Compositions Comprising (Per)Fluoropolyether Polymers

Abstract

The present invention relates to a composition comprising a (per)fluoropolyether polymer as a base oil and a salt of a (per)fluoropolyether polymer as an additive, thereby having a volume resistivity suitable for use as a lubricant.

Description

[Technical Field]

[0001] This application claims priority to European application No. 23151333.4 filed on January 12, 2023, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a composition comprising a (per)fluoropolyether polymer as a base oil and a salt of a (per)fluoropolyether polymer as an additive, thereby having a volume resistivity suitable for use as a lubricant. [Background technology]

[0003] (Per)fluoropolyether polymers (PFPEs) are a class of fluorinated synthetic fluids that have been known for a long time and are used in formulating lubricants that perform for long periods in harsh environments.

[0004] However, one of the challenges of PFPE-based lubricants is that they have a high dielectric constant and low electrical conductivity. Furthermore, fluorinated PFPE lubricants have poor solubility and / or compatibility with most additives due to their low polarity. Therefore, tailoring the conductivity of PFPE lubricants has proven difficult because conductive additives, which are typically polar species, are immiscible with PFPE lubricants.

[0005] Thus, several approaches have been attempted in the art to tailor the conductivity of PFPE lubricants, as disclosed, for example, in US Patent Application Publication No. 2008 / 0144219 (in the name of HGST Netherlands BV).

[0006] N Suhaila A Japar et al. (International Journal of Engineering & Technology, 7, 3.26, 2018, 23.29) also summarized findings on the use of greases containing PFPE as a base oil and solid particles (fumed silica or polytetrafluoroethylene-PTFE) as a thickener in their paper "Grease and its Application on Electrical Equipment: a Review." Summary of the Invention

[0007] Applicant recognizes that the presence of electrical components continues to increase in many different industries and for a variety of applications. However, exposure to harsh environments, including but not limited to, extreme temperatures, moisture, and corrosion, can cause premature failure of such electrical components. Such components can also experience combustion due to arcing, causing component burnout and consequently shortening their lifespan.

[0008] The applicant was therefore faced with the problem of providing a composition suitable for lubricating electrical components that is suitable for use in a variety of applications and industries, in particular the automotive and electronics industries.

[0009] Such compositions should not only exhibit good electrical conductivity, resulting in low volume resistivity (also called "electrical resistivity" or "electrical resistance"), good viscosity and a high viscosity index (measured in accordance with ASTM D227), but also good compatibility between the base oil and the additives.

[0010] The applicant has surprisingly found a composition which meets the above requirements and which may be used as a lubricant for electrical and electronic components such as electrical connectors, switchgear and circuit breakers, as well as for mechanical parts suitable for use in the automotive industry, such as for lubricating parts such as ball bearings used in electric vehicles in particular.

[0011] Furthermore, the compositions according to the invention can be used to prepare greases suitable for the same applications. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this application: - the use of parentheses around symbols or numbers identifying formulas, for example in expressions such as "polymer (P)", has the sole purpose of better distinguishing the symbols or numbers 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 prefix "(per)" in the term "(per)fluoropolyether" means that the polyether is fully or partially fluorinated.

[0013] In a first aspect, the present invention provides a composition [Composition (COMP)] comprising: - at least one block copolymer [PFPE copolymer] comprising first and second (per)fluoropolyether chains [PFPE chains] each having two chain ends, wherein the first chain ends of the first and second PFPE chains comprise a perfluoroalkyl group, and the second chain ends of the first and second PFPE chains comprise - Formula (I): [ka] (In the formula, n is 0 or an integer of 1 to 3, R1 to R4 each independently represent a fluorine atom, a linear or branched perfluoroalkyl 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 divalent / trivalent / tetravalent perfluoroalkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or containing at least one oxygen atom; t is zero or one, z is an integer from 1 to 3, R 11 ~R 15 are each independently selected from the group including, preferably consisting of, a fluorine atom and a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. and a group of formula (III): -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T (III) (In the formula, a^ is zero or one, 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 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) is the basis of E^ is the formula -(CR 100^ R 101^ CR 102^ R 103^ )- (In the formula, R 100^ and R 101^ are independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, and R 102^ and R103^ is a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S, -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 -CF2OR 201 is a group of R 201 is a perfluoroalkyl 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^ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom. is the basis of C is a PFPE chain, and T is a perfluoroalkyl group. and preferably selected from the group consisting of: at least one 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 zero or an integer from 1 to 250; L is zero or an integer from 1 to 250, and the sum of n* and L is 0 or 1 to 250, R 1^ and R 2^ are independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, and R3^ and R 4^ is a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S, -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 -CF2OR 201 is a group of R 201 is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R 1* and R 2* One of the two and R 3* and R 4* is a fluorine atom, and R 1* and R 2* The other and R 3* and R 4* together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, E has the same meaning as provided for E^ above) at least one second block [block (2)] according to - optionally at least a third block comprising a PFPE chain [block (3)] are connected to each other via In the PFPE copolymer, -- at least one of n, n* and L is different from 0; -- the blocks (1), (2) and, if present, (3) 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 one of which is a group of formula (III) 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 - up to 20.0 wt.-%, based on the total weight of the composition (COMP), of at least one salt of a (per)fluoropolyether polymer [PFPE additive], comprising a (per)fluoropolyether backbone having two chain ends attached to either side of said backbone, wherein at least one chain end is (i)-COO - , [ka] an acid group selected from the group consisting of: (ii) an ammonium group and at least one inorganic or organic counterion; and at least one salt of a (per)fluoropolyether polymer [PFPE additive], comprising at least one group selected from wherein the sum of said PFPE copolymer and said PFPE additive amounts to 100% by weight of composition (COMP).

[0014] If required by the end use, the composition according to the invention (COMP) may contain at least one additional ingredient.

[0015] Such at least one additional component may be selected from the group consisting of rust inhibitors, antioxidants, rheology modifiers, corrosion inhibitors, dyes, and pigments.

[0016] Each such at least one additional component may be present in an amount of 0.1 to 15 wt. %, based on the total weight of the composition (COMP).

[0017] Advantageously, depending on the end use, the composition (COMP) can be used as a lubricant without the need for the addition of solid additives. Thus, according to a preferred embodiment, the composition (COMP) does not contain any solid additives, more particularly additives in the form of solid particles.

[0018] Advantageously, the PFPE copolymer has a viscosity of at least 1,000 mm measured at 20°C according to standard methods such as ASTM D445 or at 1 rad / sec and 25°C using a dynamic mechanical spectrometer, Anton Paar MCR 502 rheometer, equipped with 25 mm parallel plates. 2 / sec viscosity.

[0019] 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 a PFPE copolymer.

[0020] Preferably, the first chain ends of the first and second PFPE chains comprise a linear perfluoroalkyl group having 1 to 3 carbon atoms.

[0021] Preferably, the perfluoroalkyl groups are the same as each other.

[0022] Preferably, the first chain ends of the first and second PFPE chains and the T in formula (III) are equal to or different from each other and are perfluoroalkyl groups having 1 to 3 carbon atoms.

[0023] For example, T and T' are equal to or different from each other and are a fluorine atom or a group selected from CF, -CFCF, -CFCFCF, -CF(CF). Other halogenated groups may still be present, such as, for example, -CFCl and -CFCFCl.

[0024] Preferably, in said first and second PFPE chains, A' and C' are equal to or different from each other.

[0025] Preferably, in the PFPE copolymer, the first PFPE chain is linked to the block (1) via a sigma bond or a group -(C)- selected from -CF2-, -CF2CF2- or -O-.

[0026] Preferably, in the PFPE copolymer, said block (2) is linked to said second PFPE chain via a sigma bond or a group -(C)- selected from -CF2-, -CF2CF2- or -O-.

[0027] Preferably, when both said block (1) and said block (2) are present, they are linked via a sigma bond.

[0028] Preferably, in the PFPE copolymer, each of the 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, equal or different in each occurrence, is F or CF, with the proviso that at least one of X is -F; (iii) -CFCFCWO- (wherein each W, which may be equal to or different from each other, is F, Cl, or H); (iv) -CF2CF2CF2CF2O-, (v)-(CF2) w -CFZ-O- (wherein w is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -Y group, and R (f-a) is a fluoropolyoxyalkene chain comprising 0 to 10 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (wherein each X is independently F or CF3, and Y is a C1 to C3 perfluoroalkyl group).

[0029] Preferably, the chain (R f ) is expressed by the following formula (R f -I) and (R f -II) Follow: (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 in each occurrence 2 , X 3 are independently -F, -CF3, with the proviso that at least one of X is -F; - g1, g2, g3 and g4, which are equal to or different from one another, are independently ≧0 such that g1+g2+g3+g4 ranges from 2 to 300, preferably from 10 to 250, even more preferably from 15 to 200, and when at least two of g1, g2, g3 and g4 are different from zero, the different repeat units are generally statistically distributed along the chain; (R f -II) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 -(CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]- (In the formula, - X 1 , X 2 , X 3 is as defined above, g1, g2, g3, g4, g5 and g6 are equal to or different from each other and independently ≧0 such that g1+g2+g3+g4+g5+g6 ranges from 2 to 300, preferably 10 to 250, provided that at least one of g5 and g6 is not 0).

[0030] In a preferred embodiment, the chain (R f ) is calculated using the above formula (R f -I).

[0031] Preferably, in the PFPE copolymer, the sum of (n+n*+v^) is 1-15, preferably 1-11, more preferably 1-9.

[0032] Preferably, in the PFPE copolymer, the sum of (L+L^) is 1-500, preferably 2-500, more preferably 2-300.

[0033] According to a preferred embodiment, the PFPE copolymer comprises first and second PFPE chains each having two chain ends, the first chain ends of said first and second PFPE chains comprising a perfluoroalkyl group and the second chain ends of said first and second PFPE chains comprising - Formula (IV): -[(CR 1* R 2* CR 3* R 4* ) n* -(E) L ]- (IV) (In the formula, n* is an integer from 1 to 250, L is an integer from 1 to 250, and the sum of n* and L is 1 to 250; R 1* and R 2* is a fluorine atom, and R 3* and R 4* is a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing a halogen atom, more preferably a fluorine or chlorine atom, and at least one heteroatom selected from O, N and S; -OR200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CF2OR 201 is a group of R 201 is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; E is a compound of the formula -(CR 100^ R 101^ CR 102^ R 103^ )- (In the formula, R 100^ and R 101^ are independently selected from halogen atoms, preferably fluorine or chlorine atoms, and R 102^ and R 103^ is a halogen atom, preferably a fluorine or chlorine atom, -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 -CF2OR 201 is a group of R 201 is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms. (which is the basis of At least one block (2) according to - optionally at least one block (3) comprising a PFPE chain; are connected to each other via

[0034] The PFPE copolymers may be prepared by known methods or by supercritical fluid fractionation, for example as disclosed in WO 2008 / 065163 (SOLVAY SOLEXIS SPA).

[0035] PFPE copolymers can be made to react with other polymers in the presence of ultraviolet light or heat. at least one (per)fluoropolyether polymer containing peroxide groups [PFPE peroxy], - Formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 each independently represents a fluorine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, R 10 is an oxygen atom or a perfluoroalkyl chain containing 2 to 18 carbon atoms, optionally and preferably interrupted by and / or containing at least one oxygen atom, t is 0 or 1, preferably 1; Each of z* and z** is independently 1 or 2. and / or at least one perfluoro compound of at least one compound [compound (O)], (i) hydrogenated or (per)halogenated olefins containing 2 to 8 carbon atoms, preferably ethylene (E), propylene (PP), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE) and 1,1-difluoroethylene (VDF); (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 a perfluoro-2-propoxypropyl group (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"), a group -CF2OR f2 (hereinafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), and R f2is 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 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)] selected from the group consisting of provided that the amount of the compound of formula (Xp) is less than 5% by weight of the amount of PFPE peroxy.

[0036] The viscosity of the PFPE copolymer can be measured using a variety of methods depending on the viscosity of the PFPE copolymer itself.

[0037] Preferably, the PFPE copolymer has a viscosity of 1,000 mm at 20° C. 2 / sec, more preferably 2,000 mm at 20°C 2 / sec, and even more preferably 3,000 mm at 20°C 2 / sec.

[0038] Preferably, the PFPE copolymer has a viscosity of 5,000,000 mm at 20°C. 2 / sec, more preferably less than 2,500,000 mm at 20°C 2 / sec, and even more preferably less than 2,000,000 mm at 20°C 2 viscosities of less than 1 / sec.

[0039] Preferably, the PFPE copolymer has a viscosity of 3,000 to 1,500,000 mm at 20°C. 2 / sec, more preferably 3,500 to 1,000,000 mm at 20°C 2 / sec, and even more preferably 4,000 to 950,000 mm at 20°C 2 / sec viscosity.

[0040] The viscosity of the PFPE copolymers according to the present invention is measured at 0°C according to standard methods such as ASTM D445, or at 1 rad / s and 25°C with a dynamic mechanical spectrometer Anton Paar MCR502 rheometer equipped with 25 mm parallel plates.

[0041] Preferably, the PFPE additive is in an amount of at least 0.1 wt. %, based on the total weight of the composition (COMP).

[0042] More preferably, the PFPE additive is present in an amount of 0.1 to 20.0 wt %, even more preferably 0.5 to 15 wt %, and even more preferably 1.0 to 12 wt %, based on the total weight of the composition (COMP).

[0043] Preferably, in PFPE additive (i), the acid group is a carboxyl group.

[0044] Such carboxyl groups may be salified with either inorganic metal salts or organic salts selected from ammonium and phosphonium salts.

[0045] Preferably, in the PFPE additive (i), the at least one inorganic metal salt is selected from alkali metals, more preferably the alkali metals are selected from the group comprising sodium, potassium, cesium, lithium, magnesium and calcium.

[0046] Preferably, in the PFPE additive (i), the organic ammonium salt has the formula: N+H(R 21 )(R 22 )(R 23 ) (In the formula, R 21 , R 22 , R 23 each of which is a chain or branched C1-C optionally containing at least one heteroatom, preferably —O— 20 aliphatic chains or R 21 , R 22 , R 23 together form a 5- or 6-membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and / or optionally substituted by at least one linear or branched alkyl chain containing 1 to 10 carbon atoms and optionally containing at least one heteroatom, preferably a heteroatom selected from -O- and -N-, and R 21 , R 22 , R 23 the third of which is as defined above) The following are selected from:

[0047] More preferably, the organic ammonium salt is selected from triethanolammonium, triethylammonium, pyridinium, trimethylammonium, tributylammonium, 1-methylimidazolium, di(ethyl)cyclohexylammonium, benzimidazolium, 1-benzylimidazolium.

[0048] Preferably, in PFPE additive (ii), the ammonium group has the formula: §-N + (R 31 )(R 32 )(R 33 ) (In the formula, § indicates a bond to the (per)fluoropolyether backbone, and R 31 , R 32 , R 33each of which is a straight-chain or branched C1-C optionally containing at least one heteroatom, preferably —O— 20 aliphatic chains or R 31 , R 32 , R 33 together form a 5- or 6-membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and / or optionally substituted by at least one linear or branched alkyl chain containing 1 to 10 carbon atoms and optionally containing at least one heteroatom, preferably a heteroatom selected from -O- and -N-, and R 31 , R 32 , R 33 the third of which is as defined above) The following are selected from:

[0049] More preferably, the ammonium group is selected from di(methyl)benzyl-ammonium, di(methyl)octyl-ammonium, tri(methyl)ammonium, tri(butyl)ammonium, tri(tert-butyl)ammonium, di(cyclohexane)methylammonium, tri(pentyl)ammonium, di(ethyl)cyclohexylammonium, di(butyl)methylammonium, di(ethyl)butylammonium, 1-butylimidazolium, 1-methylimidazolium, 1-benzylimidazolium, benzimidazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,2,4-triazolium.

[0050] Preferably, in PFPE additive (ii), the at least one inorganic or organic counterion is Br - , I - , Cl - , BF4 - , NO3 - , O.H. - , [(CF3SO2)2N] - , sulfonates and sulfates.

[0051] The sulfonates are preferably selected in the group comprising triflates, nonaflates, mesylates and tosylates.

[0052] Preferably, the PFPE additive comprises a (per)fluoropolyether backbone according to formula (II*) below: -(X*) a* -O-(R f^ )-(X**) b* - (II*) wherein a* and b*, which may be equal to or different from each other, are 1 or greater; X* and X**, which are equal to or different from each other, are selected from -CF2-, -CF2CF2-, -CF(CF3)- and -CF2CH2-; R f^ is a fully or partially fluorinated chain comprising, preferably consisting of, repeating units R°, said repeating units being (i) -CFXO- (wherein X is -F or -CF3), (ii) -CF₂C₂X₅O₂-, where X, equal or different in each occurrence, is -F or -CF₃, provided that at least one of X is -F; (iii) -CF2CF2CF2O-, (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 is a group, and R (f-a) is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, said repeating units being selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (where each X is independently -F or -CF3), and T is a C1 to C3 perfluoroalkylalkyl chain). are independently selected from the group consisting of:

[0053] Preferably, the chain (R f^ ) follows the formula below: (Rf* -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- During the ceremony, - X 1 is independently selected from -F and -CF3; - X's that are equal or different from each other and in each occurrence 2 , X 3 are independently -F, -CF3, with the proviso that at least one of X is -F; g1, g2, g3 and g4, which are equal to or different from one another, are independently integers greater than or equal to 0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100, and when at least two of g1, g2, g3 and g4 are different from zero, the different repeat units are generally statistically distributed along the chain.

[0054] More preferably, the chain (R f^ ) is a chain of the following expressions: (R f^ -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]- (wherein a1 and a2 are independently integers of 0 or more, whereby the number average molecular weight is 400 to 100,000, preferably 400 to 50,000, both a1 and a2 are preferably not 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 100,000, preferably 400 to 50,000, and preferably b1, b2, b3, and b4 are greater than 0), (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 greater than or equal to 0, whereby the number average molecular weight is 400 to 100,000, preferably 400 to 50,000, and preferably c1, c2, and c3 are all greater than 0, and the ratio c3 / (c1+c2) is generally less than 0.2. is selected from.

[0055] More preferably, the chain (R f^ ) follows one of the following formulas: (R f^ -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]- (wherein a1 and a2 are integers greater than 0 such that the number average molecular weight is 400 to 100,000, preferably 400 to 50,000, and the ratio a1 / a2 is generally 0.1 to 10, more preferably 0.2 to 5), (R f^ -IIB)-[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]- (In the formula, b1, b2, b3, and b4 are independently integers of 0 or more, whereby the number average molecular weight is 400 to 100,000, preferably 400 to 50,000, and preferably each of b1, b2, b3, and b4 is greater than 0).

[0056] According to one embodiment, the PFPE additive (i) comprises a carboxyl group at one or both chain ends salified with at least one inorganic metal salt, wherein the at least one inorganic metal salt is as defined above.

[0057] Preferably, the PFPE additive comprises a carboxyl group at one or both chain ends salified with at least one organic ammonium salt, wherein the at least one organic ammonium salt is as defined above.

[0058] More preferably, the PFPE additive comprises a salified carboxyl group, as defined hereinabove, at one chain end and a neutral group at the other chain end.

[0059] Such a neutral group is preferably a fluorine atom or a perfluoroalkyl chain containing from 1 to 6 carbon atoms.

[0060] According to this embodiment, the chain end containing an acid group is preferably linked to the above-defined formula (R f^ ) is bonded to a (per)fluoropolyether backbone according to

[0061] The PFPE additive (i) may be prepared according to methods known in the art, such as by following the procedures disclosed in US Pat. No. 5,000,864 (Ausimont SpA).

[0062] According to another embodiment, the PFPE additive (ii) comprises an ammonium group and at least one inorganic or organic counterion at one or both chain ends.

[0063] Preferably, said ammonium group is as defined above.

[0064] Preferably, said at least one inorganic or organic counterion is as defined above.

[0065] According to this second embodiment, the chain end containing an ammonium group is preferably connected to a group of formula (R) defined above via a group of formula -CF- or -CFCH-. f ) is bonded to a (per)fluoropolyether backbone according to

[0066] According to this second embodiment, the chain end containing an ammonium group is preferably an alkoxylated chain [chain (R a )) to the sigma bond or group (B1).

[0067] Preferably, the chain (R a ) is expressed by the following formula (R a-I )~(R a-III ) satisfies one of the following conditions. (R a-I )-(OCH2CH2) j1 -H (R a-II )-[OCH(CH3)CH2]j2-H (R a-III )-[(OCH2CH2) j3 -(OCH(CH3)CH2) j4 ] j(x) -H In the formula, j1 and j2 each independently represent an integer of 1 to 10, more preferably an integer of 1 to 5. j3, j4, and j(x) are integers from 1 to 25, and the sum of j3 and j4 is from 2 to 50.

[0068] The PFPE additive (ii) may be prepared according to methods known in the art, such as according to the methods disclosed in WO 2022 / 078766 (Solvay Specialty Polymers Italy SpA).

[0069] In a further object, the present invention relates to the use of said composition (COMP) as a lubricant for electrical components suitable for use in a variety of applications and industries, particularly in the automotive and electronics industries, including, but not limited to, electrical and electronic components such as electrical connectors, switchgear and circuit breakers.

[0070] In a further object, the present invention relates to the use of said composition (COMP) as a lubricant for machine parts suitable for use in the automotive industry, in particular for electric vehicles (EVs), including but not limited to ball bearings.

[0071] In a further object, the present invention relates to the use of a composition according to the invention (COMP) for the manufacture of a grease.

[0072] In another object, the present invention relates to a grease comprising a composition according to the invention (COMP) and at least one other ingredient.

[0073] Such greases may be advantageously used as lubricants for electrical, electronic or mechanical components, examples of which are given above and include, but are not limited to, electrical connectors, switchgear and circuit breakers, and ball bearings.

[0074] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that a term may be unclear, the statements of this application shall control.

[0075] The present invention will now be described in more detail with reference to the following examples, the purpose of which is illustrative only and is not intended to limit the scope of the present disclosure. [Example]

[0076] material COMP1: Cyphos IL-169 (hydrogenated liquid additive) from Solvay Technology Solutions was used as a comparison. COMP2: Fine silver powder (solid particle size = 5-8 μm) purchased from Sigma Aldrich was also used as a comparison. ADD1:Formula-(CF2CF2O) m (CF2O) n - the triflate salt of a 1-butylimidazolium monofunctional PFPE comprising the backbone and having a Mw of 2520 g / mol as measured by nuclear magnetic resonance (NMR) spectroscopy. ADD2:Formula-(CF2CF2O) m (CF2O) n - backbone and having a Mw of 4760 g / mol as determined by NMR spectroscopy. ADD3:Formula-(CF2CF2O) m (CF2O) n - backbone and having a Mw of 2580 g / mol as determined by NMR spectroscopy. ADD4:Formula-[CF2CF(CF3)O] p -(CF2O) q -[CF(CF3)O] q -OCF2COO - , -OCF(CF3)COO - , -OCF2C(=O)CF3, triethanolamine salts of a mixture of neutral, monofunctional and difunctional salts containing the groups -OCF3.

[0077] Fomblin® HV25 is commercially available from Solvay Specialty Polymers Italy SpA and has a viscosity of 25,000 mm measured at 25°C. 2 / sec viscosity.

[0078] Comparative and inventive compositions were prepared by mixing the ingredients detailed in Table 1 below.

[0079] [Table 1]

[0080] The additive used in the composition of Example 1C was Fomblin (R) It was not soluble in HV and therefore such compositions were not tested further.

[0081] Other compositions were evaluated for volume resistivity according to ASTM D257 at two different temperatures, namely 25° C. and 80° C. A voltage of 500 V was applied and measurements were recorded after 60 seconds.

[0082] [Table 2]

[0083] The comparative composition of Example 2C, which contained solid particles, exhibited a higher volume resistivity compared to the composition according to the invention.

[0084] The comparative composition of Example 2C was also evaluated for its shelf life: after 4 days, visual inspection showed separation between the two phases.

[0085] The composition according to the present invention exhibited a lower volume resistivity at 25°C than Comparative Composition 2C, and also exhibited a lower volume resistivity at 80°C than Comparative Composition 8C.

Claims

1. A composition [composition (COMP)] comprising: at least one block copolymer [PFPE copolymer] 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 perfluoroalkyl group and the second chain ends of said first and second PFPE chains comprise Formula (I): 【Chemistry 1】 (In the formula, n is 0 or an integer from 1 to 3, R １ ~R ４ are each independently a fluorine atom, a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a group represented by formula (II): (().() １０ ) ｔ [() １１ () １２ )?|() １３ () １４ () １５ ) ｚ (In the formula, R １０ is an oxygen atom or a divalent / trivalent / tetravalent perfluoroalkyl chain containing 1 to 24 carbon atoms, optionally interrupted by and / or containing at least one oxygen atom; t is zero or one; z is an integer from 1 to 3; R １１ ~R １５ are each independently a fluorine atom, a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and a group represented by the formula (III): -[(A^) ａ＾ -(B^) ｖ＾ -(E^) Ｌ＾ ] ｕ＾ -(C^)-T (III) (In the formula, a^ is zero or one, 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^ has the formula: -[C(R １＾ )(R ２＾ )-C(R ３＾ )(R ４＾ )]- (In the formula, R １＾ ~R ４＾ are each independently R １ ~R ４ each of which has the meaning defined above) is the basis of E^ is the formula -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ )- (In the formula, R １００＾ and R １０１＾ are independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, and R １０２＾ and R １０３＾ is a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S, -OR ２００ and R ２００ is a linear or branched perfluoro chain containing 1 to 6 carbon atoms or a group of formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluoroalkyl 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＾ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom. is the basis of C^ is a PFPE chain, and T is a perfluoroalkyl group. and preferably selected from the group consisting of: At least one 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 zero or an integer from 1 to 250; L is zero or an integer from 1 to 250, and the sum of n* and L is 0 or 1 to 250; R １＊ and R ２＊ are independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, and R ３＊ and R ４＊ is a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S, -OR ２００ and R ２００ is a linear or branched perfluoro chain containing 1 to 6 carbon atoms or a group of formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １＊ and R ２＊ One of the two and R ３＊ and R ４＊ is a fluorine atom, and R １＊ and R ２＊ The other and R ３＊ and R ４＊ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, E has the same meaning as provided for E^ above. At least one second block [block (2)] according to - optionally at least a third block comprising a PFPE chain [block (3)] are connected to each other via In the PFPE copolymer, -- at least one of n, n* and L is different from 0; -- said block (1), said block (2) and, if present, said block (3) are statistically distributed; In the formula (I), --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): In the formula (III) and the formula (IV), -- the repeat units are statistically distributed, In the formula (III), -- at least one block copolymer [PFPE copolymer], wherein when a^ is 1, at least one of v^ and L^ is different from 0; - up to 20.0% by weight, based on the total weight of the composition (COMP), of at least one salt of a (per)fluoropolyether polymer [PFPE additive], comprising a (per)fluoropolyether backbone having two chain ends attached to either side of said backbone, at least one chain end being (i) -COO － , -OSO ３ ２－ , -OPO ３ ２－ , -SO ３ － wherein the acid group is salified with at least one inorganic metal salt or an organic salt selected from ammonium salts and phosphonium salts, (ii) an ammonium group and at least one inorganic or organic counterion; and at least one salt of a (per)fluoropolyether polymer [PFPE additive], comprising at least one group selected from wherein the sum of said PFPE copolymer and said PFPE additive is 100% by weight of composition (COMP) [composition (COMP)].

2. 2. The composition (COMP) according to claim 1, containing at least one additional component preferably selected in the group comprising rust inhibitors, antioxidants, rheology modifiers, corrosion inhibitors, dyes, pigments.

3. 3. A composition (COMP) according to claim 1 or 2, which does not contain any additives in the form of solid particles.

4. The PFPE copolymer has a viscosity of at least 1,000 mm as measured at 20°C according to standard methods such as ASTM D445, or at 1 rad / sec and 25°C with a dynamic mechanical spectrometer Anton Paar MCR 502 rheometer equipped with 25 mm parallel plates. ２ 4. The composition (COMP) according to any one of claims 1 to 3, having a viscosity of 1 / s.

5. 5. The composition (COMP) of any one of claims 1 to 4, wherein the first chain ends of the first and second PFPE chains comprise a linear perfluoroalkyl group having 1 to 3 carbon atoms.

6. - the first PFPE chain is a sigma bond or -CF ２ -, -CF ２ CF ２ - or -O-, and / or said block (2) is a sigma bond or -CF ２ -, -CF ２ CF ２ - or -O-, and / or A composition (COMP) according to any one of claims 1 to 5, in which, if both said block (1) and said block (2) are present, they are linked via a sigma bond.

7. Each of said PFPE chains is a partially or fully fluorinated chain [chain (R ｆ ) ], and the repeating unit is (i) -CFXO- (wherein X is F or CF ３ (which is (ii) -CFXCFXO-, where X, equal or different in each occurrence, is F or CF ３ where at least one of X is -F. (iii)-CF ２ CF ２ CW ２ O—, wherein each of W, which may be equal to or different from each other, is F, Cl, or H; (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v)-(CF ２ ) ｗ -CFZ-O- (wherein w is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -Y group, and R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O—(wherein each X is independently F or CF ３ and Y is selected from C １ ~C ３ perfluoroalkyl groups) The composition (COMP) according to any one of claims 1 to 6, independently selected from the group consisting of:

8. The PFPE copolymer comprises first and second PFPE chains each having two chain ends, the first chain ends of the first and second PFPE chains comprising a perfluoroalkyl group, and the second chain ends of the first and second PFPE chains comprising - Formula (IV): -[(CR １＊ R ２＊ CR ３＊ R ４＊ ) ｎ＊ -(E) Ｌ ]- (IV) (In the formula, n* is an integer from 1 to 250, L is an integer from 1 to 250, and the sum of n* and L is 1 to 250; R １＊ and R ２＊ is a fluorine atom, and R ３＊ and R ４＊ is a linear or branched alkyl chain containing from 1 to 6 carbon atoms, optionally containing a halogen atom, more preferably a fluorine or chlorine atom, and at least one heteroatom selected from O, N and S; -OR ２００ and R ２００ is a linear or branched perfluoro chain containing 1 to 6 carbon atoms or a group of formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; E is a group represented by the formula -(CR １００＾ R １０１＾ CR １０２＾ R １０３＾ )- (In the formula, R １００＾ and R １０１＾ are independently selected from halogen atoms, preferably fluorine or chlorine atoms, and R １０２＾ and R １０３＾ is a halogen atom, preferably a fluorine or chlorine atom, —OR ２００ and R ２００ is a linear or branched perfluoro chain containing 1 to 6 carbon atoms or a group of formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluoroalkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms. (based on and at least one block (2) according to optionally at least one block (3) comprising a PFPE chain; The composition (COMP) according to any one of claims 1 to 7, wherein the polymers are bonded to each other via

9. The composition (COMP) according to any one of claims 1 to 8, wherein the PFPE additive is in an amount of at least 0.1 wt% and at most 20.0 wt%, based on the total weight of the composition (COMP).

10. In the PFPE additive (i), the acid group is a carboxyl group salified with an inorganic metal salt or with an organic salt selected from ammonium and phosphonium salts, or said organic ammonium salt having the formula: N ＋ H(R ２１ )(R ２２ )(R ２３ ) (In the formula, R ２１ , R ２２ , R ２３ Each of the groups is a linear or branched C group optionally containing at least one heteroatom. １ ~C ２０ aliphatic chains or R ２１ , R ２２ , R ２３ together form a 5- or 6-membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and / or optionally substituted with at least one linear or branched alkyl chain containing 1 to 10 carbon atoms and optionally containing at least one heteroatom, and R ２１ , R ２２ , R ２３ the third of which is as defined above) The composition (COMP) according to any one of claims 1 to 9, selected from:

11. In the PFPE additive (ii), said ammonium group having the formula: §-N ＋ (R ３１ )(R ３２ )(R ３３ ) (In the formula, § indicates a bond to the (per)fluoropolyether backbone, and R ３１ , R ３２ , R ３３ Each of the groups is a linear or branched C group optionally containing at least one heteroatom. １ ~C ２０ aliphatic chains or R ３１ , R ３２ , R ３３ together form a 5- or 6-membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and / or optionally substituted with at least one linear or branched alkyl chain containing 1 to 10 carbon atoms and optionally containing at least one heteroatom, and R ３１ , R ３２ , R ３３ the third of which is as defined above) and said at least one inorganic or organic counterion is Br － , I － , Cl － , B.F. ４ － , NO ３ － , O.H. － , [(CF ３ SO ２ ) ２ N] － 11. A composition (COMP) according to any one of claims 1 to 10, wherein the hydroxybenzoates are selected from the group comprising hydroxybenzoates, sulfonates and sulfates.

12. The PFPE additive (ii) has the following formula (II*): (︊) ａ＊ -() ｆ＾ )(()) ｂ＊ (I)) (Wherein, a* and b*, which may be equal to or different from each other, are 1 or more; X* and X**, which are equal to or different from each other, are -CF ２ -, -CF ２ CF ２ -, -CF(CF ３ )- and -CF ２ CH ２ - is selected from, R ｆ＾ is a fully or partially fluorinated chain comprising, preferably consisting of, repeating units R°, said repeating units being (i) -CFXO- (wherein X is -F or -CF ３ (which is (ii) -CFXCFXO-, where X, equal or different in each occurrence, is -F or -CF ３ where at least one of X is -F. (iii)-CF ２ CF ２ CF ２ O-、 (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v)-(CF ２ ) ｊ -CFZ-O- (where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T group, and R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O— (wherein each X is independently —F or —CF ３ and T is selected from C １ ~C ３ perfluoroalkyl alkyl chain) (independently selected from the group consisting of 12. A composition (COMP) according to any one of claims 9 to 11, comprising a (per)fluoropolyether backbone according to

13. The composition (COMP) according to any one of claims 1 to 12, - electrical components, preferably selected in the group comprising electrical connectors, switchgears and circuit breakers, and / or - mechanical parts, preferably selected from ball bearings For use as a lubricant.

14. A grease comprising a composition (COMP) according to any one of claims 1 to 12.

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