Hydrofluoroether polymers

Abstract

The present invention relates to new polymers comprising (per)(halo)aromatic groups, to methods for their manufacture and to derivatives thereof that are useful additives for compositions suitable for several industries and applications.

Description

SSPI 2024 / 030DescriptionHydrofluoroether polymersCross reference to related patent application

[0001] This application claims priorities from application EP 24214014.3 filed on 19 November 2024 and application EP 24214155.4 filed on 20 November 2024, the whole content of each of these applications being incorporated herein by reference for all purposes.Technical field

[0002] The present invention relates to new polymers comprising (per)(halo)aromatic groups, to methods for their manufacture and to their use as additives for compositions suitable for several industries and applications.Background

[0003] In the past, partially fluorinated polyether polymers comprising aromatic moieties in their backbone have been disclosed for example in GB 1294656 (in the name of UK Secretary of State for Defense), wherein polymers having elastomeric properties were disclosed having for example the following general formula: -[X-O-RF-O]- wherein RF is preferably a group -CH2-(CF2)n-CH2- with n being from 1 to 8.

[0004] US 2002 / 0057882 (in the name of Zen Photonics Co. Ltd.) disclosed fluorinated polyethers having a fluorinated aliphatic group in the main chain: E-[RF-AM ]x-[O-Ar2-O-An ]y-E whereinRF represents -OCH2(CF2)nCH2O- or -OCH2CF2O(CF2CF2O)nCF2CH2O- with n ranging from 1 to 12.

[0005] More recently, CN 102584545 (in the name of HUBEI GURUN TECHNOLOGY CO LTD) discloses oligomers obtained by the reaction of aSSPI 2024 / 030 fluorine-containing aromatic monomer and vinyl ether as end group, having the following formulae:which are said to be useful as photocurable coatings, capable of improving weather resistance and chemical resistance.

[0006] Further derivatives of hexafluorobenzene have been disclosed in WO 15 / 173374 and WO 16 / 079053 (both in the name of Solvay Specialty Polymers Italy S.p.A.), WO 2009 / 112577 (in the name of Solvay Solexis), wherein hexafluorobenzene was reacted with perfluoropolyether polymers having statistically disposed recurring units, and in WO 2014 / 170196 (in the name of Solvay Specialty Polymers Italy S.p.A.) wherein hexafluorobenzene was reacted with hydrogenated oils, such as polyalphaolefins (PAO).Summary of the invention

[0007] The Applicant is aware that there is a strong need for developing polymers that can be used in many different industries and applications.

[0008] In this scenario, the Applicant surprisingly found new polymers that can be easily synthesized, thus obtaining polymers suitable as additives for several compositions and materials and capable of changing the properties of the compositions and materials to which they are added.

[0009] Thus, in a first aspect, the present invention relates to new polymers comprising - in their backbone - at least two (per)(halo)aromatic groups.SSPI 2024 / 030

[0010] Such polymers can be synthesized as a mixture of polymers having non functional end groups and functional end groups. Both such non functional and functional polymers can be used as additives in compositions for use in several industries.Disclosure of the invention

[0011] In the present application:- the use of parentheses around symbols or numbers identifying the formulae, for example in expressions like “polymer (P)”, etc., has the mere purpose of better distinguishing the symbol or number from the rest of the text and, hence, said parenthesis can also be omitted;- the expression “(per)(halo)aromatic group(s)” is intended to indicate one or more partially halogenated aromatic groups or fully halogenated aromatic groups or fully hydrogenated aromatic group.

[0012] In a first aspect, the present invention relates to a polymer [polymer (P)] of formula (I(I) T*-wherein p is an integer from 1 to 65;Ar is a group of formulain whichHal is selected from Cl, Br or I, and r is 0 or an integer from 1 to 4, w is 0 or an integer from 1 to 4, provided that at least one of r and w is different from 0;SSPI 2024 / 030 q is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t is 0 or 1 ;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, s is 0 or an integer from 1 to 3, and m is an integer equal to 1 or 2; p* is 0 or an integer from 1 to 65Ar* is a group of formulain which q* is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t* is 0 or 1 ,Hal is selected from Cl, Br or I, and r* is 0 or an integer from 1 to 4, w* is 0 or an integer from 1 to 4, provided that at least one of r* and w* is different from 0;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms,SSPI 2024 / 030 s* is 0 or an integer from 1 to 3, and m* is an integer equal to 1 or 2; p** is 0 an integer from 1 to 65;Ar** is a group of formulain which q** is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t** is 0 or 1 ,Hal is selected from Cl, Br or I, and r** is 0 or an integer from 1 to 4, w** is 0 or an integer from 1 to 4, provided that at least one of r** and w** is different from 0;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, s** is 0 or an integer from 1 to 3, and m** is an integer equal to 1 or 2; n is an integer from 1 to 50; each of Y1, Y2and Ynis independently selected from a sigma bond or a group complying with one of the following formulae:(Y-l)SSPI 2024 / 030wherein each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, and u is an integer from 1 to 20;(Y-ll)whereinRe1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 6, preferably from 1 to 4 carbon atoms, Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, Mi is a group -CJH2J- wherein J is from 1 to 4M2 is a group -CKH2K- wherein K is from 1 to 4 andJ+K is from 3 to 5, preferably 3 or 4, more preferably 4;(Y-lll)SSPI 2024 / 030whereinX10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 6, preferably from 1 to 4 carbon atoms, v is 0 or an integer from 1 to 3, andQi and Q2 , each independently, are selected from a sigma bond, a linear or branched alkylene chain having from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, or one of Q1 and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having a total of 5 or 6 members, such aromatic ring being fused with such phenyl ring;T* is selected from halogen, preferably fluorine atom, or a group RT0-Y- whereinY is any of Y1, Y2or Ynas defined above;RTis selected from hydrogen atom, an alkali metal cation, preferably selected from sodium, potassium, lithium, cesium, or an organic cation, such as ammonium or NR4+with R being a linear or branched alkyl chain having 1 to 3 carbon atoms; andT’ is selected from a hydrogen atom, or a group selected from:(T’-i) -(ArA)mA-RfAwherein mAis 1 or 2,ArAcomplies with any of Ar, Ar* or Ar** defined above, andRfAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined above; or(T’-ii) -(ArAA)mAA-O-YAA-RdAAwhereinSSPI 2024 / 030ArAAcomplies with any one of Ar, Ar* and Ar** as defined above, mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above, andRdAAis hydrogen atom, an alkali metal cation, preferably selected from sodium, potassium, lithium, cesium, or an organic cation, such as ammonium or NR4+with R being a linear or branched alkyl chain having 1 to 3 carbon atoms.

[0013] In formula (I) the recurring units p, p* and p** are randomly distributed along the backbone chain of the polymer (P).

[0014] Preferably, the total amount of recurring units p, p* and p** is from 2 to 66, more preferably from 4 to 30, even more preferably from 4 to 15

[0015] Preferably, p is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0016] Preferably, R1 is a linear or branched alkyl chain having from 1 to 3 carbon atoms.

[0017] Preferably, r is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0018] Preferably, q is 0 or an integer from 1 to 3, more preferably 1 to 2, even more preferably q is 1 .

[0019] Preferably, m is 1 .

[0020] Preferably, when p* and p** are 0, then:Z is a linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms and q is 0 or an integer from 1 to 3; or q is 1 to 3, more preferably 1 or 2, and Z is a sigma bond or linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms.

[0021] Preferably, Ar is a group of formula:SSPI 2024 / 030wherein w is an integer from 1 to 4, r and s are each 0, q is 0 or 1 , t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 3 carbon atoms, optionally substituted with at least one fluorine atom; more preferably wherein: w is 2 or 3, r and s are each 0, q is 1 or 2, t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 3 carbon atoms, optionally substituted with at least one fluorine atom.

[0022] Preferably, p* is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0023] Preferably, r* is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0024] Preferably, q* is 0 or an integer from 1 to 2.

[0025] Preferably, m* is 1 .SSPI 2024 / 030

[0026] Preferably, Ar* is a group of formula:wherein w* is an integer from 1 to 4, r* and s* are each 0, q* is 0 or 1 , t* is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 3 carbon atoms, optionally substituted with at least one fluorine atom.

[0027] Preferably, p** is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0028] Preferably, r** is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0029] Preferably, q** is 0 or an integer from 1 to 2.

[0030] Preferably, m** is 1 .

[0031] Preferably, Ar** is a group of formula:wherein w** is an integer from 1 to 4, r** and s** are each 0, q** is 0 or 1 , t** is 1 andSSPI 2024 / 030Rg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 3 carbon atoms, optionally substituted with at least one fluorine atom.

[0032] Preferably, n is an integer from 2 to 25, more preferably from 2 to 15 and even more preferably from 2 to 10.

[0033] Preferably, the sum of (p+p*+p**+n) is from 2 to 66, preferably from 4 to 30, more preferably from 4 to 15.

[0034] In certain embodiments, in formula (I) p* and p** are both 0.

[0035] Preferably, Z is a sigma bond or a linear or branched alkylene chain having from 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

[0036] Preferably, u is an integer from 1 to 10, more preferably from 1 to 4.

[0037] Preferably, in formula (Y-l): each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 3 carbon atoms, and u is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3.

[0038] Preferably, in formula (Y-l I):Re1 and Re2 each independently is a sigma bond or a linear or branched alkyl chain having from 1 to 3, preferably 1 or 2 carbon atoms,Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 3 carbon atoms, preferably methyl,Mi is a group -CJH2J- wherein J is from 1 or 2, preferably 2,M2 is a group -CKH2K- wherein K is from 1 or 2, preferably 2, and M+J is 4.

[0039] Preferably, in formula (Y-l 11): v is 0 or an integer equal to 1 or 2,X10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms, andSSPI 2024 / 030Qi and Q2 each independently is a sigma bond, a linear or branched alkylene chain having from 1 to 3 carbon atoms, or one of Qi and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having 6 members, such aromatic ring being fused with such phenyl ring.

[0040] According to a preferred embodiment, Y1, Y2and Ynare identical to each other.

[0041] Polymer (P) according to this embodiment is obtained by using one di-alcohol as starting material in the synthesis, as described in more detail below.

[0042] According to another preferred embodiment, at least two of Y1, Y2and Ynare different from each other.

[0043] Polymer (P) according to this embodiment is obtained by using at least two different di-alcohols as starting material in the synthesis, as described in more detail below.

[0044] Preferably, two or more di-alcohols having different chemical formulae are used as starting material. For example, two, three, four, five or even a higher number of di-alcohols can be used as starting materials. As a consequence, when two di-alcohols having different chemical formulae are used, polymer (P) is obtained wherein groups -Y1- and -Y2- are different from each other. When three di-alcohols having different chemical formulae are used, polymer (P) is obtained wherein groups -Y1- , -Y2- and -Y3- are different from one another. Even more, when four di-alcohols having different chemical formulae are used, polymer (P) is obtained wherein groups -Y1- , -Y2- , -Y3- and -Y4- are different from one another. Accordingly, in substituent -Yn- , the apex ‘n’ is intended to indicate that a number ‘n’ of di-alcohols, such as 2 or 3 di-alcohols having different chemical formulae are used as starting materials for the synthesis of polymer (P).

[0045] According to this embodiment, polymer (P) can be represented as follows: T*-{ [(Ar)m-O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m**-O-Y3]PH(ArA)m -O-Y4]PA ...- [(ArA)m-O-Yn]pA }n-T’ wherein the substituents have the meanings defined above and each of Y1, Y2, Y3, Y4and Ynderives from a di-alcohol.SSPI 2024 / 030

[0046] According to this embodiment, polymer (P) can also be represented by formula(II):(II) T*- {[(Ar)m-O-Yx]Px}n -T’ whereinT*, T’ and Ar, have the same meaning as for the polymer of formula (I), Ar being the same or different in each of the m recurring units; m is an integer equal to 1 or 2; n is an integer from 1 to 50; pxis an integer from 2 to 66, preferably from 4 to 30, more preferably from 4 to 15;Y^ the same or different in each of the pxrecurring units, is selected from sigma bond or Y-l, Y-ll and Y-lll, wherein Y-l, Y-ll and Y-lll have the same meaning as for the polymer of formula (I), with the proviso that when Yxis the same in each of the pxrecurring units then:- Z is a linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms, and q is 0 or an integer from 1 to 3; or- q is 1 to 3, more preferably 1 or 2, and Z is a sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms.

[0047] In formula (II) the recurring units pxare randomly distributed along the backbone chain of the polymer (P).

[0048] In a second aspect, the present invention relates to a method [method (MP)] for the manufacture of polymer (P) as defined above, wherein said method (MP) comprises the steps of:(i) providing at least one di-alcohol [compound (HO-Y-OH)](ii) providing a (per)(halo)aromatic compound [compound (PX)](iii) contacting said compound (HO-Y-OH) and said compound (PX) in theSSPI 2024 / 030 presence of at least one organic or inorganic base, and(iv) letting the reaction proceed, thus obtaining polymer (P) as defined above.

[0049] Preferably, step (iii) is performed such that the molar ratio between said compound (HO-Y-OH) and said compound (PX) is from 2:1 to 0.5:1 , more preferably from 1.5:1 to 0.8:1 , even more preferably from 1.3:1 and 1.1 :1.

[0050] Preferably, step (iii) is performed in the presence of at least one organic or inorganic base that is in a molar ratio to the hydroxyl groups of said compound (HO-Y-OH) from 1.5:1 to 0.5:1 , more preferably from 1.2:1 to 0.8:1 and even more preferably about 1 :1.

[0051] Preferably, said organic or inorganic base is selected from NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NaHCO3, KHCO3, CH3-ONa, CH3-OK, tBu-ONa, tBu-OK, NaH.

[0052] Preferably, each step (iii) and step (iv) is performed at a temperature from 20°C to 80°C.

[0053] Preferably, each step (iii) and step (iv) is performed in at least one solvent, more preferably selected from at least one partially fluorinated solvent, even more preferably selected from: trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers.

[0054] Optionally, such partially fluorinated solvent is in admixture with a tertiary- alcohol, such as for example tert-butanol.

[0055] Optionally, method (MP) comprises, after step (iv), a step (v) of treating said mixture (M1 ) with an aqueous acid solution, thus obtaining polymer (P) wherein:T* is selected from halogen, preferably fluorine atom, or a group RTO-Y- whereinY is any of Y1, Y2or Ynas defined above;RTis selected from hydrogen atom; andT’ is selected from a hydrogen atom, or a group selected from: (T’-i) -(ArA)mA-RcAwherein mAis 1 or 2,SSPI 2024 / 030ArAcomplies with any of Ar, Ar* or Ar** defined above, andRcAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined above; or(T’-ii) -(ArAA)m-O-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above, mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above.

[0056] According to a preferred embodiment, when polymer (P) comprises two chain ends wherein both said chain ends comprise a neutral group, such as for example when T* is selected from halogen atom, preferably fluorine atom and T’ is selected from (T’-i) -(ArA)m-RfAwherein mAis 1 or 2, ArAcomplies with any of Ar, Ar* or Ar** defined above, and RfAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined above, such polymer (P) is referred to as ‘neutral polymer (P)’ or ‘non-functional polymer (P)’.

[0057] Such neutral polymer (P) according to the present invention can be advantageously used as lubricants for application in several industries, including machinery, automotive, manufacturing, power generation, construction, and marine industries.

[0058] According to another preferred embodiment, the present invention relates to polymer (P) wherein:T* is selected from fluorine atom or a group RTO-Y- wherein Y is any of Y1, Y2or Ynas defined above and RTis a hydrogen atom, andSSPI 2024 / 030T’ is selected from a hydrogen atom, or a group selected from: (T’-ii) -(ArAA)m-O-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above, mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above.

[0059] Such polymer (P) comprising two chain ends wherein at least one chain end comprises a functional group, in other words wherein at least one of T* and T’ is different from fluorine atoms, and is referred to as ‘functional polymer (P)’.

[0060] A more preferred aspect of the present invention relates polymer (P) wherein: T* is selected from group RTO-Y- wherein Y is any of Y1, Y2or Ynas defined above and RTis a hydrogen atom, andT’ is selected from a hydrogen atom, or a group selected from: (T’-ii) -(ArAA)m-O-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above, mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above.

[0061] Indeed, polymer (P) comprising one -OH group at at least one of its chain ends, more preferably at both of its chain ends, is advantageously used as an intermediate compound for the synthesis of a functional derivative, i.e. a polymer having at least one functional group at one, more preferably at both, of its chain ends.

[0062] Preferably, method (MP) comprises after step (iv) or after step (v), at least one additional step (vi) of separation of the polymer (P) from any solvent and / or at least one additional step (vii) of separation (also referred to as purification) of said functional polymer (P) from said neutral polymer (P).

[0063] Preferably such a step (vi) is performed by distillation.

[0064] Preferably such a step (vii) is performed by thin film distillation, fractionation with a supercritical fluid, such as supercritical CO2 (SCO2), preferably whenSSPI 2024 / 030 polymer (P) is in the form of a salt, or by adsorption / desorption on silica gel or functionalized resins when polymer (P) comprises at least one -OH group.

[0065] Without being bound by any theory, method (MP) developed by the Applicant advantageously allows to synthetize functional polymers (P) or non-functional polymers (P) by properly selecting the molar ratio between compound (HO-Y- OH) and compound (PX).

[0066] More in detail, a molar excess of compound (HO-Y-OH) allows the selective synthesis of polymer (P) having a group -OH at both its chain ends.Differently, a molar excess of compound (PX) allows the selective synthesis of polymer (P) having neutral groups at both its chain ends.

[0067] Preferably, said compound (HO-Y-OH) is selected from those complying with the following formulae: (y-i)wherein each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, and u is an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 4;(y-ll)SSPI 2024 / 030 whereinRe1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 6, preferably from 1 to 4 carbon atoms, Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, Mi is a group -CJH2J- wherein J is from 1 to 4M2 is a group -CKH2K- wherein K is from 1 to 4 andJ+K is from 3 to 5, preferably 3 or 4, more preferably 4;(y-lll)whereinX10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 6, preferably from 1 to 4 carbon atoms, and v is 0 or an integer from 1 to 3,Qi and Q2 , each independently, are selected from a sigma bond, a linear or branched alkylene chain having from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, or one of Qi and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having 5 or 6 members, said aromatic ring being fused with such phenyl ring;(y-IV) HO-Y-(Ar)m-O-Y-H whereinAr and m have the meanings defined above andY complies with any one of formulae (Y-l), (Y-ll), (Y-lll) defined above.

[0068] Preferably, in formula (y-l), Z is a linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably 1 or 2 carbon atoms.SSPI 2024 / 030

[0069] Preferably, in formula (y-l), each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 3 carbon atoms, and q is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3.

[0070] Preferably, in formula (y-ll), Re1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 3, preferably 1 or 2 carbon atoms,Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 3 carbon atoms, preferably methyl,Mi is a group -CJH2J- wherein J is from 1 or 2, preferably 2, M2 is a group -CKH2K- wherein K is from 1 or 2, preferably 2, and J+K is 4.

[0071] Preferably, in formula (y-lll), X10 is a hydrogen atom or a linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms, v is 0 or an integer equal to 1 or 2, andQi and Q2 each independently is a sigma bond, a linear or branched alkylene chain having from 1 to 3 carbon atoms, or one of Qi and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having 6 members, such aromatic ring being fused with such phenyl ring.

[0072] Suitable examples of compounds of formula (y-lll) are 2,3,5,6-tetrafluoro- 1 ,4- benzenediol and 3,4,5,6-tetrafluoro-1 ,2- benzenediol.

[0073] Preferably, compound (y-IV) is prepared via a method [method (MPy)] comprising the following steps:(iy) providing at least one di-alcohol [compound (HO-Y-OH)] complying with formula (y-l), (y-ll), and (y-lll) as defined above,(iiy) providing a (per)(halo)aromatic compound [compound (PX)], (iiiy) contacting said compound (HO-Y-OH) and said compound (PX) in the presence of at least one organic or inorganic base,SSPI 2024 / 030 wherein the molar ratio between said compound (HO-Y-OH) and said compound (PX) is from 50:1 to 6:1 , preferably from 30:1 to 15:1 and more preferably from 15:1 to 30:1 , and the molar ratio between said at least one organic or inorganic base and compound (PX) is from 1 .8:2 to 2:1 .8 and more preferably 2:1 ;(ivy) letting the reaction proceed, thus obtaining compound (y-IV).

[0074] Preferably, after step (ivy), a step comprising treating the reaction mixture with an aqueous acid solution is performed, thus obtaining compound (y-IV).

[0075] Preferably, said compound (PX) is selected from the group comprising, more preferably consisting of: hexafluorobenzene, decafluorobiphenyl, pentafluoronitrobenzene; pentafluorobenzene, iodo-pentafluoro-benzene, di- iodo-tetrafluorobenzene, di-bromo-pentafluorobenzene, chloro-pentafluoro- benzene, bromo-pentafluorobenzene; 1-bromo-3,5-di- fluorobenzene, 5- bromo-1 , 2, 3-trif luoro- benzene, decafluoro-biphenyl; or compound of formula (PX-I): (PX-I) Z-[(ArA)m-O-Y-(ArA)m-Z’ wherein each of Z and Z’ is independently selected from halogen atom selected from F, Cl, I or a group -[(Rg)t-H]qwherein Rg is a chain -OR2- or -R3- wherein each of R2 and R3 are independently selected from linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms, more preferably fluorine atoms, t is 0 or 1 and q is 0 or an integer from 1 to 4; or a group -(R1 )swherein R1 is a linear or branched alkylene chain having from 1 to 6 carbon atoms and s is 0 or an integer from 1 to 4;ArAcomplies with any one of formulae Ar, Ar* or Ar** as defined above m each independently is an integer equal to 1 or 2 andY complies with any formula (Y-l) to (Y-IV) defined above; or a compound of formula (PX-II): (PX-II)SSPI 2024 / 030in which q is an integer from 1 to 2, t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine.

[0076] To the best of the Applicant’s knowledge, compound (PX-II) having the chemical formula disclosed above is not a commercial product and has not been disclosed in previous documents.

[0077] For this reason, a further aspect of the present invention relates to compound (PX-II).

[0078] Preferably, in said compound (PX-II), q is 1 , t is 1 and Rg is a chain -OR2- wherein R2 is a linear alkylene chain comprising from 1 to 3 carbon atoms and being optionally substituted with at least one fluorine atom.

[0079] More preferably, such compound of formula (PX-II) is synthesized by a method [method (PX-II)] comprising contacting hexafluorobenze with an optionally fluorinated alcohol comprising a linear alkyl chain having from 1 to 3 carbon atoms.

[0080] Preferably, said method (PX-II) is performed in a partially fluorinated solvent.

[0081] Preferably, said method (PX-II) is performed in the presence of a strong base.

[0082] Still another aspect of the present invention relates to the use of compound (PX-II) for the synthesis of polymer (P).

[0083] Preferably, said compound of formula (PX-I) is prepared via a method [method (MPX-I)] comprising the following steps:(ix) providing at least one di-alcohol [compound (HO-Y-OH)] complying with formula (y-l), (y-ll), and (y-lll) as defined above,SSPI 2024 / 030(iix) providing a (per)(halo)aromatic compound [compound (PX)] as defined above,(iiix) contacting said compound (HO-Y-OH) and said compound (PX) in the presence of at least one organic or inorganic base, wherein the molar ratio between said compound (HO-Y-OH) and said compound (PX) is from 1 :50 to 1 :6, preferably from 1 :30 to 1 :15 and more preferably from 1 :15 to 1 :30, and the molar ratio between said at least one organic or inorganic base and the hydroxyl groups of said at compound (HO-Y-OH) is from 0.9:1 to 1 :0.9, preferably 1 :1 ;(ivx) letting the reaction proceed, thus obtaining compound (PX-I).

[0084] Preferably, method (MPX-I) comprises, after step (iv*), a step (v*) of treating said mixture (m-v) with an aqueous acid solution.

[0085] Preferably, said organic or inorganic base is selected from NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NaHCO3, KHCO3, CH3ONa, CH3-OK, tBu-ONa, tBu-OK, NaH.

[0086] Preferably, each of said step (iii*) and step (iv*) is performed at a temperature from 20°C to 80°C.

[0087] Preferably, each of said step (iii*) and step (iv*) is performed in at least one solvent, more preferably selected from at least one partially fluorinated solvent, even more preferably selected from: trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers.

[0088] Optionally, such partially fluorinated solvent is in admixture with a tertiary- alcohol, such as for example tert-butanol.

[0089] Preferably, method (MP) comprises after step (iv*) or after step (v*), at least one additional step (vi*) of separation of the polymer (PX-I) from any solvent and / or at least one additional step (vii*) of purification of polymer (PX-I).

[0090] Advantageously, neutral polymer (P) according to the present invention and functional polymer (P) according to the present invention are used for different applications.SSPI 2024 / 030

[0091] As disclosed above, neutral polymer (P) according to the present invention can be advantageously used as such as lubricant for application in several industries, including machinery, automotive, manufacturing, power generation, construction, and marine industries. Also, neutral polymer (P) can be used as additive to neutral lubricating oil and greases, for example as an anti-rust or anti-wear additive or to modify the rheological properties of the oil or grease.

[0092] Preferably, functional polymers (P) according to the present invention can be used as such, as an additive in lubricating oil and greases, for example to modify their rheological properties, or in admixture with hydrogenated polymers.

[0093] Furthermore, functional polymer (P) can be further derivatized by performing a chemical reaction on the final hydroxyl group. Such derivatives of functional polymer (P) can be then used as additives as described above, in particular in coating formulations for substrates such as glass, plastic and metal.

[0094] Without being limited by the following description, functional polymer (P) according to the present invention can undergo the following chemical reactions to provide derivatives on the hydroxyl group functional group.

[0095] For example, the terminal hydroxyl group of polymer (P) can be reacted with the following compounds:I) O=C=N-R-Si(OR)3 , with R being alkylene chain, to provide urethane silane group;II) O=C=R-O-C(=O)-CR=CH2 with R being alkylene chain, to provide urethane acrylate group;III) CI-C(=O)-CR=CH2 with R being alkylene chain, to provide ester acrylic group;IV) Br-CH2-CH=CH2to provide -O-CH2-CH=CH2;V) epichlorohydrin or epibromohydrin to provide epoxide groups, which can be further reacted;VI) epoxy-containing compound such as glycidol, to provide multiple -OH groups;SSPI 2024 / 030VII) sulfonyl chloride such as mesyl-chloride or tosyl-chloride to provide a sulfonate group suitable for nucleophile substitution;VIII) phosphorus pentoxide, to provide phosphorus-containing derivative such as -O-P(=O)(OH)2 or esters thereof;IX) 1-halo-nitrobenzene, to provide nitro-derivatives.

[0096] 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.

[0097] The present 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 disclosure.

[0098] EXAMPLES

[0099] Materials

[0001] The reagents used in the following examples were commercially available, unless otherwise specified.

[0100] Methods1H-NMR and19F-NMR were recorded on an Agilent System 500 operating at 499.86 MHz for1H-NMR and at 470.30 MHz for19F-NMR.

[0101] Example 1

[0102] Polymer (P1 ) complying with the following chemical formula was synthesized as described herein after:T-{ [(HF2C-CH2O)C6F3]-O-CH2CH2-O-}n-T* wherein n is 7 (as average), T is -F or -OCH2CH2OH and T* is -H or - (C6F4OCH2CF2H)

[0103] Step 1 - Preparation of compound (PX-II)

[0104] Nucleophilic reaction of 2,2 difluoroethanol with hexafluorobenzene in ratio1 :9 catalyzed by potassium tert-butyl oxide added in 1 .2 ratio equivalent toSSPI 2024 / 030 the hydroxyl groups. The reaction was run at temperature from 20°C to 80°C and in bistrifluoro-methyl-benzene. The reaction was run at a temperature of 60°C for 6 hours and in a mixture of tert-butanol and bis(trifluoromethyl)- benzene. The reaction mass was then cooled to room temperature, transferred into a plastic flask and treated with an aqueous acidic solution and the intermediate having the following chemical structure: C6F5-O-CH2CF2H (PX-II) was recovered as residual of the lower phase after removal of the solvents.[001051 Step 2

[0106] One pot nucleophilic reaction between ethylene glycol and compound (PX-II) prepared as disclosed in Step 1 above, in ratio 1.13:1 catalyzed by potassium tert-butyl oxide added in 1 .03 ratio equivalent to the hydroxyl groups. The reaction was run at a temperature of 60°C for 8 hours, in a mixture of tertbutanol and bis(trifluoromethyl)- benzene. The reaction mass was cooled down to room temperature and then transferred into a plastic flask and was then treated with an aqueous acidic solution and the polymer (P1 ) was recovered as residual of the lower phase after removal of the solvents.

[0107] Example 2

[0108] Polymer (P1 ) complying with the following chemical formula was synthesized as described herein after: T-[(C6F4)-O-CH2CH2-O-]n-T* wherein n is 8 (as average), T is -F or -OCH2CH2OH and T* is -H or -(CeFs)

[0109] Step 1 - Preparation of Compound PX-I

[0110] Nucleophilic reaction of ethylene glycol with hexafluorobenzene in ratio 1 :14 catalyzed by potassium tert-butyl oxide added in 1.15 ratio equivalent to the hydroxyl groups. The reaction was run at temperature from 20°C to 80°C in bis(trifluoromethyl)benzene. The reaction was run at a temperature of 60°C for 6 hours and in a mixture of tert-butanol and bis(trifluoromethyl)benzene. The reaction mass was then cooled to room temperature, transferred into aSSPI 2024 / 030 plastic flask and treated with an aqueous acidic solution and the intermediate having the following chemical structure: C6F5-O-CH2CH2-O-C6F5 was recovered as residual of the lower phase after removal of the solvents.[001111 Step 2

[0112] One pot nucleophilic reaction between ethylene glycol with intermediate from step 1 in ratio 1.12:1 catalyzed by potassium tert-butyl oxide added in 1.05 ratio equivalent to the hydroxyl groups. The reaction was run at a temperature of 60°C for 8 hours, in a mixture of tert-butanol and bis(trifluoromethyl)- benzene. The reaction mass was cooled down to room temperature and then transferred into a plastic flask and was then treated with an aqueous acidic solution and the polymer (P1 ) was recovered as residual of the lower phase after removal of the solvents.

[0113] Step 3 - Synthesis of urethane silane from oligomer obtained in step 2

[0114] One pot reaction between the oligomer obtained in step 2 and (3-isocyanato- propyl)triethoxysilane in ratio 1 :1 .05 catalyzed by catalytic quantity of dibutyltin dilaurate (2.5x1 O’3eq per hydroxy equivalent). The reaction was run at a temperature of 60°C for 8 hours, in methyl ethyl ketone. At the end of the reaction methanol is added to quench the residual of (3-isocyanatopropyl) triethoxysilane. The reaction mass was cooled down and the polymer was recovered as residual after removal of the solvents.

[0115] Example 3

[0116] Polymer (P1 ) complying with the following chemical formula was synthesized as described herein after: T-[(C6F4)-O-CH2C(CH3)2CH2-O-(C6F4)-O-CH2CH2OCH2CH2O-]n-T* wherein n is 4 (as average), T is -F or -OCH2CH2OCH2CH2H and T* is -H or - (C6F5)

[0117] Step 1 - Preparation of compound (PX-I)Nucleophilic reaction of 2,2 dimethyl-1 ,3- propanediol with hexafluorobenzene in ratio 1 :15 catalyzed by potassium tert-butyl oxide added in 1.04 ratioSSPI 2024 / 030 equivalent to the hydroxyl groups. The reaction was run at temperature from 20°C to 80°C and in bis(trifluoromethyl)benzene. The reaction was run at a temperature of 60°C for 6 hours and in a mixture of tert-butanol and bis(trifluoromethyl)benzene. The reaction mass was then cooled to room temperature, transferred into a plastic flask and treated with an aqueous acidic solution and the intermediate oligomer intermediate having the following chemical structure: (C6F5)-O-CH2C(CH3)2CH2-O-(C6F5) was recovered as residual of the lower phase after removal of the solvents. [001181 Step 2

[0001] One pot nucleophilic reaction between diethylene glycol (Mw = 106 g / mol) and the intermediate of formula (PX-I) in ratio 1.12:1 , catalyzed by potassium tert-butyl oxide added in molar ratio equivalent to the hydroxyl groups. The reaction was run at 60°C in a mixture of tert-butanol and bis(trifluoromethyl)- benzene for 8 hrs. The reaction mass was then cooled to room temperature, transferred into a plastic flask and treated with an aqueous acidic solution and the polyether polymer (P1 ) was recovered as residual of the lower phase after removal of the solvents.

Claims

SSPI 2024 / 030Claims1 . A polymer [polymer (P)] of formula (I):(I) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -0-Yn]P**}n-T wherein p is an integer from 1 to 65;Ar is a group of formulain whichHal is selected from Cl, Br or I, and r is 0 or an integer from 1 to 4, w is 0 or an integer from 1 to 4, provided that at least one of r and w is different from 0; q is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t is 0 or 1 ;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, s is 0 or an integer from 1 to 3, and m is an integer equal to 1 or 2; p* is 0 or an integer from 1 to 65SSPI 2024 / 030Ar* is a group of formulain which q* is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t* is 0 or 1 ,Hal is selected from Cl, Br or I, and r* is 0 or an integer from 1 to 4, w* is 0 or an integer from 1 to 4, provided that at least one of r* and w* is different from 0;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, s* is 0 or an integer from 1 to 3, and m* is an integer equal to 1 or 2; p** is 0 an integer from 1 to 65;Ar** is a group of formulain which q** is 0 or an integer from 1 to 3,Rg is a chain -OR2- or -R3- wherein each of R2 and R3 independently is aSSPI 2024 / 030 linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, and t** is 0 or 1 ,Hal is selected from Cl, Br or I, and r** is 0 or an integer from 1 to 4, w** is 0 or an integer from 1 to 4, provided that at least one of r** and w** is different from 0;R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, s** is 0 or an integer from 1 to 3, and m** is an integer equal to 1 or 2; n is an integer from 1 to 50; each of Y1, Y2and Ynis independently selected from a sigma bond or a group complying with one of the following formulae:(Y-l)wherein each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, and u is an integer from 1 to 20;(Y-ll)SSPI 2024 / 030Rfl whereinRe1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 6, preferably from 1 to 4 carbon atoms, Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, Mi is a group -CJH2J- wherein J is from 1 to 4M2 is a group -CKH2K- wherein K is from 1 to 4 andJ+K is from 3 to 5, preferably 3 or 4, more preferably 4;(Y-lll)whereinX10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 6, preferably from 1 to 4 carbon atoms, v is 0 or an integer from 1 to 3, andQi and Q2 , each independently, are selected from a sigma bond, a linear or branched alkylene chain having from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, or one of Q1 and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having a total of 5 or 6 members, such aromatic ring being fused with such phenyl ring;T* is selected from halogen, preferably fluorine atom, or a group RT0-Y- whereinY is any of Y1, Y2or Ynas defined above;RTis selected from hydrogen atom, an alkali metal cation, preferably selectedSSPI 2024 / 030 from sodium, potassium, lithium, cesium, or an organic cation, such as ammonium or NR4+with R being a linear or branched alkyl chain having 1 to 3 carbon atoms; andT’ is selected from a hydrogen atom, or a group selected from:(T’-i) -(ArA)m-RfAwherein mAis 1 or 2,ArAcomplies with any of Ar, Ar* or Ar** defined above, andRfAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined above; or(T’-ii) -(ArAA)m— O-YAA-RdAAwhereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above, mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above, andRdAAis hydrogen atom, an alkali metal cation, preferably selected from sodium, potassium, lithium, cesium, or an organic cation, such as ammonium or NR4+with R being a linear or branched alkyl chain having 1 to 3 carbon atoms.

2. The polymer (P) according to Claim 1 , wherein: when p* and p** are 0, then:(i) Z is a linear or branched alkylene chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms and q is 0 or an integer from 1 to 3; or(ii) Z is a sigma bond or linear or branched alkylene chain having from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms and q is 1 to 3, more preferably 1 or 2.SSPI 2024 / 0303. The polymer (P) according to Claim 1 or 2, wherein- in formula (Y-l): each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms,Z is sigma bond or a linear or branched alkylene chain having from 1 to 3 carbon atoms, and u is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3; and / or- in formula (Y-l I):Re1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 3, preferably 1 or 2 carbon atoms, Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 3 carbon atoms, preferably methyl,Mi is a group -CJH2J- wherein J is from 1 or 2, preferably 2,M2 is a group -CKH2K- wherein K is from 1 or 2, preferably 2, andM+J is 4; and / or- in formula (Y-l 11): v is 0 or an integer equal to 1 or 2,X10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms, andQi and Q2 each independently is a sigma bond, a linear or branched alkylene chain having from 1 to 3 carbon atoms, or one of Qi and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having 6 members, such aromatic ring being fused with such phenyl ring.

4. The polymer (P) according to any one of Claims 1 to 3, wherein Y1, Y2and Ynare equal to each other.SSPI 2024 / 0305. The polymer (P) according to any one of Claims 1 to 4, wherein at least two of Y1, Y2and Ynare different from each other.

6. The polymer (P) according to anyone of Claims 1 to 5, said polymer (P) being a neutral polymer (P) having two chain ends wherein both said chain ends comprise a neutral group, wherein:T* is selected from halogen atom, preferably fluorine atom andT’ is selected from(T’-i) -(ArA)mA-RfAwherein mAis 1 or 2,ArAcomplies with any of Ar, Ar* or Ar** as defined in Claim 1 , andRfAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined in any one of Claims 1 or 2.

7. The polymer (P) according to anyone of Claims 1 to 5, said polymer (P) being a functional polymer (P) having two chain ends wherein at least one chain end comprise a group -OH, wherein:T* is selected from fluorine atom or a group RT0-Y- wherein Y is any of Y1, Y2or Ynas defined in Claim 1 and RTis a hydrogen atom, andT’ is selected from a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)mAA-O-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined in Claim 1 , mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined in Claim 1 .

8. The polymer (P) according to Claim 7, said polymer (P) being a bifunctional polymer (P) having two chain ends wherein both chain ends comprise a group -OH, wherein :SSPI 2024 / 030T* is selected from group RT0-Y- wherein Y is any of Y1, Y2or Ynas defined in Claim 1 and RTis a hydrogen atom, andT’ is selected from a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)m-O-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined in Claim 1 , mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined in Claim 1 .

9. A polymer [polymer (P)] of formula (II):(II) T*- {[(Ar)m-0-Yx]Px}n -T’ wherein:T*, T’ and Ar have the same meaning as for the polymer (P) of formula (I), Ar being the same or different in each of the pxrecurring units; m is an integer equal to 1 or 2; n is an integer from 1 to 50; pxis an integer from 2 to 66, preferably from 4 to 30, more preferably from 4 to 15;Yx, the same or different in each of the pxrecurring units, is selected from a sigma bond, Y-l, Y-ll and Y-lll, wherein Y-l, Y-ll and Y-lll have the same meaning as for the polymer of formula (I), with the proviso that when Yxis the same in each of the pxrecurring units then:- Z is a linear or branched alkylene chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, and q is 0 or an integer from 1 to 3; or q is 1 to 3, more preferably 1 or 2, and Z is a sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms.SSPI 2024 / 03010. A method [method (MP)] for the manufacture of polymer (P) according to any one of Claims 1 to 9, wherein said method (MP) comprises the steps of:(i) providing at least one di-alcohol [compound (HO-Y-OH)](ii) providing a (per) (halo)aromatic compound [compound (PX)](iii) contacting said compound (HO-Y-OH) and said compound (PX) in the presence of at least one organic or inorganic base, and(iv) letting the reaction proceed, thus obtaining polymer (P).

11. The method (MP) according to Claim 10, wherein in step (iii):- the molar ratio between said compound (HO-Y-OH) and said compound (PX) is from 2:1 to 0.5:1 , more preferably from 1 .5:1 to 0.8:1 , even more preferably from 1.3:1 and 1.1 :1 ; and / or- the molar ratio of said organic or inorganic base to the molar ratio of said hydroxyl groups of said compound (HO-Y-OH) is from 1.5:1 to 0.5:1 , more preferably from 1 .2:1 to 0.8:1 and even more preferably about 1 :1.

12. The method (MP) according to any one of Claims 10 or 11 , wherein after step (iv), a step (v) of treating said mixture (M1 ) with an aqueous acid solution is performed, thus obtaining polymer (P) wherein:T* is selected from halogen, preferably fluorine atom, or a group RTO-Y- whereinY is any of Y1, Y2or Ynas defined in Claim 1 ;RTis selected from hydrogen atom; andT’ is selected from a hydrogen atom, or a group selected from:(T’-i) -(ArA)m-RcAwherein mAis 1 or 2,ArAcomplies with any of Ar, Ar* or Ar** defined in Claim 1 , andRcAis selected from H, F, Hal or R1 , wherein Hal and R1 are as defined in any one of Claims 1 or 2;SSPI 2024 / 030 or(T’-ii) -(ArAA)m— 0-YAA-H whereinArAAcomplies with any one of Ar, Ar* and Ar** as defined in Claim 1 , mAAis an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined in Claim 1 .

13. The method (MP) according to any one of Claims 10 to 12, wherein said method (MP) comprises after step (iv) or after step (v), at least one additional step (vi) of separation of the polymer (P) from any solvent and / or at least one additional step (vii) of separation of functional polymer (P) and neutral polymer (P).

14. The method (MP) according to any one of Claims 10 to 13, wherein said compound (HO-Y-OH) is selected from those complying with the following formulae:(y-i)wherein each of Ra, Rb, Rc and Rd is independently hydrogen atom or linear or branched alkyl chain having from 1 to 6 carbon atoms;Z is sigma bond or a linear or branched alkylene chain having from 1 to 6 carbon atoms, and u is an integer from 1 to 20;(y-ll)SSPI 2024 / 030whereinRe1 and Re2 each independently is a sigma bond or a linear or branched alkylene chain having from 1 to 6,Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 6 carbon atoms,Mi is a group -CJH2J- wherein J is from 1 to 4M2 is a group -CKH2K- wherein K is from 1 to 4 andJ+K is from 3 to 5;whereinX10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 6, and v is 0 or an integer from 1 to 4,Qi and Q2 , each independently, are selected from a sigma bond, a linear or branched alkylene chain having from 1 to 4 carbon atoms, or one of Qi and Q2 together with two carbon atoms of the phenyl ring forms an aromatic ring having 5 or 6 members, said aromatic ring being fused with such phenyl ring; (y-IV) H0-Y-(Ar)m-0-Y-H whereinAr and m have the meanings defined in Claim 1 andSSPI 2024 / 030Y complies with any one of formulae (Y-l), (Y-ll), (Y-lll) defined in Claim 1 .

15. The method (MP) according to any one of Claims 10 to 14 wherein said compound (PX) is selected from the group comprising, more preferably consisting of: hexafluorobenzene, decafluorobiphenyl, pentafluorobenzene, iodo-pentafluoro-benzene, di-iodo-tetrafluorobenzene, chloro-pentafluoro- benzene, bromo-pentafluorobenzene; 1 -bromo-3,5-difluorobenzene, 1 -bromo- 4-tert-butylbenzene, 5-bromo-1 ,2,3-trifluoro-benzene, decafluoro-biphenyl, 4- fluoro-toluene, 3-fluoro-toluene, 2-fluoro-toluene, 4-chloro-toluene, fluorobenzene, 4-chloro-2 -fluoro-toluene, 2-chloro-4-fluoro-toluene; or from compound of formula (PX-I): (PX-I) Z-(ArA)m-0-Y-(ArA)m -Z’ wherein each of Z and Z’ is independently selected from halogen atom selected from F, Cl, I or a group -[(Rg)t-H]qwherein Rg is a chain -OR2- or -R3- wherein each of R2 and R3 are independently selected from linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms, more preferably fluorine atoms, t is 0 or 1 and q is 0 or an integer from 1 to 4; or a group -(R1 )swherein R1 is a linear or branched alkyl chain having from 1 to 6 carbon atoms and s is 0 or an integer from 1 to 4; ArAcomplies with any one of formulae Ar, Ar* or Ar** as defined in Claim 1 m each independently is an integer equal to 1 or 2 andY complies with any formula (Y-l) to (Y-IV) defined in Claim 1 ; or a compound of formula (PX-II):(PX-II)in whichSSPI 2024 / 030 q is an integer from 1 to 2, t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine.

16. Use of polymer (P) according to Claims 7 or 8 as an intermediate compound for the synthesis of polymer (P) comprising at least at one chain end a group selected from: urethane silane, urethane acrylate, acrylic ester, -O-CH2- CH=CH2, epoxide, sulfonate, -O-P(=O)(OH)2 or ester thereof, nitro-containing group, alkyl chain comprising at least two -OH groups.

17. Compound of formula (PX-II):(PX-II) in which q is an integer from 1 to 2, t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine.

18. Use of compound (PX-II) according to Claim 16 for the synthesis of polymer (P) as defined in any one of Claims 1 to 9.

19. Use of polymer (P) according to Claim 6 as lubricant, preferably for machinery, automotive, manufacturing, power generation, construction, and marine industries; as additive to neutral lubricating oil and grease, preferably as anSSPI 2024 / 030 anti-rust or anti-wear additive or to modify the rheological properties of such oil or grease.

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