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 / 031DescriptionHydrofluoroether polymersTechnical field

[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-EwhereinRF 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 / 031fluorine-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 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, such polymers being capable of changing the properties of the compositions and materials to which they are added.SSPI 2024 / 031

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

[0010] Such new functional polymers can be synthesized from starting polymers having one hydroxyl group at one or both the chain ends. In particular, polymers with complex functional groups can be prepared, which can be used as additives in compositions 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] Polymer (Pder) according to the present inventionThus, in a first aspect the present invention relates to a polymer [polymer (Pder)] complying with formula (Ider):(Ider) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -O-Yn]p**}n-T’ whereinp is an integer from 1 to 65;Ar is a group of formulain whichSSPI 2024 / 031Hal is selected from Cl, Br or I, andr 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, andt 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, andm is an integer equal to 1 or 2;p* is 0 or an integer from 1 to 65Ar* is a group of formulain whichq* 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, andt* is 0 or 1,Hal is selected from Cl, Br or I, andr* is 0 or an integer from 1 to 4,w* is 0 or an integer from 1 to 4,SSPI 2024 / 031provided 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, andm* is an integer equal to 1 or 2;p** is 0 an integer from 1 to 65;Ar** is a group of formulain whichq** 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, andt** is 0 or 1,Hal is selected from Cl, Br or I, andr** 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, andm** 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 / 031Ra Rcwhereineach 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 alkyl chain having from 1 to 6 carbon atoms, andu 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, M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5, preferably 3 or 4, more preferably 4; (Y-III)SSPI 2024 / 0311^1 ok'whereinXw 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 a group RT0-Y-whereinY is any of Y1, Y2or Ynas defined above;RTis selected from:A) -C(=O)-NH-R10-Si(R11)n(OR12)3-nwhereineach of R11and R12is independently selected from linear or branched C1-C6alkyl group,R10is a linear or branched Ci-Ce alkylene group, andn is an integer selected from 1 or 2, preferably 1;B) -C(=O)-NH-R20-R21-CRH=CH2whereinRH is -H or a linear or branched C1-C6alkyl group;R20is a Ci-Ce alkylene group, optionally substituted with a group comprising a tri-alkoxy-silyl group;R21is a sigma bond or a divalent group of formula -O-C(=O)-, -O-C(=O)-NH-CO-, -O-C(=O)-RA-SSPI 2024 / 031wherein RAis selected from the group consisting of (RA-I ) and (RA-II):(RA-I)[O-C(=O) -CRH=CH2]-5— N-RB-O-C(=O) - H I[O-C(=O) -CRH=CH2]j5whereineach of j5 is independently 0 or 1 andRBis a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S;(RA-II){O-[C(=O)]j6-CRH=CH2}j7H H IXN O-RB-O-[C(=O)]j6-RB* J {O-[C(=O)]j6-CRH=CH2}j7whereinj6 is 0 or 1;each of j7 is independently 0 or 1;RB’ is a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S; andSSPI 2024 / 031RB* has the same meanings defined above for RB’ or it is a group of formula (RB-I):U-OCH2CH2-O-C(wherein U is selected from the groups (U-I) to (U-III)(U-I) -O-C(=O)-CRH=CH2(U-II) -O-C(=O)-NH-CO-CRH=CH2(U-III) -O-C(=O)-RA-CRH=CH2wherein RAand RH are as defined above;C) -C(=O)-C(R30)=C(R31)(R32)herein each of R30, R31and R32is independently H or -CH3:D) -CH2-CH=CH2E) -CH2-CH(O)CH2 with (0) being an epoxide group;F) linear or branched alkyl chain comprising at least one -OH group, said alkyl chain being optionally substituted with at least one alkyl group having from 1 to 3 carbon atoms;G) sulfonate group;H) phosphorus-containing group such as -O-P(=O)(OH)2 or esters thereof; I) -C6H4(NO2);andT’ is selected from a group selected from:(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,SSPI 2024 / 031YAAcomplies with any one of Y1, Y2or Ynas defined above, andRdAAhas the same meanings provided above for RT.

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

[0014] Preferably, p is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0015] 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.

[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 2.

[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; orq 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:whereinw is an integer from 1 to 4,r and s are each 0,q is 0 or 1,SSPI 2024 / 031t 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.

[0026] Preferably, Ar* is a group of formula:whereinw* 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 havingSSPI 2024 / 031from 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:whereinw** 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.

[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 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.

[0034] Preferably, the sum of (p+p*+p**+n) is from 2 to 66, preferably from 4 to 30, more preferably from 4 to 15.

[0035] In certain embodiments, in formula (I) p* and p** are both 0.

[0036] Preferably, Z is a sigma bond or a linear or branched alkyl chain having from 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

[0037] Preferably, u is an integer from 1 to 10, more preferably from 1 to 4.SSPI 2024 / 031

[0038] 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, andu is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3.

[0039] 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, andM+J is 4.

[0040] 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, and Qi 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.

[0041] According to an embodiment, Y1, Y2and Ynare identical to each other.

[0042] The number of different recurring units containing Y depends on the number of di-alcohols having different chemical formulae that are used as starting materials for the synthesis of polymer (Pder).

[0043] Accordingly, polymer (Pder) can also be represented by formula ( I Ider):(llder) T*- {[(Ar)m-0-Yx]Px}n -T’whereinSSPI 2024 / 031T*, T’ and Ar have the same meaning as for the polymer of formula (Ider), 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 to 1 or 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 (Ider).

[0044] In formula (I Ider) the recurring units pxare randomly distributed along the backbone chain of the polymer (Pder).

[0045] Polymer (P)Polymer (Pder) according to the present invention are advantageously obtained starting from certain polymers [polymer (P)] prepared by the Applicant, and complying with the the following formula (I):(I) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -0-Yn]P**}n-T whereinp is an integer from 1 to 65;Ar is a group of formulain whichHal is selected from Cl, Br or I, andr 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 / 031q 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, andt 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, andm is an integer equal to 1 or 2;p* is 0 or an integer from 1 to 65Ar* is a group of formula(Hal)r[(Rg)t-H]3in whichq* 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, andt* is 0 or 1,Hal is selected from Cl, Br or I, andr* 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 / 031s* is 0 or an integer from 1 to 3, andm* is an integer equal to 1 or 2;p** is 0 an integer from 1 to 65;Ar** is a group of formulain whichq** 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, andt** is 0 or 1,Hal is selected from Cl, Br or I, andr** 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, andm** 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 / 031Ra Rcwhereineach 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, andu 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, M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5, preferably 3 or 4, more preferably 4; (Y-III)SSPI 2024 / 031whereinX10 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-RfAwhereinmAis 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 / 031ArAAcomplies 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.

[0046] Preferably, p is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0047] Preferably, R1 is a linear or branched alkyl chain having from 1 to 3 carbon atoms.

[0048] Preferably, r is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0049] Preferably, q is 0 or an integer from 1 to 2.

[0050] Preferably, m is 1.

[0051] Preferably, Ar is a group of formula:whereinw 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.

[0052] Preferably, p* is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.SSPI 2024 / 031

[0053] Preferably, r* is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0054] Preferably, q* is 0 or an integer from 1 to 2.

[0055] Preferably, m* is 1.

[0056] Preferably, Ar* is a group of formula:whereinw* 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.

[0057] Preferably, p** is an integer from 2 to 50, more preferably from 2 to 25 and even more preferably from 2 to 10.

[0058] Preferably, r** is 0 or an integer from 1 to 3, more preferably 0 or 1 or 2.

[0059] Preferably, q** is 0 or an integer from 1 to 2.

[0060] Preferably, m** is 1.

[0061] Preferably, Ar** is a group of formula:whereinw** is an integer from 1 to 4,SSPI 2024 / 031r** 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.

[0062] Preferably, n is an integer from 2 to 25, more preferably from 2 to 15 and even more preferably from 2 to 10.

[0063] 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.

[0064] Preferably, the sum of (p+p*+p**+n) is from 2 to 66, preferably from 4 to 30, more preferably from 4 to 15.

[0065] 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.

[0066] Preferably, u is an integer from 1 to 10, more preferably from 1 to 4.

[0067] 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, andu is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3.

[0068] Preferably, 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.SSPI 2024 / 031

[0069] Preferably, in formula (Y-lll):v is 0 or an integer equal to 1 or 2,Xw 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, and Qi 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.

[0070] According to an embodiment, Y1, Y2and Ynare identical to each other.

[0071] 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.

[0072] According to another embodiment, at least two of Y1, Y2and Ynare different from each other.

[0073] 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.

[0074] 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).SSPI 2024 / 031

[0075] 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]P**-[(ArA)mA -0-Y [(ArA)m-O-Y }n-T’wherein the substituents have the meanings defined above and each of Y1, Y2Y3, Y4and Ynderives from a di-alcohol.

[0076] 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 to 1 or 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).

[0077] In formula (II) the recurring units pxare randomly distributed along the backbone chain of the polymer (P).

[0078] When polymer (P) comprises two chain ends wherein both said chain ends comprise a neutral group, such as for example when:T* selected from halogen atom, preferably fluorine atom andT’ selected from(T’-i) -(ArA)mA -RfAwhereinmAis 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,such polymer (P) is referred to as ‘neutral polymer (P)’ or ‘non-functional polymer (P)’.SSPI 2024 / 031

[0079] When polymer (P) comprises 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, it is referred to as ‘functional polymer (POH)’.

[0080] For example, functional polymer (POH) are those 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, andT’ selected from a hydrogen atom, or a group selected from:(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 a hydrogen atom.

[0081] When T* is fluorine atom and T’ is a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)m-O-YAA-RdAAas above defined,such functional polymer (POH) is referred to as mono-functional polymer (POH).

[0082] When T* is a group RTO-Y- as defined above andT’ selected from a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)m-O-YAA-RdAAas defined above,such functional polymer (POH) is referred to as bi-functional polymer (POH).

[0083] Mono-functional polymer (POH), and more preferably bi-functional polymer (POH), is advantageously used for the synthesis of polymer (Pder) according to the present invention.

[0084] Method for preparing polymer (P)Polymer (P) as above defined is prepared via a method [method (P)], which comprises the steps of:(i) providing at least one di-alcohol [compound (HO-Y-OH)](ii) providing a (per)(halo)aromatic compound [compound (PX)]SSPI 2024 / 031(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) as defined above.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Preferably, each step (iii) and step (iv) is performed at a temperature from 20°C to 80°C.

[0089] 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.

[0090] Optionally, such partially fluorinated solvent is in admixture with a tertiary- alcohol, such as for example tert-butanol.

[0091] Preferably, said compound (HO-Y-OH) is selected from those complying with the following formulae:(y-i)whereineach of Ra, Rb, Rc and Rd is independently hydrogen atom or linear orSSPI 2024 / 031branched 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 alkyl chain having from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, andu is an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 4;(y-ll)whereinRe1 and Re2 each independently is a sigma bond or a linear or branched alkyl 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, andv is 0 or an integer from 1 to 4,Qi and Q2, each independently, are selected from a sigma bond, a linear or branched alkyl chain having from 1 to 4 carbon atoms, preferably 1 or 2SSPI 2024 / 031carbon 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-Ra-(Ar)m-Rb-O-Y-HwhereinRa, Rb, Ar and m have the meanings defined above andY complies with any one of formulae (Y-l), (Y-ll), (Y-lll) defined above.

[0092] 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.

[0093] 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 alkyl chain having from 1 to 3 carbon atoms, andq is an integer from 1 to 15, preferably from 1 to 5, more preferably from 1 to 3.

[0094] Preferably, in formula (y-ll), 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, andJ+K is 4.

[0095] 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 alkyl 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.SSPI 2024 / 031

[0096] 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.

[0097] Preferably, compound (y-IV) is prepared via a method [method (Py)] comprising the following steps:(jy) 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)] as defined above,(iiiy) contacting said compound (HO-Y-OH) and said compound (PX) in the presence of at least one organic or inorganic base,whereinthe 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, andthe molar ratio between said at least one organic or inorganic base and compound (PX) is from 0.9:1 to 1:0.9, preferably 1:1;(ivy) letting the reaction proceed, thus obtaining compound (y-IV).

[0098] Preferably, after step (ivy), a step comprising treating the reaction mixture with an aqueous acid solution is performed, thus obtaining compound (y-IV).

[0099] Preferably, said compound (PX) is selected from the group comprising, more preferably consisting of: hexafluorobenzene, decafluorobiphenyl, pentafluorobenzene, pentafluoronitrobenzene; iodo-pentafluoro-benzene, di- iodo-tetrafluorobenzene, chloro-pentafluoro-benzene, bromo- pentafluorobenzene; 1-bromo-3,5-di- fluorobenzene, 5-bromo-1,2,3-trifluoro- benzene, decafluoro-biphenyl; orcompound of formula (PX-I):(PX-I) Z-(ArA)m-O-Y-(ArA)m - Z’whereineach 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 branchedSSPI 2024 / 031alkylene 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 above m each independently is an integer equal to 1 or 2 andY complies with any formula (Y-l) to (Y-IV) defined above; ora compound of formula (PX-II):(PX-II)[(Rg)t-H]ain whichq 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.

[0100] Preferably, said compound of formula (PX-I) is prepared via a method [method (PX-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,(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,whereinthe molar ratio between said compound (HO-Y-OH) and said compound (PX)SSPI 2024 / 031is from 1:50 to 1:6, preferably from 1:30 to 1:15 and more preferably from 1:15 to 1:30, andthe 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).

[0101] Preferably, method (PX-I) comprises, after step (ivx), a step (vx) of treating said mixture (m-v) with an aqueous acid solution.

[0102] 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.

[0103] Preferably, each of said step (iiix) and step (ivx) is performed at a temperature from 20°C to 80°C.

[0104] Preferably, each of said step (iiix) and step (ivx) 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.

[0105] Optionally, such partially fluorinated solvent is in admixture with a tertiary- alcohol, such as for example tert-butanol.

[0106] Preferably, method (PX-I) comprises after step (ivx) or after step (vx), at least one additional step (vix) of separation of the polymer (PX-I) from any solvent and / or at least one additional step (viix) of purification of polymer (PX-I).

[0107] Optionally, method (P) comprises, after step (iv), a step (v) of treating said mixture (M1) with an aqueous acid solution, thus obtaining polymer (POH) 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-RcASSPI 2024 / 031whereinmAis 1 or 2,ArAcomplies 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-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 a hydrogen atom.

[0108] According to method (P) as disclosed above, a mixture of polymer (P) is obtained comprising neutral polymer (P), mono-functional polymer (POH) and bi-functional polymer (POH).

[0109] More preferably, method (P) developed by the Applicant advantageously allows to synthetize functional polymers (POH) or neutral polymers (P) by properly selecting the molar ratio between compound (HO-Y-OH) and compound (PX).

[0110] For example, a molar excess of compound (HO-Y-OH) allows the selective synthesis of polymer (POH) having group -OH at both its chain ends.Differently, although not preferred in the present invention, a molar excess of compound (PX) allows the selective synthesis of polymer (P) having neutral groups at both its chain ends.

[0111] When polymer (P) is obtained at the end of method (P) disclosed above as a mixture of neutral and mono- and / or di-functional polymer (P), such mono- and / or di-functional polymer (POH) can be separated from the neutral polymer (P).

[0112] Preferably, the method (P) of the present invention comprises after step (iv) or after step (v), at least one additional step (vi) of separation of the polymerSSPI 2024 / 031(POH) from any solvent and / or at least one additional step (vii) of separation (also referred to purification) of polymer (POH) from polymer (P).

[0113] Preferably such a step (vi) of separation is performed by distillation.

[0114] Preferably such a step (vii) of separation is performed by fractionation with a supercritical fluids, such as supercritical CO2 (SCO2) when polymer (P) is in the form of a salt, or by adsorption / desorption on silica gel when polymer (POH) comprises at least one -OH group.

[0115] Advantageously, such mono- and bi-functional polymer (POH) can be further reacted by performing a chemical reaction on the hydroxyl group.

[0116] Method for preparing polymer (Pder) according to the present invention Thus, in a second aspect the present invention relates to a method [method (Pder)] for the synthesis of polymer (Pder) as defined above, said method (Pder) comprising- providing at least one polymer (POH) as defined above, whereinT* selected from fluorine atom or a group RTO-Y- wherein Y is any of Y1, Y2or Ynas defined above and RTis a hydrogen atom, andT’ selected from a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)m-O-YAA-RdAAwhereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above,m is an integer egual to 1 or 2, YAAcomplies with any one of Y1, Y2or Ynas defined above andRdAAis a hydrogen atom,- contacting said at least one polymer (POH) with at least one compound selected in the group comprising, preferably consisting of:a) O=C=N-R10-Si(R11)n(OR12)3-nwhereineach of R11and R12is independently selected from linear or branched C1-C6alkyl group,SSPI 2024 / 031

[0117] R10is a linear or branched Ci-Ce alkylene group, andn is an integer selected from 1 or 2, preferably 1;b) O=C=N-R20-R21-CRH=CH2whereinRH is -H or a linear or branched C1-C6alkyl group;R20is a Ci-C6alkylene group, optionally substituted with a group comprising a tri-alkoxy-silyl group;R21is a sigma bond or a divalent group of formula -O-C(=O)-, -O-C(=O)-NH- CO-, -O-C(=O)-RA- wherein RAis selected from the group consisting of (RA-I) and (RA-I I):(RA-I)[O-C(=O) -CRH=CH2]j5— N— RB— O-C(=O)- H I[O-C(=O) -CRH=CH2]j5whereineach of j5 is independently 0 or 1 andRBis a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S;(RA-II){O-[C(=O)]je-CRH=CH2}j7H H I^N^.0— RB— O-[C(=O)]j6-RB’ J {O-[C(=O)]j6-CRH=CH2}j7whereinj6 is 0 or 1;each of j7 is independently 0 or 1;SSPI 2024 / 031RB’ is a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S; andRB* has the same meanings defined above for RB’ or it is a group of formula (RB-I):N NU-OCH2CH2-O- (RB-I)wherein U is selected from the groups (U-I) to (U-III)(U-I) -O-C(=O)-CRH=CH2(U-II) -O-C(=O)-NH-CO-CRH=CH2(U-III) -O-C(=O)-RA-CRH=CH2wherein RAand RH are as defined above;c) X-C(=O)-C(R30)=C(R31)(R32)wherein X is halogen atom, more preferably Cl,each of R30, R31and R32is independently H or -CH3:d) X-CH2-CH=CH2wherein X is a halogen atom selected from Cl, B r, I or a leaving group for a nucleophilic substitution reaction:e) epichlorohydrin or epibromohydrin, to provide epoxy group;f) epoxy-containing compound;g) sulfonyl halide;h) phosphorus oxychloride, phosphorus pentoxide, pyrophosphoric acid, polyphosphoric acid and the like, to provide phosphorus-containing derivative such as -O-P(=O)(OH)2 or esters thereof;SSPI 2024 / 031i) 1-halo-nitrobenzene;thus obtaining polymer (Pder).

[0118] Polymer (POH) is a mono- or bi-functional polymer (POH) or a mixture of mono- and bi-functional polymers (POH).

[0119] Advantageously, polymer (POH) is prepared according to steps (i), (ii), (iii) and (iv) of method (P).

[0120] More preferably, in step (iii) of method (P), compound (HO-Y-OH) is in molar excess over compound (PX), such as for example from 50: 1 to 1.01: 1, preferably from 30:1 to 1.05:1 and more preferably from 2:1 to 1.1:1.

[0121] Preferably, compounds of formula a) are selected from 3-(triethoxy- silyl)propyl isocyanate, 3-(methoxy-silyl)propyl isocyanate; diethoxy(methyl) silyl-isocyanate; to provide urethane silane group.

[0122] Preferably, compounds of formula b) are selected from:b-l) O=C=N-R20-O-C(=O)-CRH=CH2whereinR20is a linear or branched alkyl chain having from 1 to 3 carbon atoms, RH is hydrogen or -CH3b-ll) O=C=N-CH2CH=CH2;to provide urethane acrylate group of formula

[0123] More preferably, compounds of formula b-l) are selected from 2-isocyanate- ethyl-methacrylate, 2-isocyanate ethyl-acrylate, 3-isocyanate propyl-acrylate, 3-isocyanato-propyl methacrylate, and 2-(2-isocyanato-ethoxy)ethyl methacrylate, allyl isocyanate.

[0124] Preferably, compounds of formula c) are selected from acryloyl chloride, crotonyl chloride, methacryloyl chloride, 3,3-dimethyl acryloyl chloride, trans 2-methyl-2-butenoyl chloride, to provide ester acrylic group.

[0125] Preferably, compounds of formula f) are selected from oxirane compounds such as ethylene oxide, propylene oxide; glycidol, glycidyl isopropyl ether, 2- ethylhexyl glycidyl ether, 1,2-epoxyoctane, 1,2-epoxy-2-methylpropane, cyclohexene oxide; 1,3-butadiene diepoxide; to provide linear or branched alkyl chain comprising at least one -OH group, said alkyl chain beingSSPI 2024 / 031optionally substituted with at least one alkyl group having from 1 to 3 carbon atoms.

[0126] Preferably, compounds of formula g) are selected from mesyl-chloride or tosyl-chloride, to provide a sulfonate group suitable for nucleophile substitution.

[0127] Preferably, compounds of formula h) are selected from pyrosphosphoric acid.

[0128] Preferably, compounds of formula i) are selected from 1-iodo-4-nitrobenzene or 1-chloro-4-nitrobenzene, to provide nitro-derivatives.

[0129] When at least one compound of formula a) and / or b) is used as the reactant with polymer (P), the reaction is preferably performed by reacting, in at least one solvent, polymer (P) having at least one hydroxyl end group with at least one compound of formula a) and / or b) in an equivalent ratio from 1: 1.0 to 1:1.2, preferably 1:1.05.

[0130] Preferably, the reaction is performed at a temperature from 25°C to 70°C, preferably around 60°C.

[0131] Preferably, the reaction is performed in the presence of a catalyst, such as for example alkyltin carboxylates or zirconium chelates.

[0132] Suitable solvents are selected from polar hydrogenated solvents, such as methyl ethyl ketone; partially fluorinated solvents, such as trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers, and mixtures thereof.

[0133] At the end of the reaction, methanol is preferably added to quench the residual isocyanate. The reaction mass is then cooled down and the polymer of the present invention comprising a urethane functional group is recovered as residual after removal of the solvents.

[0134] When at least one compound of formula c) and / or g) is used as the reactant with polymer (P), the reaction is preferably performed by reacting, in at least one solvent, polymer (P) having at least one hydroxyl end group with at least one reagent (acyl chloride or sulfonyl chloride) in an equivalent ratio from 1:1 to 1:1.3 preferably 1:1.1.

[0135] Preferably, the reaction is performed in the presence of a tertiary amine, preferably triethylamine.SSPI 2024 / 031

[0136] Preferably, the reaction is performed at a temperature from room temperature to 50°C, preferably below 30°C.

[0137] Said at least one solvent is preferably selected from partially fluorinated solvents, such as trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers.

[0138] At the end of the reaction, water is added and the resulting polymer according to the present invention is isolated as a residue of the distillation of the organic phase.

[0139] When at least one compound of formula d), e), f) and / or i) is used as the reactant with polymer (P), the reaction is preferably performed by reacting, in at least one solvent, polymer (P) having at least one hydroxyl end group with at least one reagent having high reactivity towards nucleophilic attack, such as for example allyl iodide, in an equivalent ratio from 1: 1.0 to 1: 1.2, preferably 1:1.05.

[0140] Preferably, the reaction is performed at a temperature from 25°C to 90°C, preferably around 70°C.

[0141] Preferably, the reaction is performed in the presence of a strong base, to form the alkoxide of polymer P which in turn reacts with the compound of formula d), e) or i). More preferably, said strong base is selected from hydroxides and alkoxides of alkaline metals, including lithium, sodium and potassium hydroxides; or organic alkoxides, such as potassium tert-butoxide, and the like. More preferably, said strong base is used in a stoichiometric amount or in excess (on an equivalent basis) to the hydroxyl equivalent content.

[0142] Said at least one solvent is preferably selected from partially fluorinated aprotic solvents, such from trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers, optionally in an admixture with polar hydrogenated solvents, such as acetonitrile and tertiary-alcohols, preferably tert-butanol.

[0143] At the end of the reaction, the reaction mixture is brought to neutrality by adding an aqueous acidic solution, preferably aqueous HCI, and the resultingSSPI 2024 / 031polymer according to the present invention is isolated as a residue of the distillation of the separated organic phase.

[0144] When at least one compound of formula h) is used as the reactant with polymer (P), the reaction is preferably performed by reacting, in at least one solvent, polymer (P) having at least one hydroxyl end group with at least a compound of formula h).

[0145] Preferably, the equivalent ratio between polymer (P) and said at least one compound h) is from 1: 15 to 1: 1.3 preferably about 1:1.1.

[0146] Preferably, the reaction is performed at a temperature from 15°C to 100°C, preferably at 70°C.

[0147] Preferably, said at least one solvent is selected from the group comprising partially fluorinated aprotic solvents, such as trifluorotoluene, bis(trifluoromethyl)benzene, perfluorinated cyclic ethers. Optionally, such solvent can be used in an admixture with at least one polar hydrogenated solvent, preferably selected in the group comprising toluene and xylene.

[0148] At the end of the reaction, the reaction mixture is added with an aqueous solution, preferably an aqueous acidic solution, and the resulting polymer according to the present invention is isolated as a residue of the distillation of the separated organic phase.

[0149] Use of polymer (Pder)Polymer (Pder) according to the present invention is advantageously used as additive, in particular in formulations suitable for coating substrates selected from glass, plastic and metal.

[0150] Polymer (Pder) according to the present invention can be used as such or in a composition further comprising at least one solvent, preferably a nonfluorinated solvent.

[0151] Thus, in a further aspect, the present invention relates to a composition comprising at least one polymer (Pder) as defined above and at least one solvent, preferably a non-fluorinated solvent.SSPI 2024 / 031

[0152] Furthermore, the present invention relates to the use of polymer (Pder) as defined above or of the composition as defined above, for coating a substrate selected from glass, plastic and metal.

[0153] 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.

[0154] 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.

[0155] EXAMPLES

[0156] Materials

[0157] The reagents used in the following examples were commercially available, unless otherwise specified.

[0158] 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.

[0159] Example 1

[0160] 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 - OCH2CH2OC(=O)NHCH2CH2CH2Si(OCH2CH3)3 and T* is - C(=O)NHCH2CH2CH2Si(OCH2CH3)3

[0161] Step 1 - Preparation of Compound PX-I

[0162] 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 inSSPI 2024 / 031bis(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 having the following chemical structure:C6F5-O-CH2CH2-O-C6F5was recovered as residual of the lower phase after removal of the solvents.[001631 Step 2

[0164] One pot nucleophilic reaction between ethylene glycol with intermediate from step 1 in ratio 1.13:1 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.

[0165] Step 3 - Synthesis of urethane silane from oligomer obtained in step 2

[0166] 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 ( 2.5x10’3eq for hydroxy equivalent)). The reaction was run at a temperature of 60°C for 8 hours, 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.

[0167] Example 2

[0168] 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 -SSPI 2024 / 031OCH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 and T* is C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0169] Step 1 and Step 2 were performed as disclosed above in Example 1.

[0170] Step 3 - Synthesis of urethane methacrylate from oligomer obtained in step 2

[0171] One pot reaction between the oligomer obtained in step 2 and 2- Isocyanatoethyl methacrylate in ratio 1:1.05 catalyzed by catalytic quantity of dibutyltin dilaurate (2.5x10’3eq for hydroxy equivalent). The reaction was run at a temperature of 60°C for 8 hours, methyl ethyl ketone. At the end of the reaction methanol is added to quench the residual of 2-lsocyanatoethyl methacrylate. The reaction mass was cooled down and the polymer was recovered as residual after removal of the solvents.

[0172] Example s

[0173] 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 -OCH2CH2OC(=O)NHCH2CH=CH2 and T* is C(=O)NHCH2CH=CH2

[0174] Step 1 and Step 2 were performed as disclosed above in Example 1.

[0175] Step 3 - Synthesis of urethane allyl from oligomer obtained in step 2

[0176] One pot reaction between the oligomer obtained in step 2 and Allyl isocyanate in ratio 1:1.05 catalyzed by catalytic quantity of dibutyltin dilaurate (2.5x10’3eq for hydroxy equivalent). The reaction was run at a temperature of 60°C for 8 hours, methyl ethyl ketone. At the end of the reaction methanol is added to quench the residual of allyl isocyanate. The reaction mass was cooled down and the polymer was recovered as residual after removal of the solvents.

[0177] Example 4

[0178] Polymer (P1) complying with the following chemical formula was synthesized as described herein after:SSPI 2024 / 031T-[(C6F4)-O-CH2CH2-O-]n-T*wherein n is 8 (as average), T is -F or -OCH2CH2OP(=O)(OH)2 and T* is OP(=O)(OH)2

[0179] Step 1 and Step 2 were performed as disclosed above in Example 1.

[0180] Step 3 - Synthesis of phosphoric ester from oligomer obtained in step 2

[0181] One pot reaction between the oligomer obtained in step 2 and Pyrophosphoric acid molar in molar ratio 1.5 for hydroxy equivalent. The reaction was run at a temperature of 80°C for 6 hours, in bis(trifluoromethyl)benzene. At the end of the reaction mass was treated with chloridric acid at 10% and isobutyl alcohol. The polymer was recovered as residual of bottom phase after removal of the solvents and aqueous phase.

[0182] Example 5

[0183] 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 - OCH2CH2OC(=O)NHCH2CH2CH2Si(OCH2CH3)3 and T* is - C(=O)NHCH2CH2CH2Si(OCH2CH3)3

[0184] Step 1 - Preparation of compound (PX-II)

[0185] Nucleophilic reaction of 2,2 difluoroethanol with hexafluorobenzene in ratio 1:9 catalyzed by potassium tert-butyl oxide added in 1.2 ratio equivalent to 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.

[0186] Step 2SSPI 2024 / 031

[0187] 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 1.02 eq 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.

[0188] Step 3 - Synthesis of urethane silane from oligomer obtained in step 2

[0189] 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 (2.5x10’3eq for 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.

[0190] Example 6

[0191] 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 - OCH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 and T* is C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0192] Step 1 and Step 2 were performed as disclosed above in Example 5.

[0193] Step 3 - Synthesis of urethane allyl from oligomer obtained in step 2

[0194] One pot reaction between the oligomer obtained in step 2 and Allyl isocyanate in ratio 1:1.05 catalyzed by catalytic quantity of dibutyltin dilaurate (2.5x10’3eq for hydroxy equivalent)). The reaction was run at a temperature of 60°C for 8 hours, methyl ethyl ketone. At the end of the reaction methanol is added to quench the residual of allyl isocyanate. The reaction mass wasSSPI 2024 / 031cooled down and the polymer was recovered as residual after removal of the solvents.

[0195] Example 7

[0196] 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),? is -F or -OCH2CH2OC(=O)NHCH2CH=CH2and T* is C(=O)NHCH2CH=CH2

[0197] Step 1 and Step 2 were performed as disclosed above in Example 5.

[0198] Step 3 - Synthesis of urethane allyl from oligomer obtained in step 2

[0199] One pot reaction between the oligomer obtained in step 2 and Allyl isocyanate in ratio 1:1.05 catalyzed by catalytic quantity of dibutyltin dilaurate (2.5x10’3eq for 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 allyl isocyanate. The reaction mass was cooled down and the polymer was recovered as residual after removal of the solvents.

[0200] Example 8

[0201] 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 -OCH2CH2OP(=O)(OH)2 and T* is OP(=O)(OH)2

[0202] Step 1 and Step 2 were performed as disclosed above in Example 5.

[0203] Step 3 - Synthesis of phosphoric ester from oligomer obtained in step 2

[0204] One pot reaction between the oligomer obtained in step 2 and Pyrophosphoric acid molar in molar ratio 1.5 for hydroxy equivalent. The reaction was run at a temperature of 80°C for 6 hours, in bis(trifluoromethyl)benzene. At the end of the reaction mass was treated withSSPI 2024 / 031chloridric acid at 10% and isobutyl alcohol. The polymer was recovered as residual of bottom phase after removal of the solvents and aqueous phase.

[0205] Example 9

[0206] 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 - OCH2CH2OCH2CH2OC(=O)NHCH2CH2CH2Si(OCH2CH3)3 and T* is - C(=O)NHCH2CH2CH2Si(OCH2CH3)3

[0207] 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 ratio 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.

[0208] Step 2

[0209] 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.SSPI 2024 / 031

[0210] Step 3 - Synthesis of urethane silane from oligomer obtained in step 2

[0211] 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 (2.5x10’3eq for 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.

Claims

SSPI 2024 / 031Claims1. A polymer [polymer (Pder)] complying with formula (Ider):( Ider) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -O-Yn]P**}n-T’ whereinp is an integer from 1 to 65;Ar is a group of formulain whichHal is selected from Cl, Br or I, andr 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, andt 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, andm is an integer equal to 1 or 2;p* is 0 or an integer from 1 to 65SSPI 2024 / 031Ar* is a group of formulain whichq* 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, andt* is 0 or 1,Hal is selected from Cl, Br or I, andr* 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, andm* is an integer equal to 1 or 2;p** is 0 an integer from 1 to 65;Ar** is a group of formulain whichq** 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 / 031linear or branched alkylene chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, andt** is 0 or 1,Hal is selected from Cl, Br or I, andr** 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, andm** 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)whereineach 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, andu is an integer from 1 to 20;(Y-ll)SSPI 2024 / 031 Re2whereinRe1 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, M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5, preferably 3 or 4, more preferably 4; (Y-III)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 a group RT0-Y-whereinY is any of Y1, Y2or Ynas defined above;RTis selected from:SSPI 2024 / 031A) -C(=O)-NH-R10-Si(R11)n(OR12)3-nwhereineach of R11and R12is independently selected from linear or branched C1-C6alkyl group,R10is a linear or branched Ci-Ce alkylene group, andn is an integer selected from 1 or 2, preferably 1;B) -C(=O)-NH-R20-R21-CRH=CH2whereinRH is -H or a linear or branched C1-C6alkyl group;R20is a C1-C6alkyl group, optionally substituted with a group comprising a tri-alkoxy-silyl group;R21is a sigma bond or a divalent group of formula -O-C(=O)-, -O-C(=O)-NH-CO-, -O-C(=O)-RA-wherein RAis selected from the group consisting of (RA-I) and (RA-I I):(RA-i)[O-C(=O) -CRH=CH2]j5— N-RB-O-C(=O) - H I[O-C(=O) -CRH=CH2]j5whereineach of j5 is independently 0 or 1 andRBis a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S;(RA-II)SSPI 2024 / 031{O-[C(=O)]j6-CRH=CH2}j7H H I / N O-RB'-O - [C(=O)]j6-RB* J {O-[C(=O)]j6-CRH=CH2}j7whereinj6 is 0 or 1;each of j7 is independently 0 or 1;RB’ is a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S; andRB* has the same meanings defined above for RB’ or it is a group of formula (RB-I):wherein U is selected from the groups (U-I) to (U-III)(U-I) -O-C(=O)-CRH=CH2(U-II) -O-C(=O)-NH-CO-CRH=CH2(U-III) -O-C(=O)-RA-CRH=CH2wherein RAand RH are as defined above;C) -C(=O)-C(R30)=C(R31)(R32)herein each of R30, R31and R32is independently H or -CH3:D) -CH2-CH=CH2E) -CH2-CH(O)CH2 with (0) being an epoxide group;F) linear or branched alkyl chain comprising at least one -OH group, said alkyl chain being optionally substituted with at least one alkyl group having from 1 to 3 carbon atoms;G) sulfonate group;SSPI 2024 / 031H) phosphorus-containing derivative such as -O-P(=O)(OH)2 or esters thereof;I) -C6H4(NO2);andT’ is selected from a group selected from:(T’-ii) -(ArAA)m-O-YAA-RdAAwhereinArAAcomplies with any one of Ar, Ar* and Ar** as defined above,m is an integer equal to 1 or 2,YAAcomplies with any one of Y1, Y2or Ynas defined above, andRdAAhas the same meanings provided above for RT.

2. The polymer (Pder) according to Claim 1, 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 alkyl chain having from 1 to 3 carbon atoms, andu 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,SSPI 2024 / 031X10 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.

3. The polymer (Pder) according to any one of Claims 1 and 2, wherein Y1, Y2and Ynare equal to each other.

4. The polymer (Pder) according to any one of Claims 1 to 3, wherein at least two of Y1, Y2and Ynare different from each other.

5. The polymer (Pder) according to any one of Claims 1 to 4, wherein in said polymer (Pder):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 as defined in Claim 1, andT’ is selected from a hydrogen atom, or a group selected from:(T’-ii) -(ArAA)m-O-YAA-RdAAwhereinArAAcomplies 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 andRdAAis as defined in Claim 1.

6. The polymer (Pder) according to Claim 5, wherein in said polymer (Pder):T* is selected from group RT0-Y- wherein Y is any of Y1, Y2or Ynas defined in Claim 1 and RTis as defined in Claim 1, andT’ is selected from a hydrogen atom, or a group selected from:SSPI 2024 / 031(T’-ii) -(ArAA)m— O-YAA-RdAAwhereinArAAcomplies 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 and RdAAis as defined in Claim 1.

7. Polymer (Pder) of formula (I Ider):(I Ider) T*- {[(Ar)m-O-Yx]px}n -T’whereinT*, T’ and Ar have the same meaning as for the polymer of formula (Ider), 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 to 1 or 50;pxis an integer from 2 to 66,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 (Ider).

8. A method [method (Pder)] for the manufacture of polymer (Pder) according to any one of Claims 1 to 6, wherein said method comprises the steps of: - providing a polymer (POH) complying with formula (I)(I) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -0-Yn]P**}n-T whereinp is an integer from 1 to 65;Ar is a group of formulaSSPI 2024 / 031in whichHal is selected from Cl, Br or I, andr 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 alkyenel chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom, more preferably selected from fluorine, andt 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, andm is an integer equal to 1 or 2;p* is 0 or an integer from 1 to 65Ar* is a group of formulain whichq* 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, optionallySSPI 2024 / 031substituted with at least one halogen atom, more preferably selected from fluorine, andt* is 0 or 1,Hal is selected from Cl, Br or I, andr* 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, andm* is an integer equal to 1 or 2;p** is 0 an integer from 1 to 65;Ar** is a group of formulain whichq** 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, andt** is 0 or 1,Hal is selected from Cl, Br or I, andr** 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, andm** is an integer equal to 1 or 2;SSPI 2024 / 031n 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)whereineach 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, andu 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, M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5, preferably 3 or 4, more preferably 4; (Y-III)SSPI 2024 / 031whereinX10 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 fluorine atom or a group RT0-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-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 a hydrogen atom,- reacting said polymer (POH) with at least one compound selected from the group comprising, more preferably consisting of:a) O=C=N-R10-Si(R11)n(OR12)3-nwhereineach of R11and R12is independently selected from linear or branched C1-C6alkyl group,SSPI 2024 / 031R10is a linear or branched Ci-Ce alkylene group, andn is an integer selected from 1 or 2, preferably 1;b) O=C=N-R20-R21-CRH=CH2whereinRH is -H or a linear or branched C1-C6alkyl group;R20is a Ci-C6alkylene group, optionally substituted with a group comprising a tri-alkoxy-silyl group;R21is a sigma bond or a divalent group of formula -O-C(=O)-, -O-C(=O)-NH-CO-, -O-C(=O)-RA-wherein RAis selected from the group consisting of (RA-I) and (RA-I I):(RA-I)[O-C(=O) -CRH=CH2]j5— N— RB-O-C(=O)- H I[O-C(=O) -CRH=CH2]j5whereineach of j5 is independently 0 or 1 andRBis a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S;(RA-II){O-[C(=O)]j6-CRH=CH2}j7H H I—N— O—RB'—O—[C(=O)]j6-RB' J {O-[C(=O)]J6-CRH=CH2}j7whereinSSPI 2024 / 031j6 is 0 or 1;each of j7 is independently 0 or 1;RB’ is a divalent, trivalent or tetravalent group selected from the group consisting of C1-C10 aliphatic group; C3-C12 cycloaliphatic group; C5-C14 aromatic or alkylaromatic group, optionally comprising at least one heteroatom selected from N, 0 and S; andRB* has the same meanings defined above for RB’ or it is a group of formula (RB-I):U-OCH2CH2-O-wherein U is selected from the groups (U-I) to (U-III)(U-I) -O-C(=O)-CRH=CH2(U-II) -O-C(=O)-NH-CO-CRH=CH2(U-III) -O-C(=O)-RA-CRH=CH2wherein RAand RH are as defined above;c) X-C(=O)-C(R30)=C(R31)(R32)wherein X is halogen atom, more preferably Cl,each of R30, R31and R32is independently H or -CH3:d) X-CH2-CH=CH2wherein X is a halogen atom selected from Cl, B r, I or a leaving group for a nucleophilic substitution reaction:e) epichlorohydrin or epibromohydrin;f) epoxy-containing compound;g) sulfonyl halide;h) phosphorus pentoxide, pirophosphoric acid, polyphosphoric acid and the like;SSPI 2024 / 031i) 1-halo-nitrobenzene;thus obtaining polymer (Pder).

9. The method (Pder) according to Claim 8, wherein said polymer (POH) is prepared via a method [method (P)] comprising:(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 (POH) complying with formula (I):(I) T*- { [(Ar)m -O-Y1]P- [(Ar*)m* -O-Y2]P* - [(Ar**)m** -O-Yn]P**}n-T’ whereinp is an integer from 1 to 65;Ar is a group of formulain whichHal is selected from Cl, Br or I, andr 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, andSSPI 2024 / 031t 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, andm is an integer equal to 1 or 2;p* is 0 or an integer from 1 to 65Ar* is a group of formula(Hal)rin whichq* 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, andt* is 0 or 1,Hal is selected from Cl, Br or I, andr* 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, andm* is an integer equal to 1 or 2;p** is 0 an integer from 1 to 65;SSPI 2024 / 031Ar** is a group of formulain whichq** 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, andt** is 0 or 1,Hal is selected from Cl, Br or I, andr** 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, andm** 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)whereinSSPI 2024 / 031each 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, andu 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, M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5, preferably 3 or 4, more preferably 4; (Y-III)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, andQ1 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;whereinT* 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) -RaA-(ArA)m-RbA-RfAwherein RaAand RbAeach independently is selected from a sigma bond, a linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,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) -RaAA-(ArAA)m-RbAA-O-YAA-RdAAwhereineach of RaAAand RbAAis independently selected from sigma bond or a linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,ArAAcomplies 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 carbonSSPI 2024 / 031atoms;(v) treating said mixture (M1) with an aqueous acid solution,thus obtaining polymer (POH).

10. The method (P) according to Claim 9, wherein in step (iii) said compound (HOY-OH) is in molar excess to said compound (PX), preferably the molar ratio being from 50:1 to 1.01:1, and step (v) is not performed.

11. The method (P) according to any one of Claims 8 to 10, wherein said compound (HO-Y-OH) is selected from those complying with the following formulae:(y-i)whereineach 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, andu 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,SSPI 2024 / 031Rf1 and Rf2 each independently is a hydrogen atom or a linear or branched alkyl chain from 1 to 6 carbon atoms,M1 is a group -CJH2J- wherein J is from 1 to 4 M2 is a group -CKH2K- wherein K is from 1 to 4 and J+K is from 3 to 5; (y-III)whereinX10 is selected from a hydrogen atom or a linear or branched alkyl chain having from 1 to 6, andv 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 Q1 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-Ra-(Ar)m-Rb-O-Y-HwhereinRa, Rb, Ar and m have the meanings defined in Claim 1 andY complies with any one of formulae (Y-l), (Y-ll), (Y-lll) defined in Claim 1.

12. The method (P) according to any one of Claims 8 to 11, 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-SSPI 2024 / 031fluoro-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-Ra’-(ArA)m-Rb’-O-Y-Ra”-(ArA)m-Rb”- Z’whereineach of Ra’, Rb’, Ra” and Rb” is independently selected from sigma bond or a linear or branched alkyl chain having from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,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 alkyl 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 )s wherein 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; ora compound of formula (PX-II):(PX-II)[(Rg)t-H]ain whichq is an integer from 1 to 2,t is 1 andRg is a chain -OR2- wherein R2 is a linear or branched alkyl chain having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom,SSPI 2024 / 031more preferably selected from fluorine.

13. A composition comprising at least one polymer (Pder) according to any one of Claims 1 to 7 and at least one solvent, preferably a non-fluorinated solvent.

14. Use of polymer (Pder) according to any one of Claims 1 to 7 as additive, or as polymer modifier.

15. Use of the composition according to Claim 13, for coating a substrate selected from glass, plastic and metal.

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