Description

Perfluoropolyether polymers

Cross reference to related patent application

[0001] This patent application claims priority filed on 28 September 2022 in Europe with Nr 22198267.1 , the whole content of this application being incorporated herein by reference for all purposes.

Technical field

[0002] The present invention relates to new copolymers comprising (per)fluoropolyether chains and functional groups.

Background Art

[0003] (Per)fluoropolyether polymers (in the following referred to as “PFPE polymers”) have been long known as base oils or as additives in several lubricant applications.

[0004] Several syntheses of PFPE polymers have been disclosed in the art. The first synthesis of unspecified perfluorinated polyether mixtures was reported in 1953, when an oily product was obtained in the course of photoligomerization of hexafluoropropene. Since then, a number of different perfluorinated polyethers have been synthesised and described in literature.

[0005] US 4,500,739 (in the name of Montedison) discloses the reaction of a peroxidic PFPE with - among the others - perfluoro butadiene (Group II of fluoroolefins). Example 4 discloses the reaction with perfluoro butadiene, with a large excess of perfluorinated bis-olefin, resulting in pendant unsaturated groups along the macromolecular chain such that the reaction can further proceed in the presence of hexamethylenediamine.

[0006] US 8,258,090 (in the name of Solvay Solexis S.p.A.) discloses fluorinated lubricants of formula:

(I) T-O-[A-B]Z-[A’-B’]Z-A-T’ wherein

T and T’ are C1.3 perfluoroalkyl or Ci-e alkyl, A and A’ are a perfluoropolyether chain, B derives from two different olefins, of which at least one homopolymerizable by radical route, of formula:

(la) -[(CR1 R ₂ -CR3R4)j-(CR5R6-CR ₇ R8)j’]- wherein j is from 1 to 5, j’ is from 0 to 4 and the sum of j+j’ is between 2 and 5;

R1 to Rs are halogen, H, Ci-e (per)haloalkyl, Ci-e alkyl, Ci-e oxy(per)fluoroalkyl; z is higher than or equal to 2, z’ is an integer and the sum of z and z’ is such that the number average molecular weight of the polymer of formula (I) is in the range 500-500 000;

B’ is (la) but at least one of R1 to Rs has a meaning different from that in B.

[0007] This patent discloses block copolymers characterised by a linear backbone, without any branching. Indeed, no branching is obtained within B, notably comprising (per)fluoropolyether chains. [0008] PFPE polymers comprising functional groups along the backbone have been disclosed in the art, being useful as reactive intermediate compounds and as additives.

[0009] Perfluoropolyether polymers obtained from the reaction of polyperoxidic perfluoropolyether and fluorinated olefin in the presence of U.V. radiation have been disclosed in US 4,500,739 (Montedison S.p.A., February 19, 1985).

[0010] US 6,403,539 (Ausimont S.p.A., June 11, 2002) discloses perfluoro-polyether polymers containing sulphonyl fluoride groups pending along the backbone. This patent application discloses a process wherein the sulphonyl fluoride-containing monomer is contemporaneously fed with an O2 flow in a liquid reaction medium, thus obtaining perfluoropolyethers containing in the chain peroxidic groups. However, the presence of the peroxidic groups is not desired for safety concerns. Hence, this patent application discloses that to obtain non peroxidic products without chain scission, the peroxidic perfluoropolyethers are subjected to a thermal treatment at temperatures generally in the range from 150°C to 250°C or to a photochemical treatment, optionally in the presence of a solvent. The process herein disclosed - in which the functionalized monomer is added at the beginning of the polymerization - does not allow the synthesis of a polymer having segregated blocks from the functionalized monomer but rather it allows for the synthesis of a PFPE polymer having randomly distributed functional groups.

[0011] Polyfunctional (per)fluoropolyether polymers have been further disclosed in US 5,719,259 (E.l. DuPont de Nemours and Company, February 17, 1998), US 4,853,097 (Ausimont S.r.l., August 1 , 1989), US 5,104,911 (Ausimont S.r.l., April 14, 1992).

[0012] US 2011/0230631 (Solvay Solexis S.p.A, September 22, 2011) discloses (per)fluoropolyethers comprising at least one (per)fluoropolyoxyalkylene chain comprising at least one recurring unit of formula -CF2-CF(CF2O-SC>2F)-O-, wherein fluorosulfate group in brackets is a pendant group, which is subsequently reacted with a nucleophilic agent to provide functional groups, such as notably carboxylic acid, acyl fluoride, amide and esters.

[0013] CN 103724559 (ZHONGHAO CHENGUANG RES INST CHEMICAL IND, .April 16, 2014) discloses a method comprising placing the perfluoropolyether peroxide prepared by a photo-oxidation method in an inert fluorine-containing solvent, introducing perfluoro-olefin under an ultraviolet irradiation condition, and reacting the perfluoro-olefin with the peroxide to form a stable perfluoropolyether compound.

[0014] WO 2019/048394 (Solvay Specialty Polymers Italy S.p.A., March 14, 2019) discloses polyfunctional perfluoropolyether derivatives including a plurality of ionisable groups selected from the group consisting of -SOsXa, -PChXa and - COOXa, wherein Xa is H, ammonium group or a monovalent metal.

Summary of invention

[0015] The Applicant faced the problem of providing new functional PFPE copolymers characterised by an increased viscosity (as measured by complex viscosity at 0.1 rad/s at 25°C), while maintaining low glass transition temperature (Tg) and still being in the liquid state at room temperature.

[0016] Furthermore, the new functional PFPE copolymers according to the present invention are characterised by an increased viscosity index, notably between 40°C and 100°C.

[0017] In addition and more surprisingly, the new functional PFPE copolymers according to the present invention are characterised by an increased thermal stability (as shown in the examples via TGA analysis), which makes them suitable for use in harsh environments and applications. [0018] Furthermore, the new PFPE copolymers comprising functional groups are suitable for use as additives in different technical fields, including as anti-rust, anti-wear, to increase compatibility among base oils and thickeners and other ingredients dispersed in such base oils. Furthermore, as will be explained in more detail in the detailed description, the functional groups can be further reacted or derivatized to provide further functionalized derivatives.

Detailed description of the invention

[0019] For the purpose of the present description and of the following claims:

- 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 acronym “PFPE” stands for "perfluoropolyether” and, when used as substantive, is intended to mean either the singular or the plural form, depending on the context;

- the term “functionality (F)” is intended to indicate the amount of functional groups in the copolymer according to the present invention as measured via NMR or titration.

[0020] In a first aspect, the present invention relates to a block copolymer [copolymer (P)] comprising a first and a second perfluoropolyether chain [PFPE chain] each having two chain ends, wherein the first chain end of each one of said first and second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from a perfluorinated linear or branched alkyl chain comprising from 1 to 6 carbon atoms, -C(=O)F and -OC(=O)F, and the second chain ends of said first and second PFPE chain are bonded to each other via:

- at least one first block [block (1)] complying with formula (I): wherein m is 0 or an integer from 1 to 5, preferably from 1 to 2;

Rs to Rs, each independently, is selected in the group comprising, preferably consisting of, -F, perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms, and group of formula (II):

(II) -R ₂₀ -(X) _y wherein

R20 is a sigma bond, or linear or branched perfluoroalkyl chain comprising from 1 to 12 carbon atoms, preferably comprising and/or interrupted by at least one oxygen atom,

X is a functional group, preferably selected from: -SO2F, -SO3H, -COOH, -COF, - CN, -Br and -CONH2; and y is an integer equal to 1 or 2; with the proviso that in formula (I), at least one, preferably one, of Rs to Rs is group of formula (II);

- at least one second block [block (2)] complying with formula (III):

(III) wherein n is an integer from 1 to 3;

Ri to R4, each independently, is selected in the group comprising, preferably consisting of, fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms, group of formula (IV):

(IV) -(Rio)t[C(Rii)(Ri ₂ )-C(Ri3)(Ri ₄ )(Ri5)]z wherein

R10 is an oxygen atom, or a bi-/tri-/tetravalent perfluorinated alkyl chain comprising from 1 to 24 carbon atoms and being optionally interrupted by at least one oxygen atom, t is zero or 1 , z is an integer from 1 to 3,

R11 to R15, each independently, is selected in the group comprising, preferably consisting of: fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms and group of formula (V): -[(A) _a -(B) _b -(F) _f ] _u -(A)-T (V) wherein u is zero or an integer from 1 to 50;

T is a perfluorinated alkyl group; a is zero or 1 , each A is a PFPE chain; b is zero or an integer from 1 to 3,

B is a block of formula (III*):

-[C(RIA)(R ₂ A)-C(R ₃ )(R ₄ )]- (III*) wherein

RIA to R4A each independently has the meaning defined above for each of R1 to R4, respectively; f is 0 or an integer from 1 to 5, preferably from 1 to 2;

F is a block of formula (I*):

-[C(R5A)(R6A)-C(R ₇ A)(R ₈ A)]- wherein

Rs" to R ₈ A, each independently, has the meaning provided above for each of Rs to R ₈ , respectively; with the proviso that : in said formula (III), at least one of R1 to R4 is a group of formula (IV), in said formula (III*), at least one of R to R4A is a group of formula (IV) in said formula (IV), one of Rn or R12 and one of R13 to R15, is a group of formula (V), in said formula (V), the recurring units (A), (B) and (F) are statistically distributed; and

- optionally, at least one third block [block (3)] comprising a PFPE chain; with the proviso that, in copolymer (P): the sum of (m+f) is at least 1 , preferably from 1 to 100; the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11, even more preferably from 1 to 9; and said at least one block (1), said at least one block (2), and when present said at least one block (3) are statistically distributed.

[0021] It will be understood by those skilled in the art that said first chain end of said first and second PFPE chain correspond to the two chain ends of copolymer (P).

[0022] Preferably, in copolymer (P), each of said PFPE chain is a fully fluorinated chain [chain (Rf)] comprising, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:

(i) -CFXO-, wherein X is -F or -CF3;

(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is -F or -CF3, with the proviso that at least one of X is -F;

(iii) -CF2CF2CF2O-;

(iv) -CF2CF2CF2CF2O-;

(v) -(CF2)j-CFZ-O- wherein j is an integer from 0 to 3 and Z is a group of general formula -O-R(f. _a )-T, wherein R(f. _a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the following : -CFXO- , -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of X being independently -F or -CFs and T being a C1-C3 perfluoroalkyl alkyl chain.

[0023] Preferably, chain (Rf) complies with the following formula:

(Rf-I)

-[(CFX ¹ O) _g i(CFX ² CFX ³ O) _g 2(CF2CF2CF2O) _g 3(CF2CF2CF2CF ₂ O) _g 4]- wherein

- X ¹ is independently selected from -F and -CF3,

- X ² , X ³ , equal or different from each other and at each occurrence, are independently -F, -CF3, with the proviso that at least one of X is -F;

- g1, g2 , g3, and g4, equal or different from each other, are independently integers >0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100; should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.

[0024] More preferably, chain (Rf) is selected from chains of formula:

(Rf-IIA) -[(CF2CF ₂ O) _a i(CF ₂ O) _a 2]- wherein:

- a1 and a2 are independently integers > 0 such that the number average molecular weight is between 400 and 100,000 as determined via NMR, preferably between 400 and 50,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10;

(Rf-I IB) -[(CF2CF2O) _b i(CF2O) _b 2(CF(CF3)O) _b 3(CF ₂ CF(CF3)O) _b 4]- wherein: b1, b2, b3, b4, are independently integers > 0 such that the number average molecular weight is between 400 and 100,000 as determined via NMR, preferably between 400 and 50,000; preferably each of b1 , b2, b3, b4 are > 0;

(Rf-IIC) -[(CF ₂ CF2O)cl(CF2O)c2(CF2(CF2)cwCF ₂ O)c3]- wherein: cw = 1 or 2; c1 , c2, and c3 are independently integers > 0 chosen so that the number average molecular weight is between 400 and 100,000 as determined via NMR, preferably between 400 and 50,000; preferably c1, c2 and c3 are all > 0, with the ratio c3/(c1+c2) being generally lower than 0.2.

[0025] Still more preferably, chain (Rf) complies with formula (Rf-I 11) here below: (Rf-lll)-[(CF2CF2O) _a i(CF ₂ O) _a 2]- wherein:

- a1 , and a2 are integers > 0 such that the number average molecular weight is between 400 and 100,000 as determined via NMR, preferably between 400 and 50,000, with the ratio a1/a2 being generally between 0.1 and 10, more preferably between 0.2 and 5.

[0026] Preferably, in block (1), m is 0 or an integer from 1 to 2.

[0027] Preferably, in block (1), one of Rs to Rs is a group of formula (II).

[0028] Preferably, in block (1), R20 is a sigma bond or a group selected from those of formula (R2o-i) to (R2o-iv) as represented hereinafter:

(R20-D

-(CF ₂ )S1-O-(CF ₂ )S2- wherein each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3;

(R20-H)

-O-(CF ₂ )S3- wherein s3 is an integer from 1 to 6, preferably from 1 to 5;

(R2o-iii)

-O-R400-O-R401- wherein

R400 is a linear or branched perfluorinated alkyl chain comprising from 1 to 6, preferably from 1 to 3, carbon atoms, and more preferably complying with formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF ₂ CF(CF ₃ )-; and

R401 is a linear or branched perfluorinated alkyl chain comprising from 1 to 3 carbon atoms, more preferably complying with formula -CF2-, -CF2CF2-, - CF(CF ₂ )-;

(R20-1V) wherein

Rsoo is a linear perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms and optionally interrupted by at least one oxygen atom;

R501 is a chain of formula -OR503 wherein R503 is a linear perfluorinated alkyl chain comprising from 1 to 3 carbon atoms;

R502 is a linear perfluorinated alkyl chain comprising from 1 to 4 carbon atoms and optionally interrupted by at least one oxygen atom; each of R501 and R502 bonding a group X as defined above in formula (II).

[0029] Preferably, in block (2) and formula (IV), R complies with one of the following formulae:

(Rw-i) -(CF ₂ )d(O)e(CF2O)fRcF(O)e*(CF ₂ )d*(CF2O)f* wherein each of d, d*, e, e*, f and f* is independently zero or 1 and

RCF is either a perfluoroalkyl chain comprising from 1 to 12, preferably from 1 to 8 carbon atoms, optionally interrupted by one or more oxygen atoms

(Rw-ii) -O-(C3F6O CF ₂ )i-(C3F ₆ O) _r O- wherein h = j and h + j is from 2 to 6, and i is from 2 to 6.

[0030] In a second aspect, the present invention relates to a process [process (P)] for the manufacture of copolymer (P) as defined above. The process according to the present invention can be easily scaled up from laboratory scale to pilot and industrial scale.

[0031] Advantageously, copolymer (P) of the present invention is prepared via a process (P) comprising at least the following steps :

(a) contacting:

- at least one perfluoropolyether polymer comprising at least one peroxidic group [PFPE peroxy];

- at least one perfluorinated compound of formula (X-p):

(X-p) wherein each of R21 to R23 is independently -F or perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms,

R20, X and y are as defined above for formula (II);

- at least one perfluorinated compound of formula (XX-p):

(XX-p) wherein each of R21 to R23 are as defined above in formula (X-p), each of R31 to R33 is independently -F or perfluorinated alkyl group having from 1 to 6 carbon atoms,

R10 is an oxygen atom, a perfluorinated alkyl chain comprising from 1 to 24 carbon atoms, optionally interrupted by at least one oxygen atom, t is zero or 1 ; each of z* and z** is independently 1 or 2; and

(b) reacting said PFPE peroxy, said at least one compound of formula (X-p) and said at least one compound of formula (XX-p) in the presence of UV radiation or under heating.

[0032] In step (a), the order in which the reactants are added is not limited. Accordingly, the PFPE peroxy, the compound of formula (X-p) and the compound of formula (XX-p) can be supplied to the reaction environment in any order.

[0033] Before step (a), the PFPE peroxy can be subjected to partial reduction ofthe peroxide bonds, for example by chemical reduction or UV treatment or thermal treatment.

[0034] Preferably, said PFPE peroxy is a peroxidic perfluoropolyether polymer having two chain ends, each comprising a group selected from a linear or branched perfluorinated alkyl chain comprising from 1 to 6 carbon atoms or-C(=O)F, said two chain ends being bonded to opposite sides of a perfluoropolyether chain [chain (Rf)] comprising, preferably consisting of, repeating units (R°) being independently selected from the group consisting of formulae (i) to (v) as above defined and having a peroxidic content (PO), defined as grams of active oxygen (Mw = 16) in 100 g of PFPE peroxy between 0.1 and 4, preferably between 0.1 and 3.5.

[0035] Preferably, in said PFPE peroxy, chain (Rf) complies with formulae (Rf-I), or (Rf- IIA), (Rf-IIB), (Rf-IIC) or (Rf-lll) as defined above.

[0036] Preferably, in said at least one compound of formula (X-p), each of R21, R22 and R23 is -F. [0037] Preferably, in said compound (X-p), R20 is a sigma bond or a group selected from those of formula (R2o-i) to (R2o-iv) as defined hereinafter: (R20-D

-(CF ₂ )S1-O-(CF ₂ )S2- wherein each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3;

(R20-H)

-O-(CF ₂ )S3- wherein s3 is an integer from 1 to 6, preferably from 1 to 5;

(R2o-iii)

-O-R400-O-R401- wherein

R400 is a linear or branched perfluorinated alkyl chain comprising from 1 to 6, preferably from 1 to 3, carbon atoms, and more preferably complying with formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF ₂ CF(CF ₃ )-; and

R401 is a linear or branched perfluorinated alkyl chain comprising from 1 to 3 carbon atoms, more preferably complying with formula -CF2-, -CF2CF2-, - CF(CF ₂ )-;

(R20-1V) wherein

R500 is a linear perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms and optionally interrupted by at least one oxygen atom;

R501 is a chain of formula -OR503 wherein R503 is a linear perfluorinated alkyl chain comprising from 1 to 3 carbon atoms;

R502 is a linear perfluorinated alkyl chain comprising from 1 to 4 carbon atoms and optionally interrupted by at least one oxygen atom; each of R501 and R502 bonding a group X as defined above.

[0038] Preferably, said at least one compound of formula (X-p) is selected in the group comprising, more preferably consisting of :

CF2=CFCF ₂ OCF2CF ₂ COOH

CF ₂ =CFOCF ₂ COOH

CF ₂ =CFO(CF ₂ ) ₅ COOH

CF2=CFOCF ₂ CF2OCF ₂ COOH

CF ₂ =CFOCF ₂ CF ₂ COOH

CF2=CFCF ₂ OCF2CF ₂ COF

CF ₂ =CFOCF ₂ COF

CF ₂ =CFO(CF ₂ ) ₃ OCF(CF ₃ )COF

CF ₂ =CFO(CF ₂ ) ₅ COF

CF2=CFOCF ₂ CF(CF ₃ )OCF2CF ₂ CN

CF ₂ =CFOCF ₂ CN

CF ₂ =CFO(CF ₂ ) ₅ CN

CF ₂ =CFO(CF ₂ ) ₃ OCF(CF ₃ )CN

CF2=CFCF ₂ OCF2CF ₂ CN

CF ₂ =CFOCF ₂ CF ₂ Br

CF2=CFCF ₂ OCF2CF ₂ Br

CF2=CFOCF ₂ CF(CF ₃ )OCF2CF ₂ Br

CF ₂ =CFCF2OCF2CF ₂ CONH2 CF ₂ =CFOCF ₂ CONH ₂

CF ₂ =CFOCF ₂ CF ₂ CONH ₂

CF ₂ =CFOCF ₂ CF ₂ SO ₂ F

CF ₂ =CFSO ₂ F

CF ₂ =CFOCF ₂ CF(SO ₂ F) ₂

CF ₂ =CFOCF ₂ CF(CF ₂ OCF2CF2SO ₂ F)(OCF ₂ CF ₂ SO ₂ F)

CF ₂ =CFOCF ₂ CF(CF ₂ CF ₂ SO ₂ F)(OCF ₂ CF ₂ SO ₂ F) CF ₂ =CFOCF ₂ OCF ₂ CF(CF ₂ OCF ₂ CF ₂ SO ₂ F)(SO ₂ F).

[0039] Some exemplary compounds of formula (X-p) and the preparation thereof are provided in WO 03/106515 (in the name of Daikin Ind.), JP 2017-025242 (in the name of ASAHI GLASS CO., LTD.) and in US 2008/138685 (in the name of AGC Inc.).

[0040] Preferably, in said compound of formula (XX-p), when t is 1, the one, two, three or four unsaturated moieties are bonded to the same or different atoms, preferably carbon atoms, belonging to R .

[0041] Preferably, said at least one compound of formula (XX-p) complies with the following formula: CF ₂ =CF(Rio) _t CF=CF ₂ wherein t is zero or 1 , and

Rio complies with one of the following formulae:

(Rw-i) -(CF ₂ )d(O)e(CF ₂ O)fRcF(O)e*(CF ₂ ) _d *(CF2O)f* wherein each of d, d*, e, e*, f and f* is independently zero or 1 and

RCF is either a perfluoroalkyl chain comprising from 1 to 12, preferably from 1 to 8 carbon atoms, optionally interrupted by one or more oxygen atoms (Rw-ii) -O-(C3F6O)h-(CF ₂ ) _i -(C ₃ F6O)j-O- wherein h = j and h + j is from 2 to 6, and i is from 2 to 6.

[0042] According to a particularly preferred embodiment, said at least one compound of formula (XX-p) complies with the following formula: CF ₂ =CF(Rio) _t CF=CF ₂ wherein t is 1 and

Rio complies with formula:

(Rw-i) -(CF ₂ )d(O)e(CF ₂ O)fRcF(O)e*(CF ₂ ) _d *(CF2O)f* wherein d, f, d* and f* are zero, e and e* are 1 , and RCF is a linear perfluoroalkyl chain comprising from 1 to 10, preferably from 1 to 8 carbon atoms.

[0043] Preferably, said compound of formula (XX-p) is selected from the group comprising, more preferably consisting of: CF ₂ =CFCF=CF ₂ CF ₂ =CFOCF=CF ₂ CF ₂ =CFCF ₂ OCF ₂ CF=CF ₂ CF ₂ =CFO-(CF ₂ ) ₃ CF=CF ₂ CF ₂ =CFCF ₂ O(CF ₂ ) ₃ OCF ₂ -CF=CF ₂ CF ₂ =CFCF ₂ CF=CF ₂ CF ₂ =CF(CF ₂ ) ₂ CF=CF ₂ CF ₂ =CF(CF ₂ ) ₃ CF=CF ₂ CF ₂ =CF(CF ₂ ) ₄ CF=CF ₂ CF ₂ =CFOCF ₂ OCF=CF ₂ CF ₂ =CFO(CF ₂ ) ₂ OCF=CF ₂ CF ₂ =CFO(CF ₂ ) ₃ OCF=CF ₂ CF ₂ =CFO(CF ₂ ) ₄ OCF=CF ₂ CF ₂ =CF(CF ₂ ) ₂ OCF=CF ₂ wherein h and j are the same and their sum is from 2 to 6 and i is from 2 to 6.

[0044] The amount of each of said at least one compound (X-p) and compound (XX-p) is not limited.

[0045] For example, the equivalents of double bonds of said compound (X-p) to the equivalents of peroxidic groups preferably range from 1 :100 to 5000:100.

[0046] Also, the equivalents of double bonds of said compound (XX-p) to the equivalents of peroxidic groups preferably range from 1 :100 to 100:100.

[0047] Step (a) of process (P) can be advantageously performed by contacting said PFPE peroxy with one compound of formula (X-p).

[0048] Alternatively, said step (a) can be performed by contacting said PFPE peroxy with two or more compounds of formula (X-p).

[0049] Step (a) of process (P) can be advantageously performed by contacting said PFPE peroxy with one compound of formula (XX-p).

[0050] Alternatively, said step (a) can be performed by contacting said PFPE peroxy with two or more compounds of formula (XX-p).

[0051] Step (a) and step (b) can be performed in the presence of a fluorinated solvent.

[0052] Preferably said fluorinated solvent is selected in the group comprising: perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, hydrofluoropolyethers.

[0053] Preferably, step (b) is performed in the presence of UV radiation for a time from 2 to 150 hours, more preferably from 5 to 100 hours.

[0054] Preferably, step (b) is performed in the presence of UV radiation at a temperature from -60°C to +150°C, more preferably from -20°C to +100°C and even more preferably from 0°C to 60°C.

[0055] As an alternative, step (b) can be performed under thermal treatment, preferably by heating at a temperature from 150 °C to 250 °C.

[0056] Preferably, said step (b) is performed in an inert atmosphere.

[0057] Preferably, said process (P) comprises after step (b), step (c) of removal of the solvent and/or step (d) of fractionation.

[0058] Said step (c) of removal of the solvent can be carried out by evaporation, for example by distillation under vacuum.

[0059] Said step (d) of fractionation can be performed via solvent extraction, using supercritical CO ₂ , hexafluoroxylene or hydrofluorocarbons as solvents, and mixtures thereof when the fractionation step is performed via precipitation fractionation. Supercritical CO ₂ is preferred.

[0060] In a third aspect, the present invention relates to copolymer (P) obtained via process (P) as described above.

[0061] Advantageously, the functional groups introduced as pendant groups in block (1) of copolymer (P), such as notably -SO ₂ F, -SO ₃ H, -COOH, -COF, -CN, -Br and - CONH ₂ , as well as the functional groups at the chain ends of copolymer (P), such as notably -COF and -OC(O)F, can be properly reacted to obtain other different functional groups.

[0062] The expression “can be reacted” is intended to indicate that such functional groups can for example be salified, hydrolyzed, reduced, oxidised, or undergo a different chemical reaction to provide functional group(s) endowed with the desired reactivity, taking into consideration the final use of copolymer (P).

[0063] Advantageously, copolymer (PF) according to the present invention is obtained from process (P) as described above, which further comprises after said step (b) , at least one step (c) comprising at least one of salification, hydrolyzation, oxidation, reduction or another chemical reaction capable of providing functional group(s) of interest.

[0064] The present invention further encompasses copolymer (PF) obtained at the end of step (c) of process (P).

[0065] Hence, the present invention encompasses a block copolymer [copolymer (F»] comprising a first and a second perfluoropolyether chain [PFPE chain] each having two chain ends, wherein the first chain end of each one of said firstand second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from a perfluorinated linear or branched alkyl chain comprising from 1 to 6 carbon atoms, -COOH and salts thereof with an organic cation, preferably onium cation, more preferably ammonium, or an inorganic cation, preferably an alkaline metal, more preferably Na ⁺ , K ⁺ ; -COOR wherein R is a linear or branched alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably 1 carbon atoms; -COF; -CONH2; - CON(R ₃ OO)(R3OI) wherein each of R300 and R301 have the same meanings defined for R; -(R)cOH with c being 0 or 1 and R being as defined above; -C(O)-O-C(O)R with R being as defined above; with the proviso that (i) at least one chain end of said first and second PFPE chain comprises a group different from a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms and (ii) when one chain end comprises group -COF, the other chain end does not comprises a perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms or-COF; and the second chain ends of said first and second PFPE chain are bonded to each other via:

- at least one first block [block (1)] complying with formula (I): wherein m, R5 to Rs, have the meanings defined above;

- at least one second block [block (2)] complying with formula (III):

(HI) wherein n, R1 to R4, have the meanings defined above; and

- optionally, at least one third block [block (3)] comprising a PFPE chain; with the proviso that, in copolymer (PF): the sum of (m+f) is at least 1 , preferably from 1 to 100; the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11 , even more preferably from 1 to 9; and said at least one block (1), said at least one block (2), and, when present, said at least one block (3) are statistically distributed.

[0066] In another aspect, the present invention relates to a mixture [mixture (PF)] comprising two or more copolymers (PF) as defined above.

[0067] While purification steps can be performed after any of step (b) and/or step (c) of said process (P), mixtures of copolymers (P) or copolymers (PF) according to the present invention are typically obtained.

[0068] Thus, in a further aspect, the present invention relates to a mixture [mixture (P)] comprising two or more copolymers (P) as defined above.

[0069] It will be clear to those skilled in the art that mixture (P) is obtained via process (P) as described above.

[0070] Advantageously, said mixture (P) can be subjected to one or more purification steps (also referred to as “fractionation” steps) as disclosed above, thus obtaining separate copolymers (P) characterised by different viscosities and/or number average molecular weights as measured by ¹⁹ F-NMR and/or functionality (F), preferably from 3 to 102.

[0071] Said mixtures can further contain the PFPE peroxy used as starting material and/or mixtures of copolymers (P) containing peroxy groups [copolymer (Po-o)] and/or mixtures of copolymers (PF) containing peroxy groups [copolymers (PF-O-O)] can be obtained.

[0072] Advantageously, copolymer (Po-o) and/or copolymer (PF-O-O) can be isolated and used as intermediate in other processes.

[0073] While the amount of peroxy groups that can be present in the mixture containing copolymer (P) or copolymer (PF) of the present invention can be up to 99% based on the amount of the starting peroxy groups in the PFPE peroxy, depending on the final application the amount of said peroxy groups can be properly adjusted for example up to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5%.

[0074] More preferably, the amount of said peroxy groups is up to 1 , even more preferably up to 0.5 % and still more preferably up to 0.1%.

[0075] In another aspect, the present invention relates to a block copolymer [copolymer (Po-o)] comprising a first and a second perfluoropolyether chain [PFPE chain], wherein each of said first and second PFPE chain is a chain (Rf) as defined above or is a chain (Rfo-o) wherein (Rfo-o) is a repeating units complying with any one of formulae (i) to (v) as defined above for (R°) and having a peroxidic content (PO), defined as grams of active oxygen (Mw = 16) in 100 g of PFPE peroxy between 0.1 and 4, preferably between 0.1 and 3.5, each of said first and second PFPE chain having two chain ends, wherein the first chain end of each one of said first and second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from a perfluorinated linear or branched alkyl chain comprising from 1 to 6 carbon atoms, -C(=O)F and -OC(=O)F; and the second chain ends of said first and second PFPE chain are bonded to each other via:

- at least one first block [block (1)] complying with formula (I) as defined above;

- at least one second block [block (2)] complying with formula (III) as defined above; and/or

- optionally, at least one third block [block (3)] comprising a PFPE chain as defined above; with the proviso that

* in copolymer (Po-o)

- said block (1), said block (2) and when present said block (3) are statistically distributed,

- the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11 , even more preferably from 1 to 9;

- the sum of (m+f) is at least 1, preferably from 1 to 100.

[0076] In a still another embodiment, the present invention relates to a block copolymer [copolymer (PF-O-O)] comprising comprising a first and a second perfluoropolyether chain [PFPE chain], wherein each of said first and second PFPE chain is a chain (Rf) as defined above or is a chain (Rfo-o) wherein (Rfo-o) is a repeating units complying with any one of formulae (i) to (v) as defined above for (R°) and having a peroxidic content (PO), defined as grams of active oxygen (Mw = 16) in 100 g of PFPE peroxy between 0.1 and 4, preferably between 0.1 and 3.5, each of said first and second PFPE chain having two chain ends, wherein the first chain end of each one of said first and second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from a perfluorinated linear or branched alkyl chain comprising from 1 to 6 carbon atoms, -COOH and salts thereof with an organic cation, preferably onium cation, more preferably ammonium, or an inorganic cation, preferably an alkaline metal, more preferably Na ⁺ , K ⁺ ; -COOR with R being as defined above; -COF; -CON(R3OO)(RSOI) wherein each of R300 and R301 are a hydrogen atom or have the same meanings defined for R; -(R)cOH with c being 0 or 1 and R being as defined above; -C(O)-O-C(O)R with R being as defined above; -Br; -CN2; and the second chain ends of said first and second PFPE chain are bonded to each other via:

- at least one first block [block (1)] complying with formula (I) as defined above;

- at least one second block [block (2)] complying with formula (III) as defined above; and/or

- optionally, at least one third block [block (3)] comprising a PFPE chain as defined above; with the proviso that

* in copolymer (PF-O-O)

- said block (1), said block (2), and when present said block (3) are statistically distributed,

- the sum of (n+b) is at least 1, preferably from 1 to 15, more preferably from 1 to 11 , even more preferably from 1 to 9;

- the sum of (m+f) is at least 1, preferably from 1 to 100.

[0077] In still another aspect, the present invention related to a mixture [mixture (M1)] comprising at least one copolymer (P) as defined above, and at least one of said PFPE peroxy used as starting material and/or one or more of copolymers (Po-o).

[0078] In still another aspect, the present invention relates to a mixture [mixture (M2)] comprising at least one copolymer (PF) as defined above, and at least one of at least one of copolymer (P) as defined above, said PFPE peroxy used as starting material, said one or more copolymers (Po-o), and/or said one or more copolymers (PF-O-O).

[0079] Copolymer (P) and/or copolymer (PF) according to the present invention can be used for different applications in several industries, wherein outstanding resistance and durability at high temperature and harsh environments is required. For example, copolymer (P) and/or copolymer (PF) can be used as base oils as lubricants. Alternatively, copolymer (P) and/or copolymer (PF) can be used as additives in halogenated oils and/or greases.

[0080] To this aim and advantageously, the copolymers according to the present invention as well as the mixtures described herein, are in the liquid state at room temperature, or even at temperatures lower than room temperature, with advantages in handling and storage of the copolymers.

[0081] Hence, advantageously, copolymer (P) is in the liquid state at room temperature.

[0082] Also, advantageously, copolymer (PF) is in the liquid state at room temperature.

[0083] In addition, each of copolymer (Po-o) and copolymer (PF-O-O) as well as each of mixture (M1) and mixture (M2) is in the liquid state at room temperature.

[0084] In addition, each of copolymer (Po-o) and copolymer (PF-O-O) as well as each of mixture (M1) and mixture (M2) is in the liquid state at room temperature.

[0085] 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.

[0086] The invention will be hereinafter illustrated in greater detail by means of the Examples contained in the following Experimental Section; the Examples are merely illustrative and are by no means to be interpreted as limiting the scope of the invention.

Experimental section

[0087] Materials

[0088] Peroxidic perfluoropolyether oil was obtained by Solvay Specialty Polymers Italy S.p.A., complying with formula XO-(CF ₂ CF ₂ O)ai (CF ₂ O) _a2 (O) _h -X’ wherein

X and X’ were -CF3, -CF ₂ COF, -COF and having the following properties: Mn = 31 990 g/mol; P.O.= 1.61%; a1/a2 = 1.0

[0089] The following was purchased by Anles LTD and used as such: (8CNVE) CF ₂ =CFOCF ₂ CF(CF ₃ )OCF ₂ CF ₂ CN (PBVE) CF ₂ =CFOCF ₂ CF ₂ CF ₂ OCF=CF ₂

[0090] Perfluorinated solvents Galden(R) HT200 and Galden(R) D100, as well as tetrafluoroethylene (TFE) and perfluoro-methylvinyl-ether (PMVE), and perfluorinated sulfonyl vinyl ether (VEFS) CF ₂ =CFOCF ₂ CF ₂ SO ₂ F were obtained by Solvay Specialty Polymers Italy S.p.A..

[0091] Methods:

[0092] ¹⁹ F-NMR-Varian Mercury 300 MHz spectrometer working for the ¹⁹ F nucleus was used to obtain the structure, molecular weight, chain end composition of the perfluoropolyether oils. The ¹⁹ F-NMR spectrum was obtained on pure samples using CFC as internal reference.

[0093] The peroxidic content (PO) was expressed as grams of peroxidic oxygen per 100 g of polymer. The analysis of the peroxide content was carried out by iodometric titration using a Mettler DL40 device equipped with platinum electrode. The sensitivity limit for the PO determination was 0.0002%.

[0094] The complex viscosity was measured by means of frequency sweep tests, using an MCR502 Anton-Paar rheometer with parallel plate geometry (25mm diameter). The viscosity was measured in this way at 25°C and 100°C and its value at 0.1 rad/s of oscillation is reported.

[0095] Viscosity index was calculated according to ASTM D2270 measuring viscosity at about 40°C and about 100°C.

[0096] TGA analysis was performed with a TGA 5500 analyzer from TA Instruments with a heating rate of 10°C/min in an oxygen-containing atmosphere (air), measuring the temperatures at which a loss of 10% and 50% of the weight of the samples occurred. [0097] FT-IR spectra were acquired on a Thermo Fisher IS10 Spectrometer on liquid samples as thin films on KBr.

[0098] GPC analyses to measure the average molecular weights (Mw and Mn) were performed on a Waters GPC equipped with an Rl detector and operating at 35°C. All average molecular weight results are reported compared to perfluoropolyethers linear neutral internal standards.

[0099] Example 1 - PFPE copolymers with 8CNVE, PBVE

[00100] 249.2 g of the peroxidic perfluoropolyether oil described above were charged in a 1500 mL stirred cylindrical photochemical reactor equipped with a high pressure mercury lamp model HANAU TQ150, a thermocouple, a condenser and a mechanical stirrer.

[00101] The oil was diluted with 1876 g of Galden(R) D100. Next, 19.4 g of 8CNVE and 2.5 g of PBVE were added to the reactor. The mixture was then purged with nitrogen under stirring, and the UV lamp was switched on for 42 hours at 20°C. After this time, the lamp was switched off and the reaction mixture was transferred into a 2-L round bottom flask. The mixture was stripped at 120°C for 6h under reduced pressure (0.1 mbar).

[00102] 265 g of copolymer in the form of a clear viscous oil were obtained as residue.

[00103] ¹⁹ F-NMR analysis confirmed the incorporation of 8CNVE in the copolymer at a concentration of 8.1 weight %.

[00104] The copolymer had a2/a1 = 0.9 and X and X’= -CF3, -CF2COF and -OCOF.

[00105] The introduction of the -CN functional groups was also confirmed by FT-IR spectroscopy measurements, confirming the presence of the peak at 2269 cm ^-1 .

[00106] Comparative Example 1 - PFPE copolymers with 8CNVE

[00107] 252.1 g of the peroxidic perfluoropolyether oil described above were charged in the same reactor as Example 1. The oil was diluted with 1873 g of Galden(R) HT200. Next, 19.45 g of 8CNVE were added to the reactor and the mixture was purged with nitrogen. The mixture was then purged with nitrogen under stirring, and the UV lamp was switched on for 41 hours at 20°C.

[00108] After this time, the lamp was switched off and the reaction mixture was transferred into a 2-L round bottom flask. The mixture was stripped at 120°C for 6h under reduced pressure (0.1 mbar).

[00109] 224.5 g of copolymer in the form of a clear viscous oil were obtained as residue.

[00110] ¹⁹ F-NMR analysis of the product confirmed the copolymer structure as follows, with 8CNVE at a concentration of 8.0 wt.%: XO-(CF ₂ CF ₂ O)a2(CF ₂ O)ai (CF ₂ CFO(CF ₂ CF(CF ₃ )OCF ₂ CF ₂ CN)) _m -X’ where a2/a1 = 0.9, m = 6.4

X and X’= -CF ₃ , -CF ₂ COF and -OCOF.

[00111] Number average molecular weight (M _n ) = 31100 g/mol.

[00112] The introduction of the -CN functional groups was also confirmed by FT-IR spectroscopy measurements, confirming the presence of the peak at 2269 cm ^-1 .

[00113] Example 2 - PFPE copolymers with VEFS and PBVE

[00114] 250.5 g of the peroxidic perfluoropolyether oil described above were charged in the same reactor as Example 1. The oil was diluted with 1877 g of Galden(R) HT200. Next, 14.0 g of VEFS and 2.5 g of PBVE were added to the reactor and the mixture was purged with nitrogen. The UV lamp was then switched on and the reaction was conducted at 20°C for 7h. After this time, the UV lamp was switched off. [00115] The obtained solution was distilled at 240°C for 4h in a round bottom flask equipped with a magnetic stirrer in order to remove the solvent and unreacted monomer traces. The distillation was conducted first at atmospheric pressure, then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[00116] 220.3 g of copolymer in the form of a clear viscous oil were obtained as residue.

[00117] ¹⁹ F-NMR analysis confirmed the absence of residual peroxide units and the incorporation of VEFS in the copolymer at a concentration of 5.8 weight %.

[00118] The copolymer had a2/a1 = 1.0 and X and X’= -CF3, -CF2COF and -OCOF.

[00119] Comparative Example 2a - PFPE copolymers with VEFS

[00120] 250 g of the peroxidic perfluoropolyether oil described above were charged in the same reactor as Example 1. The oil was diluted with 1875 g of Galden(R) HT200. Next, 14.0 g of VEFS were added to the reactor and the mixture was purged with nitrogen. The UV lamp was then switched on and the reaction was conducted at 20°C for 7h. After this time, the UV lamp was switched off.

[00121] The obtained solution was distilled at 240°C for 4h in a round bottom flask equipped with a magnetic stirrer in order to remove the solvent and unreacted monomer traces. The distillation was conducted first at atmospheric pressure, then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[00122] 215.9 g of copolymer in the form of a clear oil were obtained as residue.

[00123] ¹⁹ F-NMR analysis of the product confirmed the absence of residual peroxide, the incorporation of VEFS at a concentration of 6.0 wt.% and the structure:

XO-(CF ₂ CF ₂ O)a2(CF ₂ O)a2(CF ₂ CFO(CF ₂ CF ₂ SO ₂ F)) _m -X’ where a2/a1 = 1.0, m = 5.6 on average

X and X’= -CF ₃ , -CF ₂ COF and -OCOF; and number average molecular weight (Mn) = 30400 g/mol.

[00124] Comparative Example 2b - PFPE copolymer with VEFS, TFE, PMVE and PBVE

[00125] 250.3 g of the peroxidic perfluoropolyether oil described above were charged in a 1500 mL stirred cylindrical photochemical reactor equipped with a high pressure mercury lamp model HANAU TQ150, a thermocouple, a condenser and a mechanical stirrer.

[00126] The oil was diluted with 1876 g of Galden(R) HT200 and then 23.0 g of VEFS and 1.1 g of PBVE were added to the reactor.

[00127] The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor, at a rate of 14.6 and 8.0 g/h, respectively. After the flow started, the UV lamp was switched on and the reaction was conducted at 20°C for 7h. After this time the olefin flows were interrupted, the UV lamp was switched off.

[00128] The obtained solution was distilled at 240°C for 4h in a round bottom flask equipped with a magnetic stirrer in order to remove the solvent and unreacted monomer traces. The distillation was conducted first at atmospheric pressure, then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[00129] 298.0 g of copolymer in the form of a clear viscous oil were obtained as residue, which was analysed by iodometric titration to confirm the complete removal of the peroxide units.

[00130] ¹⁹ F-NMR analysis confirmed the absence of residual peroxide units.

[00131] The incorporation of VEFS, TFE and MVE in the copolymer was at a concentration respectively of 5.3, 13.9 and 9.8 weight %. [00132] The copolymer had a1/a2 = 0.9 and X and X’= -CF3, -CF2COF and -OCOF.

[00133] The properties of the copolymers according to the invention and of comparison are summarised in Table 1 below.

(*) comparative n/p = not performed

[00134] The polymers of Example 2 and Comparative Example 2a were also subjected to TGA analysis to determine their weight loss under heating conditions. The results are reported in the following Table 2.

Table 2

(*) comparative