Lubricant composition with perfluoropolyether
By introducing alkoxylated (all)fluoropolyether polymers and conductive particles into the lubricant, the problems of separation and poor conductivity of fluoropolyether lubricants at high temperatures are solved, thereby improving the stability and conductivity of the lubricant at high temperatures, making it suitable for electrical and electronic components.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOLVAY SPECIALTY POLYMERS ITALY SPA
- Filing Date
- 2024-11-11
- Publication Date
- 2026-06-05
AI Technical Summary
Existing fluoropolyether lubricants are prone to separation and evaporation at high temperatures, leading to a decline in lubrication performance. At the same time, their high dielectric properties and low polarity result in poor electrical conductivity, making it difficult to meet the stability and conductivity requirements of electrical components in harsh environments.
A lubricant composition comprising an alkoxylated (fully) fluoropolyether polymer and a solid particulate conductive additive is used. The compatibility with the base oil is improved by the -OH groups at the alkoxylated chain ends, and conductive particles are added to enhance the electrostatic charge dissipation capability.
It achieves improved thermal stability and electrical conductivity of lubricants at high temperatures, making it suitable for electrical and electronic components, reducing the risk of electrical corrosion, and meeting the requirements for use of electrical components in harsh environments.
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Abstract
Description
Technical Field
[0001] This application claims priority to European application filed on 13 November 2023 under number 23209539, the entire contents of which are incorporated herein by reference for all purposes. Technical Field
[0002] This invention relates to a lubricant composition comprising a base oil, an alkoxylated (per)fluoropolyether polymer as a conductive additive, at least one thickener, and at least one additive in the form of solid particles. Background Technology
[0003] It is known that certain hydrogen-based lubricants, particularly certain lubricating oils, from natural or synthetic sources, possess excellent lubricating properties and are commercially available at a reasonable cost. Examples of hydrogen-based lubricants include hydrocarbon-based mineral oils, hydrogenated animal and vegetable oils, synthetic hydrogenated oils including polyalphaolefins (PAOs), diesters, polyol esters, phosphate esters, polyesters, alkylated naphthalenes, polyphenylene ethers, polybutenes, polyalkylated cyclopentanes, silanes, siloxanes, and polyalkylene glycols.
[0004] For operation at high temperatures, thickening additives should possess excellent thermal and chemical stability. Furthermore, fluorinated oils and greases undergo degradation at high temperatures in the presence of metals and in oxidizing environments, thereby breaking down the main chain and generating volatile products. This leads to a loss of lubricating properties in both oils and greases.
[0005] To overcome this deficiency, it is known from the prior art that additives that stabilize oils and greases in high-temperature, oxidizing environments and in the presence of metals are used, thereby ensuring their stability during use.
[0006] Liquid stabilizers are disclosed in the prior art. However, for applications requiring continuous use at temperatures above 200°C, increasing the amount of additive is necessary, typically to a value exceeding approximately 5% by weight relative to the total weight of the oil or grease. A drawback of using large amounts of liquid stabilizers in grease preparation is that the ratio between the liquid component (oil plus additive) and the solid component (thickener) of the grease is altered. As temperature increases, the increased liquid content leads to increased liquid-to-solid separation, thus changing the initial grease consistency. Oil separation becomes significant above 200°C. Furthermore, liquid additives tend to evaporate more readily as operating temperatures rise.
[0007] For example, WO 2007 / 082829 (Solvay Solexis SpA) discloses the use of polymers that are solid at room temperature and have a melting point above 150°C. This patent application discloses the use of polymers containing at least one aromatic ring in their main chain as additives for stabilizing polyfluoroether oils. The compositions disclosed in this patent application comprise aromatic polymer powder having an average size preferably between 0.1 μm and 1,000 μm. In addition to the aromatic polymer powder, preferred embodiments also include PTFE powder.
[0008] Possible alternatives to hydrogen-based lubricants are (per)fluoropolyether (PFPE) lubricants, which are lubricants containing perfluoroalkylene groups (i.e., chains containing repeating units with at least one ether bond and at least one fluorocarbon moiety). PFPE lubricants exhibit high heat and chemical resistance, making them useful in applications characterized by harsh conditions such as very high temperatures, the presence of oxygen, the use of corrosive chemicals, and radiation. However, PFPE oils are more expensive than hydrogenated oils, and therefore they are only used when high performance is required.
[0009] Fluorinated polyether polymers (PFPEs) belong to the family of fluorinated synthetic fluids, which are well known and used to formulate lubricants that function for extended periods in extreme environments.
[0010] However, one problem with PFPE-based lubricants is that they are highly dielectric and have poor electrical conductivity. Furthermore, the low polarity of fluorinated PFPE lubricants leads to poor solubility and / or poor affinity with most additives. Therefore, adjusting the conductivity of PFPE lubricants has proven problematic, as conductive additives are typically polar substances and immiscible with PFPE lubricants.
[0011] Therefore, several methods have been explored in the field to adjust the electrical conductivity of PFPE lubricants, such as those disclosed in US2008 / 0144219 (under the name of HGST Netherlands BV).
[0012] Furthermore, N Suhaila A Japar et al. (International Journal of Engineering & Technology, 7, 3.26, 2018, 23.29) summarized findings related to the use of greases containing PFPE as a base oil and solid particles (fumed silica or polytetrafluoroethylene-PTFE) as thickeners in their article "Grease and its Application on Electrical Equipment: a Review". Summary of the Invention
[0013] The applicant recognizes that the presence of electrical components continues to increase across many different industries and various applications. However, their exposure to harsh environments, including but not limited to very high temperatures, humidity, and corrosion, can accelerate the failure of such electrical components. Furthermore, these components may be subject to arc discharge burning, which leads to component burn-out and thus shortens their lifespan.
[0014] In addition to the above, the applicant notes that the properties of aromatic polymer powders used in this field are no longer suitable for meeting the growing requirements of specialty industries.
[0015] Therefore, the problem facing the applicant is to provide a composition suitable for lubricating electrical components applicable to various applications and industries, such as the electrical, electronic and automotive industries.
[0016] In fact, the applicant recognized that electrical corrosion in rolling bearings is a major challenge for electric vehicles today for many reasons, including: inverter control systems may cause complex shaft voltages; EDM bearing currents occur when the bearing voltage exceeds the threshold voltage of the insulating lubricating film; energy from capacitors is released through destructive currents and arc discharges; and discharge currents may damage bearing surfaces and degrade grease (free radical formation, overheating).
[0017] Such compositions need to exhibit good electrostatic dissipation and thus reduced volume resistivity (also known as "resistivity" or "resistivity"), good viscosity and high viscosity index ("as measured according to ASTM D227"), and excellent compatibility between the base oil and the additives.
[0018] The applicant unexpectedly discovered a composition that meets the above requirements and is therefore usable as a lubricant, etc., for electrical and electronic components (including electrical connectors, switching devices and circuit breakers) and for mechanical components particularly suitable for the automotive industry, including for lubricating parts used in electric vehicles, such as ball bearings. Detailed Implementation
[0019] In this application:
[0020] - 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 may be omitted;
[0021] - The acronym "PFPE" stands for "(per)fluoropolyether" and when used as a noun, it is intended to mean either the singular or plural form depending on the context;
[0022] - The prefix "(full)" in the term "(full) fluorinated polyether" means that the polyether may be fully or partially fluorinated.
[0023] In a first aspect, the present invention relates to a composition [composition (COMP)] comprising:
[0024] (A) At least one base oil, wherein the at least one base oil is selected from hydrogenated oil or (per)fluorinated oil;
[0025] (B) At least one (per)fluoropolyether polymer [PFPE additive], based on a total weight of 0.1 to 20.0 wt.% of the composition (COMP), the (per)fluoropolyether polymer comprising a (per)fluoropolyether chain [PFPE chain] having two chain ends bonded to opposite sides of the main chain, wherein at least one chain end comprises at least one -OH group, the -OH group being bonded to the (per)fluoropolyether main chain via an alkoxylated chain [chain (Ra)];
[0026] (C) Based on 100% of the composition (COMP), at least one thickener comprising 0.1% to 35.0% by weight, preferably 1.0% to 32.0% by weight, wherein the at least one thickener is selected from the group consisting of: soap-based thickeners, preferably selected from metallic soaps and complex soaps; and non-soap-based thickeners, preferably selected from polyurea, clay, fumed silica, fluorinated polymers and / or aromatic polymers; and
[0027] (D) At least one additive in the form of solid particles, in an amount of 0.01 to 25 wt. based on the total weight of the composition (COMP).
[0028] Preferably, the solid particles of at least one additive (D) are conductive particles.
[0029] Unexpectedly, the applicant found that the composition (COMP) has excellent thermal and thermal oxidative stability, while the PFPE additive dissipates static charge.
[0030] Unbound by any theory, the applicant believes that the presence of the chain (Ra) allows for increased compatibility between the PFPE additive and at least one base oil.
[0031] Preferably, the at least one hydrogenated oil is a mineral oil or synthetic oil, such as polyalphaolefin (PAO) and polyalkylene glycol (PAG); ester; silicone oil; polyphenylene ether; etc.
[0032] Preferably, the (per)fluorinated base oil is a (per)fluorinated polyether base oil [PFPE base oil].
[0033] Preferably, the PFPE base oil is selected from the group consisting of:
[0034] (AI) (per)fluoropolyether polymers [PFPE polymers] comprising linear or branched (per)fluoropolyether chains [PFPE chains] having two chain ends bonded to opposing sites on the chain, each chain end comprising a linear or branched perfluorinated alkyl chain having 1 to 6 carbon atoms, the polymer having a number average molecular weight of 500 to 100,000, preferably 2,000 to 50,000, as measured by NMR; or
[0035] (A-II) At least one block copolymer [PFPE copolymer] comprising first and second (per)fluoropolyether chains [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 via:
[0036] - At least one first block of conformation (I) [block (1)]:
[0037] (I)
[0038] in
[0039] n is 0 or an integer from 1 to 3;
[0040] 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).
[0041] (II) -(R 10 ) t [C(R 11 (R) 12)-C(R 13 (R) 14 (R) 15 )] z
[0042] in
[0043] R 10 It is an oxygen atom, or optionally an oxygen atom inserted into and / or containing at least one oxygen atom, a divalent / trivalent / tetravalent perfluorinated alkyl chain comprising 1 to 24 carbon atoms.
[0044] t is zero or 1,
[0045] z is an integer from 1 to 3;
[0046] R 11 To R 15 Each is 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):
[0047] -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T(III)
[0048] in
[0049] a^ is zero or 1.
[0050] v^ is zero or an integer from 1 to 3.
[0051] L^ is zero or an integer from 1 to 250.
[0052] u^ is zero or an integer from 1 to 50;
[0053] A^ is a PFPE chain
[0054] B^ is a group having the following formula:
[0055] -[C(R 1^ (R) 2^ )-C(R 3^ (R) 4^ )]-
[0056] Where R 1^ To R 4^ Each of them independently possesses the meaning defined above for each of R1 to R4.
[0057] E^ is a formula -(CR) 100^ R 101^ CR 102^ R 103^)- group
[0058] in
[0059] R 100^ and R 101^ Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms, and
[0060] R 102^ and R 103^ Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted; or
[0061] R 100^ and R 101^ One of them and R 102^ and R 103^ One of them is a fluorine atom and R 100^ and R 101^ Another one in and R 102^ and R 103^ The other one in the mixture can optionally contain heteroatoms such as oxygen atoms to form a fully halogenated cyclic ring with 4 to 6 members;
[0062] C^ is a PFPE chain, and
[0063] T stands for perfluorinated alkyl group;
[0064] - At least one second block of conformation (IV) [block (2)]:
[0065] (IV)
[0066] in
[0067] n It is zero or an integer from 1 to 250.
[0068] L is zero or an integer from 1 to 250, and
[0069] n The sum of L and L is 0 or between 1 and 250;
[0070] and Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms, and
[0071] and Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted; or
[0072] and One of them and and One of them is a fluorine atom and and Another one in the middle and and The other one in the mixture can optionally contain heteroatoms such as oxygen atoms to form a fully halogenated cyclic ring with 4 to 6 members;
[0073] E has the same meaning as E^ above;
[0074] - Optionally, at least one third block [block (3)] containing a PFPE chain;
[0075] The premise is:
[0076] In the PFPE copolymer:
[0077] -- n、n At least one of L is different from 0;
[0078] -- The segments (1), (2), and (3) -- when present -- are statistically distributed;
[0079] In equation (I):
[0080] -- At least one of R1 to R4 is a group having formula (II),
[0081] -- R 11 or R 12 One of them and R 13 To R 15 One of them is a group having formula (III);
[0082] In equations (III) and (IV)
[0083] -- These repeating units are statistically distributed,
[0084] In equation (III)
[0085] -- When a^ is 1, at least one of v^ and L^ is different from 0.
[0086] Preferably, in both the PFPE polymer and the PFPE copolymer, each of the aforementioned PFPE chains is a partially or fully fluorinated chain [chain (R f The chain comprises repeating units R°, preferably composed of repeating units R°, wherein the repeating units are independently selected from the group consisting of:
[0087] (i)-CFXO-, where X is F or CF3;
[0088] (ii) -CFXCFXO-, where X, which is the same or different each time it appears, is either F or CF3, provided that at least one of X is -F;
[0089] (iii)-CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H;
[0090] (iv)-CF2CF2CF2CF2O-;
[0091] (v)-(CF2) w -CFZ-O-, where w is an integer from 0 to 3, and Z is a variable with the general formula -OR (f-a) -Y group, where R (f-a) It is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and Y is a C1-C3 perfluoroalkyl group.
[0092] Preferably, the chain (R) f It conforms to the following formula (R) f -I) and (R f -II):
[0093] (R f -I)
[0094] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O)g4 ]-
[0095] in
[0096] - X 1 Independently selected from -F and -CF3,
[0097] - X 2 X 3 They are either the same as or different from each other and are independently -F or -CF3 each time they appear, provided that at least one of X is -F;
[0098] - g1, g2, g3, and g4, which may be the same as or different from each other, are independently ≥ 0, such that g1 + g2 + g3 + g4 are in the range of 2 to 300, preferably 10 to 250, or even more preferably 15 to 200; if at least two of g1, g2, g3, and g4 are different from zero, these different repeating units are statistically distributed along the chain in general.
[0099] (R f -II)
[0100] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 - (CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]-
[0101] in
[0102] - X 1 X 2 X 3 It is as defined above;
[0103] - g1, g2, g3, g4, g5 and g6, which may be the same as or different from each other, and are independently ≥ 0, such that g1 + g2 + g3 + g4 + g5 + g6 are in the range of 2 to 300, preferably 10 to 250, provided that at least one of g5 and g6 is different from 0.
[0104] In a preferred embodiment, the chain (R) f It conforms to the above formula (R) f -I).
[0105] Preferably, the PFPE base oil is an (AI) (all) fluoropolyether polymer [PFPE polymer].
[0106] According to this embodiment, the PFPE polymer comprises a straight-chain PFPE chain having two chain ends bonded to opposing sites on the chain, each chain end comprising a straight-chain perfluorinated alkyl chain having 1 to 6 carbon atoms, and the PFPE polymer having a number-average molecular weight of 2,000 to 50,000, more preferably 3,000 to 20,000, as measured by NMR.
[0107] Preferably, the PFPE polymer comprises a product conforming to the above formula (R f -I) chain (R) f ).
[0108] Preferably, in the chain (R) f In -I), X 1 Yes, it is -F.
[0109] Preferably, in the chain (R) f In -I), X 2 and X 3 All are -F.
[0110] Preferably, in the chain (R) f In -I), g1 and g2 are both and independently > 0.
[0111] Preferably, in the chain (R) f In -I), both g3 and g4 are 0.
[0112] Preferably, in the chain (R) f In -I), g1 + g2 is in the range of 20 to 200.
[0113] Preferably, the PFPE base oil is an (A–II) PFPE copolymer.
[0114] Preferably, the PFPE copolymer has a diameter of at least 1,000 mm. 2 The viscosity was measured at 0.1 rad / s according to standard methods such as ASTM D445 at 20°C, or using an Anton Paar MCR502 rheometer equipped with a 25 mm parallel plate dynamic mechanical spectrometer at 25°C.
[0115] It should be understood that the first chain end of the first and second PFPE chains corresponds to the two chain ends of the PFPE copolymer.
[0116] Preferably, the first chain end of the first and second PFPE chains comprises a perfluorinated straight-chain alkyl group having 1 to 3 carbon atoms.
[0117] Preferably, the perfluorinated alkyl groups are identical to each other.
[0118] Preferably, the first chain ends of the first and second PFPE chains and the T in formula (III) are the same as or different from each other, and are perfluorinated alkyl groups having 1 to 3 carbon atoms.
[0119] For example, T and T', which may be the same as or different from each other, are fluorine atoms or groups selected from -CF3, -CF2CF3, -CF2CF2CF3, and -CF(CF3)2. Other halogenated groups may also be present, such as -CF2Cl and -CF2CF2Cl.
[0120] Preferably, in the first and second PFPE chains, A^ and C^ are the same as or different from each other.
[0121] Preferably, in the PFPE copolymer, the first PFPE chain is bonded to the block (1) via a σ bond or a group selected from -CF2-, -CF2CF2- or -O- (C)-.
[0122] Preferably, in the PFPE copolymer, the block (2) is bonded to the second PFPE chain via a σ bond or a group selected from -CF2-, -CF2CF2- or -O- (C)-.
[0123] Preferably, when both the segment (1) and the segment (2) are present, they are connected via σ bonds.
[0124] Preferably, in the PFPE copolymer, (n + n The sum of + v^) is 1 to 15, preferably 1 to 11, and more preferably 1 to 9.
[0125] Preferably, in the PFPE copolymer, the sum of (L + L^) is 1 to 500, more preferably 2 to 500, and even more preferably 2 to 300.
[0126] According to a preferred embodiment, the PFPE copolymer comprises 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 via the following:
[0127] - At least one block (2) conforming to expression (IV):
[0128] (IV)
[0129] in
[0130] n It is an integer from 1 to 250.
[0131] L is an integer from 1 to 250, and
[0132] n The sum of L and L ranges from 1 to 250;
[0133] and It is a fluorine atom, and
[0134] and Independently selected from halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N, and S; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted;
[0135] E is a formula -(CR) 100^ R 101^ CR 102^ R 103^ )- group
[0136] in
[0137] R 100^ and R 101^ Independently selected from halogen atoms, preferably fluorine or chlorine atoms, and
[0138] R 102^ and R 103^ Independently selected from halogen atoms, preferably fluorine or chlorine atoms; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted;
[0139] as well as
[0140] - Optionally, at least one segment (3) contains a PFPE chain.
[0141] Depending on the viscosity of the PFPE copolymer itself, different methods can be used to measure the viscosity of the PFPE copolymer.
[0142] Preferably, the PFPE copolymer has a thickness greater than 1,000 mm at 20°C. 2 / s, more preferably above 2,000 mm at 20°C 2 / s, and even more preferably above 3,000 mm at 20°C. 2 Viscosity per second.
[0143] Preferably, the PFPE copolymer has a thickness of less than 5,000,000 mm at 25°C. 2 / s, more preferably below 2,500,000 mm at 25°C. 2 / s, and even more preferably less than 2,000,000 mm at 25°C. 2 Viscosity per second.
[0144] Preferably, the PFPE copolymer has a thickness of 3,000 to 1,500,000 mm at 25°C. 2 / s, more preferably 3,500 to 1,000,000 mm at 25°C. 2 / s, and even more preferably 4,000 to 950,000 mm at 25°C. 2 Viscosity per second.
[0145] The viscosity of the PFPE copolymer according to the invention was measured at 25°C according to standard methods such as ASTM D445, or at 1 rad / s and 25°C using an Anton Paar MCR 502 rheometer equipped with a 25 mm parallel plate.
[0146] PFPE copolymers can be prepared by known methods (such as those disclosed in WO 2008 / 065163 (Solvays)) or by supercritical fluid fractionation.
[0147] More preferably, the PFPE copolymer can be prepared by method [method (P)], which includes:
[0148] (a) In the presence of UV radiation or under heating, the following items are brought into contact:
[0149] - At least one peroxy group-containing (per)fluoropolyether polymer [PFPE peroxide];
[0150] and
[0151] - At least one perfluorinated compound having the formula (Xp):
[0152] (Xp)
[0153] in
[0154] R 21 To R 23 and R 31 To R 33 Each of these is independently a fluorine atom, a perfluorinated alkyl group having 1 to 3 carbon atoms.
[0155] R 10 It is an oxygen atom, or optionally and preferably a perfluorinated alkyl chain containing 2 to 18 carbon atoms with and / or containing at least one oxygen atom.
[0156] t is zero or 1, preferably 1;
[0157] z and z Each of them is either 1 or 2 independently;
[0158] and / or
[0159] - At least one compound selected from the group consisting of, preferably, the following [compound (O)]:
[0160] (i) Hydrogenated or (fully)halogenated olefins containing 2 to 8 carbon atoms, preferably ethylene (E), propylene (PP), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluorochloroethylene (CTFE) and 1,1-difluoroethylene (VDF).
[0161] (ii) CF2=CFOR f ,
[0162] in
[0163] R f It is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, or -C3F7 (hereinafter also referred to as "PAVE"); a group containing chain oxygen atoms C1-C 12 [(per)fluoro]-oxoalkyl, preferably perfluoro-2-propoxypropyl (hereinafter also referred to as "perfluoro-oxy-alkyl-vinyl ether"); group -CF2OR f2 (Hereinafter also referred to as "perfluoromethoxyvinyl ether" or "MOVE"), wherein R f2 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 It can be -CF2CF3 (MOVE1), -CF2CF2OCF3 (MOVE2), or -CF3 (MOVE3);
[0164] (iii) Perfluorinated m-dioxanes having the following formula:
[0165]
[0166] Where R f3 R f4 R f5 R f6 Each of these 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 that optionally contain one or more oxygen atoms, such as notably -CF3, -C2F5, -C3F7, -OCF3, and -OCF2CF2OCF3.
[0167] The premise is that the amount of the compound having formula (Xp) is less than 5 wt. of the amount of PFPE peroxide.
[0168] Optionally, a fluorination step may be performed.
[0169] Preferably, in the PFPE additive, the PFPE chain is a partially or fully fluorinated chain [chain (R f The chain contains repeating units R°, preferably composed of repeating units R°, which are independently selected from the group consisting of:
[0170] (i)-CFXO-, where X is F or CF3;
[0171] (ii) -CFXCFXO-, where X, which is the same or different each time it appears, is either F or CF3, provided that at least one of X is -F;
[0172] (iii)-CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H;
[0173] (iv)-CF2CF2CF2CF2O-;
[0174] (v)-(CF2) w -CFZ-O-, where w is an integer from 0 to 3, and Z is a variable with the general formula -OR (f-a) -Y group, where R (f-a) It is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and Y is a C1-C3 perfluoroalkyl group.
[0175] Preferably, the chain (R) f It conforms to the following formula (R) f-I) and (R f -II):
[0176] (R f -I)
[0177] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]-
[0178] in
[0179] - X 1 Independently selected from -F and -CF3,
[0180] - X 2 X 3 They are either the same as or different from each other and are independently -F or -CF3 each time they appear, provided that at least one of X is -F;
[0181] - g1, g2, g3, and g4, which may be the same as or different from each other, are independently ≥ 0, such that g1 + g2 + g3 + g4 are in the range of 2 to 300, preferably 10 to 250, or even more preferably 15 to 200; if at least two of g1, g2, g3, and g4 are different from zero, these different repeating units are statistically distributed along the chain in general.
[0182] (R f -II)
[0183] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 - (CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]-
[0184] in
[0185] - X 1 X 2 X 3 It is as defined above;
[0186] - g1, g2, g3, g4, g5 and g6, which may be the same as or different from each other, and are independently ≥ 0, such that g1 + g2 + g3 + g4 + g5 + g6 are in the range of 2 to 300, preferably 10 to 250, provided that at least one of g5 and g6 is different from 0.
[0187] In a preferred embodiment, the chain (R) f It conforms to the above formula (R) f -I).
[0188] Preferably, the chain (R) f It conforms to the above formula (R) f -I), and is a straight chain, in which
[0189] - X 1 X 2 and X 3 Each is -F.
[0190] - g3 and g4 are 0, and
[0191] - g1 and g2, which may be the same as or different from each other, are independent integers > 0, such that g1 + g2 is in the range of 2 to 300, preferably 10 to 250, or even more preferably 15 to 200; and the repeating units are statistically distributed along the chain.
[0192] Preferably, the chain (Ra) conforms to one of the following formulas (Ra-I) to (Ra-III):
[0193] (Ra-I) -(OCH2CH2) j1 -
[0194] (Ra-II)-[OCH(CH3)CH2] j2 -
[0195] (Ra-III) -[(OCH2CH2) j3 -(OCH(CH3)CH2) j4 ] j(x) -
[0196] Where j1 and j2 are each an independent integer from 1 to 10;
[0197] j3, j4 and j(x) are integers from 1 to 25, and the sum of j3 and j4 is from 2 to 50.
[0198] Preferably, in formula (Ra-I), j1 is an integer from 1 to 8, more preferably from 1 to 6.
[0199] Preferably, in formula (Ra-II), j2 is an integer from 1 to 8, more preferably from 1 to 6.
[0200] Preferably, in formula (Ra-III), j3, j4 and j(x) are each independently an integer from 1 to 8, more preferably from 1 to 6, and the sum of j3 and j4 is from 2 to 16, more preferably from 2 to 12.
[0201] Preferably, the chain (Ra) conforms to formula (Ra-I).
[0202] Preferably, the number of -OH groups in the PFPE additive is at least 80% of the total number of chain ends, more preferably at least 85%, and even more preferably at least 90%.
[0203] According to an embodiment, this PFPE additive contains 100% -OH groups based on the total number of chain ends, when all chain ends contain at least one -OH group. This PFPE additive is also referred to as a "bifunctional polymer".
[0204] According to an embodiment, one of the two chain ends statistically contains at least one -OH group, and the other chain end contains a neutral group selected from -CF3, -C2F5, and -C3F7. This PFPE additive is also referred to as a "monofunctional polymer".
[0205] PFPE additives can be provided as monofunctional polymers, difunctional polymers, or mixtures of monofunctional and difunctional polymers.
[0206] PFPE additives can be prepared according to methods known in the art, such as the procedures disclosed in WO 2014 / 090649 (in the name of Solvay Specialty Polymers Italy SpA).
[0207] Preferably, the amount of the PFPE additive is at least 0.1 wt.% based on the total weight of the composition (COMP).
[0208] More preferably, the amount of the PFPE additive is 0.1 to 20.0 wt.% based on the total weight of the composition (COMP), even more preferably 0.5 to 15 wt.%, and even more preferably 0.7 to 12 wt.%.
[0209] The thickener is present in an amount of 0.1 to 45.0 wt.%, preferably 5 to 40 wt.%, based on the total weight of the composition (COMP). More preferably, the thickener is present in an amount of 0.1 to 35 wt.%, preferably 1.0 to 32 wt.%, based on the total weight of the composition (COMP).
[0210] Preferably, the thickener is in powder form and has an average particle size (d) greater than 1 micrometer, more preferably greater than 2 micrometers, and even more preferably greater than 3 micrometers, as measured by laser diffraction particle size distribution. 50 ).
[0211] Preferably, the thickener is in powder form and has a particle size distribution of less than 15 micrometers, more preferably less than 12 micrometers, and even more preferably less than 10 micrometers, as measured by laser diffraction particle size distribution. 50 .
[0212] According to an embodiment, the thickener is selected from soap-based thickeners.
[0213] Soap thickeners include, for example, simple soaps and compound soaps. Simple soaps are organic salts of long-chain organic acids and alkali metals such as lithium, calcium, sodium, aluminum, and barium. Compound soaps comprise both a simple soap and a compounding agent. Suitable examples are lithium 12-hydroxystearate, lithium complexes, calcium complexes, and aluminum complexes.
[0214] According to an embodiment, the thickener is selected from non-soap thickeners.
[0215] Non-soap thickeners include, for example, polyurea, clay, fumed silica, fluorinated polymers and / or aromatic polymers.
[0216] Preferably, the thickener is a fluorinated polymer.
[0217] According to this embodiment, the fluorinated polymer is poly(tetrafluoroethylene) (PTFE).
[0218] Preferably, the thickener is an aromatic polymer.
[0219] According to this embodiment, the aromatic polymer has a melting point of at least 150°C.
[0220] Preferably, the aromatic polymer is in powder form, having a particle size distribution in the range of greater than 1 micrometer and up to 15 micrometers as measured by laser diffraction particle size analysis. 50 and 0.5 to less than 5 m 2 / g surface area (determined according to ISO 9277 by gas adsorption using the BET method).
[0221] The at least one aromatic polymer is advantageously selected from the group consisting of, preferably, the following:
[0222] (a) Poly(aryl sulfide) (PAS) polymer;
[0223] (b) Poly(phenylene oxide) (PPO) polymers;
[0224] (c) Poly(aryl ether ketone) (PAEK) polymers; and
[0225] (d) Poly(aryl ether sulfone) (PAES) polymer.
[0226] Preferably, (a) the poly(aryl sulfide) (PAS) is a polymer comprising:
[0227] -(Ar-S)- repeating unit, where Ar is aryl, also referred to as repeating unit (RPA) in this paper.
[0228] The arylene group in PAS can be substituted or unsubstituted.
[0229] Additionally, the PAS may include any isomerism of sulfide linkage in the polymer; for example, when the arylene is phenylene, the sulfide linkage may be ortho, meta, para, or a combination thereof.
[0230] Preferably, the PAS polymer comprises repeating units (RPAs) of at least 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, or 98 mol.% of the total moles in the PAS. According to embodiments, the PAS is substantially composed of repeating units (RPAs).
[0231] Preferably, the PAS polymer is selected from the group consisting of: poly(2,4-toluene sulfide), poly(4,4'-biphenylene sulfide), poly(p-phenylene sulfide) (PPS), poly(o-phenylene sulfide), poly(m-phenylene sulfide), poly(xylene sulfide), poly(ethyl isopropyl phenylene sulfide), poly(tetramethyl phenylene sulfide), poly(butylcyclohexyl phenylene sulfide), poly(hexyl dodecyl phenylene sulfide), poly(octadecyl phenylene sulfide), poly(phenyl phenylene sulfide), poly-(toluene phenylene sulfide), poly(benzyl phenylene sulfide), and poly[octyl-4-(3-methylcyclopentyl)phenylene sulfide].
[0232] More preferably, the PAS is a PPS comprising repeating units represented by Formula I:
[0233] (I).
[0234] Even more preferably, the PPS comprises at least 50 mol.% of repeating units having Formula I based on the total molar percentage of the PPS polymer. For example, at least about 60 mol.%, at least about 70 mol.%, at least about 80 mol.%, at least about 90 mol.%, at least about 95 mol.%, and at least about 99 mol.% of repeating units in the PPS are repeating units having Formula I.
[0235] According to an embodiment of the invention, the PPS polymer is such that approximately 100 mol.% of the repeating units are repeating units having Formula I. According to this embodiment, the PPS polymer is essentially composed of repeating units (RPP) having Formula I.
[0236] The PAS polymer of the present invention can be obtained by methods known in the art. Notably, references can be made to WO2015 / 095362 (Chevron Philipps), WO 2015 / 177857 (Solvay), and WO 2016 / 079243 (Solvay).
[0237] Preferably, the (b) poly(phenylene oxide) (PPO) polymer comprises repeating units conforming to formula (II):
[0238] (II)
[0239] in
[0240] R and R' are the same as or different from each other, and are H, -CH3, or -C6H5.
[0241] n is an integer that is at least equal to 1.
[0242] Preferably, the (c) poly(aryl ether ketone) (PAEK) polymer is a polymer containing more than 50 mol% repeating units (R-PAEK), wherein the repeating units (R-PAEK) include Ar-C(O)-Ar' groups.
[0243] Ar and Ar', which may be the same or different from each other, are aromatic groups.
[0244] In some embodiments, the poly(aryl ether ketone) (PAEK) comprises at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.%, at least 99.5 mol%, or at least 99.9 mol% of repeating units (R-PAEK). As used herein, mol.% is relative to the total number of moles of repeating units in the poly(aryl ether ketone) (PAEK).
[0245] In some embodiments, the repeating unit (R-PAEK) is selected from the group consisting of the following formulas (JA) to (JO):
[0246]
[0247] in:
[0248] Each R', whether identical or different from the others, is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, alkali metal or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds; and
[0249] j' is an integer from 0 to 4.
[0250] In the repeating unit (R-PAEK), the corresponding phenylene moiety may independently have 1,2-, 1,4-, or 1,3-bonded to other moiety in the repeating unit that is different from R'. Preferably, the phenylene moiety has 1,3- or 1,4-bonded, and more preferably, it has 1,4-bonded.
[0251] In some embodiments, j in the repeating unit (R-PAEK) is zero each time it appears. That is, the phenylene moiety has no substituents other than those substituents in the main chain of the polymer that enable bonding.
[0252] Therefore, the preferred repeating unit (R-PAEK) is selected from those having equations (J'-A) to (J'-0) below:
[0253]
[0254] In a preferred embodiment, polyaryletherketone (PAEK) is polyetheretherketone (PEEK).
[0255] In this embodiment, the polyetheretherketone (PEEK) has a repeating unit (R-PEEK) represented by formula (JA) or (J'-A), preferably the repeating unit (R-PEEK) is represented by formula (J'-A).
[0256] According to the examples, composition (C) comprises a variety of different poly(aryl ether ketone) polymers, each of which has a different repeating unit (R-PAEK).
[0257] Preferably, in the (d) poly(aryl ether sulfone) (PAES) polymer, at least 50 mol.% of the repeating units are repeating units having formula (IV):
[0258] (IV)
[0259] in:
[0260] (i) Each R, whether the same or different from each other, is selected from halogens, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, alkali metal or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium.
[0261] (ii) Each h, whether identical or different from the others, is an integer ranging from 0 to 4; and
[0262] (iii) T is selected from the following groups: bonds, sulfones
[0263] [-S(=O)2-] and the group -C(Rj)(Rk)-, wherein Rj and Rk, which may be the same as or different from each other, are selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, alkali metal or alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium.
[0264] Preferably, Rj and Rk are each methyl groups.
[0265] Preferably, the poly(aryl ether sulfone) (PAES) contains at least 60 mol.%, 70 mol.%, 80 mol.%, 90 mol.%, 95 mol.%, and 99 mol.%, and most preferably all repeating units are repeating units having formula (IV). As used herein, mol.% is relative to the total number of moles of repeating units in the poly(aryl ether sulfone) (PAES).
[0266] In the examples, poly(aryl ether sulfone) (PAES) is poly(biphenyl ether sulfone). Poly(biphenyl ether sulfone) polymers are poly(aryl ether sulfone) containing a biphenyl moiety. Poly(biphenyl ether sulfone) is also known as polyphenyl sulfone (PPSU) and is produced, for example, by the condensation of 4,4'-dihydroxybiphenyl (bisphenol) and 4,4'-dichlorodiphenyl sulfone.
[0267] As used herein, “poly(biphenyl ether sulfone) (PPSU)” means any polymer in which more than 50 mol.% of repeating units are repeating units (Rppsu) of formula (IV-A):
[0268] (IV-A)
[0269] Preferably, the poly(diphenyl ether sulfone) (PPSU) contains at least 60 mol.%, 70 mol.%, 80 mol.%, 90 mol.%, 95 mol.%, and 99 mol.%, and most preferably all repeating units are repeating units having the formula (IV-A).
[0270] In the examples, poly(aryl ether sulfone) (PAES) is polyether sulfone (PES).
[0271] As used herein, “poly(ethersulfone) (PES)” means any polymer in which at least 50 mol.% of the repeating units are repeating units having the formula (IV-B):
[0272] (IV-B)
[0273] Preferably, the poly(ether sulfone) (PES) contains at least 60 mol.%, 70 mol.%, 80 mol.%, 90 mol.%, 95 mol.%, and 99 mol.%, and most preferably all repeating units are repeating units having the formula (IV-B).
[0274] In the examples, poly(aryl ether sulfone) (PAES) is polysulfone (PSU). As used herein, "polysulfone (PSU)" means any polymer in which at least 50 mol.% of the repeating units are repeating units having the formula (IV-C):
[0275] (IV-C)
[0276] Preferably, the PSU contains at least 60 mol.%, 70 mol.%, 80 mol.%, 90 mol.%, 95 mol.%, and 99 mol.%, and most preferably all repeating units are repeating units having the formula (IV-C).
[0277] Preferably, the amount of the at least one additive (D) in solid particulate form is 0.05 wt.%, more preferably 0.10 wt.%, and even more preferably 0.25 wt.% based on the total weight of the composition (COMP).
[0278] Preferably, the amount of the at least one additive (D) in the form of solid particles is less than 12.00 wt.%, more preferably less than 10.00 wt.%, and even more preferably less than 9.50 wt.% based on the total weight of the composition (COMP).
[0279] Preferably, the amount of the at least one additive (D) in solid particulate form is from 0.75 wt.%, more preferably from 1.00 wt.%, and up to 8.00 wt.%, more preferably up to 7.5 wt.%, based on the total weight of the composition (COMP).
[0280] Preferably, the solid particles of at least one additive (D) are conductive particles. More preferably, the at least one additive (D) is selected from conductive carbon-based particles and transition metal particles. Even more preferably, the at least one additive (D) in solid particle form is selected from graphite, carbon black, and metals such as silver and copper. Graphite is particularly preferred.
[0281] If required by the final application, the composition (COMP) according to the invention may contain at least one additional component, such as those commonly used in lubricant compositions.
[0282] Non-limiting examples of suitable additives include: rust inhibitors, antioxidants, heat stabilizers, pour point depressants, anti-wear agents (including those used for high pressure), tracers, rheology modifiers, corrosion inhibitors, pigments, dyes, and fillers.
[0283] Each of the at least one additional ingredient may be present in an amount of 0.1 to 15 wt.% based on the total weight of the composition (COMP). The total amount of such additional ingredients in the composition (COMP) is typically in the range of 0.1 to 25 wt.% based on the total weight of the composition (COMP).
[0284] In another objective, the present invention relates to the use of the aforementioned composition (COMP) as a lubricant for electrical components suitable for various applications and industries, such as, in particular, the automotive and electronics industries. Such components include electrical and electronic components, such as, but not limited to, electrical connectors, switching devices, and circuit breakers.
[0285] In other words, the present invention relates to a method for lubricating at least one electrical or electronic component, preferably selected from electrical connectors, switching devices, and circuit breakers, the method comprising: applying a composition (COMP) as defined above to at least a portion of the component.
[0286] In yet another objective, the present invention relates to the use of the aforementioned composition (COMP) as a lubricant suitable for use in the automotive industry, particularly in mechanical components of electric vehicles (EVs). Such components include, but are not limited to, ball bearings.
[0287] In other words, the present invention relates to a method for lubricating at least one mechanical component, preferably selected from ball bearings, the method comprising: applying a composition (COMP) as defined above to at least a portion of the component.
[0288] In yet another object, the present invention relates to the use of the composition (COMP) according to the invention in the manufacture of lubricating grease.
[0289] In another object, the present invention relates to a grease comprising a composition (COMP) according to the invention and at least one other component.
[0290] This grease can be advantageously used as a lubricant for electrical, electronic, or mechanical components. Examples of such components are provided above, and include, but are not limited to, electrical connectors, switching devices and circuit breakers, and ball bearings.
[0291] If any disclosure by reference to any patent, patent application, or publication incorporated herein conflicts with the description of this application to the extent that it may make the terminology unclear, then this description shall take precedence.
[0292] The invention will now be described in more detail with reference to the following examples, which are illustrative in nature only and are not intended to limit the scope of this disclosure. Example
[0293] Material
[0294] Base grease 1, which contains (the amount is based on the total weight of the base grease):
[0295] - 70 wt.% of Fomblin with Mn = 5400 as measured by NMR (R) PFPE M07 [Neutral PFPE] (Commercially available from Solvay Specialty Polymers Italy S.A.)
[0296] - 30 wt.% Algoflon as a thickener with a particle size of 5 microns. (R) L 203R PTFE (Solvay Specialty Polymers Italy S.A.)
[0297] graphite:
[0298] TIMREX KS 6 GRAPHITE - 1001, obtained from Imerys.
[0299] additive:
[0300] ●ADD1: PFPE that meets the following formula:
[0301] HO(CH2CH2O) n CH2CF2O(CF2CF2O) p (CF2O) q CF2CH2(OCH2CH2) n OH
[0302] It has an Mn content of 1700 g / mol, as measured by nuclear magnetic resonance spectroscopy (NMR).
[0303] p / q = 1.3, n = 1.6, and contains 92.5% functionalized ethoxylated chain ends.
[0304] Available commercially from Solvay Specialty Polymers Italy S.p.A.
[0305] ●ADD2: PFPE that meets the following formula:
[0306] HO(CH2CH2O) n CH2CF2O(CF2CF2O) p (CF2O) q CF2CH2(OCH2CH2) n OH
[0307] It has an Mn concentration of 1980 g / mol, as measured by NMR.
[0308] p / q = 1.2, n = 4.3, and contains 93.8% functionalized ethoxylated chain ends.
[0309] Available commercially from Solvay Specialty Polymers Italy S.p.A.
[0310] Preparation using base grease 1
[0311] The comparative composition and the composition according to the invention were prepared by mixing the above-described base grease 1 with the following components in amounts (expressed as wt.%) detailed in Table 1.
[0312] Table 1
[0313]
[0314] ( Comparison
[0315] The above composition was subjected to volume resistivity and electrical bearing tests. The results are reported in Table 2.
[0316] Table 2
[0317]
[0318] ( Comparison
[0319] Compared with the comparative compositions, the compositions according to the present invention exhibit improved (i.e., lower) volume resistivity and are also successful in testing the resistance of electrical bearings.
Claims
1. A composition [Composition (COMP)] comprising: (A) At least one base oil, wherein the at least one base oil is selected from hydrogenated oil or (per)fluorinated oil; (B) At least one (per)fluoropolyether polymer [PFPE additive], based on a total weight of 0.1 to 20.0 wt.% of the composition (COMP), the (per)fluoropolyether polymer comprising a (per)fluoropolyether chain [PFPE chain] having two chain ends bonded to opposite sides of the main chain, wherein at least one chain end comprises at least one -OH group, the -OH group being bonded to the (per)fluoropolyether main chain via an alkoxylated chain [chain (Ra)]; (C) Based on 100% by weight of the composition (COMP), at least 0.1% to 45.0% by weight of at least one thickener, said at least one thickener being selected from the group consisting of: soap-based thickeners, preferably selected from metallic soaps and complex soaps; and non-soap-based thickeners, preferably selected from polyurea, clay, fumed silica, fluorinated polymers and / or aromatic polymers; and (D) At least one additive in the form of solid particles, in an amount of 0.01 to 25 wt. based on the total weight of the composition (COMP).
2. The composition (COMP) according to claim 1, wherein, The base oil is a (per)fluorinated oil, preferably selected from (per)fluorinated polyether polymers [PFPE base oil].
3. The composition (COMP) according to claim 2, wherein, The PFPE base oil is selected from the group consisting of: (AI) (Per)fluoropolyether polymers [PFPE polymers] comprising linear or branched (per)fluoropolyether chains [PFPE chains] having two chain ends bonded to opposing sites on the chain, each chain end comprising a linear or branched perfluorinated alkyl chain having 1 to 6 carbon atoms, the polymer having a number average molecular weight of 500 to 100,000, preferably 2,000 to 50,000, as measured by NMR; or (A-II) At least one block copolymer [PFPE copolymer] comprising first and second (per)fluoropolyether chains [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 via: - At least one first block of conformation (I) [block (1)]: (I) in n is 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 It is an oxygen atom, or optionally an oxygen atom inserted into, and / or a divalent / trivalent / tetravalent perfluorinated alkyl chain containing 1 to 24 carbon atoms. t is zero or 1, z is an integer from 1 to 3; R 11 To R 15 Each is 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^ 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(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- Where R 1^ To R 4^ Each of them independently possesses the meaning defined above for each of R1 to R4. E^ is a formula -(CR) 100^ R 101^ CR 102^ R 103^ )- group in R 100^ and R 101^ Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms, and R 102^ and R 103^ Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted; or R 100^ and R 101^ One of them and R 102^ and R 103^ One of them is a fluorine atom and R 100^ and R 101^ Another one in and R 102^ and R 103^ The other one in the mixture can optionally contain heteroatoms such as oxygen atoms to form a fully halogenated cyclic ring with 4 to 6 members; C^ is a PFPE chain, and T stands for perfluorinated alkyl group; - At least one second block of conformation (IV) [block (2)]: (IV) in n It is zero or an integer from 1 to 250. L is zero or an integer from 1 to 250, and n The sum of L and L is 0 or between 1 and 250; and Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms, and and Independently selected from hydrogen atoms, halogen atoms, more preferably fluorine or chlorine atoms; a straight-chain or branched alkyl chain comprising 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N and S; -OR 200 , where R 200 It is a straight-chain or branched perfluorinated chain containing 1 to 6 carbon atoms or having the formula -CF2OR 201 The group, wherein R 201 It is optionally a perfluorinated alkyl chain containing 1 to 6 carbon atoms with one or more oxygen ether atoms inserted; or and One of them and and One of them is a fluorine atom and and Another one in the middle and and The other one in the mixture can optionally contain heteroatoms such as oxygen atoms to form a fully halogenated cyclic ring with 4 to 6 members; E has the same meaning as E^ above; - Optionally, at least one third block [block (3)] containing the PFPE chain; The premise is: In the PFPE copolymer: -- n、n At least one of L is different from 0; -- The segments (1), (2), and (3) -- when present -- are statistically distributed; In equation (I): -- At least one of R1 to R4 is a group having formula (II), -- R 11 Or R 12 One of them and R 13 To R 15 One of them is a group having formula (III); In equations (III) and (IV) -- These repeating units are statistically distributed, In equation (III) -- When a^ is 1, at least one of v^ and L^ is different from 0.
4. The composition (COMP) according to claim 3, wherein, Each of the PFPE chains is a partially or fully fluorinated chain [chain(R] f The chain comprises repeating units R°, preferably composed of repeating units R°, wherein the repeating units are independently selected from the group consisting of: (i)-CFXO-, where X is F or CF3; (ii) -CFXCFXO-, where X, which is the same or different each time it appears, is either F or CF3, provided that at least one of X is -F; (iii)-CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H; (iv)-CF2CF2CF2CF2O-; (v)-(CF2) w -CFZ-O-, where w is an integer from 0 to 3, and Z is a variable with the general formula -OR (f-a) -Y group, where R (f-a) It is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and Y is a C1-C3 perfluoroalkyl group.
5. The composition (COMP) according to any one of claims 3 and 4, wherein, The PFPE base oil is an (AI) (per)fluoropolyether polymer [PFPE polymer] comprising a straight-chain PFPE chain having two chain ends bonded to opposite sides of the PFPE chain, each chain end comprising a straight-chain perfluorinated alkyl chain having 1 to 6 carbon atoms, and the PFPE polymer having a number average molecular weight of 2,000 to 50,000, more preferably 3,000 to 20,000, as measured by NMR.
6. The composition (COMP) according to claim 5, wherein, The PFPE chain conforms to the following formula (R) f -I) and (R f -II) chain (R f ): (R f -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- in - X 1 Independently selected from -F and -CF3, - X 2 X 3 They are either the same as or different from each other and are independently -F or -CF3 each time they appear, provided that at least one of X is -F; - g1, g2, g3, and g4, which may be the same as or different from each other, are independently ≥ 0, such that g1 + g2 + g3 + g4 are in the range of 2 to 300, preferably 10 to 250, or even more preferably 15 to 200; if at least two of g1, g2, g3, and g4 are different from zero, these different repeating units are statistically distributed along the chain in general. (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 - X 1 X 2 X 3 It is as defined above; - g1, g2, g3, g4, g5 and g6, which may be the same as or different from each other, and are independently ≥ 0, such that g1 + g2 + g3 + g4 + g5 + g6 are in the range of 2 to 300, preferably 10 to 250, provided that at least one of g5 and g6 is different from 0.
7. The composition (COMP) according to claim 6, wherein, The chain (R) f Conformation (R) f -I) and is a straight chain, where, - X 1 X 2 and X 3 Each is -F. - g3 and g4 are 0, and - g1 and g2, which may be the same as or different from each other, are independent integers > 0, such that g1 + g2 is in the range of 2 to 300, preferably 10 to 250, or even more preferably 15 to 200; and these repeating units are statistically distributed along the chain.
8. The composition (COMP) according to any one of the preceding claims, wherein, The chain (Ra) conforms to one of the following formulas (Ra-I) to (Ra-III): (Ra-I) -(OCH2CH2) j1 - (Ra-II) -[OCH(CH3)CH2] j2 - (Ra-III) -[(OCH2CH2) j3 -(OCH(CH3)CH2) j4 ] j(x) - in j1 and j2 are each an independent integer from 1 to 10; j3, j4 and j(x) are integers from 1 to 25, and the sum of j3 and j4 is from 2 to 50.
9. The composition (COMP) according to claim 8, wherein, The chain (Ra) conforms to the formula (Ra-I), wherein preferably, j1 is an integer from 1 to 8, more preferably from 1 to 6.
10. The composition (COMP) according to any one of the preceding claims, wherein, The amount of the PFPE additive is 0.5 to 15 wt.%, more preferably 0.7 to 12 wt.%, based on the total weight of the composition (COMP).
11. The composition (COMP) according to any one of the preceding claims, wherein, The thickener is in powder form with an average particle size (d). 50 )for: - Above 1 micrometer, such as those measured by volumetric particle size distribution via laser diffraction particle size analysis; and / or - Less than 15 micrometers, as measured by volumetric particle size distribution via laser diffraction particle size analysis.
12. The composition (COMP) according to any one of the preceding claims, wherein, The thickener is a fluoropolymer, preferably poly(tetrafluoroethylene) (PTFE); or an aromatic polymer, preferably selected from the group consisting of: (a) Poly(aryl sulfide) (PAS) polymer; (b) Poly(phenylene oxide) (PPO) polymers; (c) Poly(aryl ether ketone) (PAEK) polymers; and (d) Poly(aryl ether sulfone) (PAES) polymer.
13. The composition (COMP) according to any one of the preceding claims, wherein, The amount of the at least one additive (D) in solid particulate form is from 0.05 wt.% to 7.5 wt.% based on the total weight of the composition (COMP).
14. The composition (COMP) according to any one of the preceding claims, wherein, The at least one additive (D) in the form of solid particles is selected from conductive carbon-based particles and transition metal particles, more preferably from graphite, carbon black, silver and copper.
15. A method for lubricating at least one electrical or electronic component, preferably selected from electrical connectors, switching devices, and circuit breakers, the method comprising applying a composition (COMP) according to any one of claims 1 to 14 to at least a portion of the component.
16. A method for lubricating at least one mechanical component, preferably selected from ball bearings, the method comprising applying a composition (COMP) as defined in any one of claims 1 to 14 to at least a portion of the component.
17. A grease comprising the composition (COMP) according to any one of claims 1 to 14 and at least one other component.
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