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  (per) fluoropolyether additivesUSPTO Application #: 20060111250Title: (per) fluoropolyether additives Abstract: W1, W2, equal to or different from each other, are —F, —CF3: Rf is a (per)fluoropolyoxyalkylene chain having a number average molecular weight between 500 and 10,000, preferably between 800 and 5,000.
with the proviso that at least one of the two end groups T1, T2 is —CH2—B—Y or —CH(CF3)O—Y, wherein B and Y are as above:
R1, R2, R3, R4, equal to or different from each other are H, linear or branched C1-C8 perfluoroalkyl, NO2, CN, preferably H;
wherein:
Y is a substituent formed of a ring having a heterocyclic structure having the following formula:
—CH2—B—Y, —CH(CF3)O—Y, wherein: B═O, S:
F, CF3, C2F5, (C2F4)Cl
T1, T2, equal to or different from each other, have the following meanings:
wherein
T1-CFW1—O—Rf—CFW2-T2 (I)
Compounds usable as stabilizing additives of perfluoropolyether fluids working at high temperatures, higher than 200° C. and/or in the presence of metals and/or in the presence of Lewis acids, are formed of (per)fluoropolyether chains and of end groups having a heteroaromatic structure, according to the following general formula: (end of abstract)
Agent: Arent Fox PLLC - Washington, DC, US Inventors: Antonio Russo, Claudio Tonelli USPTO Applicaton #: 20060111250 - Class: 508182000 (USPTO) Related Patent Categories: Solid Anti-friction Devices, Materials Therefor, Lubricant Or Separant Compositions For Moving Solid Surfaces, And Miscellaneous Mineral Oil Compositions, Lubricants Or Separants For Moving Solid Surfaces And Miscellaneous Mineral Oil Compositions (e.g., Water Containing, Etc.), Inorganic Compound (except Water) (overbased Or Carbonated Organic Acidic Compounds Are Not Classified In This Subclass Or Its Indents On The Basis Of Inorganic Overbasing Or Carbonating Agents; The Overbased Or Carbonated Compounds Are Treated As Complexes, And Are Classified With The Particular Organic Acidic Compound), With Compound Having Ether Group The Patent Description & Claims data below is from USPTO Patent Application 20060111250. Brief Patent Description - Full Patent Description - Patent Application Claims
[0001] The present invention relates to stabilizing additives for lubricating oils and greases towards Lewis acids. [0002] More specifically the invention relates to the use of fluorinated additives as stabilizing agents of fluorinated oils and greases, preferably having a perfluoropolyether structure, for their use in the presence of Lewis acids at high temperature, for example higher than 200.degree. C. up to 280.degree. C. The present invention also refers to the process for preparing said additives and to compositions of oils and greases, preferably having a perfluoropolyether structure, comprising said additives. [0003] It is known in the prior art that perfluoropolyethers have high chemical and thermal stability and are therefore used in many applications as lubricating oils and greases, or hydraulic fluids. However in some extremely severe operating conditions, perfluoropolyethers show the drawback to have an insufficient thermal stability and they tend therefore to decompose. [0004] Particularly critical applications are also those wherein lubricants having a perfluoropolyether structure are in the presence of Lewis acids. It is indeed known that Lewis acids, in particular aluminum, iron, titanium, vanadium and other fluorides, catalyze perfluoropolyether degradation. The applications wherein lubricants are in contact with Lewis acids are for example lubrication of magnetic discs. In this case the Lewis acid is generated by reading head of the hard disk. This process of degradation leads to the breaking and fragmentation of the perfluoropolyether chains. In some cases it is also possible to arrive to the total decomposition of the perfluoropolyether fluid. Under these conditions volatile fractions are produced which evaporate under the lubricant use conditions, so that the lubricant can be completely lost. Furthermore, the fluid decomposition is generally associated to a progressive metal corrosion, when in contact with the fluid. [0005] It is known in the prior art that the stability to Lewis acids of oils and greases having a perfluoropolyether structure, when used at high temperatures, can be impoved by using specific stabilizing additives. European patent application No. 04011149.4 (publication No. EP 1 479 753) describes stabilizing additives having a (per)fluoropolyether structure for lubricating oils and greases towards Lewis acids ended with pyridine groups, optionally substituted. [0006] Other stabilizing additives towards Lewis acids are known in the prior art, see U.S. Pat. No. 6,083,600. The additives of this patent have a (per)fluoropolyether structure and are ended at both ends with substituted amine groups. In the Examples it is shown that said compounds are stable in the presence of Lewis acids at the temperature of 200.degree. C. for a time not higher than 4 hours (see the Example 7 and FIG. 3). The stability of these compounds at temperatures higher than 200.degree. C., up to 280.degree. C., is not reported. [0007] The need was felt to have available compounds to be used as additives for fluorinated lubricating fluids, preferably having a perfluoropolyether structure, said compounds having the following combination of properties: [0008] capable to stabilize fluorinated oils and greases in the presence of Lewis acids at temperatures higher than 200.degree. C., up to 280.degree. C., even in the presence of metals; [0009] obtainable by simple method in high yields, higher than 80%, preferably higher than 90%, by using not very expensive and non toxic reactants and mild synthesis conditions. [0010] The Applicant has surprisingly and unexpectedly found compounds to be used as additives to stabilize fluorinated oils and greases in the presence of Lewis acids, having the above combination of properties. [0011] An object of the present invention are compounds usable as stabilizing additives of fluorinated, preferably perfluoropolyether, fluids, working at high temperatures, higher than 200.degree. C., up to 280.degree. C. in the presence of Lewis acids, optionally even in the presence of metals, said compounds being formed of (per)fluoropolyether chains and end groups having a heteroaromatic structure, having the following general formula: T.sub.1-CFW.sub.1--O--R.sub.f--CFW.sub.2-T.sub.2 (I) wherein [0012] T.sub.1, T.sub.2, equal to or different from each other, have the following meanings: [0013] F, CF.sub.3, C.sub.2F.sub.5, (C.sub.2F.sub.4)Cl; [0014] --CH.sub.2--B--Y, --CH(CF.sub.3)O--Y, wherein: [0015] B.dbd.O, S; [0016] Y is a substituent formed of a ring having a heterocyclic structure having the following formula: [0017] wherein: [0018] Q is equal to O, S or to the --CH.dbd.N-- group; R.sub.1, R.sub.2, R.sub.3, R.sub.4, equal to or different from each other are H; linear or branched C.sub.1-C.sub.8 perfluoroalkyl, NO.sub.2, CN, preferably H; [0019] with the proviso that at least one of the two end groups T.sub.1, T.sub.2 is --CH.sub.2--B--Y or --CH(CF.sub.3)O--Y; [0020] W.sub.1 and W.sub.2, equal to or different from each other, are F, --CF.sub.3, preferably F; [0021] Rf is a (per)fluoropolyoxyalkylene chain comprising one or more repeating units, statistically distributed along the polymeric backbone, having the following structure: (CFXO), (C.sub.2F.sub.4O), (CF.sub.2CF.sub.2CF.sub.2O), (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O), (C.sub.3F.sub.6O), (CR.sub.5R.sub.6CF.sub.2CF.sub.2O); [0022] wherein X is F, CF.sub.3; R.sub.5 and R.sub.6, equal to or different from each other, are selected from H, Cl, or perfluoroalkyl from 1 to 4 carbon atoms, [0023] R.sub.f having a number average molecular weight between 500 and 10,000, preferably between 800 and 8,000, still more preferably between 2,000 and 5,000. [0024] Preferably in formula (I--B) of Y when Q is CH.dbd.N, N is linked to the aromatic ring and the compound belongs to the quinoxaline class. [0025] The repeating unit (C.sub.3F.sub.6O) of the (per)fluoropolyoxyalkylene chain represents units of formula: --(CF.sub.2CF(CF.sub.3)O)-- or --(CF(CF.sub.3)CF.sub.2O)--. [0026] The preferred perfluoropolyether chain Rf is selected from the following structures: --(CF.sub.2CF(CF.sub.3)O).sub.a(CFXO).sub.b--CF.sub.2(R'.sub.f)CF.sub.2--- O--(CF.sub.2CF(CF.sub.3)O).sub.a(CFXO).sub.b-- (A) [0027] wherein R'.sub.f is a fluoroalkylene group from 1 to 4 C atoms; X is as above; a and b are integers such that the number average molecular weight is in the above range; a/b is between 10 and 100 where b is different from 0; --(CF.sub.2CF.sub.2O).sub.c(CF.sub.2O).sub.d(CF.sub.2(CF.sub.2).sub.zO).s- ub.h-- (B) [0028] wherein c, d and h are integers such that the number average molecular weight is within the above range; c/d is between 0.1 and 10 where d is different from 0; h/(c+d) is between 0 and 0.05 where (c+d) is different from 0, z is 2 or 3, h can also be equal to 0; --(C.sub.3F.sub.6O).sub.e(CF.sub.2CF.sub.2O).sub.f(CFXO).sub.g-- (C) [0029] wherein X is as above; e, f, g are integers such that the number average molecular weight is within the above range; e/(f+g) is between 0.1 and 10 where (f+g) is different form 0; f/g is between 2 and 10 where g is different from 0; --(CF.sub.2(CF.sub.2).sub.zO).sub.s-- (D) [0030] wherein s is an integer such as to give the molecular weight in the above range, z has the meaning as above; --(CR.sub.5R.sub.6CF.sub.2CF.sub.2O).sub.p'--R'.sub.f--O--(CR.sub.5R.sub.- 6CF.sub.2CF.sub.2O).sub.q'-- (E) [0031] wherein R.sub.5 and R.sub.6 are equal to or different from each other and selected from H, Cl or perfluoroalkyl from 1 to 4 C atoms; R'.sub.f has the above meaning, p' and q' are integers such that the molecular weight is in the above range; --(CF(CF.sub.3)CF.sub.2O).sub.j''--R'.sub.f--O--(CF(CF.sub.3)CF.sub.2O).s- ub.j''-- (F) [0032] j'' being an integer such as to give the above molecular weight, R'.sub.f being as above. [0033] Particularly preferred (per)fluoropolyoxyalkylene structures are (A) and (B), preferably (B). [0034] The above described (per)fluoropolyoxyalkylene structures can be obtained by using the synthesis methods described in GB 1,104,482, U.S. Pat. No. 3,715,378, U.S. Pat. No. 3,242,218, U.S. Pat. No. 4,647,413, EP 148,482, U.S. Pat. No. 4,523,039, EP 340,740, WO 90/03357, U.S. Pat. No. 3,810,874, EP 239,123, U.S. Pat. No. 5,149,842, U.S. Pat. No. 5,258,110. [0035] The compounds of the present invention are transparent and odourless viscous liquids. [0036] A further object of the present invention are lubricating formulations comprising: [0037] a fluorinated oil or grease, preferably having a perfluoropolyether structure; [0038] from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, still more preferably from 0.5% to 2%, on the whole composition, of the compounds of formula (I) of the present invention. [0039] The perfluoropolyethers usable as oils or as components for preparing greases are selected from the following classes: E-O--[CF(CF.sub.3)CF.sub.2O].sub.m'(CFXO).sub.n'-E' (1) [0040] wherein: [0041] X is as above; [0042] E and E', equal to or different from each other, are selected from --CF.sub.3, --C.sub.2F.sub.5 or --C.sub.3F.sub.7; [0043] m' and n' are integers such that the m'/n' ratio is between 20 and 1000 where n' is different from 0 and the viscosity of the product measured at 20.degree. C. is within the limits indicated below; the above indicated repeating units are statistically distributed along the chain. [0044] These compounds can be obtained by perfluoropropene photooxidation as described in GB 1,104,432, and by subsequent conversion of the end groups as described in GB 1,226,566. C.sub.3F.sub.7O--[CF(CF.sub.3)CF.sub.2O].sub.o'-D [0045] wherein: [0046] D is equal to --C.sub.2F.sub.5 or --C.sub.3F.sub.7; [0047] o' is an integer such that the viscosity of the product is within the range indicated below. These products can be prepared by ionic oligomerization of perfluoropropylenoxide and subsequent treatment with fluorine as described in U.S. Pat. No. 3,242,218. {C.sub.3F.sub.7O--[CF(CF.sub.3)CF.sub.2O].sub.p'--CF(CF.sub.3)--}.sub.2 (3) [0048] wherein: [0049] p' is an integer such that the viscosity of the product is within the range indicated below. [0050] These products can be obtained by ionic telomerization of perfluoropropylenoxide and subsequent photochemical dimerization as reported in U.S. Pat. No. 3,214,478. E-O--[CF(CF.sub.3)CF.sub.2O].sub.q'(C.sub.2F.sub.4O).sub.r'(CFX).sub.s'-E- ' (4) [0051] wherein: [0052] X is as above; [0053] E and E', equal to or different from each other, are as above; [0054] q', r' and s' are integers, including 0, such that the viscosity of the product is within the range indicated below. [0055] These products are obtainable by photooxidation of a mixture of C.sub.3F.sub.6 and C.sub.2F.sub.4 and subsequent treatment with fluorine as described in U.S. Pat. No. 3,665,041. E-O--(C.sub.2F.sub.4O).sub.t'(CF.sub.2O).sub.u'-E' (5) [0056] wherein: [0057] E and E', equal to or different from each other, are as above; [0058] t' and u' are integers such that the t'/u' ratio is between 0.1 and 5 where u' is different from 0, and the viscosity of the product is within the limits indicated below. [0059] These products are obtained by photooxidation of C.sub.2F.sub.4 as reported in U.S. Pat. No. 3,715,378 and subsequent treatment with fluorine as described in U.S. Pat. No. 3,665,041. E-O--(CF.sub.2CF.sub.2CF.sub.2O).sub.v'-E' (6) [0060] wherein: [0061] E and E', equal to or different from each other are as above; [0062] v' is a number such that the viscosity is within the range indicated below. [0063] These products are obtained as reported in EP 148,482. D-O--(CF.sub.2F.sub.2O).sub.z'-D' (7) [0064] wherein: [0065] D and D', equal to or different from each other, are as above; [0066] z' is an integer such that the viscosity of the product is within the range indicated below. [0067] These products can be obtained as described in U.S. Pat. No. 4,523,039. [0068] The perfluoropolyethers of the above classes from (1) to (7) are liquids having a very low vapour pressure and having a kinematic viscosity measured at 20.degree. C. generally from 10 to 10,000 cSt, preferably from 300 to 2,000 cSt. [0069] The preferred perfluoropolyether oils are those of the classes (1), (4), (5) and are available on the market with the trademark FOMBLIN.RTM. marketed by Solvay Solexis. [0070] The formulations of the invention can contain other additives commonly used in fluorinated lubricant formulations, preferably having a perfluoropolyether structure. For example anti-wear, anti-rust additives and Lewis anti-acid additives can be mentioned. Anti-wear additives are for example those having a perfluoropolyether structure linked to phosphazene rings. For example those described in EP 1,336,614 in the name of the Applicant can be used. [0071] Furthermore, in case of lubricating greases, the formulations contain as essential components, besides one or more perfluoropolyether oils belonging to one or more of the above classes and to the additive of formula (I), also thickening additives as for example PTFE, optionally sodium terephthalate, calcium or lithium soaps, polyurea. As thickening agent, PTFE (polytetrafluoroethylene) is preferably used. [0072] Other components, generally contained in the greases, are the following: dispersing agents as for example surfactants, in particular nonionic surfactants and preferably with a perfluoropolyether or perfluoroalkyl structure; besides talc or inorganic fillers. The lubricating greases having a perfluoropolyether polyether structure can also contain other additives commonly used in grease formulations. Continue reading... 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