Copolymers comprising (PER)fluoropolyether chains and manufacturing process and use thereof

Abstract

This patent application relates to copolymers containing (fully)fluoropolyether chains, characterized by increased viscosity.

Description

Technical Field

[0001] This patent application relates to copolymers containing (fully)fluoropolyether chains, characterized by increased viscosity. [Cross-reference to related patent applications]

[0002] This application claims priority to European application No. 21183256.3 filed on July 1, 2021, the entire contents of which are incorporated herein by reference for all purposes. Prior Technology

[0003] Lubrication is a crucial aspect of maintaining the normal operation of machinery. Mechanical components such as bearings, pins, shafts, gears, and joints require proper lubrication between their moving surfaces to reduce friction, prevent contamination, minimize wear, and facilitate heat dissipation. Inadequate lubrication can lead to premature wear and component or system failure.

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

[0005] Several PFPE polymers have been synthesized in this field. The first synthesis of an unspecified mixture of perfluorinated polyethers was reported in 1953, yielding an oily product during the photoligomerization of hexafluoropropylene. Since then, many different perfluorinated polyethers have been synthesized and described in the literature.

[0006] [US 4500739(] [With Monte Edison Company] (Montedison) [in the name of] [] revealed the reaction of PFPE peroxide, particularly with perfluorobutadiene (a type II fluoroolefin). Example 4 revealed the reaction with perfluorobutadiene and a large excess of perfluorinated diene, generating unsaturated side-chain groups along the macromolecular chain, allowing the reaction to proceed further in the presence of hexamethylenediamine.

[0007] [US 8,258,090 B2(] [Solvizole] [(Solvay Solexis SpA)] [in the name of] [)] discloses fluorinated lubricants having the following formula: (I) TO-[AB]z-[A'-B']z'-A-T' in T and T' series are C1-3 perfluoroalkyl or C1-6 alkyl groups. A and A' series of perfluoropolyether chains, B is derived from two different olefins, at least one of which can be homopolymerized via a free radical pathway. B has the following formula: (Ia) -[(CR 1R 2-CR 3R 4) j-(CR 5R 6-CR 7R 8) j']- in The series j ranges from 1 to 5, the series j' ranges from 0 to 4, and the sum of j+j' is between 2 and 5; R1 to R8 series halogens, H, C1-6 (all) haloalkyl, C1-6 alkyl, C1-6 oxy (all) fluoroalkyl; z is greater than or equal to 2, z' is an integer, and the sum of z and z' is such that the average molecular weight of the polymers having formula (I) is in the range of 500-500,000; B' series (Ia), but at least one of R1 to R8 has a different meaning than that in B. This patent discloses a block copolymer characterized by a linear backbone without any branching. In fact, no branching is achieved in B, especially in the presence of (per)fluoropolyether chains.

[0008] Polymers obtained using PFPE polymer units have been disclosed in the art. Crosslinked fluoroelastomers are one such example. In this regard, SP Krukovsky et al. – J of Fluorine Chemistry 96(1999)31-33 – disclosed copolymerization of perfluoroolefins containing peroxy groups in the chain with perfluorodivinyl ethers under UV radiation and heating to provide crosslinked polymers called elastomers. This literature does not disclose any amounts of reactants, nor does it provide a method for manufacturing polymers suitable for lubricants. Summary of the Invention

[0009] Although recent research and development have focused on mono- and / or bifunctional (per)fluoropolyether (PFPE) polymers, the applicant believes there is still a need to provide neutral PFPE polymers that can be used as lubricants.

[0010] The problem faced by the applicant is to provide a new neutral PFPE polymer characterized by increased viscosity (e.g., measured by a complex viscosity of 0.1 rad / s at 25°C) while maintaining a low glass transition temperature (Tg) and remaining liquid at room temperature.

[0011] The applicant has unexpectedly discovered that neutral branched (per)fluoropolyether polymers, characterized by increased viscosity due to the increase in number-average molecular weight, can be provided by a method that is easily implemented on an industrial scale.

[0012] Advantageously, this method allows for the manufacture 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 suitable as lubricants for harsh environments, including 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 ends, wherein the first ends of the first and second PFPE chains comprise perfluorinated alkyl groups and the second ends of the first and second PFPE chains are bonded to each other by means of: - The first block of conformation (I) [block (1)] in n is either 0 or an integer from 1 to 3; R1 to R4 are each independently selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (II): (II) -(R 10) t[C(R 11)(R 12)-C(R 13)(R 14)(R 15)] z in R 10 series oxygen atoms, or, as needed, divalent / trivalent / tetravalent perfluorinated alkyl chains containing 1 to 24 carbon atoms with and / or containing at least one oxygen atom. t is zero or 1. z represents integers from 1 to 3. R 11 to R 15 are each independently selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (III): -[(A^) a^-(B^) v^-(E^) L^] u^-(C^)-T (III) in a^ is zero or 1, v^ represents zero or an integer from 1 to 3. L^ represents zero or an integer from 1 to 250. u^ represents zero or an integer from 1 to 50. A^ series PFPE chain, B^ series has groups with the following formula: -[C(R 1^)(R 2^)-C(R 3^)(R 4^)]- Each of R1^ to R4^ independently has the meaning defined above for each of R1 to R4. The E^ system has groups of the formula -(CR 100^R 101^CR 102^R 103^)-. in R100^ and R101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms, and R 102^ and R 103^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 is a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the formula -CF 2OR 201, wherein R 201 is a perfluorinated alkyl chain comprising 1 to 6 carbon atoms with one or more oxyether atoms inserted as desired; or One of R100^ and R101^ and one of R102^ and R103^ are fluorine atoms, and the other of R100^ and R101^ and the other of R102^ and R103^ together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; C^ series PFPE chain, and T-series perfluorinated alkyl groups; as well as - The second block of conformation (IV) [block (2)]: -[(CR 1*R 2*CR 3*R 4*) n*-(E) L]- (IV) in n* represents zero or an integer from 1 to 10. L represents zero or an integer from 1 to 250; Each of R1* to R4* is selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, groups having formula (II) as defined above. E has the same meaning as E^ above; Its premise is: In the copolymer (P) The sum of (n+n*+v^) ranges from 1 to 15, preferably from 1 to 11, and even better from 1 to 9; -- The sum of (L+L^) ranges from 1 to 500, preferably from 2 to 500, and even better from 2 to 300. -- The blocks (1) and (2) are systematically distributed; In the above formula (I): -- At least one of R1 to R4 has a group of formula (II), -- One of R11 or R12 and one of R13 to R15 are groups having formula (III); In equations (III) and (IV) -- The systematic distribution of these repeating unit systems, In the above formula (III) -- When a is 1, at least one of v^ and L^ is not 0, and In the above formula (IV) -- At least one of n* and L is not zero.

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

[0015] Advantageously, the copolymer (P) according to the invention is prepared by a method [method (P)], which includes contacting the following in the presence of UV radiation or under heating: - At least one peroxy group-containing (per)fluoropolyether polymer [PFPE peroxide]; - At least one perfluorinated compound having the formula (Xp): in Each of R 21 to R 23 and R 31 to R 33 is independently a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms. R 10 series oxygen atoms, or, if desired and preferably, perfluorinated alkyl chains containing 2 to 18 carbon atoms with and / or containing at least one oxygen atom, inserted. The t series can be either zero or 1, with 1 being preferable. Each of z* and z** is independently 1 or 2; and - At least one compound selected from the group consisting of, preferably, the following: [compound(O)] (i) Fully halogenated olefins containing 2 to 8 carbon atoms, preferably tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and trifluorochloroethylene (CTFE); (ii) CF 2 = CFOR f, in R f series C1-C6 (per)fluoroalkyl, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"); C1-C12 [(per)fluoro]oxoalkyl group containing a chain oxygen atom, preferably perfluoro-2-propoxypropyl (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"); group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein R f2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom, preferably R f2 series -CF2CF3 (MOVE1), -CF2CF2OCF3 (MOVE2), or -CF3 (MOVE3); (iii) Perfluorodioxole having the following formula: Each of Rf3, Rf4, Rf5, and Rf6 may be the same as or different from the others, and is independently selected from the group consisting of: fluorine atoms and C1-C6 perfluoroalkyl groups containing one or more oxygen atoms as needed, such as especially -CF3, -C 2F 5, -C 3F 7, -OCF 3, -OCF 2CF 2OCF 3; The premise is that the amount of the compound having formula (Xp) is less than 5 wt. of the amount of the PFPE peroxide.

[0016] In the method according to the invention, it is important to appropriately select the amount of the compound having the formula (Xp) to be lower than the amount of PFPE peroxide.

[0017] Advantageously, by selecting such an amount, more than 85%, more than 90%, and even more than 95% of the unsaturated portion of the compound having formula (III) reacts with at least one peroxy group of the starting PFPE peroxide, and a branched block copolymer (P) without unsaturated portions (also called "functional groups") as side groups is obtained.

[0018] The copolymer (P) advantageously does not contain side groups that include any portion capable of undergoing further chemical reactions. In particular, the copolymer (P) does not contain unsaturated portions as side groups.

[0019] In a third aspect, the present invention relates to copolymers (P) obtained by the method (P) described above.

[0020] Although the purification step can be performed at the end of the method (P), those skilled in the art will understand that the copolymer (P) according to the invention is obtained as a mixture at the end of the method (P).

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

[0022] Those familiar with this technique will know that the mixture (P) is obtained by the method (P) described above.

[0023] Advantageously, the mixture (P) can undergo one or more purification steps (also known as "gradation" steps) to obtain individual copolymers (P) characterized by different viscosities. Implementation

[0024] For the purposes of this specification and the following claims: - The use of parentheses around identifying symbols or numbers, such as in expressions like "polymer (P)," serves only to better distinguish the symbol or number from the rest of the text, and therefore the parentheses can be omitted; - The acronym "PFPE" stands for "(per)fluoropolyether" and when used as a noun, it refers to either the singular or plural form depending on the context; - The term "(full) fluorinated polyether" is intended to refer to polyether polymers that are fully or partially fluorinated.

[0025] [, copolymer , ] [, (P) , ]

[0026] Advantageously, the copolymer (P) is characterized by a complex viscosity ranging from 10 Pa*s to 2000 Pa*s, measured at 0.1 rad / s and 25°C. [] []

[0027] Those skilled in the art will understand that the first chain end of the first and second PFPE chains corresponds to the two chain ends of the copolymer (P).

[0028] Preferably, the first end of the first and second PFPE chains comprises a perfluorinated straight-chain alkyl group having 1 to 3 carbon atoms.

[0029] Preferably, the perfluorinated alkyl groups are identical to each other.

[0030] Preferably, the first chain ends of the first and second PFPE chains and the T in formula (III) are the same or different from each other, and are perfluorinated alkyl groups having 1 to 3 carbon atoms.

[0031] Preferably, the first and second PFPE chains, A^ and C^ are the same as or different from each other.

[0032] Preferably, in the copolymer (P), the first PFPE chain is bonded to the block (1) by a σ bond or a group selected from -CF 2-, -CF 2CF 2- or -O- (C)-.

[0033] Preferably, in the copolymer (P), the block (2) is bonded to the second PFPE chain by a σ bond or a group selected from -CF 2-, -CF 2CF 2- or -O- (C)-.

[0034] Preferably, when both the segment (1) and the segment (2) exist, they are connected by a σ bond.

[0035] Preferably, in the copolymer (P), each system of the PFPE chain comprises a repeating unit R°, preferably a partially or fully fluorinated chain [chain (Rf)] composed thereof, the repeating unit being independently selected from the group consisting of: (i)-CFXO-, where X is F or CF 3; (ii) -CFXCFXO-, where X is the same or different each time it appears, and is a series F or CF 3, wherein at least one of X is a series -F; (iii) -CF 2CF 2CW 2O-, where each W is the same or different from the others, and the series are F, Cl, and H; (iv)-CF 2CF 2CF 2CF 2O-; (v)-(CF 2) j-CFZ-O-, where j is an integer from 0 to 3 and Z is a group having the general formula -OR (fa)-T, where R (fa) is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, the repeating units being selected from the following: -CFXO-, -CF 2CFXO-, -CF 2CF 2CF 2O-, -CF 2CF 2CF 2CF 2O-, where each X is independently F or CF 3 and T-series C 1-C 3 perfluoroalkyl.

[0036] Preferably, the chain (Rf) conforms to the following formula: (R fI) -[(CFX 1O) g1(CFX 2CFX 3O) g2(CF 2CF 2CF 2O) g3(CF 2CF 2CF 2CF 2O) g4]- in - X 1 is selected independently from -F and -CF 3, - X2 and X3 are either the same as or different from each other and are independent each time they appear. -F, -CF 3, wherein at least one of the presuppositions X is -F; - g1, g2, g3 and g4 are the same or different from each other, and are independent integers ≥ 0, such that g1 + g2 + g3 + g4 is in the range of 2 to 300, preferably from 2 to 100; if at least two of g1, g2, g3 and g4 are not zero, then the different repeating units are statistically distributed along the chain in general.

[0037] More preferably, the chain (Rf) is selected from chains having the following formula: (R f-IIA) -[(CF 2CF 2O) a1(CF 2O) a2]- in: - a1 and a2 are independently integers ≥ 0, such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; both a1 and a2 are preferably non-zero, wherein the ratio a1 / a2 is preferably between 0.1 and 10; (R f-IIB) -[(CF 2CF 2O) b1(CF 2O) b2(CF(CF 3)O) b3(CF 2CF(CF 3)O) b4]- in: b1, b2, b3, and b4 are independently integers ≥ 0, such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably, b1 is 0, and b2, b3, and b4 are > 0, wherein the ratio b4 / (b2+b3) ≥ 1; (R f-IIC) -[(CF 2CF 2O) c1(CF 2O) c2(CF 2(CF 2) cwCF 2O) c3]- in: cw = 1 or 2; c1, c2, and c3 are independently integers ≥ 0, which are selected such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably, c1, c2, and c3 are all > 0, wherein the ratio c3 / (c1+c2) is typically less than 0.2.

[0038] Even better, the chain (Rf) conforms to the following equation (Rf-III): (R f-III) -[(CF 2CF 2O) a1(CF 2O) a2]- in: - a1 and a2 are integers > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, wherein the ratio a1 / a2 is typically between 0.1 and 10, preferably between 0.2 and 5.

[0039] Preferably, in formula (I), at least one of the substituents R1 to R4 has a group of formula (II), and the other substituents are each independently selected from fluorine atoms or perfluorinated alkyl chains having 1 to 3 carbon atoms, more preferably fluorine atoms or perfluorinated alkyl chains having 1 carbon atom.

[0040] According to one implementation, in equation (II), t is 0.

[0041] According to another embodiment, in equation (II), t is 1, and R 10 satisfies one of the following formulas: (R 10-i) -(CF 2) d(O) e(CF 2O) fR CF(O) e*(CF 2) d*(CF2O) f* in Each of d, d*, e, e*, f, and f* is independently zero or 1, and R CF series refers to perfluorinated alkyl chains containing 1 to 12, preferably 1 to 8, carbon atoms, with one or more oxygen atoms inserted as needed. (R 10-ii) -O-(C 3F 6O) h-(CF 2) i-(C 3F 6O) jO- Where h = j and h + j ranges from 2 to 6, and i ranges from 2 to 6.

[0042] According to this implementation method, R 10 preferably conforms to the following formula: (R 10-i) -(CF 2) d(O) e(CF 2O) fR CF(O) e*(CF 2) d*(CF2O) f* in d, f, d*, and f* are all zero. e and e* series 1, and The R CF series comprises straight-chain perfluorinated alkyl chains of 1 to 10, preferably 1 to 8, carbon atoms.

[0043] Preferably, in formula (II), z equals 1 and R is a 10-series oxygen atom or a divalent perfluorinated alkyl chain containing 1 to 24 carbon atoms and, if necessary, inserted with and / or containing at least one oxygen atom.

[0044] Preferably, in formula (II), one of the substituents R11 and R12 has 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. According to a preferred embodiment, one of the substituents R11 and R12 has a group of formula (III), and the other substituent is a fluorine atom.

[0045] Preferably, in formula (II), one of the substituents R13 to R15 has a group of formula (III), and the other two substituents are independently selected from fluorine atoms or perfluorinated alkyl chains having 1 to 3 carbon atoms, more preferably fluorine atoms or perfluorinated alkyl chains having 1 carbon atom. Even more preferably, the two substituents are identical and are fluorine atoms.

[0046] Preferably, in equation (III), v^ is an integer ranging from 1 to 3, and more preferably 1.

[0047] Preferably, in equation (III), L^ is an integer from 1 to 250, more preferably from 2 to 250.

[0048] Preferably, in equation (III), -(E^) L^- conforms to the following equation: -(CR 100^R 101^CR 102^R 103^) l^-(CR 110^R 111^CR 112^R 113^) m^- in l^ and m^ are each independent integers from 1 to 250, more preferably from 2 to 250, such that the sum of L+m is from 2 to 250; R100^, R101^, R110^, and R111^ 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 halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 comprises a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the following formula: -CF 2OR 201, where R 201 refers to a perfluorinated alkyl chain containing 1 to 6 carbon atoms, to which one or more oxygen ether atoms are inserted as needed; or One of R100^ and R101^ and one of R102^ and R103^ are fluorine atoms, and the other of R100^ and R101^ and the other of R102^ and R103^ together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; or One of R110^ and R111^ and one of R112^ and R113^ are fluorine atoms, and the other of R110^ and R111^ and the other of R112^ and R113^ together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; Its premise is -(CR 100^R 101^CR 102^R 103^) l^- and -(CR 110^R 111^CR 112^R 113^) m^- are distinct from each other and are statistically distributed.

[0049] Preferably, in equation (IV), n* is an integer ranging from 1 to 10, more preferably from 1 to 5, even more preferably from 1 to 3, and still more preferably from 1.

[0050] Preferably, in equation (IV), L is an integer from 2 to 250.

[0051] Preferably, in equation (IV), -(E)L- conforms to the following equation: -(CR 100R 101CR 102R 103) l-(CR 110R 111CR 112R 113) m- in l and m are each independent integers from 1 to 250, more preferably from 2 to 250, such that the sum of L+m is from 2 to 250; R100, R101, R110, and R111 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 halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 comprises a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the following formula: -CF 2OR 201, where R 201 refers to a perfluorinated alkyl chain containing 1 to 6 carbon atoms, to which one or more oxygen ether atoms are inserted as needed; or One of R100 and R101 and one of R102 and R103 are fluorine atoms, and the other of R100 and R101 and the other of R102 and R103 together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; or One of R110 and R111 and one of R112 and R113 are fluorine atoms, and the other of R110 and R111 and the other of R112 and R113 together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; Its premise is -(CR 100R 101CR 102R 103) l- and -(CR 110R 111CR 112R 113) m- are distinct from each other and are statistically distributed.

[0052] Preferably, in equation (IV), l refers to an integer from 1 to 250.

[0053] According to a first preferred embodiment, the copolymer (P) of the present invention (hereinafter referred to as "copolymer (P-1)") is a block copolymer comprising first and second PFPE chains each having two ends, wherein the first ends of the first and second PFPE chains comprise perfluorinated alkyl groups and the second ends of the first and second PFPE chains are bonded to each other by means of the following: - Segments conforming to (IV): -[(CR 1*R 2*CR 3*R 4*) n*-(E) L]- (IV) in n* represents integers from 1 to 10, preferably from 1 to 5, even better from 1 to 3, and even better still, integers of 1. L series zero or integers from 1 to 250, preferably from 2 to 250; Each of R1* to R4* is selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 3 carbon atoms, and groups having formula (II): (II) -(R 10) t[C(R 11)(R 12)-C(R 13)(R 14)(R 15)] z in R 10 series oxygen atoms, or, as needed, divalent / trivalent / tetravalent perfluorinated alkyl chains containing 1 to 24 carbon atoms with and / or containing at least one oxygen atom. t is zero or 1. z represents integers from 1 to 3. R 11 to R 15 are each independently selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 3 carbon atoms, and groups having formula (III): -[(A^) a^-(B^) v^-(E^) L^] u^-(C^)-T (III) in a^ is zero or 1, v^ represents zero or an integer from 1 to 3. L^ is an integer ranging from 1 to 250, preferably from 2 to 250. u^ represents integers from 1 to 50; A^ series PFPE chain, B^ series has groups with the following formula: -[C(R 1^)(R 2^)-C(R 3^)(R 4^)]- Each of R1^ to R4^ independently has the meaning defined above for each of R1 to R4. The E^ system has groups of the formula -(CR 100^R 101^CR 102^R 103^)-. in R100^ and R101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms, and R 102^ and R 103^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 is a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the formula -CF 2OR 201, wherein R 201 is a perfluorinated alkyl chain comprising 1 to 6 carbon atoms with one or more oxyether atoms inserted as desired; or One of R100^ and R101^ and one of R102^ and R103^ are fluorine atoms, and the other of R100^ and R101^ and the other of R102^ and R103^ together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; C^ series PFPE chain, and T-series perfluorinated alkyl groups; E has the same meaning as E^ above; Its premise is - In the copolymer (P-1): The sum of (n*+v^) ranges from 1 to 15. The sum of (L+L^) ranges from 2 to 500, preferably from 3 to 300, and even better from 4 to 250. -- The repeating units in equations (III) and (IV) are systematically distributed; and - In equation (IV): -- At least one of R1^ to R4^ has a group of formula (II), -- One of R11 or R12 and one of R13 to R15 are groups having formula (III).

[0054] According to a second preferred embodiment, the copolymer (P) of the present invention (hereinafter referred to as "copolymer (P-2)") is a block copolymer comprising first and second PFPE chains each having two ends, wherein the first ends of the first and second PFPE chains comprise perfluorinated alkyl groups and the second ends of the first and second PFPE chains are bonded to each other by the following: - The first block of conformation (I) [block (1)] in n is an integer from 1 to 3; R1 to R4 are each independently selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (II): (II) -(R 10) t[C(R 11)(R 12)-C(R 13)(R 14)(R 15)] z in R 10 series oxygen atoms, or, as needed, divalent / trivalent / tetravalent perfluorinated alkyl chains containing 1 to 24 carbon atoms with and / or containing at least one oxygen atom. t is zero or 1. z represents integers from 1 to 3. R 11 to R 15 are each independently selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (III): -[(A^) a^-(B^) v^-(E^) L^] u^-(C^)-T (III) in a^ is zero or 1, v^ represents zero or an integer from 1 to 3. L^ is an integer ranging from 1 to 250, preferably from 2 to 250. u^ represents zero or an integer from 1 to 50. A^ series PFPE chain, B^ series has groups with the following formula: -[C(R 1^)(R 2^)-C(R 3^)(R 4^)]- Each of R1^ to R4^ independently has the meaning defined above for each of R1 to R4. The E^ series has groups with the following formula: -(CR 100^R 101^CR 102^R 103^)- in R100^ and R101^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms, and R 102^ and R 103^ are independently selected from halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 is a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the formula -CF 2OR 201, wherein R 201 is a perfluorinated alkyl chain comprising 1 to 6 carbon atoms with one or more oxyether atoms inserted as desired; or One of R100^ and R101^ and one of R102^ and R103^ are fluorine atoms, and the other of R100^ and R101^ and the other of R102^ and R103^ together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; C^ series PFPE chain, and T-series perfluorinated alkyl groups; as well as - The second block of conformation (IV) [block (2)]: -[(CR 1*R 2*CR 3*R 4*) n*-(E) L*]- (IV) in n* represents 0 or numbers from 1 to 10, preferably from 1 to 5, even better from 1 to 3, and still even better, integers of 0 or 1. L* represents 0 or integers from 1 to 250, preferably from 2 to 250; Each of R1* to R4* is selected from the group consisting of, preferably, the following: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, groups having formula (II) as defined above. E has the same meaning as E^ above; Its premise is: In the copolymer (P-2): The sum of (n+n*+v) ranges from 1 to 15, preferably from 1 to 11, and even better from 1 to 9; The sum of -- (L^+L*) ranges from 1 to 500, preferably from 2 to 500, and even better from 3 to 300. -- The blocks (1) and (2) are systematically distributed; In the above formula (I): -- At least one of R1 to R4 has a group of formula (II), -- One of R11 or R12 and one of R13 to R15 have a group of formula (III); and In equations (III) and (IV), the repeating unit systems are structurally distributed. In the above formula (III) -- When a is 1, at least one of v^ and L^ is not 0, and In the above formula (IV) -- At least one of n* and L* is not zero.

[0055] Preferably, in the copolymers (P-1) and (P-2), each of (E) and (E^) has a group of the following formula: -(CR 100R 101CR 102R 103) L-(CR 110R 111CR 112R 113) m- in L and m are each independent integers from 1 to 250, more preferably from 2 to 250, such that the sum of L+m is from 2 to 250; R100, R101, R110, and R111 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 halogen atoms, preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR 200, wherein R 200 is a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the formula -CF 2OR 201, wherein R 201 is a perfluorinated alkyl chain comprising 1 to 6 carbon atoms with one or more oxyether atoms inserted as desired; or One of R100 and R101 and one of R102 and R103 are fluorine atoms, and the other of R100 and R101 and the other of R102 and R103 together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; or One of R110 and R111 and one of R112 and R113 are fluorine atoms, and the other of R110 and R111 and the other of R112 and R113 together form a fully halogenated cyclic ring with 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed; Its premise is -(CR 100R 101CR 102R 103) L- and -(CR 110R 111CR 112R 113) m- are distinct from each other and are statistically distributed.

[0056] The copolymer (P) according to the invention can be advantageously prepared by a method that can be easily scaled up.

[0057] Preferably, in the method (P) of the present invention, the amount of the compound having formula (Xp) is less than 3 wt.% of the amount of PFPE peroxide, or even more preferably less than 1 wt.%.

[0058] Preferably, the PFPE peroxide system comprises a per-fluoropolyether polymer having two ends, each of which comprises a per-fluoroalkyl chain having 1 to 3 carbon atoms, and optionally contains one or more chlorine atoms or a functional end group selected from fluoropolymers, fluoroformates and ketones, the ends being bonded to the opposite side of the per-fluoropolyether chain, the per-fluoropolyether chain comprising, preferably, the following: repeating units independently selected from the group consisting of formulas (Rf-i) to (Rf-v) as defined above and having a peroxide content (PO) between 0.1 and 4, preferably between 0.1 and 3.5, the peroxide content being defined as the number of grams of active oxygen in 100 g of PFPE peroxide (Mw=16).

[0059] PFPE peroxides can be used as is, or they can undergo partial reduction of peroxide bonds, for example by chemical reduction, UV treatment, or heat treatment.

[0060] Preferably, in the compound having formula (Xp), when t is 1, one, two, three or four unsaturated portions are bonded to the same or different atoms belonging to R 10, preferably carbon atoms.

[0061] Preferably, the at least one compound having formula (Xp) conforms to the following formula: CF² = CF(R 10) tCF = CF² Where t is zero or 1, R 10 satisfies one of the following formulas: (R 10-i) -(CF 2) d(O) e(CF 2O) fR CF(O) e*(CF 2) d*(CF2O) f* in Each of d, d*, e, e*, f, and f* is independently zero or 1, and R CF series refers to perfluorinated alkyl chains containing 1 to 12, preferably 1 to 8, carbon atoms, with one or more oxygen atoms inserted as needed. (R 10-ii) -O-(C 3F 6O) h-(CF 2) i-(C 3F 6O) jO- Where h = j and h + j ranges from 2 to 6, and i ranges from 2 to 6.

[0062] Preferably, the compound having formula (Xp) is selected from the group consisting of, more preferably, the following: CF 2=CFCF=CF 2 CF 2=CFOCF=CF 2 CF² = CFCF² + 2OCF² + 2CF = CF² CF² = CFO - (CF²) 3CF = CF² CF 2=CFCF 2O(CF 2) 3OCF 2-CF=CF 2 CF 2=CFCF 2CF=CF 2 CF² = CF(CF²) 2CF = CF² CF² = CF(CF²) 3CF = CF² CF² = CF(CF²) 4CF = CF² CF² = CFOCF² + 2OCF = 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 CF 2=CFCF 2O(CF 2) 2OCF 2O-CF=CF 2 CF 2=CFCF 2O(CF 2) 3OCF 2O-CF=CF 2 CF 2=CFCF 2O(CF 2) 4OCF 2OCF=CF 2 CF 2=CFCF 2O(CF 2) 6OCF 2CF=CF 2 CF 2=CFO-CF 2O-(CF 2) 2O-CF 2O-CF=CF 2 CF 2=CFO-CF 2O-(CF 2) 3O-CF 2O-CF=CF 2 CF 2=CFO-CF 2O-(CF 2) 4O-CF 2O-CF=CF 2 CF² = CFO - (CF²O)⁶ - CF = CF² CF 2=CFO-(CF 2CF 2O) 2-CF=CF 2 CF 2=CFO-(CF 2CF 2O) 2-CF 2OCF=CF 2 CF 2=CFO(C 3F 6O) h-(CF 2) i-(C 3F 6O) j-OCF=CF 2 Where h and j are the same and Their sum is from 2 to 6 and i is from 2 to 6.

[0063] According to a particularly preferred embodiment, the at least one compound having formula (Xp) conforms to the following formula: CF² = CF(R 10) tCF = CF² Where t is 1 and R 10 conforms to the following formula: (R 10-i) -(CF 2) d(O) e(CF 2O) fR CF(O) e*(CF 2) d*(CF2O) f* in d, f, d*, and f* are all zero. e and e* series 1, and The R CF series comprises straight-chain perfluorinated alkyl chains of 1 to 10, preferably 1 to 8, carbon atoms.

[0064] According to a preferred embodiment, the method (P) of the present invention is carried out by contacting PFPE peroxide and the compound having the formula (Xp) with at least two of the compounds (O).

[0065] Preferably, the first compound (O) is selected from the group consisting of, and more preferably, of: fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and trifluorochloroethylene (CTFE). TFE and HFP are particularly preferred.

[0066] Preferably, the second compound (O) is selected from the group consisting of, and more preferably, the following: (ii) CF 2 = CFOR f, in R f series C1-C6 (per)fluoroalkyl, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"); C1-C12 [(per)fluoro]oxoalkyl group containing a chain oxygen atom, preferably perfluoro-2-propoxypropyl (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"); group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein R f2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom, preferably R f2 series -CF2CF3 (MOVE1). -CF 2CF 2OCF 3 (MOVE2), or -CF 3 (MOVE3); (iii) Perfluorinated dioxins having the following formula: Each of Rf3, Rf4, Rf5, and Rf6 may be the same as or different from each other, and is independently selected from the group consisting of fluorine atoms and C1-C6 perfluoroalkyl groups that contain one or more oxygen atoms as desired, such as especially -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, and particularly preferably PAVE and MOVE as defined in (i).

[0067] According to a first embodiment, the method [method (P1)] for manufacturing the copolymer (P1) as defined above includes the following steps: a*) Contact at least one peroxide (per)fluoropolyether polymer [PFPE peroxide] with the following: - At least one perfluorinated compound having the formula (Xp): in Each of R 21 to R 23 and R 31 to R 33 is independently a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms. R 10 series oxygen atoms, or, if desired and preferably, perfluorinated alkyl chains containing 2 to 18 carbon atoms with and / or containing at least one oxygen atom, inserted. The t series can be either zero or 1, with 1 being preferable. Each of z* and z** is independently 1 or 2; and - At least one compound selected from the group consisting of, preferably, the following: [compound(O)] (i) Fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and trifluorochloroethylene (CTFE); (ii) CF 2 = CFOR f, in R f series C1-C6 (per)fluoroalkyl, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"); C1-C12 [(per)fluoro]oxoalkyl group containing a chain oxygen atom, preferably perfluoro-2-propoxypropyl (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"); group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein R f2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom, preferably R f2 series -CF2CF3 (MOVE1). -CF 2CF 2OCF 3 (MOVE2), or -CF 3 (MOVE3); (iii) Perfluorinated dioxins having the following formula: Each of Rf3, Rf4, Rf5, and Rf6 may be the same as or different from each other, and is independently selected from the group consisting of: fluorine atoms and C1-C6 perfluoroalkyl groups containing one or more oxygen atoms as needed, such as especially -CF3, -C2F5, -C3F7, -OCF3, and -OCF2CF2OCF3; in The amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide; b*) React the PFPE peroxide, the compound having the formula (Xp), and the at least one compound (O) in the presence of UV radiation or heating; c*) fluorination is performed to obtain the copolymer (P1).

[0068] Preferably, step (a*) includes contacting the at least one PFPE peroxide with at least one compound having the formula (Xp) and the compound (O) in two ways.

[0069] Preferably, the first compound (O) is selected from the group consisting of, and more preferably, of: fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and trifluorochloroethylene (CTFE). TFE and HFP are particularly preferred.

[0070] Preferably, the second compound (O) is selected from the group consisting of, and more preferably, the following: (ii) CF 2 = CFOR f, in R f series C1-C6 (per)fluoroalkyl, preferably -CF3, -C2F5, -C3F7 (hereinafter also referred to as "PAVE"); C1-C12 [(per)fluoro]oxoalkyl group containing a chain oxygen atom, preferably perfluoro-2-propoxypropyl (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"); group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein R f2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom, preferably R f2 series -CF2CF3 (MOVE1). -CF 2CF 2OCF 3 (MOVE2), or -CF 3 (MOVE3); (iii) Perfluorinated dioxins having the following formula: Each of Rf3, Rf4, Rf5, and Rf6 may be the same as or different from each other, and is independently selected from the group consisting of fluorine atoms and C1-C6 perfluoroalkyl groups that contain one or more oxygen atoms as desired, such as especially -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, and particularly preferably PAVE and MOVE as defined in (i).

[0071] Steps (a*) and (b*) can be performed in the presence of a fluorinated solvent. Preferably, the fluorinated solvent is selected from the group consisting of: perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, and hydrofluoropolyethers.

[0072] Preferably, step (b*) is performed in the presence of UV radiation for a period of 2 to 60 hours.

[0073] Preferably, step (b*) is performed in the presence of UV radiation at a temperature ranging from -60°C to +60°C, more preferably from -20°C to +40°C, and even more preferably from 0°C to 30°C.

[0074] As an alternative, step (b*) can be performed under heat treatment, preferably by heating at a temperature ranging from 100°C to 250°C.

[0075] Those skilled in the art will know 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.

[0076] Preferably, step (c*) is performed by fluorine treatment in the presence of anhydrous nitrogen gas.

[0077] Preferably, step (c*) is performed in the presence of UV radiation or under heating. Alternatively, step (c*) can be performed as a chemically assisted fluorination.

[0078] Preferably, the method (P1) includes a solvent removal step (d*) and / or a fractionation step (e*) after step (c*).

[0079] The solvent removal step (d*) can be carried out by evaporation, for example by vacuum distillation.

[0080] The fractionation step (e*) can be carried out by solvent extraction. When the fractionation step is carried out by precipitation fractionation, supercritical CO2, hexafluoroxylene, or hydrofluorocarbons and mixtures thereof are used as solvents. Supercritical CO2 is preferred.

[0081] As explained above, although purification steps can be performed, those skilled in the art will understand that at the end of method (P1), copolymers (P) according to the invention are obtained in the form of a mixture containing more than one copolymer (P), each copolymer being characterized by different viscosities and / or molecular weights and / or substituents.

[0082] According to the second embodiment, the method for manufacturing copolymer (P2) [method (P2-a)] includes the following steps: a') Contact at least one peroxide (per)fluoropolyether polymer [PFPE peroxide] with at least one compound (O) as defined above; b') React the PFPE peroxide and the compound (O) in the presence of UV radiation or heating; c') Stop the UV radiation or heating; d') Contact the reaction mixture with at least one perfluorinated compound having the formula (Xp): in Each of R 21 to R 23 and R 31 to R 33 is independently a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms. R 10 series oxygen atoms, or preferably perfluorinated alkyl chains containing 2 to 18 carbon atoms with and / or containing at least one oxygen atom inserted, The t series can be either zero or 1, with 1 being preferable. Each of z* and z** is independently 1 or 2. in The amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide; e') Allow the reaction to proceed in the presence of UV radiation or heating; and f') fluorination, thereby obtaining the copolymer (P2).

[0083] Preferably, step (a') includes contacting the at least one PFPE peroxide with at least two compounds (O).

[0084] Advantageously, the first compound (O) and the second compound (O) conform to the definitions provided above.

[0085] Alternatively, the method for manufacturing copolymer (P2) [method (P2-b)] includes the following steps: a”) Contact at least one peroxy(per)fluoropolyether polymer [PFPE peroxide] with at least one perfluorinated compound having the formula (Xp): in Each of R 21 to R 23 and R 31 to R 33 is independently a fluorine atom and a perfluorinated alkyl group having 1 to 3 carbon atoms. R 10 series oxygen atoms, or preferably perfluorinated alkyl chains containing 2 to 18 carbon atoms with and / or containing at least one oxygen atom inserted, The t series can be either zero or 1, with 1 being preferable. Each of z* and z** is independently 1 or 2. in The amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide; b) React the PFPE peroxide and the compound having formula (Xp) in the presence of UV radiation or heating; c) Stop the UV radiation or heating; d”) Contact the reaction mixture obtained in step c”) with at least one compound (O) as defined above; e”) allows the reaction to proceed in the presence of UV radiation or heating; and The copolymer (P2) is obtained by fluorination of f”).

[0086] Preferably, step (d”) includes contacting the reaction mixture obtained in step (c”) with at least two compounds (O).

[0087] Advantageously, the first compound (O) and the second compound (O) conform to the definitions provided above.

[0088] Steps (a') to (c') and steps (a”) to (c”) can be carried out in the presence of a fluorinated solvent.

[0089] Preferably, the fluorinated solvent is selected from the group consisting of: perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, and hydrofluoropolyethers.

[0090] Preferably, steps (b') and (b”) are performed independently in the presence of UV radiation for a period of 2 to 60 hours.

[0091] Preferably, steps (b') and (b”) are carried out independently in the presence of UV radiation at temperatures ranging from -60°C to +60°C, more preferably from -20°C to +40°C, and even more preferably from 0°C to 30°C.

[0092] Alternatively, steps (b') and (b”) are performed independently under heat treatment, preferably by heating at a temperature ranging from 100°C to 250°C.

[0093] Those skilled in the art will know 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.

[0094] Preferably, steps (f') and (f”) are each performed by fluorine treatment in the presence of anhydrous nitrogen gas.

[0095] Preferably, steps (f') and (f'') are each performed in the presence of UV radiation or under heating. Alternatively, steps (f') and (f''') are each performed as chemically assisted fluorination.

[0096] Preferably, the methods (P2-a) and (P2-b) include solvent removal steps (g') and (g”) and / or fractionation steps (h') and (h”) after steps (f') and (f”), respectively.

[0097] The solvent removal step (g') or (g”) can be carried out by evaporation, for example by vacuum distillation.

[0098] The fractionation step (h') or (h”) can be carried out by solvent extraction. When the fractionation step is carried out by precipitation fractionation, supercritical CO2, hexafluoroxylene, or hydrofluorocarbons and mixtures thereof are used as solvents. Supercritical CO2 is preferred.

[0099] As explained above, although purification steps can be performed, it will be clear to those skilled in the art that at the end of step (c) or step (d) of methods (P), methods (P1), methods (P2-a) and methods (P2-b), a copolymer (P) according to the invention is obtained as a mixture (P) in the form of a mixture containing more than one copolymer (P), each copolymer being characterized by different viscosities and / or molecular weights and / or substituents.

[0100] Copolymers (P) are advantageously used as lubricants, especially in harsh environments, such as those subjected to a wide range of operating temperatures.

[0101] The copolymer (P) or mixture (P) can be used as is or mixed with one or more additives known to those skilled in the art of lubrication to obtain a composition [composition (CL)].

[0102] For example, the composition (CL) may contain other suitable lubricants as base oils, such base oils being selected from the group consisting of partially fluorinated, fully fluorinated and hydrogenated base oils, provided that the base oils are capable of forming a solution with the copolymer (P).

[0103] Non-limiting examples of fully fluorinated lubricant base oils are based on Those identified as compounds (1)-(8) in [EP 2100909]A (Solvezux).

[0104] For example, suitable additives are selected from thickeners, rust inhibitors, antioxidants, heat stabilizers, pour point depressants, anti-wear agents (including those used for high pressure), dispersants, tracers, dyes, talc, and inorganic fillers.

[0105] Examples of thickeners include talc, silicon dioxide, boron nitride, polyurea, alkali metal or alkaline earth metal terephthalates, calcium soaps and lithium soaps and their complexes, and PTFE (polytetrafluoroethylene); among them, PTFE is preferred.

[0106] Examples of dispersants include surfactants, preferably nonionic surfactants, more preferably (per)fluoropolyether surfactants and (per)fluoroalkyl surfactants.

[0107] Solvents can also be used if required by the application.

[0108] Examples of solvents include fluorinated or partially fluorinated solvents such as Galden® PFPE, Novec® HFE, and other organic solvents such as fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, fluoroalcohols, ketones such as methyl ethyl ketones, alcohols such as isopropanol, esters such as butyl acetate, hydrofluorocarbons, etc.

[0109] Therefore, in another aspect, the present invention relates to a method for lubricating at least one surface of at least one article, the method comprising contacting the copolymer (P) or the mixture (P) with the at least one surface.

[0110] There are no particular limitations on articles that can benefit from the lubricating properties of the copolymer (P), mixture (P), or composition (CL) according to the present invention.

[0111] The article preferably includes at least one metal surface.

[0112] Examples of the 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 for fan clutches or cooling fans; or automatic clutches for heavy-duty trucks, and more particularly, bearings for said clutches.

[0113] The copolymers (P), mixtures (P) or compositions (CL) according to the invention can be advantageously used as damper fluids in damping devices.

[0114] Therefore, in another aspect, the present invention relates to a method for counteracting vibrations and / or shocks in a device, the method comprising providing an apparatus including a damper device comprising at least one copolymer (P), mixture (P), or composition (CL) as defined above.

[0115] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may lead to ambiguity in terminology, then this description shall take precedence.

[0116] The invention will now be described with reference to the following examples, which are merely illustrative and not intended to limit the scope of the invention. [] [Experimental Section]

[0117] [Material]

[0118] Perfluoropolyether oil with peroxide has the following formula: TO-(CF 2CF 2O) m(CF 2O) n-(O) h-T' Number average molecular weight (Mn) = 48600 g / mol m / n = 1.0 and PO = 1.65% T, T'=-CF 3(83%), -C(=O)F(6%), -CF 2C(=O)F(11%) It was obtained by Solvay Specialty Polymers Italy SpA.

[0119] Tetrafluoroethylene (TFE), perfluoro(methyl vinyl ether) (PMVE), and Galden® HT200 are derived from Solvay Specialty Polymers, Italy.

[0120] The perfluoro(bisvinyl ether) (PBVE) was obtained by Anles LLC.

[0121] Hexafluorobenzene is obtained from Sigma Aldrich.

[0122] [method]

[0123] [19F-NMR] [Spectroscopic method:]

[0124] The structure, number-average molecular weight, and composition of the PFPE oils reported in the following examples were obtained using a Varian Mercury 200 MHz spectrometer designed for fluorine nuclei. 19F-NMR spectra were obtained on pure samples using CFCl3 as an internal standard. Hexafluorobenzene was also used as a solvent.

[0125] [Peroxide content] [(PO)] [Confirmed:]

[0126] Peroxide content (PO) is expressed as grams of oxygen peroxide per 100 g of polymer. Peroxide content was analyzed by iodometric titration using a Mettler DL40 apparatus equipped with a platinum electrode. The sensitivity limit for PO determination is 0.0002%.

[0127] [Determination of complex viscosity:]

[0128] According to ISO 6271 Part 10, complex viscosity is measured by frequency sweep test using an MCR502 Anton-Paar rheometer with a parallel plate geometry (25 mm diameter).

[0129] Gel permeation chromatography (GPC) [:]

[0130] HFE7100 was used as the eluent, and analysis was performed using a mixed CCD column and a Waters 410 refractometer detector.

[0131] [Example] [1 -] [Copolymer] [(1)] [The synthesis of] [] []

[0132] The reaction was carried out using a 1000 mL cylindrical photochemical glass reactor equipped with a high-pressure mercury lamp (HANAU TQ150) enclosed in a quartz cylinder, a magnetic stirrer, a thermocouple, and a condenser.

[0133] 200.0 g of starting perfluoropolyether peroxide oil was added together with 1499 g of Galden® HT200 into a photochemical reactor and stirred thoroughly to obtain a homogeneous mixture. The reaction mixture was then cooled to approximately 10°C using an ice / water bath.

[0134] Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 and 1.60 Nl / h, respectively. After the flow started, the UV lamp was turned on. After 4 h, the UV lamp was turned off, and 1.31 g of PBVE was added to the reactor. The UV lamp was then turned on again under vigorous stirring and nitrogen atmosphere.

[0135] After irradiation for 51 hours, the lamp was turned off and the reaction mixture was transferred to a second glass reactor and fluorinated for a total of 24 hours at 40°C in the presence of UV radiation with fluorine gas at a rate of 1.0 Nl / h. 19F-NMR analysis confirmed complete fluorination of the product and the absence of -CF2COF and -COF ends at the chain ends.

[0136] The obtained solution was distilled at 240°C for 4 h in a round-bottom flask equipped with a magnetic stirrer to remove the solvent.

[0137] Distillation is first carried out at atmospheric pressure, then under reduced pressure (0.1 mbar) until the solvent is completely removed.

[0138] 203.4 g of copolymer (1) in the form of a transparent, viscous oil was obtained as a residue and analyzed by iodometric titration to confirm the complete removal of the peroxide units.

[0139] 19F-NMR analysis confirmed the absence of residual peroxides, and the incorporation concentrations of TFE and PMVE were 10.2 and 10.1 wt%, respectively.

[0140] The copolymer (1) has m / n=0.96 and chain ends T, T'= -CF 3.

[0141] [Example] [2 -] [Copolymer] [(2)] [The synthesis of]

[0142] This example uses the same photochemical equipment and perfluoropolyether peroxide precursor as in Example 1.

[0143] 200.8 g of initial perfluoropolyether peroxide oil was loaded into a photochemical reactor along with 1494 g of Galden HT200 and 1.35 g of PBVE and stirred thoroughly to obtain a homogeneous mixture.

[0144] The reaction mixture was then cooled to approximately 10°C using an ice / water bath. Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 and 1.60 Nl / h, respectively. The UV lamp was turned on immediately after the olefin stream started. After 4 h, the olefin stream was interrupted, and the reaction continued under UV radiation for another 51 h.

[0145] Turn off the lamp and transfer the reaction mixture to a second glass reactor for fluorination at 40°C in the presence of UV radiation with fluorine gas at a rate of 1.0 Nl / h for a total of 24 hours.

[0146] 19F-NMR analysis confirmed that the product was fully fluorinated and that there were no -COF or -CF2COF ends at the chain ends.

[0147] The obtained solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240°C for 4 h to remove the solvent. The distillation was first carried out at atmospheric pressure, and then under reduced pressure (0.1 mbar) until the solvent was completely removed.

[0148] 205.8 g of copolymer (2) in the form of a transparent, viscous oil was obtained as a residue and analyzed by iodometric titration to confirm the complete removal of the peroxide unit.

[0149] 19F-NMR analysis confirmed the absence of residual peroxides, and the incorporation concentrations of TFE and PMVE were 8.8 and 11.8 wt%, respectively.

[0150] The copolymer (2) has m / n=0.99, T, T'=-CF 3.

[0151] [Example] [3C -] [No] [PBVE] [Comparative polymers] [(C-1^)] [The synthesis of]

[0152] This comparative example uses the same photochemical equipment and perfluoropolyether peroxide precursor as in Example 1.

[0153] 200.4 g of the initial perfluoropolyether peroxide oil was loaded into the photochemical reactor along with 1502 g of Galden® HT200 and stirred thoroughly to obtain a homogeneous mixture.

[0154] The reaction was carried out as described in Example 2. The reaction mixture was then cooled to approximately 10°C using an ice / water bath. Two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 2.20 and 1.60 Nl / h, respectively. The UV lamp was turned on immediately after the olefin stream started. After 4 h, the olefin stream was interrupted and the reaction was continued under UV irradiation for 51 h.

[0155] 19F-NMR analysis confirmed that the product was fully fluorinated and that there were no -CF 2COF and -COF ends at the chain ends.

[0156] Distillation is performed as described in Example 2.

[0157] 206.3 g of the comparative polymer (C-1^) in the form of a transparent, viscous oil was obtained as a residue and analyzed by iodometric titration to confirm the complete removal of the peroxide unit.

[0158] 19F-NMR analysis confirmed the absence of residual peroxides. The contrast polymer (C-1^) has m / n=1.0 and T, T'=-CF 3.

[0159] The increased molecular weight distribution and complex viscosity of the copolymers (1) and (2) according to the invention confirm chain elongation 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 ends, wherein the first ends of the first and second PFPE chains comprise perfluorinated alkyl groups and the second ends of the first and second PFPE chains are bonded to each other by: - ​​a first block [block (1)] conforming to formula (I) where n is 0 or an integer from 1 to 3; R1 to R4 are each independently selected from the group comprising: fluorine atoms, perfluorinated linear or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (II): (II) -(R10)t[C(R11)(R12)-C(R13)(R14)(R15)]z where R10 is an oxygen atom, or, if desired, a divalent / trivalent / tetravalent perfluorinated alkyl chain having 1 to 24 carbon atoms with and / or containing at least one oxygen atom inserted, t is zero or 1, and z is an integer from 1 to 3. R11 to R15 are each independently selected from the group consisting of: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (III): -[(A^)a^-(B^)v^-(E^)L^]u^-(C^)-T (III) where a^ is zero or 1, v^ is zero or an integer from 1 to 3, L^ is zero or an integer from 1 to 250, u^ is zero or an integer from 1 to 50, A^ is a PFPE chain, B^ is a group having the following formula: -[C(R1^)(R2^)-C(R3^)(R4^)]- where R1^ to R4^ each independently has the meaning defined above for each of R1 to R4, and E^ is a group having the formula -(CR100^R101^CR102^R103^)-. Wherein R100^ and R101^ are independently selected from halogen atoms, and R102^ and R103^ are independently selected from halogen atoms; a straight-chain or branched alkyl chain containing 1 to 6 carbon atoms; -OR200, wherein R200 is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or a group having the formula -CF2OR201, wherein R201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted as desired; or one of R100^ and R101^ and one of R102^ and R103^ is a fluorine atom and the other of R100^ and R101^ and the other of R102^ and R103^ together form a perhalogenated cyclic ring having 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; C^ is a PFPE chain, and T is a perfluorinated alkyl group;And - the second block [block (2)] conforming to formula (IV): -[(CR1*R2*CR3*R4*)n*-(E)L]- (IV) where n* is zero or an integer from 1 to 10, L is zero or an integer from 1 to 250; each of R1* to R4* is selected from the group consisting of: fluorine atoms, perfluorinated linear or branched alkyl groups having 1 to 6 carbon atoms, groups having formula (II) as defined above, E having the same meaning as provided above for E^; the premise being: - in the copolymer (P) -- the sum of (n+n*+v^) is from 1 to 15; -- the sum of (L+L^) is from 1 to 500, -- the blocks (1) and the blocks (2) are systematically distributed; - in formula (I): -- at least one of R1 to R4 has a group of formula (II), -- One of R11 or R12 and one of R13 to R15 have a group of formula (III); - in formula (III) and formula (IV) -- the repeating unit is systematically distributed; - in formula (III) -- when a is 1, at least one of v^ and L^ is not 0; and - in formula (IV) -- at least one of n* and L is not zero.

2. The copolymer (P) as claimed in claim 1, wherein: - The first chain ends of the first and second PFPE chains and the T in formula (III) are the same or different from each other, and are perfluorinated alkyl groups having 1 to 3 carbon atoms; and / or - The first and second PFPE chains, the A^ and the C^ are the same or different from each other; and / or - The first PFPE chain is bonded to the block (1) by a σ bond or a group selected from -CF2-, -CF2CF2- or -O- by a group -(C)-; and / or - The block (2) is bonded to the second PFPE chain by a σ bond or a group selected from -CF2-, -CF2CF2- or -O- by a group -(C)-; and / or - Each of the PFPE chains comprises a partially or fully fluorinated chain [chain (Rf)] containing a repeating unit R°, the repeating unit being independently selected from the group consisting of: (i) -CFXO-, wherein X is F or CF3; (ii) -CFXCFXO-, wherein X is the same or different each time it appears, and is of the F or CF3 series, wherein at least one of X is of the -F series; (iii) -CF2CF2CW2O-, wherein each W is the same or different from one another, and is of the F, Cl, or H series; (iv) -CF2CF2CF2CF2O-; (v) -(CF2)j-CFZ-O-, wherein j is an integer from 0 to 3 and Z is a group having the general formula -OR(fa)-T, wherein R(fa) is a fluoropolyoxyalkyl chain comprising 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently of the F or CF3 series and T is of the C1-C3 perfluoroalkyl series.

3. The copolymer (P) as claimed in claim 1 or claim 2, wherein, In formula (II): - t series 0; or - t series 1 and R10 conforms to one of the following formulas: (R10-i) -(CF2)d(O)e(CF2O)fRCF(O)e*(CF2)d*(CF2O)f* where each of d, d*, e, e*, f and f* is independently zero or 1, and the RCF series is a perfluoroalkyl chain containing 1 to 12 carbon atoms with one or more oxygen atoms inserted as needed (R10-ii) -O-(C3F6O)h-(CF2)i-(C3F6O)jO- where h=j and h+j series from 2 to 6, and i series from 2 to 6.

4. The copolymer (P) as claimed in claim 1, wherein, In formula (II): - z equals 1 and R10 is an oxygen atom or, as needed, a divalent perfluorinated alkyl chain containing 1 to 24 carbon atoms with and / or containing at least one oxygen atom; and / or - one of the substituents R11 and R12 is a group having formula (III), and the other substituent is selected from fluorine atoms or a perfluorinated alkyl chain having 1 to 3 carbon atoms; and / or - one of the substituents R13 to R15 is a group having formula (III), and the other two substituents are independently selected from fluorine atoms or a perfluorinated alkyl chain having 1 to 3 carbon atoms.

5. The copolymer (P) as claimed in claim 1, wherein: - In equation (III), -(E^)L^- satisfies the following equation: -(CR100^R101^CR102^R103^)l^-(CR110^R111^CR112^R113^)m^- where l^ and m^ are each independent integers from 1 to 250, such that the sum of L+m ranges from 2 to 250; R100^, R101^, R110^, and R111^ are independently selected from halogen atoms, and R102^, R103^, R112^, and R113^ are independently selected from halogen atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms; -OR200, wherein R200 is a straight-chain or branched perfluorinated chain comprising 1 to 6 carbon atoms or a group having the formula -CF2OR201, wherein R201 is a perfluorinated alkyl chain comprising 1 to 6 carbon atoms with one or more oxygen ether atoms inserted as desired; or one of R100^ and R101^ is selected from halogen atoms. A fluorine atom in one of R102^ and R103^ and another of R100^ and R101^ together with another of R102^ and R103^ form a fully halogenated cyclic ring having 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; or a fluorine atom in one of R110^ and R111^ and another of R112^ and R113^ together with another of R110^ and R111^ and another of R112^ and R113^ form a fully halogenated cyclic ring having 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; The premise is that -(CR100^R101^CR102^R103^)l^- and -(CR110^R111^CR112^R113^)m^- are distinct from each other and are statistically distributed; and / or - in equation (IV), -(E)L- conforms to the following: -(CR100R101CR102R103)l-(CR110R111CR112R113)m- where each of l, m, R100, R101, R110, R111, R102, R103, R112 and R113 has the meaning defined above for l^, m^, R100^, R101^, R110^, R111^, R102^, R103^, R112^ and R113^ respectively.

6. The copolymer (P) of claim 1, wherein the copolymer (P) does not contain side groups comprising any portion capable of further chemical reaction, such as unsaturated portions.

7. The copolymer (P) of claim 1, wherein the copolymer (P) is a block copolymer [(P-1)] comprising: first and second PFPE chains each having two ends, wherein the first end of the first and second PFPE chains comprises a perfluorinated alkyl group and the second ends of the first and second PFPE chains are bonded to each other by: - ​​a block conforming to formula (IV): -[(CR1*R2*CR3*R4*)n*-(E)L]- (IV) wherein n* is an integer from 1 to 10; L is zero or an integer from 1 to 250; each of R1* to R4* is selected from the group comprising: fluorine atoms, perfluorinated linear or branched alkyl groups having 1 to 3 carbon atoms, and groups having formula (II): (II) -(R10)t[C(R11)(R12)-C(R13)(R14)(R15)]z R10 refers to an oxygen atom, or, as needed, a divalent / trivalent / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms with and / or containing at least one oxygen atom; t refers to zero or 1; z refers to an integer from 1 to 3; R11 to R15 are each independently selected from the group consisting of: fluorine atoms, perfluorinated straight-chain or branched alkyl groups having 1 to 3 carbon atoms, and groups having formula (III): -[(A^)a^-(B^)v^-(E^)L^]u^-(C^)-T (III) where a^ refers to zero or 1, v^ refers to zero or an integer from 1 to 3, L^ refers to an integer from 1 to 250, and u^ refers to an integer from 1 to 50; A^ refers to a PFPE chain, and B^ refers to a group having the following formula: -[C(R1^)(R2^)-C(R3^)(R4^)]- Wherein R1^ to R4^ each independently has the meaning defined above for each of R1 to R4, and E^ is a group having the formula -(CR100^R101^CR102^R103^)-. Wherein R100^ and R101^ are independently selected from halogen atoms, and R102^ and R103^ are independently selected from halogen atoms; a straight-chain or branched alkyl chain containing 1 to 6 carbon atoms; -OR200, wherein R200 is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or a group having the formula -CF2OR201, wherein R201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxyether atoms inserted as needed; or one of R100^ and R101^ and one of R102^ and R103^ is a fluorine atom and the other of R100^ and R101^ and the other of R102^ and R103^ together form a perhalogenated cyclic ring having 4 to 6 members, which may contain heteroatoms such as oxygen atoms as needed;C is a PFPE chain, and T is a perfluorinated alkyl group; E has the same meaning as provided above for E^; The premise is 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, and -- the repeating units in formulas (III) and (IV) are systematically distributed; and - in formula (IV): -- at least one of R1^ to R4^ has a group of formula (II), -- one of R11 or R12 and one of R13 to R15 have a group of formula (III).

8. The copolymer (P) of claim 1, wherein the copolymer (P) is a block copolymer [(P-2)] comprising first and second PFPE chains each having two ends, wherein, The first end of the first and second PFPE chains comprises a perfluorinated alkyl group and the second end of the first and second PFPE chains are bonded to each other by the following: - a first block conforming to formula (I) [block (1)] where n is an integer from 1 to 3; R1 to R4 are each independently selected from the group comprising: fluorine atom, perfluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and a group having formula (II): (II) -(R10)t[C(R11)(R12)-C(R13)(R14)(R15)]z where R10 is an oxygen atom, or a divalent / trivalent / tetravalent perfluorinated alkyl chain having 1 to 24 carbon atoms with and / or containing at least one oxygen atom inserted as needed, t is zero or 1, and z is an integer from 1 to 3. R11 to R15 are each independently selected from the group comprising: fluorine atoms, perfluorinated linear or branched alkyl groups having 1 to 6 carbon atoms, and groups having formula (III): -[(A^)a^-(B^)v^-(E^)L^]u^-(C^)-T (III) where a^ is zero or 1, v^ is zero or an integer from 1 to 3, L^ is an integer from 1 to 250, u^ is zero or an integer from 1 to 50, A^ is a PFPE chain, B^ is a group having the following formula: -[C(R1^)(R2^)-C(R3^)(R4^)]- where R1^ to R4^ each independently has the meaning defined above for each of R1 to R4, and E^ is a group having the following formula: -(CR100^R101^CR102^R103^)- Wherein R100^ and R101^ are independently selected from halogen atoms, and R102^ and R103^ are independently selected from halogen atoms; a straight-chain or branched alkyl chain containing 1 to 6 carbon atoms; -OR200, wherein R200 is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or a group having the formula -CF2OR201, wherein R201 is a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted as desired; or one of R100^ and R101^ and one of R102^ and R103^ is a fluorine atom and the other of R100^ and R101^ and the other of R102^ and R103^ together form a perhalogenated cyclic ring having 4 to 6 members, which may contain heteroatoms such as oxygen atoms as desired; C^ is a PFPE chain, and T is a perfluorinated alkyl group;And - the second block [block (2)] conforming to formula (IV): -[(CR1*R2*CR3*R4*)n*-(E)L*]- (IV) where n* is 0 or an integer from 1 to 10, L* is 0 or an integer from 1 to 250; each of R1* to R4* is selected from the group containing: fluorine atom, perfluorinated straight-chain or branched alkyl group having 1 to 6 carbon atoms, group having formula (II) as defined above, E has the same meaning as provided above for E^; The premise is that: - In the copolymer (P-2): -- The sum of (n+n*+v) is from 1 to 15; -- The sum of (L^+L*) is from 1 to 500, and -- The blocks (1) and (2) are systematically distributed; and - In the formula (I): -- At least one of R1 to R4 has a group of formula (II), -- One of R11 or R12 and one of R13 to R15 have a group of formula (III); And - in equations (III) and (IV), the repeating unit system is systematically distributed, - in equation (III) -- when a is 1, at least one of v^ and L^ is not 0, and - in equation (IV), at least one of n* and L* is not zero.

9. A mixture [mixture (P)] comprising two or more copolymers (P) as defined in any one of claims 1 to 8.

10. A method [method (P)] for manufacturing a copolymer (P) as defined in any one of claims 1 to 8, said method (P) comprising at least one step of contacting the following in the presence of UV radiation or under heating: - at least one (per)fluoropolyether polymer [PFPE peroxide] containing a peroxy group; - at least one perfluorinated compound having the formula (Xp): wherein each of R21 to R23 and R31 to R33 is independently a fluorine atom, a perfluorinated alkyl group having 1 to 3 carbon atoms, R10 is an oxygen atom, or, if desired, a perfluorinated alkyl chain having 2 to 18 carbon atoms with and / or containing at least one oxygen atom inserted, t is zero or 1; each of z* and z** is independently 1 or 2; and - at least one compound [compound (O)] selected from the group consisting of: (i) a fully halogenated olefin having 2 to 8 carbon atoms; (ii) CF2=CFORf, Wherein Rf is a C1-C6 (per)fluoroalkyl group; a C1-C12 [(per)fluoro]-oxyalkyl group containing a chain oxygen atom; a group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein Rf2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom; (iii) a perfluorodioxane having the following formula: wherein each of Rf3, Rf4, Rf5, and Rf6 is the same as or different from each other, and is independently selected from the group consisting of: fluorine atoms and C1-C6 perfluoroalkyl containing one or more oxygen atoms as desired, such as especially -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; provided that the amount of the compound having formula (Xp) is less than 5 wt. of the amount of the PFPE peroxide.

11. As in the method (P) of request item 10, wherein, The PFPE peroxide system comprises a per-fluoropolyether polymer with two ends, each of which comprises a per-fluoroalkyl chain having 1 to 3 carbon atoms and, if desired, one or more chlorine atoms or functional end groups selected from fluoropolymers, fluoroformates and ketones, the ends being bonded to opposite sides of the per-fluoropolyether chain, the per-fluoropolyether chain comprising repeating units independently selected from the group consisting of formulas (Rf-i) to (Rf-v) as defined above and having a peroxide content (PO) between 0.1 and 4, the peroxide content being defined as the number of grams of active oxygen in 100 g of PFPE peroxide (Mw=16).

12. As in method (P) of request item 10 or 11, wherein, The at least one compound having the formula (Xp) conforms to the following formula: CF2=CF(R10)tCF=CF2 where t is zero or 1, R10 conforms to one of the following formulas: (R10-i) -(CF2)d(O)e(CF2O)fRCF(O)e*(CF2)d*(CF2O)f* where each of d, d*, e, e*, f and f* is independently zero or 1, and RCF is a perfluoroalkyl chain containing 1 to 12 oxygen atoms as needed (R10-ii) -O-(C3F6O)h-(CF2)i-(C3F6O)jO- where h=j and h+j is from 2 to 6, and i is from 2 to 6.

13. As in the method (P) of request item 10, wherein, Two of the compounds (O) are used.

14. As in the method (P) of request item 13, wherein, - The first compound (O) is selected from the group consisting of: fully halogenated olefins containing 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and trifluorochloroethylene (CTFE); and - The second compound (O) is selected from the group consisting of: (ii) CF2=CFORf, wherein Rf is a C1-C6 (per)fluoroalkyl group; a C1-C12 [(per)fluoro]-oxyalkyl group containing a chain oxygen atom; a group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein Rf2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom; (iii) a perfluorodioxane having the following formula: Each of Rf3, Rf4, Rf5, and Rf6 may be the same as or different from each other, and is independently selected from the group consisting of fluorine atoms and C1-C6 perfluoroalkyl groups that, as needed, contain one or more oxygen atoms, such as especially -CF3, -C2F5, -C3F7, -OCF3, and -OCF2CF2OCF3.

15. A method for manufacturing a copolymer (P-1) as defined in claim 7 [method (P1)], said method (P1) comprising the steps of: a*) contacting at least one peroxy(per)fluoropolyether polymer [PFPE peroxide] with: - at least one perfluorinated compound having the formula (Xp): wherein each of R21 to R23 and R31 to R33 is independently a fluorine atom, a perfluorinated alkyl group having 1 to 3 carbon atoms, R10 being an oxygen atom, or, if desired, a perfluorinated alkyl chain having 2 to 18 carbon atoms with and / or containing at least one oxygen atom, t being zero or 1; each of z* and z** being independently 1 or 2; and - at least one compound selected from the group consisting of: (i) a fully halogenated olefin having 2 to 8 carbon atoms, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluorochloroethylene (CTFE); (ii) CF2=CFORf, Wherein Rf is a C1-C6 (per)fluoroalkyl group; a C1-C12 [(per)fluoro]-oxyalkyl group containing a chain oxygen atom; a group -CF2ORf2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), wherein Rf2 is selected from the group consisting of: C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl containing at least one chain oxygen atom; (iii) a perfluorodioxane having the following formula: wherein each of Rf3, Rf4, Rf5, and Rf6 is the same as or different from each other, and is independently selected from the group consisting of: fluorine atoms and C1-C6 perfluoroalkyl containing one or more oxygen atoms as desired, such as especially -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; wherein the amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide. b*) React the PFPE peroxide, the compound having the formula (Xp), and the at least one compound (O) in the presence of UV radiation or heating; c*) Fluoride to obtain the copolymer (P-1).

16. A method for producing a copolymer (P-2) as defined in claim 8 [method (P2-a)], said method (P2-a) comprising the steps of: a') contacting at least one peroxy(per)fluoropolyether polymer [PFPE peroxide] with at least one compound (O) as defined above; b') reacting the PFPE peroxide and the compound (O) in the presence of UV radiation or heating; c') stopping the UV radiation or heating; d') contacting the reaction mixture with at least one perfluorinated compound having the formula (Xp): wherein each of R21 to R23 and R31 to R33 is independently a fluorine atom, a perfluorinated alkyl group having 1 to 3 carbon atoms, R10 is an oxygen atom, or, if desired, a perfluorinated alkyl chain having 2 to 18 carbon atoms with and / or containing at least one oxygen atom, t is zero or 1; each of z* and z** is independently 1 or 2. The amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide; e') the reaction is carried out in the presence of UV radiation or heating; and f') fluorination is performed to obtain the copolymer (P-2).

17. A method for manufacturing a copolymer (P-2) as defined in claim 8 [method (P2-b)], wherein, The method (P2-b) comprises the following steps: a”) contacting at least one perfluorinated (per)fluoropolyether polymer [PFPE peroxide] with at least one perfluorinated compound having formula (Xp): wherein each of R21 to R23 and R31 to R33 is independently a fluorine atom, a perfluorinated alkyl group having 1 to 3 carbon atoms, R10 is an oxygen atom, or, as desired, a perfluorinated alkyl chain having 2 to 18 carbon atoms with and / or containing at least one oxygen atom, t is zero or 1; each of z* and z** is independently 1 or 2, wherein the amount of the compound having formula (Xp) is less than 5 wt.% of the amount of the PFPE peroxide; b”) reacting the PFPE peroxide and the compound having formula (Xp) in the presence of UV radiation or heating; c”) stopping the UV radiation or heating; d”) contacting the reaction mixture obtained in step c”) with at least one compound (O) as defined above; e”) to carry out the reaction in the presence of UV radiation or heating; and f”) fluorination, thereby obtaining the copolymer (P-2).

18. A composition [Composition (CL)] comprising at least one copolymer (P) as defined in any one of claims 1 to 8 or a mixture (P) as defined in claim 9, and at least one base oil selected from the group consisting of partially fluorinated, fully fluorinated, and hydrogenated base oils, provided that the base oil is capable of forming a solution with the copolymer (P) and, if desired, at least one additive selected from thickeners, rust inhibitors, antioxidants, heat stabilizers, pour point depressants, anti-wear agents—including those for high pressure, dispersants, tracers, dyes, talc, and inorganic fillers.

19. A method for lubricating at least one surface of at least one article, the method comprising contacting at least one copolymer (P) as defined in any one of claims 1 to 8, or the mixture (P) as defined in claim 9, or the composition (CL) as defined in claim 18, with said at least one surface.

20. As in request item 19, wherein, The article is selected from pumps used in oil and gas applications, such as electric submersible pumps; rotating machines, such as steam turbines and gas turbines; electrical connectors; bearings for fan clutches or cooling fans; or automatic clutches for heavy-duty trucks, and more particularly, bearings for said clutches.

21. A method for counteracting vibrations and / or shocks in a device, the method comprising providing an apparatus including a damper device comprising at least one copolymer (P) as defined in any one of claims 1 to 8, or the mixture (P) as defined in claim 9, or the composition (CL) as defined in claim 18.