Copolymers containing (per)fluoropolyether chains

Abstract

The present patent application relates to block copolymers containing (per)fluoropolyether chains which are useful as lubricants and which are characterized by increased viscosity.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED PATENT APPLICATIONS This application claims priority to European Patent Application Publication No. 21183256.3, filed July 1, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present patent application relates to copolymers containing (per)fluoropolyether chains, characterized by an increased viscosity. [Background technology]

[0003] Lubrication is a key factor in maintaining machinery in proper operating condition. Machine elements such as bearings, pins, shafts, gears and joints require proper lubrication between their moving surfaces to reduce friction, prevent contamination, reduce wear and dissipate heat. Improper lubrication can lead to premature wear of components and failure of components or systems.

[0004] (Per)fluoropolyether polymers (hereinafter referred to as "PFPE polymers") have long been known as additives in base oils or in some lubricating applications.

[0005] Several syntheses of PFPE polymers have been disclosed in the art. The first synthesis of an unspecified perfluorinated polyether mixture was reported in 1953, where an oily product was obtained during the photo-oligomerization of hexafluoropropene. Since then, a large number of different perfluorinated polyethers have been synthesized and described in the literature.

[0006] U.S. Patent No. 4,500,739 (Montedison) discloses the reaction of peroxidic PFPEs with, among other things, perfluorobutadiene (a Group II fluoroolefin). Example 4 discloses the reaction of perfluorobutadiene with a large excess of perfluorinated bisolefins, resulting in pendant unsaturated groups along the polymer chain, so that the reaction can proceed further in the presence of hexamethylenediamine.

[0007] US Patent No. 8,258,090B2 (in the name of Solvay Solexis SpA) discloses a compound of the formula: (I) TO-[AB]z-[A'-B']z'-AT (In the formula, T and T' are C 1-3 Perfluoroalkyl or C 1-6 is alkyl, A and A are perfluoropolyether chains, B has the following formula: (Ia)-[(CR1R2-CR3R4) j -(CR5R6-CR7R8) j’ ]- (In the formula, j is 1 to 5, j' is 0 to 4, and the sum of j+j' is 2 to 5, R1 to R8 are halogen, H, C 1-6 (Per)Haloalkyl, C 1-6 Alkyl, C 1-6 oxy(per)fluoroalkyl are derived from two different olefins, at least one of which is homopolymerizable by a radical pathway, z is 2 or more, 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 of 500 to 500,000; B' is (Ia), but at least one of R1 to R8 has a different meaning from B. The patent discloses block copolymers characterized by a linear backbone without branching. In fact, no branching is obtained within B, which in particular contains (per)fluoropolyether chains.

[0008] Polymers obtained using PFPE polymer units have been disclosed in the art, including crosslinked fluoroelastomers. In this regard, SPKrukovsky et al.-J of Fluorine Chemistry 96(1999)31-33 disclosed the copolymerization of perfluoroalkylene oxides containing peroxide groups in the chain with perfluorodivinyl ethers under UV irradiation and heating to obtain crosslinked polymers called elastomers. This document does not disclose the amounts of reactants, nor does it mention the preparation method of polymers suitable for use in lubricants. Summary of the Invention

[0009] While recent research and development has focused on monofunctional and / or difunctional (per)fluoropolyether (PFPE) polymers, the Applicant has recognized that a need remains to provide neutral PFPE polymers that can be used as lubricants.

[0010] Applicant was faced with the problem of providing new neutral PFPE polymers characterized by an increased viscosity (measured by complex viscosity at 0.1 rad / s at 25° C.) while maintaining a low glass transition temperature (Tg) and still remaining in a liquid state at room temperature.

[0011] The Applicant has surprisingly found that neutral branched (per)fluoropolyether polymers characterized by increased viscosity with increasing number average molecular weight can be provided by a process which is easy to carry out on an industrial scale.

[0012] Advantageously, this process allows for the production of neutral (per)fluoropolyether polymers with high thermal stability while maintaining low glass transition temperatures and good viscosity index (ASTM D2270), making such polymers particularly useful as lubricants in harsh environments, including, for example, applications requiring a wide range of operating temperatures or high heat generation.

[0013] In a first aspect, the present invention relates to a block copolymer [copolymer (P)] comprising first and second (per)fluoropolyether chains [PFPE chains] each having two chain ends, wherein the first chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group and the second chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group. - Formula (I): [ka] (In the formula, n is 0 or an integer from 1 to 3; R1 to R4 each independently represent a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, or a group represented by formula (II): (II)-(R 10 ) t [C(R 11 )(R 12 )-C(R 13 )(R 14 )(R 15 )] z (In the formula, R 10 is an oxygen atom or a di / tri / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or including at least one oxygen atom; t is 0 or 1; z is an integer from 1 to 3; R 11 ~ 15 are each independently selected from the group consisting of, preferably including, a fluorine atom and a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms. and the group of formula (III): -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T (III) (In the formula, a^ is 0 or 1, v^ is 0 or an integer from 1 to 3; L^ is 0 or an integer from 1 to 250; u^ is 0 or an integer from 1 to 50; A^ is a PFPE chain; B^ is the formula: -[C(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- (In the formula, R 1^ ~R 4^ each independently has the meaning defined above for each of R1 to R4) Based on E^ is the formula -(CR 100^ R 101^ CR 102^ R 103^ )- (In the formula, R 100^ and R 101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102^ and R 103^ is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CFOR 201 is a group of R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100^ and R 101^ One of the two and R 102^ and R 103^is a fluorine atom, and R 100^ and R 101^ The other and R 102^ and R 103^ and the other form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom. Based on C^ is a PFPE chain, and T is a perfluorinated alkyl group. (based on and preferably selected from the group consisting of A first block [Block (1)] according to - Formula (IV): -[(CR 1* R 2* CR 3* R 4* ) n* -(E) L ]- (IV) (In the formula, n* is 0 or an integer from 1 to 10, L is 0 or an integer from 1 to 250, R 1* ~R 4* are each selected in the group including, and preferably consisting of, a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, a group of formula (II) as defined above, E has the same meaning as provided for E^ above. The second block [Block(2)] follows are coupled to each other via In the copolymer (P), -- the sum of (n+n*+v^) is 1 to 15, preferably 1 to 11, more preferably 1 to 9; -- the sum of (L+L^) is 1 to 500, preferably 2 to 500, more preferably 2 to 300; -- the block (1) and the block (2) are statistically distributed; In the formula (I), -- at least one of R1 to R4 is a group of formula (II), -- R 11 or R 12 One of and R 13 ~R 15 is a group of formula (III) In the formula (III) and the formula (IV), -- The repeat units are statistically distributed, In the formula (III), -- if a is 1, then at least one of v^ and L^ is different from 0; and In the formula (IV), -- Provided that at least one of n* and L is different from 0.

[0014] In a second aspect, the present invention relates to a process [Process (P)] for producing a copolymer (P) as defined above.

[0015] Advantageously, the copolymer (P) according to the invention undergoes, in the presence of UV radiation or under heating, - at least one (per)fluoropolyether polymer containing peroxide groups [PFPEperoxy], - Formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 each independently represents a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms; R 10 is an oxygen atom or a perfluorinated alkyl chain containing 2 to 18 carbon atoms, optionally and preferably interrupted by and / or including at least one oxygen atom, t is 0 or 1, preferably 1; Each of z* and z** is independently 1 or 2. and, at least one compound [compound (O)], (i) fully halogenated olefins containing 2 to 8 carbon atoms, preferably tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE); (ii) CF2=CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"), a group containing a catenary oxygen atom, C-C 12 [(per)fluoro]-oxyalkyl, preferably the perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CFOR f2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), where R f2 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl and C2-C6 perfluoro-oxy-alkyl containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2) or -CF3(MOVE3), Formula (iii): [ka] (In the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from one another and are independently selected from the group consisting of C1-C6 perfluoro-alkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Perfluorodioxole having and at least one compound [compound (O)], preferably selected from the group consisting of: with the proviso that the amount of the compound of formula (Xp) is less than 5% by weight of the amount of PFPE peroxy.

[0016] In the process according to the invention, it is important that the amount of the compound of formula (Xp) is appropriately selected to be less than the amount of PFPE peroxy.

[0017] Advantageously, by selecting such an amount, more than 85%, more preferably more than 90%, and even more preferably more than 95% of the unsaturated moieties of the compound of formula (III) are reacted with at least one peroxy group of the starting PFPE peroxy to obtain a branched block copolymer (P) that does not contain unsaturated moieties as pendant groups (also called "functional groups").

[0018] The copolymer (P) advantageously does not contain pendant groups containing any moiety capable of undergoing further chemical reactions, in particular the copolymer (P) does not contain unsaturated moieties as pendant groups.

[0019] In a third aspect, the present invention relates to a copolymer (P) obtainable via the process (P) described above.

[0020] It will be clear to the skilled person that a purification step may be carried out at the end of said process (P), but the copolymer (P) according to the invention is obtained at the end of the process (P) as a mixture.

[0021] Thus, in a further aspect, the present invention relates to a mixture [mixture (P)] comprising two or more copolymers (P) as defined above.

[0022] It will be clear to a person skilled in the art that the mixture (P) is obtained via the above process (P).

[0023] Advantageously, said mixture (P) can be subjected to one or more purification steps (also called "fractionation" steps) to obtain distinct copolymers (P) characterized by different viscosities. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] For purposes of this description and the claims that follow: - the use of parentheses around a symbol or number identifying a formula, such as in a phrase like "polymer (P)", has the sole purpose of better distinguishing the symbol or number from the rest of the text, and therefore said parentheses may also be omitted, - the acronym "PFPE" stands for "(Per)Fluoropolyether" and, when used as a noun, is intended to mean either the singular or the plural, depending on the context; - the term "(per)fluoropolyether" is intended to denote fully or partially fluorinated polyethers.

[0025] Copolymer (P) Advantageously, said copolymer (P) is characterized by a complex viscosity, measured at 25° C. at 0.1 rad / s, of between 10 Pa·s and 2000 Pa·s.

[0026] It will be understood by those skilled in the art that the first chain ends of the first and second PFPE chains correspond to two chain ends of copolymer (P).

[0027] Preferably, the first chain ends of the first and second PFPE chains comprise a perfluorinated straight chain alkyl group having 1 to 3 carbon atoms.

[0028] Preferably, the perfluorinated alkyl groups are the same as each other.

[0029] Preferably, the first chain ends of the first and second PFPE chains and the T of formula (III) are equal to or different from each other and are perfluorinated alkyl groups having 1 to 3 carbon atoms.

[0030] Preferably, said first and second PFPE chains, said A' and said C' are equal to or different from each other.

[0031] Preferably, in the copolymer (P), the first PFPE chain is linked to the block (1) via a sigma bond or a group -(C)- selected from -CF2-, -CF2CF2- or -O-.

[0032] Preferably, in the copolymer (P), said block (2) is linked to said second PFPE chain via a sigma bond or a group -(C)- selected from -CF2-, -CF2CF2- or -O-.

[0033] Preferably, when both said block (1) and said block (2) are present, they are linked via a sigma bond.

[0034] Preferably, in said copolymer (P), each of said PFPE chains is a partially or fully fluorinated chain [chain (R f )], wherein the repeat units are independently selected from the group consisting of: (i) -CFXO- (wherein X is F or CF3), (ii) -CFXCFXO-, where X, which is equal or different at each occurrence, is F or CF, provided that at least one of X is -F; (iii) -CF2CF2CW2O- (wherein each of W, which is equal to or different from each other, is F, Cl, or H); (iv) -CF2CF2CF2CF2O-, (v)-(CF2) j -CFZ-O- (wherein j is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -T group, R (f-a)is a fluoropolyoxyalkene chain containing 0 to 10 repeat units selected from among -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, where each X is independently F or CF3, and T is a C1 to C3 perfluoroalkyl group.

[0035] Preferably, the chain (R f ) is expressed by the following formula: (R f -I)-[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- (In the formula, -X 1 is independently selected from -F and -CF3; - X's that are equal or different from each other and for each occurrence 2 , X 3 are independently -F, -CF3, with the proviso that at least one X is -F; - g1, g2, g3 and g4, which are equal to or different from each other, are independently integers equal to or greater than 0, whereby g1+g2+g3+g4 ranges from 2 to 300, preferably from 2 to 100, and when at least two of g1, g2, g3 and g4 are different from 0, the different repeat units are generally statistically distributed along the chain. Follow.

[0036] More preferably, the chain (R f ) is the formula: (R f -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]- (In the formula, a1 and a2 are independently an integer greater than or equal to 0, so that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, a1 and a2 are both preferably different from 0 and the ratio a1 / a2 is preferably comprised between 0.1 and 10, (R f -IIB)-[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]- (wherein b1, b2, b3, and b4 are independently integers of 0 or more, whereby the number average molecular weight is 400 to 10,000, preferably 400 to 5,000, and preferably b1 is 0, b2, b3, and b4 are greater than 0, and the ratio b4 / (b2+b3) is 1 or more), (R f -IIC)-[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]- (In the formula, cw=1 or 2, c1, c2 and c3 are independently selected to be integers equal to or greater than 0, such that the number average molecular weight is 400 to 10,000, preferably 400 to 5,000, and preferably c1, c2 and c3 are all greater than 0, and the ratio c3 / (c1+c2) is generally less than 0.2. The chain is selected from:

[0037] Even more preferably, the chain (R f ) is herein represented by the following formula (R f -III): (R f -III)-[(CF2CF2O) a1 (CF2O) a2 ]- (In the formula, a1 and a2 are integers greater than 0, so that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, and the ratio a1 / a2 is generally comprised between 0.1 and 10, more preferably between 0.2 and 5. Follow.

[0038] Preferably, in formula (I), at least one of the substituents R1 to R4 is a group of formula (II), and the other substituents are each independently selected from a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms, more preferably a fluorine atom or a perfluorinated alkyl chain having 1 carbon atom.

[0039] According to one embodiment, in formula (II), t is 0.

[0040] According to another embodiment, in formula (II), t is 1, and R 10 follows one of the following formulas: (R 10 -i)-(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, Each of d, d*, e, e*, f and f* is independently 0 or 1; and R CF is a perfluoroalkyl chain containing 1 to 12, preferably 1 to 8, carbon atoms, optionally interrupted by one or more oxygen atoms; (R 10 -ii) -O-(C3F6O) h -(CF2) i -(C3F6O) j -O- (wherein h=j, and h+j is 2 to 6, and i is 2 to 6).

[0041] According to this embodiment, preferably, R10 is the expression: (R 10 -i)-(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, d, f, d*, and f* are 0; e and e* are 1, and R CF is a linear perfluoroalkyl chain containing 1 to 10, preferably 1 to 8, carbon atoms. Follow.

[0042] Preferably, in formula (II), z is equal to 1 and R 10 is an oxygen atom or a divalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or including at least one oxygen atom.

[0043] Preferably, in formula (II), the substituent R 11 and R 12 is a group of formula (III) and the other substituent is selected from a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms, more preferably a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms. 11 and R 12 is a group of formula (III) and the other substituent is a fluorine atom.

[0044] Preferably, in formula (II), the substituent R 13 ~R 15 is a group of formula (III), and the other two substituents are independently selected from a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms, more preferably a fluorine atom or a perfluorinated alkyl chain having 1 carbon atom. More preferably, the two substituents are the same and are fluorine atoms.

[0045] Preferably, in formula (III), v^ is an integer of 1 to 3, more preferably 1.

[0046] In the formula (III), L^ is preferably an integer of 1-250, more preferably 2-250.

[0047] Preferably, in formula (III), -(E^) L^ - follows the formula: -(CR 100^ R 101^ CR 102^ R 103^ ) l^ -(CR 110^ R 111^ CR 112^ R 113^ ) m^ - (In the formula, l^ and m^ are each independently an integer of 1 to 250, more preferably 2 to 250, so that the sum of L+m is 2 to 250; R 100^ , R 101^ , R 110^ and R 111^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102^ , R 103^ , R 112^ and R 113^ is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CF2OR201, R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100^ and R 101^ One of the two and R 102^ and R 103^ is a fluorine atom, and R100^ and R 101^ The other and R 102^ and R 103^ and the other of the two together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, or R 110^ and R 111^ One of the two and R 112^ and R 113^ is a fluorine atom, and R 110^ and R 111^ The other and R 112^ and R 113^ and the other of the two form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, However, -(CR 100^ R 101^ CR 102^ R 103^ ) l^ -and-(CR 110^ R 111^ CR 112^ R 113^ ) m^ - are distinct from one another and statistically distributed).

[0048] Preferably, in formula (IV), n* is an integer of 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and still more preferably 1.

[0049] In the formula (IV), L is preferably an integer of 2-250.

[0050] Preferably, in formula (IV), -(E) L - follows the formula: -(CR 100 R 101 CR 102 R 103 ) l -(CR 110 R 111 CR 112 R 113 ) m - (In the formula, l and m are each independently an integer of 1 to 250, more preferably an integer of 2 to 250, so that the sum of L+m is 2 to 250; R 100 , R 101 , R 110 and R 111 are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102 , R 103 , R 112 and R 113 is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CF2OR201, R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100 and R 101 One of the two and R 102 and R 103 is a fluorine atom, and R 100 and R 101 The other and R 102 and R 103 and the other of the two together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, or R 110 and R 111 One of the two and R 112 and R 113 is a fluorine atom, and R 110 and R 111 The other and R 112 and R 113 and the other of the two form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, However, -(CR 100 R 101 CR 102 R 103 ) l - and (CR110 R 111 CR 112 R 113 ) m - are distinct from one another and statistically distributed).

[0051] In the formula (IV), l is preferably an integer of 1-250.

[0052] According to a first preferred embodiment, the copolymer (P) according to the invention (hereinafter referred to as "copolymer (P-1)") is a block copolymer comprising first and second PFPE chains each having two chain ends, wherein the first chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group, and the second chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group. - Formula (IV): -[(CR 1* R 2* CR 3* R 4* ) n* -(E) L ]- (IV) (In the formula, n* is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1; L is 0 or an integer of 1 to 250, more preferably an integer of 2 to 250; R 1* ~R 4* Each of the formula (II): (II)-(R 10 ) t [C(R 11 )(R 12 )-C(R 13 )(R 14 )(R 15 )] z (In the formula, R 10 is an oxygen atom or a di / tri / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or containing at least one oxygen atom; t is 0 or 1; z is an integer from 1 to 3; R 11 ~R 15 are each independently selected from the group consisting of, preferably including, a fluorine atom and a linear or branched perfluorinated alkyl group having 1 to 3 carbon atoms. and the group of formula (III): -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T (III) (In the formula, a^ is 0 or 1, v^ is 0 or an integer from 1 to 3; L^ is an integer of 1 to 250, preferably 2 to 250; u^ is an integer from 1 to 50, A^ is a PFPE chain B^ is the formula -[C(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- (In the formula, R 1^ ~R 4^ each independently has the meaning defined above for each of R1 to R4) Based on E^ is the formula -(CR 100^ R 101^ CR 102^ R 103^ )- (In the formula, R 100^ and R 101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102^ and R 103^ is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CFOR201 is a group of R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100^ and R 101^ One of the two and R 102^ and R 103^ is a fluorine atom, and R 100^ and R 101^ The other and R 102^ and R 103^ and the other form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom. Based on C^ is a PFPE chain, and T is a perfluorinated alkyl group; E has the same meaning as provided for E^ above. and preferably selected from the group consisting of are connected to each other via blocks according to In said copolymer (P-1), -- The sum of (n*+v^) is 1 to 15, -- the sum of (L+L^) is 2 to 500, preferably 3 to 300, more preferably 4 to 250, and - the repeat units of formulae (III) and (IV) are statistically distributed, and In formula (IV), -- R 1^ ~R 4^ at least one of is a group of formula (II) -- R 11 or R 12 One of and R 13 ~R 15 is a group of formula (III).

[0053] According to a second preferred embodiment, the copolymer (P) according to the invention (hereinafter referred to as "copolymer (P-2)") is a block copolymer comprising first and second PFPE chains each having two chain ends, wherein the first chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group, and the second chain ends of said first and second PFPE chains comprise a perfluorinated alkyl group. - Formula (I): [ka] (In the formula, n is an integer from 1 to 3, R1 to R4 each independently represent a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, or a group represented by formula (II): (II)-(R 10 ) t [C(R 11 )(R 12 )-C(R 13 )(R 14 )(R 15 )] z (In the formula, R 10 is an oxygen atom or a di / tri / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or containing at least one oxygen atom; t is 0 or 1; z is an integer from 1 to 3; R 11 ~R 15 are each independently selected from the group consisting of, preferably including, a fluorine atom and a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms. and the group of formula (III): -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T (III) (In the formula, a^ is 0 or 1, v^ is 0 or an integer from 1 to 3; L^ is an integer of 1 to 250, preferably 2 to 250; u^ is 0 or an integer from 1 to 50; A^ is a PFPE chain; B^ is the formula -[C(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- (In the formula, R 1^ ~R 4^ each independently has the meaning defined above for each of R1 to R4) Based on E^ is the formula -(CR 100^ R 101^ CR 102^ R 103^ )- (In the formula, R 100^ and R 101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102^ and R 103^ is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CFOR 201 is a group of R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100^ and R 101^ One of the two and R 102^ and R 103^ is a fluorine atom, and R 100^ and R 101^ The other and R 102^ and R 103^ and the other form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom. Based on C^ is a PFPE chain, and T is a perfluorinated alkyl group. and preferably selected from the group consisting of A first block [Block (1)] according to - Formula (IV): -[(CR 1* R 2* CR 3* R 4* ) n* -(E) L* ]- (IV) (In the formula, n* is an integer of 0 or 1 to 10, preferably 1 to 5, more preferably 1 to 3, and even more preferably 0 or 1; L* is 0 or an integer of 1 to 250, more preferably an integer of 2 to 250; R 1* ~R 4* are each selected in the group including, and preferably consisting of, a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, a group of formula (II) as defined above, E has the same meaning as provided for E^ above. The second block [Block(2)] follows are coupled to each other via In the copolymer (P-2), -- the sum of (n+n*+v) is 1 to 15, preferably 1 to 11, more preferably 1 to 9, -- the sum of (L^+L*) is 1 to 500, preferably 2 to 500, more preferably 3 to 300, and -- the block (1) and the block (2) are statistically distributed; In the formula (I), -- at least one of R1 to R4 is a group of formula (II), -- R 11 or R 12 One of and R 13 ~R 15 is a group of formula (III), and In the formula (III) and the formula (IV), the repeating units are statistically distributed, In the formula (III), -- if a is 1, then at least one of v^ and L^ is different from 0; and In the formula (IV), Provided that at least one of n* and L* is different from 0.

[0054] Preferably, in the copolymer (P-1) and the copolymer (P-2), each of the (E) and (E^) has the formula: -(CR 100 R 101 CR 102 R 103 ) L -(CR 110 R 111 CR 112 R 113 ) m - (In the formula, L and m are each independently an integer of 1 to 250, more preferably an integer of 2 to 250, so that the sum of L+m is 2 to 250; R 100 , R 101 , R 110 and R 111 are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; and R 102 , R 103 , R 112 and R 113 is a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CFOR 201 is a group of R 201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or R 100 and R 101 One of the two and R102 and R 103 is a fluorine atom, and R 100 and R 101 The other and R 102 and R 103 and the other of the two together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, or R 110 and R 111 One of the two and R 112 and R 113 is a fluorine atom, and R 110 and R 111 The other and R 112 and R 113 and the other of the two form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, However, -(CR 100 R 101 CR 102 R 103 ) L - and (CR 110 R 111 CR 112 R 113 ) m - are different from each other and statistically distributed) is the basis.

[0055] The copolymers (P) according to the invention can be advantageously prepared via a process which is easily scalable.

[0056] Preferably, in process (P) of the present invention, the amount of compound of formula (Xp) is less than 3% by weight, even more preferably less than 1% by weight of the amount of PFPE peroxy.

[0057] Preferably, said PFPE peroxy is a peroxidic (per)fluoropolyether polymer comprising a (per)fluoropolyether chain having two chain ends, each of said chain ends comprising a (per)fluorinated alkyl chain having 1 to 3 carbon atoms, optionally containing one or more chlorine atoms or a functional end group selected from acyl fluorides, fluoroformates and ketones, said chain ends being attached to opposite sides of said (per)fluoropolyether chain, said (per)fluoropolyether chain comprising, preferably consisting of, repeat units independently selected from the group consisting of formulas (Rf-i) to (Rf-v) defined above and having a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), of 0.1 to 4, preferably 0.1 to 3.5.

[0058] The PFPE peroxy can be used as is or can be subjected to partial reduction of the peroxide bonds, such as by chemical reduction, or UV treatment, or heat treatment.

[0059] Preferably, in said compound of formula (Xp), when t is 1, 1, 2, 3 or 4 unsaturated moieties are R 10 are bonded to the same or different atoms, preferably carbon atoms, belonging to

[0060] Preferably, said at least one compound of formula (Xp) conforms to the following formula: CF2=CF(R 10 ) t CF=CF2 (In the formula, t is 0 or 1, R 10 follows one of the following formulas: (R 10 -i)-(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, Each of d, d*, e, e*, f and f* is independently 0 or 1; and R CF is a perfluoroalkyl chain containing 1 to 12, preferably 1 to 8, carbon atoms, optionally interrupted by one or more oxygen atoms; (R 10 -ii) -O-(C3F6O) h -(CF2) i -(C3F6O) j -O- (wherein h=j, and h+j is 2 to 6, and i is 2 to 6).

[0061] Preferably, said compound of formula (Xp) is selected from the group comprising, more preferably consisting of: CF2=CFCF=CF2 CF2=CFOCF=CF2 CF2=CFCF2OCF2CF=CF2 CF2=CFO-(CF2)3CF=CF2 CF2=CFCF2O(CF2)3OCF2-CF=CF2 CF2=CFCF2CF=CF2 CF2=CF(CF2)2CF=CF2 CF2=CF(CF2)3CF=CF2 CF2=CF(CF2)4CF=CF2 CF2=CFOCF2OCF=CF2 CF2 = CFO(CF2)2OCF = CF2 CF2 = CFO(CF2)3OCF = CF2 CF2=CFO(CF2)4OCF=CF2 CF2=CF(CF2)2OCF=CF2 CF2=CF(CF2)3OCF=CF2 CF2=CF(CF2)4OCF=CF2 CF2=CFCF2O(CF2)2OCF2O-CF=CF2 CF2=CFCF2O(CF2)3OCF2O-CF=CF2 CF2=CFCF2O(CF2)4OCF2OCF=CF2 CF2=CFCF2O(CF2)6OCF2CF=CF2 CF2=CFO-CF2O-(CF2)2O-CF2O-CF=CF2 CF2=CFO-CF2O-(CF2)3O-CF2O-CF=CF2 CF2=CFO-CF2O-(CF2)4O-CF2O-CF=CF2 CF2=CFO-(CF2O)6-CF=CF2 CF2=CFO-(CF2CF2O)2-CF=CF2 CF2=CFO-(CF2CF2O)2-CF2OCF=CF2 CF2=CFO(C3F6O) h -(CF2) i -(C3F6O) j -OCF=CF2 (wherein h and j are the same, and Their sum is from 2 to 6, and i is from 2 to 6).

[0062] According to a particularly preferred embodiment, said at least one compound of formula (Xp) complies with the following formula: CF2=CF(R 10 ) t CF=CF2 (wherein t is 1, and R 10 follows the formula: (R 10 -i)-(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, d, f, d*, and f* are 0; e and e* are 1, and R CF is a linear perfluoroalkyl chain containing 1 to 10, preferably 1 to 8, carbon atoms).

[0063] According to a preferred embodiment, the process (P) of the invention is carried out by contacting said PFPE peroxy and said compound of formula (Xp) with at least two of said compounds (O).

[0064] Preferably, the first compound (O) is selected in the group including, and preferably consisting of, fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), etc. TFE and HFP are particularly preferred.

[0065] Preferably, the second compound (O) is (ii) CF2=CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"), a group C1-C 12 [(per)fluoro]-oxyalkyl, preferably the perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CFOR f2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), where R f2 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl and C2-C6 perfluoro-oxy-alkyl containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2) or -CF3(MOVE3), Formula (iii): [ka] (In the formula, R f3 , R f4 , R f5 , R f6are equal to or different from one another and are independently selected from the group consisting of C1 to C6 perfluoroalkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Particularly preferred are PAVE and MOVE in definition (i).

[0066] According to a first embodiment, said process [process (P1)] for producing a copolymer (P1) as defined above, said process (P1) comprising: a*) at least one peroxy(per)fluoropolyether polymer [PFPE peroxy], - Formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 each independently represents a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms; R 10 is an oxygen atom or a perfluorinated alkyl chain containing 2 to 18 carbon atoms, optionally and preferably interrupted by and / or including at least one oxygen atom, t is 0 or 1, preferably 1; Each of z* and z** is independently 1 or 2. and at least one perfluorinated compound of at least one compound [compound (O)], (i) fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE); (ii) CF2=CFOR f (In the formula, R fis a C1- to C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"), a group C1-C 12 [(per)fluoro]-oxyalkyl, preferably the perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CFOR f2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), where R f2 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl and C2-C6 perfluoro-oxy-alkyl containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2) or -CF3(MOVE3), Formula (iii): [ka] (In the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from one another and are independently selected from the group consisting of C1 to C6 perfluoroalkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Perfluorodioxole having At least one compound [compound (O)], preferably selected from the group consisting of: wherein the amount of the compound of formula (Xp) is less than 5% by weight of the amount of PFPE peroxy; b*) reacting said PFPE peroxy, said compound of formula (Xp) and said at least one compound (O) in the presence of UV irradiation or heat; c*) fluorination, thereby obtaining said copolymer (P1) Includes.

[0067] Preferably, said step (a*) comprises contacting said at least one PFPE peroxy with at least one compound of formula (Xp) and two of said compounds (O).

[0068] Preferably, the first compound (O) is selected in the group including, and preferably consisting of, fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), etc. TFE and HFP are particularly preferred.

[0069] Preferably, the second compound (O) is (ii) CF2=CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"), a group C1-C 12 [(per)fluoro]-oxyalkyl, preferably the perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CFOR f2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), where R f2 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl and C2-C6 perfluoro-oxy-alkyl containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2) or -CF3(MOVE3), Formula (iii): [ka] (In the formula, R f3 , R f4 , R f5 , R f6are equal to or different from one another and are independently selected from the group consisting of C1 to C6 perfluoroalkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Perfluorodioxole having PAVE and MOVE in definition (i) are particularly preferred.

[0070] Step (a*) and step (b*) may be carried out in the presence of a fluorinated solvent, preferably selected in the group comprising perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, hydrofluoropolyethers.

[0071] Preferably, step (b*) is carried out in the presence of UV radiation for a period between 2 and 60 hours.

[0072] Preferably, step (b*) is carried out at a temperature between -60°C and +60°C, more preferably between -20°C and +40°C, even more preferably between 0°C and 30°C, in the presence of UV radiation.

[0073] Alternatively, step (b*) may be carried out by heating under thermal treatment, preferably at a temperature between 100°C and 250°C.

[0074] It will be clear to the skilled person that the polymer obtained at the end of step (b*) has a peroxide content (PO) of less than 0.05, preferably less than 0.001.

[0075] Preferably, said step (c*) is carried out by treatment with fluorine in the presence of a stream of anhydrous nitrogen.

[0076] Preferably, said step (c*) is carried out in the presence of UV radiation or under heating. Alternatively, said step (c*) may be carried out as a chemically assisted fluorination.

[0077] Preferably, said process (P1) comprises, after step (c*), a step (d*) of removing the solvent and / or a step (e*) of fractionation.

[0078] Said step (d*) of removing the solvent can be carried out by evaporation, for example by distillation under vacuum.

[0079] Said step (e*) of fractionation, when the fractionation step is carried out by precipitation fractionation, can be carried out by solvent extraction using supercritical CO2, hexafluoroxylene or hydrofluorocarbons and mixtures thereof as solvents. Supercritical CO2 is preferred.

[0080] As explained above, purification steps can be carried out, but it will be clear to the skilled person that at the end of process (P1), the copolymer (P) according to the invention is obtained in the form of a mixture comprising two or more copolymers (P), each characterized by a different viscosity and / or molecular weight and / or substituents.

[0081] According to a second embodiment, the process for producing the copolymer (P2) [process (P2-a)] comprises the steps of: a') contacting at least one peroxy(per)fluoropolyether polymer [PFPEperoxy] with at least one compound (O) as defined above; b') reacting the PFPE peroxy and the compound (O) in the presence of UV irradiation or heat; c') stopping the UV irradiation or heating; d') The reaction mixture is reacted with a solution of formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 each independently represents a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms; R 10is an oxygen atom or a perfluorinated alkyl chain containing 2 to 18 carbon atoms, preferably interrupted by and / or including at least one oxygen atom, t is 0 or 1, preferably 1; Each of z* and z** is independently 1 or 2. wherein the amount of the compound of formula (Xp) is less than 5% by weight of the amount of PFPE peroxy; e') allowing the reaction to proceed in the presence of UV irradiation or heat; f') fluorination, thereby obtaining said copolymer (P2); Includes.

[0082] Preferably, said step (a') comprises contacting said at least one PFPE peroxy with at least two compounds (O).

[0083] Advantageously, the first compound (O) and the second compound (O) comply with the definitions given above.

[0084] Alternatively, the process for producing the copolymer (P2) [process (P2-b)] may comprise the steps of: a'') at least one peroxy(per)fluoropolyether polymer [PFPEperoxy] having the formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 each independently represents a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms; R 10 is an oxygen atom or a perfluorinated alkyl chain containing 2 to 18 carbon atoms, preferably interrupted by and / or including at least one oxygen atom, t is 0 or 1, preferably 1; Each of z* and z** is independently 1 or 2. wherein the amount of the compound of formula (Xp) is less than 5% by weight of the amount of PFPE peroxy; b'') reacting said PFPE peroxy and said compound of formula (Xp) in the presence of UV irradiation or heat; c'') stopping the UV irradiation or heating; d″) contacting the reaction mixture obtained in step c″) with at least one compound (O) as defined above; e″) allowing the reaction to proceed in the presence of UV irradiation or heat; f″) fluorination, thereby obtaining said copolymer (P2); Includes.

[0085] Preferably, said step (d'') comprises contacting the reaction mixture obtained in step (c'') with at least two compounds (O).

[0086] Advantageously, the first compound (O) and the second compound (O) comply with the definitions given above.

[0087] Steps (a') to (c') and steps (a'') to (c'') may be carried out in the presence of a fluorinated solvent.

[0088] Preferably, said fluorinated solvent is selected in the group comprising perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, hydrofluoropolyethers.

[0089] Preferably, step (b') and step (b'') are each independently carried out in the presence of UV radiation for a period of from 2 to 60 hours.

[0090] Preferably, step (b') and step (b'') are each independently carried out in the presence of UV irradiation at a temperature between -60°C and +60°C, more preferably between -20°C and +40°C, and even more preferably between 0°C and 30°C.

[0091] Alternatively, step (b') and step (b'') are each independently carried out by heating under thermal treatment, preferably at a temperature between 100°C and 250°C.

[0092] It will be clear to the person skilled in the art that the polymer obtained at the end of step (c') or step (c'') has a peroxide content (PO) of less than 0.05, preferably less than 0.001.

[0093] Preferably, steps (f') and (f'') are each carried out by treatment with fluorine in the presence of a stream of anhydrous nitrogen.

[0094] Preferably, said steps (f') and (f'') are carried out in the presence of UV irradiation or under heating, respectively. Alternatively, steps (f') and (f'') are each carried out as a chemically assisted fluorination.

[0095] Preferably, said process (P2-a) and said process (P2-b) comprise, after steps (f') and (f''), respectively, a step (g') and step (g'') of removing the solvent and / or a fractionation step (h') and step (h'').

[0096] Said step (g') or (g'') of removing the solvent may be carried out by evaporation, for example by distillation under vacuum.

[0097] Said step (h') or (h'') of fractionation can be carried out by solvent extraction using supercritical CO2, hexafluoroxylene or hydrofluorocarbons and mixtures thereof as solvents when the fractionation step is carried out by precipitation fractionation. Supercritical CO2 is preferred.

[0098] As explained above, purification steps can be carried out, but it will be clear to the skilled person that at the end of step (c) of processes (P), (P1), (P2-a) and (P2-b) or at the end of step (d) of process (P), the copolymer (P) according to the invention is obtained in the form of a mixture comprising two or more copolymers (P), each characterized by different viscosity, and / or molecular weight, and / or substituents, as a mixture (P).

[0099] The copolymers (P) are advantageously used as lubricants, especially in harsh environment applications, for example where they are exposed to a wide range of operating temperatures.

[0100] The copolymer (P) or the mixture (P) can be used as such or mixed with additives known to those skilled in the art of lubrication, thereby obtaining a composition [composition (CL)].

[0101] For example, the composition (CL) may comprise other suitable lubricants as base oils, such base oils being selected in the group comprising partially fluorinated, fully fluorinated and hydrogenated base oils, provided that said base oils are capable of forming a solution with the copolymer (P).

[0102] Non-limiting examples of fully fluorinated lubricant base oils are those identified as compounds (1)-(8) in EP 2100909A (SOLVAY SOLEXIS SpA).

[0103] For example, suitable additives may be selected from thickeners, rust inhibitors, antioxidants, heat stabilizers, pour point depressants, antiwear agents including those for high pressures, dispersants, tracers, dyes, talc and inorganic fillers.

[0104] Examples of thickeners are talc, silica, boron nitride, polyurea, alkali or alkaline earth metal terephthalates, calcium and lithium soaps and complexes thereof, and PTFE (polytetrafluoroethylene), of which PTFE is preferred.

[0105] Examples of dispersants are, for example, surfactants, preferably non-ionic surfactants, more preferably (per)fluoropolyether surfactants and (per)fluoroalkyl surfactants.

[0106] Depending on the application, a solvent may also be used.

[0107] Examples of solvents are fluorinated or partially fluorinated solvents such as Galden® PFPE, Novec® HFE, and other organic solvents such as fluoroalkanes, fluoroaromatics, fluoroalkyl ethers, fluoroalkylamines, fluoroalcohols, ketones such as methyl ethyl ketone, alcohols such as isopropyl alcohol, esters such as butyl acetate, and hydrofluorocarbons.

[0108] Thus, in a further aspect, the present invention relates to a method for lubricating at least one surface of at least one article, said method comprising contacting said at least one surface with said copolymer (P) or said mixture (P).

[0109] The articles that can benefit from the lubricating properties of the copolymer (P), the mixture (P) or the composition (CL) according to the invention are not particularly limited.

[0110] Preferably, the article comprises at least one metal surface.

[0111] Examples of said articles are pumps used in oil and gas applications, such as electric submersible pumps, rotating machines such as steam turbines and gas turbines, electrical connectors, bearings of fan clutches or cooling fans or automatic clutches in large trucks, more particularly bearings of said clutches.

[0112] The copolymers (P), mixtures (P) or compositions (CL) according to the invention can be advantageously used as damper fluids in damper devices.

[0113] Thus, in a further aspect, the present invention relates to a method for combating vibrations and / or shocks in an apparatus, said method comprising providing an appliance comprising a damper device comprising at least one copolymer (P), mixture (P) or composition (CL) as defined above.

[0114] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements in this application to the extent that a term may be unclear, the statements in this application shall control. EXAMPLES

[0115] The present invention will now be described with reference to the following examples, the purposes of which are illustrative only and are not intended to limit the scope of the invention.

[0116] material formula TO-(CF2CF2O) m (CF2O) n -(O) h -T' Number average molecular weight (M n )=48600 g / mol, m / n=1.0 and PO=1.65% T, T'=-CF3(83%), -C(=O)F6%), -CF2C(=O)F(11%) The peroxy perfluoropolyether oil having the formula was obtained from Solvay Specialty Polymers Italy SpA.

[0117] Tetrafluoroethylene (TFE), perfluoro(methyl vinyl ether) (PMVE) and Galden® HT200 were obtained from Solvay Specialty Polymers Italy SpA.

[0118] Perfluoro(bisvinyl ether) (PBVE) was obtained from Anles Ltd.

[0119] Hexafluorobenzene was obtained from Sigma Aldrich.

[0120] method 19F-NMR spectroscopy: A Varian Mercury 200 MHz spectrometer acting on fluorine nuclei was used to obtain the structures, number average molecular weights and compositions of the PFPE oils reported in the Examples below. 19 F-NMR spectra were obtained on pure samples using CFCl3 as an internal standard. Hexafluorobenzene was also used as the solvent.

[0121] Determination of Peroxide Content (PO): The peroxide content (PO) is expressed as grams of oxygen peroxide per 100 g of polymer. Analysis of the peroxide content was performed by iodometric titration using a Mettler DL40 instrument equipped with a platinum electrode. The detection limit for PO determination was 0.0002%.

[0122] Determination of complex viscosity: The complex viscosity was measured in a frequency sweep test according to ISO 6271 part 10 using an MCR502 Anton-Paar rheometer in parallel plate geometry (diameter 25 mm).

[0123] Gel Permeation Chromatography (GPC): The analysis was carried out using a mixed CCD column with a Waters 410 refractometer detector using HFE7100 as the eluent.

[0124] Example 1 - Synthesis of copolymer (1) The reaction was carried out using a 1000 mL cylindrical photochemical glass reactor equipped with a high pressure mercury lamp (HANAU TQ150), a magnetic stirrer, a thermocouple and a condenser enclosed in a quartz cylinder.

[0125] 200.0 g of the starting peroxygenated perfluoropolyether oil was placed in a photochemical reactor along with 1499 g of Galden® HT200 and thoroughly mixed to obtain a homogenous mixture. The reaction mixture was then cooled to approximately 10° C. in an ice / water bath.

[0126] Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 Nl / h and 1.60 Nl / h, respectively. After flow was initiated, the UV lamp was switched on. After 4 hours, the UV lamp was switched off and 1.31 g of PBVE was added to the reactor. Under vigorous stirring and nitrogen, the UV lamp was switched on again.

[0127] After 51 hours of irradiation, the lamp was switched off and the reaction mixture was transferred to a second glass reactor and fluorinated with 1.0 Nl / hour of fluorine gas at 40° C. in the presence of UV irradiation for a total of 24 hours. 19 F-NMR analysis confirmed complete fluorination of the product and the absence of -CF2COF and -COF ends at the chain ends.

[0128] The resulting solution was distilled at 240° C. for 4 hours in a round bottom flask equipped with a magnetic stirrer to remove the solvent.

[0129] Distillation was carried out first at atmospheric pressure and then under reduced pressure (0.1 mbar) until the solvent was completely removed.

[0130] 203.4 g of copolymer (1) in the form of a clear viscous oil was obtained as residue, which was analyzed by iodometric titration to confirm the complete removal of the peroxide units.

[0131] 19 F-NMR analysis confirmed the absence of residual peroxides and that TFE and PMVE were incorporated at concentrations of 10.2 and 10.1 wt %, respectively.

[0132] Copolymer (1) had m / n=0.96 and chain ends T, T'=-CF3.

[0133] Example 2 - Synthesis of copolymer (2) In this example, the same photochemical equipment and peroxy perfluoropolyether precursor as in Example 1 were used.

[0134] 200.8 g of the starting peroxygenated perfluoropolyether oil was placed in a photochemical reactor along with 1494 g of Galden HT200 and 1.35 g of PBVE and thoroughly mixed to obtain a homogenous mixture.

[0135] The reaction mixture was then cooled to about 10° C. using an ice / water bath. Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 Nl / h and 1.60 Nl / h, respectively. The UV lamp was switched on immediately after the olefin flow began. After 4 hours, the olefin flow was interrupted and the reaction was continued under UV irradiation for 51 hours.

[0136] The lamp was switched off and the reaction mixture was transferred to a second glass reactor and fluorinated with 1.0 Nl / h of fluorine gas at 40° C. in the presence of UV irradiation for a total of 24 hours.

[0137] 19 F-NMR analysis confirmed complete fluorination of the product and the absence of -COF and -CF2COF ends at the chain ends.

[0138] The resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240° C. for 4 hours to remove the solvent. The distillation was carried out first at atmospheric pressure and then under reduced pressure (0.1 mbar) until the solvent was completely removed.

[0139] 205.8 g of copolymer (2) in the form of a clear viscous oil was obtained as residue, which was analyzed by iodometric titration to confirm the complete removal of the peroxide units.

[0140] 19F-NMR analysis confirmed the absence of residual peroxides and that TFE and PMVE were incorporated at concentrations of 8.8 wt % and 11.8 wt %, respectively.

[0141] Copolymer (2) had m / n=0.99, T, T'=-CF3.

[0142] Example 3C - Synthesis of Comparative Polymer (C-1^) without PBVE In this comparative example, the same photochemical equipment and peroxy perfluoropolyether precursor as in Example 1 were used.

[0143] 200.4 g of the starting peroxygenated perfluoropolyether oil was placed in a photochemical reactor along with 1502 g of Galden® HT200 and thoroughly mixed to obtain a homogenous mixture.

[0144] The reaction proceeded as described in Example 2. The reaction mixture was then cooled to about 10° C. using an ice / water bath. Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 Nl / h and 1.60 Nl / h, respectively. The UV lamp was switched on immediately after the olefin flow began. After 4 hours, the olefin flow was interrupted and the reaction was continued under UV irradiation for 51 hours.

[0145] 19 F-NMR analysis confirmed complete fluorination of the product and the absence of -CF2COF and -COF ends at the chain ends.

[0146] Distillation was also carried out as described in Example 2.

[0147] 206.3 g of comparative polymer (C-1^) in the form of a clear viscous oil was obtained as residue, which was analyzed by iodometric titration to confirm the complete removal of the peroxide units.

[0148] 19F-NMR analysis confirmed the absence of residual peroxide. The comparative copolymer (C-1^) had m / n = 1.0 and T, T' = -CF3.

[0149] [Table 1]

[0150] The increased molecular weight distribution and complex viscosity of the copolymers (1) and (2) according to the invention confirmed the chain extension relative to the comparative polymer (C-1^).

Claims

1. A block copolymer [copolymer (P)] comprising first and second (per)fluoropolyether chains [PFPE chains], each having two chain ends, wherein a first chain end of said first and second PFPE chains comprises a perfluorinated alkyl group, and a second chain end of said first and second PFPE chains is - Formula (I): 【Chemical 1】 (wherein, n is an integer of 0 or 1 to 3, R １ to R ４ each independently represents a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, formula (II): (II)-(R １０ ) ｔ [C(R １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ (wherein, R １０ is a divalent / trivalent / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, interrupted and / or containing optionally at least one oxygen atom, t is 0 or 1, z is an integer of 1 to 3, R １１ to R １５ each independently includes a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, and is preferably selected from the group consisting of these and the group of formula (III): -[(A^) ａ＾ -(B^) ｖ＾ -(E^) Ｌ＾ ｕ＾ -(C^)-T (III)​ (wherein, a^ is 0 or 1, v^ is an integer of 0 or 1 to 3, L^ is an integer of 0 or 1 to 250, u^ is an integer of 0 or 1 to 50, A^ is a PFPE chain, B^ is a group of the formula: -[C(R １＾ )(R ２＾ )-C(R ３＾ )(R ４＾ )- (wherein, R １＾ ~R ４＾ are each independently, R １ ~R ４ have the meanings defined above for each of them) of the group, E^ is the formula -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ ) - (wherein, R １００＾ and R １０１＾ are each independently selected from a halogen atom, more preferably a fluorine or chlorine atom, and R １０２＾ and R １０３＾ are independently selected from a halogen atom, more preferably a fluorine or chlorine atom, a straight or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ wherein R ２００ is a straight or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of the formula -CF ２ OR ２０１ wherein R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００＾ and R １０１＾ one of and R １０２＾ and R １０３＾ one of is a fluorine atom, and R １００＾ and R １０１＾ the other of and R １０２＾ and R １０３＾ the other of both form a perhalogenated ring having a 4- to 6-membered ring optionally containing a heteroatom such as an oxygen atom) of the group, C^ is a PFPE chain, and T is a perfluorinated alkyl group) (preferably selected from the group consisting of these)), a first block [block (1)] according to, and - Formula (IV): -[((CR １＊ R ２＊ CR ３＊ R ４＊ )) ｎ＊ -(E) Ｌ -(IV) (wherein, n* is an integer of 0 or 1 to 10, L is an integer of 0 or 1 to 250, R １＊ to R ４＊ each of which is selected from the group consisting of, preferably consisting of, a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, a group of formula (II) as defined above E has the same meaning as provided above for E^) a second block [block (2)] according to are joined to each other via, provided that - In said copolymer (P), -- The sum of (n + n* + v^) is 1 to 15, preferably 1 to 11, more preferably 1 to 9, -- The sum of (L + L^) is 1 to 500, preferably 2 to 500, more preferably 2 to 300, -- Said block (1) and said block (2) are statistically distributed, - In said formula (I), -- R １ ~ R ４ at least one of which is a group of formula (II), -- R １１ or R １２ one of and R １３ ~R １５ one of is a group of formula (III), - In said formula (III) and said formula (IV), -- The repeating units are statistically distributed, - In said formula (III), -- When a is 1, at least one of v^ and L^ is different from 0, and - In said formula (IV), -- Provided that at least one of n* and L is different from 0, a block copolymer [copolymer (P)].

2. - Said first chain ends of said first and second PFPE chains and said T of formula (III) are the same as or different from each other and are perfluorinated alkyl groups having 1 to 3 carbon atoms, and / or - Said first and second PFPE chains, said A^ and said C^ are the same as or different from each other, and / or - The first PFPE chain is bonded to the block (1) via a group -(C)- selected from a sigma bond or -CF ２ -, -CF ２ CF ２ - or -O-, and / or - The block (2) is bonded to the second PFPE chain via a group -(C)- selected from a sigma bond or -CF ２ -, -CF ２ CF ２ -, -O-, and / or - Each of said PFPE chains is a partially or fully fluorinated chain [chain (R ｆ ))] containing, preferably consisting of, repeating units R°, and said repeating units are (i)-CFXO-(wherein X is F or CF ３ is) (ii) -CFXCFXO- (wherein X, which may be the same or different each time it appears, is F or CF ３ provided that at least one of X is -F). (iii)-CF ２ CF ２ CW ２ O-(wherein each of Ws which are equal to or different from each other is F, Cl, H). (iv)-CF ２ CF ２ CF ２ CF ２ O−, (v)-(CF ２ ) ｊ -CFZ-O- (wherein j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T, R （ｆ－ａ） is a fluoropolyoxyalkene chain containing repeating units of numbers from 0 to 10, and each of the repeating units is -CFXO-, -CF ３ wherein each X is independently F or CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O- selected from, and T is a C １ to C ３ perfluoroalkyl group) The copolymer (P) according to claim 1, independently selected from the group consisting of.

3. In formula (II), -t is 0 or - t is 1, and R １０ is the following formula: (R １０ - i) - (CF ２ ) ｄ (O) ｅ (CF ２ O) ｆ R ＣＦ (O) ｅ＊ (CF ２ ) ｄ＊ (CF2O) ｆ＊ (wherein, each of d, d*, e, e*, f and f* is independently 0 or 1, and R ＣＦ is any of perfluoroalkyl chains containing 1 to 12, preferably 1 to 8 carbon atoms, optionally interrupted by one or more oxygen atoms), (R １０ -ii)-O-(C ３ F ６ O) ｈ -(CF ２ ) ｉ -(C ３ F ６ O) ｊ -O- (wherein h = j, and h + j is 2 to 6, and i is 2 to 6)) The copolymer (P) according to claim 1, which follows one of them.

4. In formula (II), - z is equal to 1, and R １０ is an oxygen atom or a divalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, interrupted and / or containing at least one oxygen atom optionally, and / or - Substituent R １１ and R １２ One of them is a group of formula (III), and the other substituent is selected from a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms, more preferably a fluorine atom or a perfluorinated alkyl chain having 1 carbon atom, and / or - Substituent R １３ ~R １５ One of them is a group of formula (III), and the other two substituents are independently selected from a fluorine atom or a perfluorinated alkyl chain having 1 to 3 carbon atoms, more preferably a fluorine atom or a perfluorinated alkyl chain having 1 carbon atom, the copolymer (P) according to claim 1.

5. - In formula (III), -(E^) Ｌ＾ - is the following formula: -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ ) ｌ＾ -(CR １１０＾ R １１１＾ CR １１２＾ R １１３＾ ) ｍ＾ - (wherein, l^ and m^ are each independently an integer from 1 to 250, more preferably from 2 to 250, whereby the sum of L + m is from 2 to 250, R １００＾ 、R １０１＾ 、R １１０＾ and R １１１＾ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms, and R １０２＾ 、R １０３＾ 、R １１２＾ and R １１３＾ are independently selected from a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ , R ２００ is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of the formula -CF ２ OR ２０１ , and R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００＾ and R １０１＾ one of and R １０２＾ and R １０３＾ one of is a fluorine atom, and R １００＾ and R １０１＾ the other of and R １０２＾ and R １０３＾ the other of both form a perhalogenated ring having a 4- to 6-membered ring optionally containing a heteroatom such as an oxygen atom, or R １１０＾ and R １１１＾ one of １１２＾ and R １１３＾ is a fluorine atom, and one of １１０＾ and R １１１＾ the other of １１２＾ and R １１３＾ the other of both form a perhalogenated ring having a 4- to 6-membered ring optionally containing a hetero atom such as an oxygen atom, However, -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ ), ｌ＾ - and -(CR １１０＾ R １１１＾ CR １１２＾ R １１３＾ ), ｍ＾ - are different from each other and are statistically distributed). in accordance with, and / or - In formula (IV), -(E) Ｌ - is the following formula: -(CR １００ R １０１ CR １０２ R １０３ ) ｌ -(CR １１０ R １１１ CR １１２ R １１３ ) ｍ - (wherein, l, m, R １００ , R １０１ , R １１０ , R １１１ , R １０２ , R １０３ , R １１２ and R １１３ each of which has the meaning defined above for l^, m^, R １００＾ , R １０１＾ , R １１０＾ , R １１１＾ , R １０２＾ , R １０３＾ , R １１２＾ and R １１３＾ (and has the meaning defined above) The copolymer (P) according to claim 1, which follows.

6. The copolymer (P) according to claim 1, which does not contain pendant groups containing any moieties capable of undergoing further chemical reactions, such as unsaturated moieties.

7. A block copolymer [(P-1)] comprising first and second PFPE chains each having two chain ends, wherein the first chain ends of the first and second PFPE chains contain perfluorinated alkyl groups, and the second chain ends of the first and second PFPE chains are - Formula (IV): -[(CR １＊ R ２＊ CR ３＊ R ４＊ ) ｎ＊ -(E) Ｌ -(IV) (wherein, n* is an integer from 1 to 10, preferably from 1 to 5, more preferably from 1 to 3, and even more preferably 1, L is 0 or an integer from 1 to 250, more preferably from 2 to 250, R １＊ ~R ４＊ Each of which is a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 3 carbon atoms, formula (II): (II)-(R １０ ) ｔ [C(R １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ (wherein, R １０ is a divalent / trivalent / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, interrupted and / or containing optionally at least one oxygen atom, t is 0 or 1, z is an integer from 1 to 3, R １１ to R １５ each independently includes a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 3 carbon atoms, and is preferably selected from the group consisting of these groups of and formula (III): -[(A^) ａ＾ -(B^) ｖ＾ -(E^) Ｌ＾ ｕ＾ -(C^)-T (III)​ (wherein, a^ is 0 or 1, v^ is 0 or an integer from 1 to 3, L^ is an integer from 1 to 250, preferably from 2 to 250, u^ is an integer from 1 to 50, A^ is a PFPE chain B^ is of the formula - [C(R １＾ )(R ２＾ )-C(R ３＾ )(R ４＾ )- (wherein, R １＾ ~R ４＾ are each independently R １ ~R ４ has the meaning defined above for each of them) groups of, E^ is the formula -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ )- (wherein, R １００＾ and R １０１＾ are each independently selected from a halogen atom, more preferably a fluorine or chlorine atom, and R １０２＾ and R １０３＾ are independently selected from a halogen atom, more preferably a fluorine or chlorine atom, a straight or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ , R ２００ is a straight or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of the formula -CF ２ OR ２０１ , R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００＾ and R １０１＾ one of and R １０２＾ and R １０３＾ one of is a fluorine atom, and R １００＾ and R １０１＾ the other of and R １０２＾ and R １０３＾ the other of both form a perhalogenated ring having a 4- to 6-membered ring optionally containing a heteroatom such as an oxygen atom) groups of, C^ is a PFPE chain, and T is a perfluorinated alkyl group, E has the same meaning as provided above for E^) containing groups of, preferably selected from the group consisting of these) blocks in accordance with are joined to each other via, provided that - In the copolymer (P-1), -- The sum of (n* + v^) is from 1 to 15, -- The sum of (L + L^) is from 2 to 500, preferably from 3 to 300, more preferably from 4 to 250, and -- The repeating units of formulas (III) and (IV) are statistically distributed, and - In the formula (IV), -- R １＾ ~ R ４＾ at least one of which is a group of formula (II), -- R １１ or R １２ one of and R １３ ~ R １５ The copolymer (P) according to claim 1, provided that one of them is a group of formula (III).

8. A block copolymer [(P-2)] comprising first and second PFPE chains each having two chain ends, wherein the first chain ends of the first and second PFPE chains contain perfluorinated alkyl groups and the second chain ends of the first and second PFPE chains are - Formula (I): 【Chemical 2】 (wherein n is an integer from 1 to 3, R １ to R ４ each independently represents a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, formula (II): (II)-(R １０ ) ｔ [C(R １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ (wherein R １０ is a divalent / trivalent / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms, interrupted and / or containing optionally at least one oxygen atom, t is 0 or 1, z is an integer from 1 to 3, R １１ to R １５ each independently includes a fluorine atom or a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, preferably selected from the group consisting of these) the group of and Formula (III): -[(A^) ａ＾ -(B^) ｖ＾ -(E^) Ｌ＾ ｕ＾ -(C^)-T (III)​ (wherein a^ is 0 or 1, v^ is 0 or an integer from 1 to 3, L^ is an integer from 1 to 250, preferably from 2 to 250, u^ is 0 or an integer from 1 to 50, A^ is a PFPE chain, B^ is the formula -[C(R １＾ )(R ２＾ )-C(R ３＾ )(R ４＾ )- (wherein R １＾ ~R ４＾ each independently has the meaning defined above for each of R １ ~R ４ ) the group of, E^ is the formula -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ )- (wherein R １００＾ and R １０１＾ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms, and R １０２＾ and R １０３＾ are independently selected from a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ , where R ２００ is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of the formula -CF ２ OR ２０１ , and R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００＾ and R １０１＾ one of and R １０２＾ and R １０３＾ one of is a fluorine atom, and R １００＾ and R １０１＾ the other of and R １０２＾ and R １０３＾ the other of both form a perhalogenated ring having a 4- to 6-membered ring optionally containing a heteroatom such as an oxygen atom) the group of, C^ is a PFPE chain, and T is a perfluorinated alkyl group) containing the group of, preferably selected from the group consisting of these) a first block [block (1)] according to - Formula (IV): -[((CR １＊ R ２＊ CR ３＊ R ４＊ )) ｎ＊ -(E) Ｌ＊ -(IV) (wherein n* is an integer from 0 or 1 to 10, preferably from 1 to 5, more preferably from 1 to 3, even more preferably 0 or 1, L* is an integer from 0 or 1 to 250, more preferably from 2 to 250, R １＊ to R ４＊ each of which is selected from the group consisting of, preferably consisting of, a fluorine atom, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, a group of formula (II) as defined above E has the same meaning as provided above for E^) a second block [block (2)] according to are joined to each other via, provided that - In the copolymer (P-2), -- The sum of (n + n* + v) is from 1 to 15, preferably from 1 to 11, more preferably from 1 to 9, -- The sum of (L^ + L*) is from 1 to 500, preferably from 2 to 500, more preferably from 2 to 300, and -- The block (1) and the block (2) are statistically distributed, and - In the formula (I), —— R １ ~R ４ at least one of which is a group of formula (II), -- R １１ or R １２ one of and R １３ ~R １５ one of is a group of formula (III), and - In the formula (III) and the formula (IV), the repeating units are statistically distributed, - In the formula (III), -- When a is 1, at least one of v^ and L^ is different from 0, and - In the formula (IV), at least one of n* and L* is different from 0, the copolymer (P) according to claim 1.

9. A mixture [(mixture (P))] comprising two or more copolymers (P) according to claim 1.

10. A process [(process (P))] for producing the copolymer (P) according to claim 1, in the presence of UV irradiation or under heating, - At least one (per)fluoropolyether polymer [PFPE peroxy] containing a peroxide group, - Formula (X-p): 【Chemical Formula 3】 (wherein R ２１ to R ２３ and R ３１ to R ３３ Each of them is independently a fluorine atom or a perfluorinated alkyl group having 1 to 3 carbon atoms, R １０ is a perfluorinated alkyl chain containing 2 to 18 carbon atoms interrupted by and / or containing an oxygen atom or preferably at least one oxygen atom, t is 0 or 1, preferably 1, each of z* and z** is independently 1 or 2) with at least one perfluorinated compound, and - at least one compound [Compound (O)] comprising (i) a fully halogenated olefin containing 2 to 8 carbon atoms, preferably tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), (ii) CF ２ = CFOR ｆ (wherein R ｆ is a C １ to C ６ (per)fluoroalkyl group, preferably -CF ３ , -C ２ F ５ , -C ３ F ７ (hereinafter also referred to as "PAVE"), a group C １ to C １２ [(per)fluoro]-oxyalkyl group containing a catenary oxygen atom, preferably a perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CF ２ OR ｆ２ (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), and R ｆ２ is a C １ to C ６ perfluoro-alkyl group containing at least one catenary oxygen atom, C ５ to C ６ cyclic perfluoro-alkyl group and C ２ to C ６ perfluoro-oxy-alkyl group, and is preferably selected from the group consisting of R ｆ２ being -CF ２ CF ３ (MOVE1), -CF ２ CF ２ OCF ３ (MOVE2) or -CF ３ (MOVE3)). (iii) a formula: 【Chemical Formula 4】 (wherein each of R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ is equal to or different from each other and contains a fluorine atom and optionally one or more oxygen atoms, especially -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ etc., and is independently selected from the group consisting of C １ -C ６ perfluoroalkyl groups) perfluorodioxole having including, preferably at least one compound [Compound (O)] selected from the group consisting of these and comprising at least one step of contacting, provided that the amount of the compound of formula (X-p) is less than 5% by weight of the amount of the PFPE peroxide, Process [Process (P)].

11. The PFPE peroxide is a peroxy(per)fluoropolyether polymer containing a (per)fluoropolyether chain having two chain ends, each of the chain ends optionally containing one or more chlorine atoms or a functional end group selected from acyl fluoride, fluoroformate and ketone, and comprising a (per)fluorinated alkyl chain having 1 to 3 carbon atoms, the chain ends being bonded to opposite sides of the (per)fluoropolyether chain, the (per)fluoropolyether chain being independently selected from the group consisting of formulas (Rf-i) to (Rf-v) defined above, and having a peroxide content (PO) of 0.1 to 4, preferably 0.1 to 3.5, defined as grams of active oxygen (Mw = 16) per 100 g of PFPE peroxide, comprising repeating units, preferably consisting of these, the process (P) according to claim 10.

12. The at least one compound of formula (X-p) has the following formula: CF ２ =CF(R １０ ) ｔ CF = CF ２ (wherein t is 0 or 1, R １０ is given by the following formula: (R １０ - i) - (CF ２ ) ｄ (O) ｅ (CF ２ O) ｆ R ＣＦ (O) ｅ＊ (CF ２ ) ｄ＊ (CF2O) ｆ＊ (wherein each of d, d*, e, e*, f and f* is independently 0 or 1, and R ＣＦ is any of perfluoroalkyl chains containing 1 to 12, preferably 1 to 8 carbon atoms, optionally interrupted by one or more oxygen atoms). (R １０ - ii) - O - (C ３ F ６ O) ｈ - (CF ２ ) ｉ - (C ３ F ６ O) ｊ - O - (wherein h = j, and h + j is 2 to 6, and i is 2 to 6)) according to one of) according to the process (P) of claim 10.

13. The process (P) according to claim 10, wherein two of the compounds (O) are used.

14. - The first compound (O) is selected from, preferably consisting of, fully halogenated olefins containing 2 to 8 carbon atoms such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), and - The second compound (O) is (ii) CF ２ = CFOR ｆ (In the formula, R ｆ is a C １ ~ C ６ (per) fluoroalkyl group, preferably -CF ３ , -C ２ F ５ , -C ３ F ７ (hereinafter also referred to as "PAVE"), a group C １ ~ C １２ [(per) fluoro] -oxyalkyl, preferably a perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CF ２ OR ｆ２ (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), R ｆ２ is a C １ ~ C ６ perfluoro-alkyl containing at least one chain oxygen atom, C ５ ~ C ６ cyclic perfluoro-alkyl and C ２ ~ C ６ perfluoro-oxy-alkyl selected from the group consisting of, preferably, R ｆ２ is -CF ２ CF ３ (MOVE1), -CF ２ CF ２ OCF ３ (MOVE2) or -CF ３ (MOVE3)), (iii) the formula: 【Chemical Formula 5】 (wherein each of R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ is equal to or different from each other and is selected independently from the group consisting of a fluorine atom and optionally one or more oxygen atoms, especially -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ etc., C １ - C ６ selected from the group consisting of perfluoroalkyl groups)) perfluorodioxole having The process (P) according to claim 13, comprising, preferably consisting of, those selected from the group consisting of PAVE and MOVE in definition (i) being particularly preferred.

15. A process [process (P1)] for producing the polymer (P-1) according to claim 7, comprising a*) at least one peroxy(per)fluoropolyether polymer [PFPE peroxy] - formula (X-p): 【Chemical Formula 6】 (wherein R ２１ to R ２３ and R ３１ to R ３３ Each of them is, independently, a fluorine atom or a perfluorinated alkyl group having 1 to 3 carbon atoms, R １０ is a perfluorinated alkyl chain containing 2 to 18 carbon atoms interrupted and / or containing at least one oxygen atom, preferably interrupted by an oxygen atom, t is 0 or 1, preferably 1, each of z* and z** is independently 1 or 2) at least one perfluorinated compound of - and at least one compound [compound (O)] (i) fully halogenated olefins containing 2 to 8 carbon atoms such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), (ii) CF ２ = CFOR ｆ (wherein, R ｆ is a C １ to C ６ (per)fluoroalkyl group, preferably -CF ３ , -C ２ F ５ , -C ３ F ７ (hereinafter also referred to as "PAVE"), a group C １ to C １２ [(per)fluoro]-oxyalkyl containing a catenary oxygen atom, preferably a perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), the group -CF ２ OR ｆ２ (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), R ｆ２ is a C １ to C ６ perfluoro-alkyl containing at least one catenary oxygen atom, C ５ to C ６ cyclic perfluoro-alkyl and C ２ to C ６ perfluoro-oxy-alkyl selected from the group consisting of, preferably, R ｆ２ is -CF ２ CF ３ (MOVE1), -CF ２ CF ２ OCF ３ (MOVE2) or -CF ３ (MOVE3)), (iii) the formula: 【Chemical Formula 7】 (wherein each of R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ is equal to or different from each other and contains a fluorine atom and optionally one or more oxygen atoms, in particular -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ etc., and is independently selected from the group consisting of C １ to C ６ perfluoroalkyl groups) perfluorodioxole having at least one compound [compound (O)] selected from, preferably consisting of, the group consisting of contacting with, wherein the amount of the compound of formula (X-p) is less than 5% by weight of the amount of the PFPE peroxy, b*) reacting the PFPE peroxy, the compound of formula (X-p), and the at least one compound (O) in the presence of UV irradiation or heating, c*) fluorinating to thereby obtain the copolymer (P1) The process [process (P1)] comprising.

16. A process [process (P2-a)] for producing the copolymer (P-2) according to claim 8, comprising a') contacting at least one peroxy(per)fluoropolyether polymer [PFPE peroxy] with at least one compound (O) as defined above, b') reacting the PFPE peroxy and the compound (O) in the presence of UV irradiation or heating, c') stopping the UV irradiation or heating, d') adding the reaction mixture to a compound of formula (X-p): 【Chemical 8】 (wherein R ２１ to R ２３ and R ３１ to R ３３ Each of them is independently a fluorine atom or a perfluorinated alkyl group having 1 to 3 carbon atoms, R １０ is a perfluorinated alkyl chain containing 2 to 18 carbon atoms, interrupted and / or containing optionally at least one oxygen atom by an oxygen atom t is 0 or 1, preferably 1, Each of z* and z** is independently 1 or 2) contacting with at least one perfluorinated compound, wherein the amount of the compound of formula (X-p) is less than 5% by weight of the amount of the PFPE peroxide; e') allowing the reaction to proceed in the presence of UV irradiation or heating; f') fluorinating to obtain the copolymer (P2) A process [process (P2-a)] comprising:

17. A process [process (P2-b)] for producing the copolymer (P-2) according to claim 8, comprising: a'') contacting at least one peroxy(per)fluoropolyether polymer [PFPE peroxide] with at least one perfluorinated compound of formula (X-p): 【Chemical Formula 9】 (wherein R ２１ to R ２３ and R ３１ to R ３３ Each of them is, independently, a fluorine atom or a perfluorinated alkyl group having 1 to 3 carbon atoms, R １０ is a perfluorinated alkyl chain containing 2 to 18 carbon atoms, interrupted and / or containing optionally at least one oxygen atom, t is 0 or 1, preferably 1, Each of z* and z** is independently 1 or 2) contacting with at least one perfluorinated compound, wherein the amount of the compound of formula (X-p) is less than 5% by weight of the amount of the PFPE peroxide; b'') reacting the PFPE peroxide and the compound of formula (X-p) in the presence of UV irradiation or heating; c'') stopping the UV irradiation or heating; d'') contacting the reaction mixture obtained in step c'') with at least one compound (O) as defined above; e'') allowing the reaction to proceed in the presence of UV irradiation or heating; f'') fluorinating to obtain the copolymer (P2) A process [process (P2-b)] comprising:

18. At least one copolymer (P) according to claim 1 or at least one base oil selected from the group consisting of a mixture (P) according to claim 9 and a partially fluorinated, fully fluorinated and hydrogenated base oil, provided that the copolymer (P) can form a solution, and optionally at least one additive selected from thickeners, rust inhibitors, antioxidants, heat stabilizers, pour point depressants, antiwear agents for high pressure, dispersants, tracers, dyes, talc and inorganic fillers. A composition [composition (CL)].

19. A method of lubricating at least one surface of at least one article, comprising contacting the at least one surface with at least one copolymer (P) according to claim 1 or the mixture (P) according to claim 9.

20. The method according to claim 19, wherein the article is selected from pumps for use in oil and gas applications such as electric submersible pumps and the like, rotating machinery such as steam turbines and gas turbines, electrical connectors, bearings of fan clutches or cooling fans, or automatic clutches of heavy trucks, more specifically the bearings of said clutches.

21. A method of countering vibrations and / or impacts in a device, the method comprising providing a device comprising a damper device comprising at least one copolymer (P) according to claim 1, or a mixture (P) according to claim 9.

22. A method of lubricating at least one surface of at least one article, the method comprising bringing the composition (CL) according to claim 18 into contact with said at least one surface.

23. A method of countering vibrations and / or impacts in a device, the method comprising providing a device comprising a damper device comprising the composition (CL) according to claim 18.

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