromatic mono- or a polynuclear group; - T and T', equal to or different from each other, is independently a bond or a divalent group optionally comprising one or more than one heteroatom;

preferably T' is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂CO and a group of formula :

preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-,

-C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

Recurring units (Rb) may be notably selected from those of formulae (SI -A) to (S 1 -D) herein below :

(Sl -A)

wherein :

- j ' is zero or is an integer from 0 to 4;

- T and T', equal to or different from each other are a bond or a divalent group optionally comprising one or more than one heteroatom; preferably T' is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-,

C(CH₃)(CH₂CH₂COOH)-, -S0₂-, and a group of formula :

preferably T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-,

-C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula

In recurring unit (Rt,), the respective phenylene moieties may independently have 1,2-, 1 ,4- or 1 ,3 -linkages to the other moieties different from R' in the recurring unit. Preferably, said phenylene moieties have 1,3- or 1 ,4- linkages, more preferably they have 1,4-linkages. Preferably, in recurring units (Rt_>), j ' is at each occurrence zero, that is to say that the phenylene moieties have no other substituents than those enabling linkage in the main chain of the polymer.

According to certain embodiments, the (t-PAES) polymer, as detailed above, comprises in addition to recurring units (R_t), as detailed above, recurring units (R_c) comprising a Ar-C(0)-Ar' group, with Ar and Ar', equal to or different from each other, being aromatic groups, said recurring units (R_c) being generally selected from formulae (

32

- j ' is zero or is an integer from 0 to 4.

In recurring unit (R_c), the respective phenylene moieties may independently have 1 ,2-, 1 ,4- or 1 ,3 -linkages to the other moieties different from R' in the recurring unit. Preferably, said phenylene moieties have 1,3- or 1 ,4- linkages, more preferably they have 1,4-linkage.

Preferably, in recurring units (R_c), j ' is at each occurrence zero, that is to say that the phenylene moieties have no other substituents than those enabling linkage in the main chain of the polymer.

The (t-PAES) polymer preferably comprises recurring units (R_t) of formula (St) as above detailed in an amount of more than 50 % moles, preferably more than 60 %, preferably more than 70 % moles, preferably more

than 75 % moles, preferably more than 85 % moles, preferably more than 90 % moles, preferably more than 90 % moles, preferably 100 % or essentially 100 %, any complement to 100 % moles being generally recurring units (Ra), as above detailed, and/or recurring units (Rb), and/or recurring units (R_c), as above detailed.

Still more preferably, essentially all the recurring units of the (t-PAES) polymer are recurring units (Rt), chain defects, or very minor amounts of other units might be present, being understood that these latter do not substantially modify the properties of the (t-PAES) polymer. Most preferably, all the recurring units of the (t-PAES) polymer are recurring units (Rt). Excellent results are obtained when the (t-PAES) polymer was a polymer of which all the recurring units are recurring units (R_t), as above detailed. Preferably, the (t-PAES) polymer is suitable for use in HP/HT applications, in particular in oil and gas downhole operations.

The (t-PAES) polymer of the invention advantageously has a number average weight (M_n) ranging from about 41 ,000 to about 90,000 g/mol, preferably from about 43,000 to about 85,000 g/mol, preferably from about 45,000 to about

80,000 g/mol.

A person of ordinary skill in the art will recognize additional molecular weight ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure.

In exemplary embodiments, the (t-PAES) polymer has a number average molecular weight (M_n) equal to or less than about 90,000 g/mol, preferably equal to or less than about 85,000 g/mol, preferably equal to or less than about 80,000 g/mol, preferably equal to or less than about 75,000 g/mol.

In exemplary embodiments, the (t-PAES) polymer has a number average molecular weight (M_n) equal to or greater than about 41 ,000 g/mol, preferably equal to or greater than about 43,000 g/mol.

The (t-PAES) polymer having such specific molecular weight (M_n) range may possess an excellent ductility (i.e high tensile elongation), good toughness while maintaining high Tg, good crystallizability, good chemical resistance, and high melt stability.

The number average molecular weight (M_n) is :

V M.^■ N.

M —^■

^■ " ∑-v,

wherein Mi is the discrete value for the molecular weight of a polymer molecule, ; is the number of polymer molecules with molecular weight Mi, then the weight of all polymer molecules is∑ Mi ; and the total number of polymer molecules is∑ N;.

M_n can be suitably determined by gel-permeation chromatography (GPC) calibrated with polystyrene standards.

Other molecular parameters which can be notably determined by GPC are the weight average molecular weight (M_w) :

wherein Mi is the discrete value for the molecular weight of a polymer molecule, i is the number of polymer molecules with molecular weight Mi, then the weight of polymer molecules having a molecular weight Mi is M;Ni.

For the purpose of the present invention, the polydispersity index (PDI) is hereby expressed as the ratio of weight average molecular weight (M_w) to number average molecular weight (M_n).

The details of the GPC measurement are described in detail in the method description given in the experimental section.

For the determination of the number average molecular weight (M_n) by GPC, the (t-PAES) polymer is generally dissolved in a solvent suitable for GPC providing hereby a polymer solution.

A specimen of said polymer solution or a diluted specimen can then be injected into conventional GPC equipment.

The concentration of the (t-PAES) polymer in the polymer solution [polymer concentration, herein after] is between 1.0 to 10.0 mg/ml, preferably between 1.5 to 5.0 mg/ml, more preferably between 2.0 to 3.0 mg/ml. Good results were obtained with a concentration of the (t-PAES) polymer in the polymer solution of about 2.5 mg/ml.

Preferred solvents and solvent blends suitable to dissolve the (t-PAES) polymer of the present invention for determination of the M_n values are for example 4-chlorophenol, 2-chlorophenol, meta-cresol. 4-chlorophenol is most preferred.

The dissolving of the (t-PAES) polymer of the present invention is advantageously carried out at a temperature from 100 to 250°C, preferably from 120 to 220°C and more preferably from 170 to 200°C.

For the determination of the M_n values by GPC, N-methyl-2- pyrrolidone (NMP) containing at least one salt is suitably used as eluent.

Suitable salts for use in NMP include lithium bromide and lithium chloride. Lithium bromide is most preferred.

The molar concentration of said salt present in NMP can vary from 0.05 mole salt per liter NMP to 0.2 mole salt per liter NMP. Good results were obtained when the molar concentration of said salt present in NMP is about 0.1 mole salt per liter NMP. In a preferred embodiment, a specimen of said polymer solution, before injecting into the GPC equipment, is further diluted by the eluent thereby providing a diluted polymer solution [polymer solution (2), herein after].

In this preferred embodiment, the concentration of the (t-PAES) polymer in the polymer solution (2) [polymer concentration (2), herein after] is between 0.05 to 0.50 mg/ml, preferably between 0.10 to 0.25 mg/ml, more preferably between 0.20 to 0.25 mg/ml. Good results were obtained with a concentration of

the (t-PAES) polymer in the polymer solution (2) of about 0.25 mg/ml.

The GPC measurements are in general carried out at a temperature ranging from 20 to 50°C, preferably from 30 to 50°C, more preferably from 35 to 45°C. Good results were obtained when the temperature was about 40°C.

The GPC measurements are in general carried out at a pump flow rate from 0.3 to 0.9 ml/min, preferably from 0.5 to 0.7ml/min. Good results were obtained when the flow rate was about 0.5ml/min.

It is understood that the calibration with the polystyrene standards is carried out according to ordinary skills in the art. The details of said calibration with the polystyrene standards can be found in the experimental section below.

Another aspect of the present invention is related to the GPC measurement as described above.

The (t-PAES) polymer may have a polydispersity index (PDI) of more than 1.95, preferably more than 2.00, more preferably more than 2.05, and more preferably more than 2.10.

The (t-PAES) polymer of the present invention generally has a polydispersity index of less than or equal to 4.0, preferably of less than or equal to 3.0, more preferably of less than or equal to 2.7.

In addition, some other analytical methods can be used as an indirect method for the determination of molecular weight including notably viscosity measurements.

In one embodiment of the present invention, the (t-PAES) polymer of the present invention has a melt viscosity of advantageously at least 6.0 kPa.s, preferably at least 6.5 kPa.s, more preferably at least 7.0 kPa.s at 420°C and a shear rate of 10 rad/sec, as measured using a parallel plates viscometer (e.g. TA ARES RDA3 model) in accordance with ASTM D4440. The (t-PAES) polymer of the present invention has a melt viscosity of advantageously of at most 45 kPa.s, preferably of at most 40 kPa.s, more preferably of at most 35 kPa.s at 420°C and a shear rate of 10 rad/sec, as measured using a parallel plates viscometer (e.g. TA ARES RDA3 model) in accordance with ASTM D4440.

A person of ordinary skill in the art will recognize additional melt viscosity ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure.

The (t-PAES) polymer of the present invention advantageously possesses a glass transition temperature of at least 210°C, preferably 220°C, more preferably at least 230°C.

Glass transition temperature (Tg) is generally determined by DSC, according to ASTM D3418.

The (t-PAES) polymer of the present invention advantageously possesses a melting temperature of at least 340°C, preferably 370°C, more preferably at least 375°C. The (t-PAES) polymer of the present invention advantageously possesses a melting temperature less than or equal to 430°C, preferably less than or equal to 420°C and more preferably less than or equal to 410°C.

The melting temperature (Tm) is generally determined by DSC, according to ASTM D3418.

It is known that the crystallinity of polymers is characterized by their degree of crystallinity and a semi-crystalline polymer having a higher number average molecular weight (M_n) is in general characterized by having a lower degree of crystallinity.

The Applicant has surprisingly found that the (t-PAES) polymers of the present invention having a number average molecular weight (M_n) ranging from 41 ,000 to 90,000 g/mol, preferably from 43,000 to 80,000 g/mol maintain good crystallization properties such as high percent crystallinity.

The degree of crystallinity can be determined by different methods known in the art such as notably by Wide Angle X-Ray diffraction (WAXD) and Differential

Scanning Calorimetry (DSC).

For the purpose of the present invention, the degree of crystallinity has been measured by DSC on compression molded samples of the (t-PAES) polymers of the present invention, as described in detail in the Examples. According to the present invention, molded parts of the (t-PAES) polymer have advantageously a degree of crystallinity less than or equal to 30 %, preferably less than or equal to 28 %, preferably less than or equal to 27 %.

According to the present invention, molded parts of the (t-PAES) polymer have advantageously a degree of crystallinity greater than or equal to 5 %, preferably greater than or equal to 7 % and more preferably greater than or equal to 8 %.

Good results were obtained when molded parts of the (t-PAES) polymer had a degree of crystallinity ranging from 9 to 26 %.

A person of ordinary skill in the art will recognize that additional crystallinity ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure.

The Applicant has found that the (t-PAES) polymers of the present invention has a solubility in an aqueous sulfuric acid solution having a density of 1.84 g/cm advantageously of less than or equal to 10.0 g/1, preferably less than or equal to 1.00 g/1 and more preferably less than or equal to 0.50 g/1.

As said, the (t-PAES) polymer of the present invention has been found to possess an excellent ductility, in other words, the (t-PAES) polymer of the present invention have high tensile yield elongation and tensile elongation at break values.

The (t-PAES) polymer of the present invention advantageously possesses a tensile yield elongation, as measured according to ASTM D638, greater than or equal to 5 %, preferably greater than or equal to 6 %, more preferably greater than or equal to 7 %.

The (t-PAES) polymer of the present invention advantageously possesses a tensile yield elongation, as measured according to ASTM D638, equal to or less than 25 %, preferably equal to or less than 20 %, more preferably equal to or less than 18 %.

The (t-PAES) polymer of the present invention advantageously possesses a tensile elongation at break, as measured according to ASTM D638, greater than or equal to 5 %, preferably greater than or equal to 6 %, more preferably greater than or equal to 7 %.

The (t-PAES) polymer of the present invention advantageously possesses a tensile elongation at break, as measured according to ASTM D638, equal to or less than 40 %, preferably equal to or less than 35 %, more preferably equal to or less than 30 %.

According to exemplary embodiments, the (t-PAES) polymer exhibits at least one of a yield strength measured according to ASTM D638 that is greater than or equal to 9,000 psi, an elongation at yield measured according to ASTM D638 that is greater than 5.0 %, and an elongation at break measured according to ASTM D638 that is greater than or equal to 5.0 %.

"Melt stability" as used herein means the melt stability as measured on a compression molded disk (25 mm in diameter by 3 mm thickness) according to ASTM D4440 under the following conditions : under nitrogen, 420°C, 10 rad/s, 5 % strain.

The complex viscosity at 40 minutes (τ ο) and at 10 minutes (ηιο) was is ratioed to estimate the melt stability. A ratio value η₄₀/ ηιο closer to 1 indicates a more melt stable product. If the material releases volatiles during the testing due to low melt stability, swelling of the sample may be observed during testing. The results of the viscosity readings obtained with swelling of the sample are not considered accurate.

Preferably, the (t-PAES) polymer exhibits no swelling during the stability testing (as evidenced by the absence of change in gap between the fixtures during the 40-minute test) and has a melt stability (η₄ο / ηιο) ranging from 0.90 to 1.40.

According to exemplary embodiments, the (t-PAES) polymer has a melt stability (η₄₀/ ηιο) that does not exceed 1.40, preferably 1.25.

A person of ordinary skill in the art will recognize that additional melt stability ranges within the explicitly disclosed ranges are contemplated and within the scope of the present disclosure.

"High melt stability" as used herein means any melt stability described above for the (t-PAES) polymer of the present invention.

Shaped Articles

The (t-PAES) polymer made by the methods described above, can be processed to yield a shaped article by melt processing (including injection moulding, extrusion moulding, compression moulding), but also by other processing procedures such as notably spray coating, powder coating selective sintering, fused deposition modelling and the like. It is another object of the present invention to provide a shaped article comprising the (t-PAES) polymer made by the methods described above.

The total weight of the (t-PAES) polymer, based on the total weight of the article, is advantageously more than 50 %, preferably more than 80 %, more preferably more than 90 %, more preferably more than 95 %, and more preferably more than 99 %. The article may consist of, or consist essentially of, the (t-PAES) polymer or a composition comprising the (t-PAES) polymer.

Advantageously, the article may be an injection moulded article, an extrusion moulded article, a shaped article, a coated article, or a casted article.

Non limiting examples of articles include bearing articles such as radial and axial bearings for auto transmission, bearings used in dampers, shock absorbers, bearings in any kind of pumps, e.g., acid pumps; hydraulically actuated seal rings for clutch components; gears or the like.

In exemplary embodiments, the article is a bearing article. The bearing article may include several parts, wherein at least one of said parts, and optionally all of them, include the (t-PAES) polymer.

The (t-PAES) polymer can also notably be used for the manufacture of membranes, films and sheets, and three-dimensional moulded parts.

The (t-PAES) polymer can be advantageously processed to yield all of the above-mentioned articles by melt processing (including injection moulding, extrusion moulding, and compression moulding).

Non-limiting examples of shaped articles that can be manufactured from the (t-PAES) polymer using different processing technologies are generally selected from the group consisting of melt processed films, solution processed films (porous and non porous films, including solution casted membranes, and membranes from solution spinning), melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, and injection and compression molded objects.

Further, shaped articles manufactured from the (t-PAES) polymer of the invention can be three-dimensional molded parts.

Compositions Including the (t-PAES) Polymer

Exemplary embodiments also include compositions that comprise at least one of the (t-PAES) polymers made by the methods described herein, preferably with at least one other ingredient. Said other ingredient can be another polymer or copolymer. It can also be a polymer other than the polymers described herein, such as polyaryletherketone or polyaryelthersulfone. Other ingredients may also include a non-polymeric ingredient such as a solvent, a filler, a lubricant, a mould release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye, an optical brightener, a stabilizer (UV, thermal, and/or oxygen stabilizer) or a combination thereof.

The polymer composition according to exemplary embodiments may be a filled or unfilled composition. The composition may include reinforcing fillers selected from continuous or discontinuous fibrous fillers and particulate fillers. Reinforcing fillers may include, for example, one or more mineral fillers, such as notably talc, mica, kaolin, calcium carbonate, calcium silicate, or magnesium carbonate; glass fiber; carbon fibers such as notably graphitic carbon fibers, amorphous carbon fibers, pitch-based carbon fibers, PAN-based carbon fibers; synthetic polymeric fiber; aramid fiber; aluminum fiber; aluminum silicate fibers; oxide of metals of such aluminum fibers; titanium fiber; magnesium fiber; boron carbide fibers; rock wool fiber; steel fiber; asbestos; wollastonite; silicon carbide fibers; boron fibers, boron nitride, graphene, carbon nanotubes (CNT), or a combination thereof.

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

It will be understood that exemplary (t-PAES) polymers made by a method disclosed herein may exhibit a combination of two or more of the properties or attributes described herein.

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

Examples

The invention will be now described in more details with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention. Raw materials

l, :4',l"-terphenyl-4,4"-diol was procured from Yongyi Chemicals

Group Co. Ltd, China and purified by washing with ethanol/water (90/10) at reflux. The purity of the resulting material was shown to be higher than 94.0 % area as measured by gas chromatography (GC).

GC analysis of l, :4',l"-terphenyl-4,4"-diol was performed on a 0.1/mL solution in Ν,Ν-dimethylformamide using an HP5890 series 1 1 gas chromatograph with a Restek RTx-5MS, 15m x 0.25mm id x 0.25um film thickness column. The following GC conditions were used :

Helium flow rate : 1 mL/minute,

Injector temperature : 300°C

FID temperature : 320°C

Oven Temperature Program : 150°C, hold 1 minute, 30°C/minute to 325°C,

hold 1 minute

Injection volume : \ μL·

Split 40:1

4,4'-difluorodiphenylsulfone was procured from Marshallton Research Laboratories, Inc., King, North Carolina (99.92 % pure by GC).

GC analysis of 4,4'-difiuorodiphenylsulfone was performed on a 0.1 g/mL solution in acetone using an HP5890 series 1 1 gas chromatograph with a Restek RTx-5MS, 15m x 0.25mm id x 0.25um film thickness column. The following GC conditions were used :

Helium flow rate : 1 mL/minute,

Injector temperature : 250°C

FID temperature : 250°C

Oven Temperature Program : 100°C, hold 1 minute, 30°C/minute to 250°C,

hold 1 minute

Injection volume : l μL

Split 40:1

Hexamethyldisilazane was procured from Aldrich, St. Louis, Missouri (97 % reagent grade.

Diphenyl sulfone (polymer grade) was procured from Proviron,

Belgium (99.8 % pure). Sodium carbonate, light soda ash, with d99.5 < 500μηι, and d90 < 250 μηι was procured from Solvay Chemicals, France.

Potassium carbonate with a d9o < 45 μηι was procured from Armand Products Company, Princeton, New Jersey.

Lithium chloride (99+ %, ACS grade) was procured from Acros Organics,

Belgium.

Comparative Example 1

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean- Stark trap with a condenser and a dry ice trap were introduced 204.50 g of diphenyl sulfone, 66.430 g of l,l^*:4',l"-terphenyl-4,4"-diol and 64.071 g of

4,4'-difluorodiphenylsulfone. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm 0₂). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 220°C. At 220°C, 35.349 g of K₂C0₃ were added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 320°C at l °C/minute. After 65 minutes at 320°C, 1.281 g of 4,4'-difiuorodiphenylsulfone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 2 minutes, 10.682 g of lithium chloride were added to the reaction mixture. 2 minutes later, another 0.641 g of 4,4'-difiuorodiphenylsulfone were added to the reactor and the reaction mixture was kept at temperature for 5 minutes.

The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone then water at pH between 1 and 12 then with acetone. The powder was then removed from the reactor and dried at 120°C under vacuum for 12 hours yielding 115 g of a light brown powder. The molecular weight of the final polymer was measured by GPC and is reported in Table 2, and the NMR spectrum is presented in Figure 1A.

Results are presented in Table 3 below. Example 2a : Preparation of Bissilylated Terphenyldiol

In a 500 mL 3-neck reaction flask fitted with a stir bar, a N₂ inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Barrett trap (in reflux position) with a condenser were introduced 75.81 g of

l,r:4',l"-terphenyl-4,4"-diol, and 163.45 g of hexamethyldisilazane. Under nitrogen, the reaction mixture was heated to 130°C and kept at reflux for 8 h. The reaction mixture was cooled down to room temperature and a solid formed. The solid was filtered on Buchner funnel and rinsed with 150 mL acetonitrile. The solid was dried at 70°C under vacuum overnie ht. By H NMR, it was shown to contain 71 % of bissilylated product + 29 % l,l':4',l"-terphenyl-4,4"-diol.

Example 2b

The procedure of Example 2a was repeated but with 75.81 g of

l,r:4',l"-terphenyl-4,4"-diol, and 135.57 g of hexamethyldisilazane and yielded l,r:4',l"-terphenyl-4,4"- bis(trimethylsiloxy) that was found by 1H NMR to contain 86 % of bissilylated product + 14 % 1 ,1 ':4',l"-terphenyl-4,4"-diol.

Comparative Example 3

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean- Stark trap with a condenser and a dry ice trap were introduced 89.26 g of diphenyl sulfone, 42.510 g of l, :4',l"-terphenyl-4,4"- bis(trimethylsiloxy) from Example 2b, 28.051 g of 4,4'-difiuorodiphenylsulfone and 0.064 g of potassium fluoride. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm 0₂). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 150°C and held at 150°C for

30 minutes, then heated up to 200°C and held at 200°C for 30 minutes, then heated up to 250°C and held at 250°C for 30 minutes. The reaction mixture was then heated up to 320°C. At 320°C, 2.1283 g of K₂C0₃ were added via a powder dispenser over a period of 5 minutes. 25 minutes after the end of the carbonate addition, 0.652 g l,l':4',l"-terphenyl-4,4"-diol and 0.51 1 g K₂C0₃ were added. At the end of the addition, the reaction mixture was held to 320°C for 25 minutes at 320°C, 0.559 g of 4,4'-difiuorodiphenylsulfone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 2.331 g of lithium chloride were added to the reaction mixture. 5 minutes later, another 0.280 g of 4,4'-difluorodiphenylsulfone were added to the reactor and the reaction mixture was kept at temperature for 5 minutes.

The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone then water at pH between 1 and 12 then with acetone. The powder was then removed from the reactor and dried at 120°C under vacuum for 12 hours yielding 47 g of a light brown powder. The molecular weight of the final polymer was measured by GPC and is reported in Table 2, and the NMR spectrum is presented in Figure IB.

Example 4

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean- Stark trap with a condenser and a dry ice trap were introduced 89.26 g of diphenyl sulfone, 14.427 g of l,l^*:4',l"-terphenyl-4,4"-diol, 20.064 g of l,l':4',l"-terphenyl- 4,4"- bis(trimethylsiloxy) from Example 2a, 14.026 g of

4,4'-difluorodiphenylsulfone and 0.064 g of potassium fluoride. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm 0₂). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 150°C and held at 150°C for 30 minutes, then heated up to 200°C and held at 200°C for 30 minutes, then heated up to 250°C and held at 250°C for 30 minutes. The reaction mixture was then heated up to 320°C. At 320°C, 7.858 g of Na₂C0₃ and 0.0490 g of K₂C0₃ were added via a powder dispenser over a period of 5 minutes, then 14.026 g of

4,4'-difluorodiphenylsulfone were added via a powder dispenser to the reaction mixture over 20 minutes. At the end of the addition, the reaction mixture was held to 320°C for 93 minutes at 320°C, 1.398 g of 4,4'-difiuorodiphenylsulfone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 15 minutes, 4.663 g of lithium chloride were added to the reaction mixture.

10 minutes later, another 0.280 g of 4,4'-difiuorodiphenylsulfone were added to the reactor and the reaction mixture was kept at temperature for 10 minutes. The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone then water at pH between 1 and 12 then with acetone. The powder was then removed from the reactor and dried at 120°C under vacuum for 12 hours yielding 47 g of a light brown powder. The molecular weight of the final polymer was measured by GPC and is reported in Table 2, and the NMR spectrum is presented in Figure 1C.

Example 5

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlet tube, a

Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean- Stark trap with a condenser and a dry ice trap were introduced 89.26 g of diphenyl sulfone, 21.640 g of l ,l':4',l"-terphenyl-4,4"-diol, 10.032 g of l ,l ':4',l"-terphenyl- 4,4"- bis(trimethylsiloxy) from Example 2a, 7.013 g of 4,4'-difluorodiphenylsulfone and 0.064 g of potassium fluoride. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm 0₂). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min). The reaction mixture was heated slowly to 150°C and held at 150°C for 30 minutes, then heated up to 200°C and held at 200°C for 30 minutes, then heated up to 250°C and held at 250°C for 30 minutes. The reaction mixture was then heated up to 320°C. At 320°C, 10.021 g of Na₂C0₃ and 0.0625 g of K₂C0₃ were added via a powder dispenser over a period of 5 minutes, then 21.039 g of

4,4'-difluorodiphenylsulfone were added via a powder dispenser to the reaction mixture over 20 minutes. At the end of the addition, the reaction mixture was held to 320°C for 63 minutes at 320°C, 1.398 g of 4,4'-difluorodiphenylsulfone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 15 minutes, 4.663 g of lithium chloride were added to the reaction mixture.

10 minutes later, another 0.280 g of 4,4'-difluorodiphenylsulfone were added to the reactor and the reaction mixture was kept at temperature for 10 minutes.

The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone then water at pH between 1 and 12 then with acetone. The powder was then removed from the reactor and dried at 120°C under vacuum for 12 hours yielding

49 g of a light brown powder. The molecular weight of the final polymer was measured by GPC and is reported in Table 2, and the NMR spectrum is presented in

Figure ID.

Analytical Methods

The following characterizations were carried out on the (t-PAES) polymers of the Examples and Comparative Examples :

Molecular weight measurements by a GPC method

GPC conditions :

Pump : 515 HPLC pump manufactured by Waters

Detector : UV 1050 series manufactured by HP

Software : Empower Pro manufactured by Waters

Injector : Waters 717 Plus Auto sampler

Flow rate : 0.5 ml/min

UV detection : 270 nm

Column temperature : 40°C

Column : 2x PL Gel mixed D, 5 micron, 300 mm X 7.5 mm 5 micron manufactured by Agilent

Injection : 20 μ liter

Runtime : 60 minutes

Eluent : N-Methyl- 2-pyrrolidone (Sigma- Aldrich, Chromasolv Plus for

HPLC >99 %) with 0.1 mol Lithium bromide (Fisher make). Mobile phase should be store under nitrogen or inert environment

Calibration standard : Polystyrene standards part number PL2010-0300

manufactured by Agilent was used for calibration. Each vial contains a mixture of four narrow polydispersity polystyrene standards (a total 1 1 standard, 371100, 238700, 91800, 46500, 24600, 10110, 4910, 2590, 1570,780 used to establish calibration curve)

Concentration of standard : 1 milliliter of mobile phase added in to each vial before

GPC injection for calibration

Calibration Curve : 1) Type : Relative, Narrow Standard Calibration 2) Fit :

3^rd order regression Integration and calculation :

Empower Pro GPC software manufactured by Waters used to acquire data, calibration and molecular weight calculation. Peak integration start and end points are manually determined from significant difference on global baseline.

Sample Preparation :

25 mg of the (t-PAES) polymer was dissolved in 10 ml of 4-chlorophenol upon heating at 170 to 200°C. A small amount (0.2 to 0.4 ml) of said solution obtained was diluted with 4 ml of N-Methyl- 2-pyrrolidone. The resulting solution was passed through to GPC column according to the GPC conditions described above.

NMR determination of % relative signal at 8.1-8.3 ppm

The NMR spectra were acquired on a Bruker Avance 400 MHz spectrometer using a TBI (1H, 13C and 19F) gradient z probe at 30°C. The NMR spectra were referenced to the protonated residual peak of the solvent C₂HDCI₄ calibrated at 6.00 ppm for 1H dimension.

The polymers were dissolved at around 7 % weight in pentafiuorophenol solvent at 150-160°C. For the NMR acquisition and quantification, the NMR samples were prepared by dissolving an exact amount of each pentafiuorophenol solution (around 400 mg) in 0.5 mL of C₂D₂C1₄. Drops of OMCTS

(octamethylcyclotetrasiloxane) were added as ^!H internal standard. For quantification we acquired 1 H{ 13 C} NMR spectra ( 1 H NMR spectrum without 13C coupling to eliminate 13C satellites). This procedure was used for accurate integration of the signals that may overlap with some 13 C NMR satellites. The quantification of each end chain was estimated (weight % in the polymer) using the quantity of the polymer present in the pentafiuorophenol solution.

For the end chain observed in some spectra at 8.1-8.2 ppm, a relative proportion was estimated according to the following equation : % relative signal 8.2 ppm = [Integral (signal at 8.2 ppm) x 24(=∑H⁺ OMCTS) x weight

(OMCTS)]/[ Integral (OMCTS at 0.2 ppm) x weight (sample) x concentration (polymer % weight in pentafiuorophenol) x MW(OMCTS)] * 1000

The ^!H NMR spectra of the Examples and Comparative Examples are shown in Figure 1. Determination of% crystallinity and melting temperature of molded plaque

25.4 mm diameter x 3 mm cylindrical plaques were prepared from

the (t-PAES) polymers by compression molding under the conditions shown in Table 1 :

Table 1

The melting temperature and the crystallinity level of the material were determined on an annealed plaque by DSC, according to ASTM D3418-03, E1356-03, E793-06, E794-06 on TA Instruments Q20 with nitrogen as a carrier gas (99.998 % purity, 50 mL/min). Temperature and heat flow calibrations were made using indium. The sample size was 5 to 7 mg. The weight was recorded ±0.01 mg.

The heat cycle was :

1^st heat cycle : 50.00°C to 450.00°C at 20.00°C/min, isothermal at 450.00°C

for 1 min.

The melting temperature (Tm melting point) was measured as the temperature at which the main melting endotherm is observed in the 1^st heat cycle. The enthalpy of fusion was determined on the 1^st heat scan. The heat of fusion was taken as the area over a linear baseline drawn from 260°C to a temperature above the last endotherm (typically 430-440°C). The level of crystallinity was calculated from the heat of fusion assuming 130J/g for 100 % crystalline material.

Determination of melt stability

The melt stability was measured on a compression molded disk (25 mm in diameter by 3 mm thickness) with a T A ARES RDA3 rheometer according to ASTM D4440 under the following conditions : under nitrogen, 420°C, 10 rad/s, 5 % strain.

The complex viscosity at 40 minutes and at 10 minutes was ratioed to estimate the melt stability. A ratio value η₄₀/ ηιο closer to 1 indicates a more melt stable product. Determination of mechanical properties

A 102 mm x 102 mm x 1.6 mm plaque was prepared from the (t-PAES) polymers by compression molding under the following conditions as shown in Table 1 below :

Table 1

The plaque was then annealed at 350°C for 3 hours under air.

The mechanical properties of the (t-PAES) polymers were tested according to ASTM D638 using a Type L impact bars (ASTM D1822, 1/8" x 3/8") as test specimen which were prepared from the annealed plaque, as mentioned above. The tensile properties were measured at 0.05 inch/minute.

Table 2 : DSC and NMR Data

Table 3 : Melt Stability and Mechanical Data

The examples surprisingly show that it is possible to prepare high molecular weight (t-PAES) polymers with use of less salts by using silylated monomers. A simplified process may therefore be used with less washing required because of the reduced amount of salts.

Comparative Example 3 was prepared using a silylated monomer and

14 mol % K₂CO₃. The final polymer exhibited a 1H NMR signal at 8.2 ppm, which is associated with melt instability of the polymer. In addition, molded parts of the polymer of Comparative Example 3 were brittle as shown by the poor mechanical properties, indicating that the polymer had partially

depolymerized during the molding.

Examples 4 and 5 surprisingly and unexpectedly show that when a silylated monomer was used, and the amount of K₂CO₃ was less than 1 mol % of the total moles of the l, :4',l"-terphenyl-4,4"-diol and the l, :4',l"-terphenyl- 4,4"- bis(trimethylsiloxy), a (t-PAES) polymer was obtained that was melt stable (as exhibited by the absence of signal at 8.2 ppm by 1H NMR), and had excellent melting temperature (Tm), % crystallinity, and mechanical properties (tensile strength > 9000 psi, elongation at break > 5 %).

Claims

C L A I M S

1. A method for making a poly(arylether sulfone)

polymer [(t-PAES) polymer], comprising : step i. reacting a monomer mixture including : a) at least one silylated terphenyl compound of Formula (SiTSi) :

(SiTSi)

j i 2* "2*

- R , R , R , R , R , and R" are independently selected from a C 1 -C5 alkyl or an aryl group; - each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary

ammonium; and

- u' is zero or an integer ranging from 1 to 4; b) optionally, at least one dihydroxyaryl compound [diol (AA)] of Formula (T) :

wherein - each of R', equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic an acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary

ammonium; and

- j' is zero or an integer ranging from 1 to 4; c) optionally, at least one dihydroxyaryl compound [diol (ΑΆ')] different from diol (AA); d) at least one dihaloaryl compound [dihalo(BB)] of Formula (S) : X-Ar¹-S0₂-[Ar²-(T-Ar³)_n-S0₂]_m-Ar⁴-X' (S) wherein :

- X and X' are independently selected from F, CI, Br, and I;

- T in Formula (S) is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-,

e) optionally, at least one dihaloaryl compound [dihalo (B'B')] different from dihalo (BB); f) at least one alkali metal fluoride; and least one polar aprotic solvent.

2. The method of claim 1 , further comprising : step ii. further reacting the monomer mixture in the presence of :

- at least one alkali metal carbonate selected from potassium

carbonate (K₂CO₃), rubidium carbonate (Rb₂C03), and caesium

carbonate (CS₂CO₃), in an amount less than or equal to 1 mol % of a total mol % of component a) and optional components b) and c).

3. The method of claim 2, wherein step ii further comprises reacting the monomer mixture in the presence of sodium carbonate (Na₂C03).

4. The method of claim 3, wherein at least 50 % of a total amount of alkali metal carbonates is sodium carbonate (Na₂C03).

5. The method of any one of claims 1 to 4, wherein the at least one alkali metal fluoride includes potassium fluoride.

6. The method of any one of claims 1 to 5, further comprising heating the monomer mixture to a temperature ranging from 150°C to 320°C prior to step ii.

7. The method of any one of claims 1 to 6, further comprising : step iii. adding an additional amount of component d) to the monomer mixture, wherein an overall amount of halo-groups and a sum of hydroxyl-groups and siloxy groups in the monomer mixture is substantially equimolecular.

8. The method of any one of claims 1 to 7, further comprising : step iv. end-capping the (t-PAES) polymer by adding an additional amount of at least one of component d) and component e) in molecular excess.

9. The method of any one of claims 1 to 8, wherein diol (ΑΆ') is present in the monomer mixture and is selected from compounds of Formula (D) : HO-Ar⁹-(T'-Ar¹⁰)_n-O-H (D) wherein - n is zero or an integer ranging from 1 to 5;

wherein

- k is zero or an integer ranging from 1 to 4;

- k' is zero or an integer ranging from 1 to 3; and

T is selected from a bond, -S0₂-, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

10. The method of any one of claims 1 to 9, wherein dihalo (Β'Β') is present in the monomer mixture and is a compound of Formula (K) :

X-Ar⁵-CO-[Ar⁶-(T-Ar⁷)_n-CO]_m-Ar⁸-X' (K) wherein : n and m, equal to or different from each other, are independently zero or an integer ranging from 1 to 5, each of Ar⁵, Ar⁶, Ar⁷ and Ar⁸, equal to or different from each other, is an aromatic moiety,

T is selected from a bond, -CH₂-, -C(O)-, -C(CH₃)₂-, -C(CF₃)₂-, -C(=CC1₂)-, -C(CH₃)(CH₂CH₂COOH)-, and a group of formula :

- X and X' are independently selected from F, CI, Br, or I.

11. The method of any one of claims 1 to 10, wherein component a)

12. The method of any one of claims 1 to 11 , wherein the (t-PAES) polymer has a number average molecular weight (M_n) of at least 41 ,000 g/mol.

13. The method of any one of claims 1 to 12, wherein the (t-PAES) polymer has a 1H NMR signal from about 8.1 ppm to about 8.3 ppm of < 1 , preferably of 0.

14. The method of at least one of claims 1 to 13, wherein the (t-PAES) polymer exhibits at least one of :

- an elongation at yield measured according to ASTM D638 that is greater than 5.0 %; and an elongation at break measured according to ASTM D638 that is greater than or equal to 5.0 %. A (t-PAES) polymer made by the method of any one of claims 1