EP1712580B1 - Additives for fluorinated oils - Google Patents
Additives for fluorinated oils Download PDFInfo
- Publication number
- EP1712580B1 EP1712580B1 EP06006673A EP06006673A EP1712580B1 EP 1712580 B1 EP1712580 B1 EP 1712580B1 EP 06006673 A EP06006673 A EP 06006673A EP 06006673 A EP06006673 A EP 06006673A EP 1712580 B1 EP1712580 B1 EP 1712580B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- equal
- different
- formula
- perfluoropolyether
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 239000000654 additive Substances 0.000 title claims description 51
- 239000003921 oil Substances 0.000 title claims description 38
- 239000010702 perfluoropolyether Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 30
- 230000000996 additive effect Effects 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000002739 metals Chemical class 0.000 claims description 20
- 239000000314 lubricant Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 11
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 11
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 230000001050 lubricating effect Effects 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 claims description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical group CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000003918 triazines Chemical class 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007866 anti-wear additive Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002396 Polyurea Polymers 0.000 claims description 2
- TVIPECTUCRNDNZ-UHFFFAOYSA-M [Na+].NC(=O)C1=CC=C(C([O-])=O)C=C1 Chemical compound [Na+].NC(=O)C1=CC=C(C([O-])=O)C=C1 TVIPECTUCRNDNZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000087 stabilizing effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- 229910000756 V alloy Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 0 CCC(CC1)C1(C(C1)C1C1)C1C(CC(C)(C)CC(CC(C)C(C)C1)(C(*)CCCC2CC2)C(C)(C)C)(CC(C)(C)C1C1(C2)C2CCC1)C(C)(C)C Chemical compound CCC(CC1)C1(C(C1)C1C1)C1C(CC(C)(C)CC(CC(C)C(C)C1)(C(*)CCCC2CC2)C(C)(C)C)(CC(C)(C)C1C1(C2)C2CCC1)C(C)(C)C 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- QEPXACTUQNGGHW-UHFFFAOYSA-N 2,4,6-trichloro-1h-triazine Chemical compound ClN1NC(Cl)=CC(Cl)=N1 QEPXACTUQNGGHW-UHFFFAOYSA-N 0.000 description 4
- LKPFWCPZERQLFI-UHFFFAOYSA-N 2,4,6-trimethylpyridine;hydrochloride Chemical compound Cl.CC1=CC(C)=NC(C)=C1 LKPFWCPZERQLFI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic phosphates Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LKPVGEQCXYXTIH-UHFFFAOYSA-N O=P(=O)C1=CC=NN=N1 Chemical class O=P(=O)C1=CC=NN=N1 LKPVGEQCXYXTIH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940055764 triaz Drugs 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/40—Six-membered ring containing nitrogen and carbon only
- C10M133/42—Triazines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
- C10M2201/103—Clays; Mica; Zeolites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/1256—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/0606—Perfluoro polymers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
- C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
- C10M2215/222—Triazines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
- C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to additives for lubricating oils and greases capable to improve their thermal stability in the presence of metals and in oxidative environment (for example air) and their preparation process.
- the invention relates to additives having a perfluoropolyether structure capable to stabilize lubricants, such as oils and greases, preferably having a perfluoropolyether structure, in combination with to the capability of conferring good anti-rust properties and good stability (high shelf life) to storage at 25°C, i.e. without phase separation.
- perfluoropolyethers have a good chemical and thermal stability, and are used as lubricating oils and greases, or as hydraulic fluids in applications where a broad thermal rating is required, and in particular severe conditions, for example in contact with corrosive compounds or with ionizing radiations.
- these lubricants show the drawback that in some extremely drastic operating conditions, as for example at temperatures higher than 280°C, in oxidative environment (for example air) and in the presence of metals, tend to decompose showing a limited thermal stability.
- the decomposition process in the above described conditions brings to the fragmentation of the perfluoropolyether chains or, in some cases, to the total decomposition of the lubricant itself, thus compromizing the lubricant performances.
- fluid decomposition is generally associated with a progressive corrosion of the metal itself.
- USP 4,681,693 describes stabilizers for perfluoropolyether lubricants having a backbone formed of arylphosphines units, or their derivatives, linked to perfluoropolyether chains through oxygen or sulphur atoms. These compounds are prepared with a multistep process comprising intermediates difficult to be prepared. Therefore this process is hardly industrially usable.
- EP 597,369 describes stabilizers for phosphazene derivatives based perfluoropolyether lubricants, having contemporaneously on the phosphazene ring both aromatic groups and (per)fluoropolyether chains.
- the synthesis of the stabilizers is not selective and does not allow to obtain an additive having a well defined chemical structure.
- the phosphazene precursor is very expensive and therefore disadvantageous from an industrial point ov view. Tests carried out by Applicant have shown that these compounds have a low stability to storage.
- USP 5,326,910 describes perfluoropolyether phosphotriazines as stabilizers for perfluoropolyether oils. These derivatives are obtained by a synthesis requiring many steps and reactants difficult to prepare, as perfluorinated epoxides.
- phosphoric esters in particular arylphosphates, wherein at least one of the substituents is a perfluoropolyether chain.
- aromatic chloroesters are used. These compounds have the drawback to be very expensive.
- the phosphoric esters are obtained by reaction of aromatic alcohols with POCl 3 , which is toxic and scalding, thus requiring specific equipments for the use on industrial scale.
- the stabilizers containing phosphor described so far are however obtained with synthesis processes comprising various steps, some of them require the use of expensive and/or difficult to prepare reactants, requiring operating conditions or technological solutions of difficult management on industrial scale. Besides some of them show a poor stability to storage.
- oligomers having a perfluoroalkylenether-triazine structure are described, as lubricants having a good stability to the oxidation in the presence of metals. These oligomers can also be used as stabilizing additives for oils and greases having a perlfuoropolyether structure.
- their synthesis requires various steps, some of them require the use of precursors of difficult preparation, with a yield in the final product lower than 40%, and therefore disadvantageous also from an economic point of view. None is said on the anti-rust properties of said compounds.
- the preferred perfluoropolyether chain R f is selected from the following structures:
- R f structures in the compounds of formula (I) are selected between the structures (A) and (B).
- the compounds of the invention can be used as additives of perfluorinated lubricants, as perfluoropolyether oils or perfluoropolyether base greases, to confer an improved thermal stability to the lubricant in oxidative environment and in the presence of metals in combination with good anti-rust properties and good shelf life at 25°C.
- the pefluoropolyether compounds having at least one aryltriazine end group are transparent and odourless viscous liquids.
- a further object of the present invention are lubricating compositions comprising:
- perfluoropolyether oils are those belonging to the following classes:
- the preferred perfluoropolyether oils are those of the class (1), (4), (5) and (8).
- perfluoropolyethers of the classes from (1) to (8) have perfluoroalkyl end groups, are liquid with a very low vapour pressure value and have a viscosity, at 20°C, generally between 10 and 100,000 cSt, preferably between 40 and 2,000 cSt.
- perfluoropolyethers usable for preparing oils and greases are available on the market as for example FOMBLIN® (Solvay Solexis).
- the lubricant compositions of the present invention have a high shelf life at room temperature and do not visually show any substantially phase separation for long periods of time.
- compositions of the present invention can also contain other additives commonly used in perfluoropolyether lubricant formulations, as for example anti-wear additives.
- a further object of the present invention is a process to obtain the triazine compounds of formula (I) comprising the following stages:
- the inert solvent is preferably selected from toluene, xylene, hexafluoroxylene, acetone, diethyl-ketone, etc.
- the used solvent amount is depending on the reactant solubility in the solvent itself.
- inorganic base NaOH, KOH, Na 2 CO 3 , K 2 CO 3 can be used;
- organic base 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine (collidine) can be used.
- base 2,4,6-trimethylpyridine is used.
- the ratio between the equivalents of the base and the sum of the equivalents of compounds (II) and (IV) used in the above mentioned three steps of stage (A) is in the range 1:1-2:1, preferably 1:1-1.5:1.
- reaction times for each step are between 2 and 8 hours, preferably between 4 and 6 hours.
- the reactants having the structure (III), (IV) are known and commercially available.
- the process of the present invention results particularly advantageous as the selective substitution of only one halogen atom of the triazine ring (III) which takes place in each step i), ii), iii) of stage A) allows the highly selective substitution of the halogen atoms of the triazine reactant (III) obtaining additives having a predetermined chemical structure.
- Said selective process allows furthermore to obtain the triazine compounds of formula (I) with a yield higher than about 90%.
- the additives of the present invention do not contain phosphor, are obtainable with a defined chemical structure in high yields by a simple and highly selective process. Said additives allow furthermore to broaden the application field of the perfluoropolyether lubricants in thermooxidative environment in the presence of metals, in particular at temperatures higher than 280°C, in combination with anti-rust properties and high shelf life at 25°C.
- the lubricating compositions comprising the additives of the present invention can be used in the presence of metals and in oxidative environment (in the presence of air and oxygen) at high temperatures, higher than 200°C, without any substantial lubricant degradation phenomenon.
- the lubricating compositions containing the additives of the present invention can be used even at temperatures of about 300°C.
- compositions of the present invention have the advantage to be stable to storage at room temperature for long periods of time, thus overcoming the prior art drawbacks.
- the compounds of the present invention although containing non fluorinated substituents as the phenol groups, are dispersible in fluorinated oils at room temperature and do not show any substantial phase separation, thus allowing stability to storage (i.e. high shelf life).
- the additives of the present invention can be used in lubricating oils and greases.
- the preferred greases are the fluorinated ones, more preferably perfluoropolyether base greases.
- the compositions contain, besides the additive of the present invention and the perfluoropolyether oil belonging to one or more of the above mentioned classes, as an essential component, a thickener, in the amounts used in the prior art, as for example PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea.
- said compositions can also contain other additives commonly used in grease technology, as talc, inorganic fillers, anti-wear additives.
- the polymer primary particle sizes measured by electronic scanning microscopy (SEM); are between 0.02 and 0.25 micron. Said particles can be obtained, for example, by known microemulsion, emulsion, suspension polymerization processes.
- microoxidation test reported in the Examples has been carried out by using the equipment described in the following publication: Carl E. Snyder, Jr. and Ronald E. Dolle, Jr., ASLE Transactions, 13(3), 171-180 (1975) .
- the used operating conditions were the following:
- the lubricating composition to be tested is introduced in the glass test tube of the equipment shown in the reference Fig. 1, and the whole is weighed and brought to the test temperature. When 24, 48 or 72 hours have elapsed, depending on the test kind, the glass test tube, cooled at room temperture, is weighed again. The difference of weight before and after the heating determines the per cent weight loss of the composition under examination.
- a series of carbon steel (C15) (UNI) sheets having 50x100x2 mm sizes are prepared by polishing with abrasive papers (400-800 mesh) followed by cleaning and degreasing with a cloth soaked in n-hexane, and then dried. These sheets are treated by dip-coating in the"test dispersion and then placed in the fog chamber.
- the sheets are left in the chamber closed and saturated with moisture and are controlled at time regular intervals by visual inspection up to the appearance of stains on the surface.
- the test evaluation is expressed according to the following classification:
- the kinematic viscosity has been measured by capillary viscometer Cannon-Fenske according to the ASTM D445 method.
- reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
- the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- the liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 96.3 g of product with a yield equal to 92% are thus obtained.
- Example 1 was repeated but by using 9.4 g (0.068 eq) of p-nitrophenol instead of phenol.
- a is an integer such that T 1 '-CFW 1 -O(C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 3770; W 1 and W 2 are equal to F or CF 3 ; T1' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O- and -CH 2 -O-.
- reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperture and left under these conditions for further 2 hours.
- the precipitated collidine hydrochloride is then removed from the reaction mxiture by filtration.
- a is an integer such that T 1 '-CFW 1 -O (C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 1295; W 1 and W 2 are equal to F or CF 3 ; T1' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O and -CH 2 -O.
- reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
- the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- T 1 '-CFW 1 -O(C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 3770; W 1 and W 2 are equal to F or CF 3 ; T 1 ' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O- and -CH 2 -O- .
- reaction mixture temperature is slowly brought to 80°C and the reaction is allowed to continue for about 6 hours.
- the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- a perfluoropolyether oil of the class (5) having kinematic viscosity at 20°C of 260 cSt, commercially known as Fomblin® Z25, are added with 0.5 g of the additive of the Example 4 and then introduced in the glass test tube for the microoxidation test, in the presence of metals. After 24 hours at 300°C under the indicated operating conditions, a weight loss of 1.1% was determined.
- the metals dipped in the fluid during the test did not show oxidation/attack signs, but resulted comparable with those not exposed to the treatment.
- composition obtained by adding the perfluoropolyether oil with the additive of the Example 4 has resulted stable at room temperature and it does not visually show any separation after 168 hours.
- Example 6 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.46% by weight was measured.
- Example 6 was repeated by using 0.5 g of the additive of the Example 1. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.98% was measured.
- the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
- composition obtained by adding the perfluoropolyether oil with the additive of the Example 1 resulted stable at room temperature and it did not visually show any phase separation after 168 hours.
- Example 8 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.6% by weight was measured.
- Example 8 was repeated but increasing the time of the microoxidation test to 72 hours. At the end of the test a loss of 2.2% by weight was measured.
- Example 6 was repeated by using 0.5 g of the additive of the Example 3. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.47% was measured.
- the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack sings, but are comparable with those not exposed to the treatment.
- composition obtained by adding the perfluoropolyether oil with the additive of the Example 3 resulted stable at room temperature and it did not visually show any separation after 168 hours.
- Example 6 was repeated by using 0.5 g of the additive of the Example 2. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.82% was measured.
- the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
- composition obtained by adding the perfluoropolyether oil with the additive of the Example 2 resulted stable at room temperture and it did not visually show any separation after 168 hours.
- Example 6 was repeated in the absence of stabilizing additives. During the test a development of white smokes was observed. After 24 hours at 300°C under the indicated operating conditions the oil was completely decomposed.
- the metals dipped into the oil during the test show evident oxidation/attack signs and a remarkable darkening of the surface.
- composition obtained by adding the perfluoropolyether oil with the additive having aryl end groups of EP 1,354,932 and not containing triazine rings shows evident phase separation at room temperature already within 24 hours.
- Example 6 was repeated but by using as stabilizing agent 0.5 g of the compound of the Example 5 (comparative).
- a lubricating composition is prepared containing 0,5 g of the additive of the Example 2, 9.5 g of a perfluoropolyether lubricant of structure (1), having kinematic viscosity at 20°C of 40 cSt, commercially known as Fomblin® Y04. Said composition is then diluted with 190 g of a fluorinated solvent commercially known as Galden® SV90.
- a metal sheet cleaned according to what reported for the fog chamber test, is treated by dipping for 1 minute in said mixture. Said time elapsed, the sheet is taken and allowed to dry in a ventilated stove for 30 minutes at 60°C to remove the solvent. Then the sheet is placed in the fog chamber for the test.
- Example 16 was repeated without adding the invention additive and by using a lubricating mixture formed of 10 g of Fomblin® Y04 oil and 190 g of fluorinated solvent Galden® SV90.
- Example 16 was repeated without using the perfluoropolyether oil and by using a mixture formed of 0.5 g of the additive of the Example 2 and 199.5 g of fluorinated solvent Galden® SV90.
- Example 16 was repeated by using only 200 g of fluorinated solvent Galden® SV90 (control test).
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Description
- The present invention relates to additives for lubricating oils and greases capable to improve their thermal stability in the presence of metals and in oxidative environment (for example air) and their preparation process.
- Particularly the invention relates to additives having a perfluoropolyether structure capable to stabilize lubricants, such as oils and greases, preferably having a perfluoropolyether structure, in combination with to the capability of conferring good anti-rust properties and good stability (high shelf life) to storage at 25°C, i.e. without phase separation.
- It is known in the prior art that perfluoropolyethers have a good chemical and thermal stability, and are used as lubricating oils and greases, or as hydraulic fluids in applications where a broad thermal rating is required, and in particular severe conditions, for example in contact with corrosive compounds or with ionizing radiations. However these lubricants show the drawback that in some extremely drastic operating conditions, as for example at temperatures higher than 280°C, in oxidative environment (for example air) and in the presence of metals, tend to decompose showing a limited thermal stability.
- The decomposition process in the above described conditions brings to the fragmentation of the perfluoropolyether chains or, in some cases, to the total decomposition of the lubricant itself, thus compromizing the lubricant performances.
- Furthermore the fluid decomposition is generally associated with a progressive corrosion of the metal itself.
- It is also known in the prior art that the resistance to oxidation of oils and greases having a pefluoropolyether structure, at high temperatures in the presence of metals, can be improved with the use of specific stabilizing additives. They must have as peculiarity a good compatibility with the perfluoropolyether oil. Stabilizing additives containing phosphor and fluorinated substituents are known.
-
USP 4,681,693 describes stabilizers for perfluoropolyether lubricants having a backbone formed of arylphosphines units, or their derivatives, linked to perfluoropolyether chains through oxygen or sulphur atoms. These compounds are prepared with a multistep process comprising intermediates difficult to be prepared. Therefore this process is hardly industrially usable. -
EP 597,369 -
USP 5,326,910 describes perfluoropolyether phosphotriazines as stabilizers for perfluoropolyether oils. These derivatives are obtained by a synthesis requiring many steps and reactants difficult to prepare, as perfluorinated epoxides. - In
USP 5,550,277 stabilizers for perfluoropolyether lubricants having the structure of aromatic phosphates or phosphonates substituted by perfluoropolyether chains are described. The synthesis process is very complicated and requires many steps and the use of organometallic reactants, as for example butyl lithium, which, as well known, are difficult to use in industry for plant safety. - In the
patent application WO 99/51,612 - The stabilizers containing phosphor described so far, although having good stabilizing properties, are however obtained with synthesis processes comprising various steps, some of them require the use of expensive and/or difficult to prepare reactants, requiring operating conditions or technological solutions of difficult management on industrial scale. Besides some of them show a poor stability to storage.
- Not containing phosphor stabilizing additives for perfluoropolyether lubricants are also known.
- For example in
USP 5,942,598 oligomers having a perfluoroalkylenether-triazine structure are described, as lubricants having a good stability to the oxidation in the presence of metals. These oligomers can also be used as stabilizing additives for oils and greases having a perlfuoropolyether structure. However their synthesis requires various steps, some of them require the use of precursors of difficult preparation, with a yield in the final product lower than 40%, and therefore disadvantageous also from an economic point of view. Nothing is said on the anti-rust properties of said compounds. - In patent appliction
EP 1,354,932 in the name of the Applicant, stabilizing additives having a perfluoropolyether structure not containing phosphor and having aryl end groups containing NO2 groups are described. The additives are used to stabilize perfluoropolyether oils and greases in thermooxidative environment in the presence of metals. Tests carried out by the Applicant have shown that, even having good stabilizing performances, these additives show however the inconvenience of phase separation at room temperature. Therefore the compositions containing said additives have poor shelf life. - The need was therefore felt to have available additives:
- capable to stabilize fluorinated lubricants, in particular having a perfluoropolyether structure, at high temperatures in oxidative environment and in the presence of metals;
- showing anti-rust properties;
- stable in fluorinated lubricating oils or greases at room temperatures without phase separation, thus obtaining compositions stable to storage (high shelf life);
- obtainable by a simple industrial process.
The Applicant has surprisingly and unexpectedly found particular compounds having a perfluoropolyether structure capable to satisfy the above combination of properties.
An object of the present invention are compounds comprising perfluoropolyether chains and having at least one aryltriazine end group, of formula: - Rf is a (per)fluoropolyoxyalkylene chain formed of one or more repeating units, statistically placed along the chain, having the following structure: (CFXO), (CF2CF2O) , (CF2CF2CF2O) , (CF2CF2CF2CF2O), (CR6R7CF2CF2O), (CF(CF3)CF2O), (CF2CF(CF3)O), wherein X = F, CF3; R6 and R7, equal to or different from each other, are selected from H, Cl, or perfluoroalkyl from 1 to 4 carbon atoms, said Rf having a number average molecular weight in the range 500-10,000, preferably 500-5,000;
- W1, W2, equal to or different frome ach other, are -F or -CF3;
- T1 is equal to -CHAa-Ba(CH2CH2O)na- wherein Aa = H, CF3; Ba = O, S, NH ; na is an integer from 0 to 6, extremes included;
- T2 is equal to -F, -CF3, -C2F5, - (C2F4)Cl, or a group of formula:
- Q1, Q2, equal to or different from each other, are a perfluorooxyalkylene chain of formula:
-T1-CFW1-O-Rf-CFW2-T'2, wherein T'2 is equal to -F, -CF3, -C2F5, -(C2F4)Cl; T1, W1 and W2 have the above meaning; - The preferred perfluoropolyether chain Rf is selected from the following structures:
- (A) -(CF2CF(CF3)O)a(CFXO)b- or
- (CF2CF (CF3) O) a (CFXO) b-CF2 (R'f) CF2-O- (CF2CF (CF3) O) a(CFXO) b-
wherein R'f is a fluoroalkylene group from 1 to 4 C atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above range; a/b is between 10 and 100, b being different from 0; - (B) - (CF2CF2O)c(CF2O)d(CF2 (CF2) zO) h-
wherein c, d and h are integers such that the number average molecular weight is within the above range; c/d, d being different from 0, is between 0.1 and 10; h/ (c+d), (c+d) being different from 0, is between 0 and 0.05; z is 2 or 3; h can also be equal to 0; - (C) - (CF2CF(CF3)O)e (CF2CF2O) f (CFXO)g-
wherein X is F or CF3; e, f, g are integers such that the number average molecular weight is in the above range; e/(f+g) is between 0.1 and 10, (f+g) being different from 0; f/g is between 2 and 10; - (D)-(CF2(CF2)zO)s-
wherein s is an integer such as to give the above molecular weight, z has the already defined meaning; - (E) - (CR6R7CF2CF2O)j' - or
- (CR6R7CF2CF2O)p'-R'f-O- (CR6R7CF2CF2O)q'-
wherein R6 and R7 are equal to or different from each other and selected from H, Cl or perfluoroalkyl from 1 to 4 C atoms; R'f is a fluoroalkylene group from 1 to 4 C atoms; j', p' and q' are integers such as to have a molecular weight as the above mentioned one; - (F) -(CF(CF3)CF2O)j"-
j" being an integer such as to give the above molecular weight. - Preferably the Rf structures in the compounds of formula (I) are selected between the structures (A) and (B).
- The Applicant has surprisingly and unexpectedly found that the compounds of the invention can be used as additives of perfluorinated lubricants, as perfluoropolyether oils or perfluoropolyether base greases, to confer an improved thermal stability to the lubricant in oxidative environment and in the presence of metals in combination with good anti-rust properties and good shelf life at 25°C.
- The pefluoropolyether compounds having at least one aryltriazine end group are transparent and odourless viscous liquids.
- A further object of the present invention are lubricating compositions comprising:
- from 99.95 to 90% by weight, preferably from 99.5 to 95%, of a perfluoropolyether oil or a PFPE based grease on perfluoropolyether oils;
- from 0.05 to 10% by weight, preferably from 0.5 to 5% by weight, of at least one of the triazine compounds of formula (I).
- Examples of perfluoropolyether oils are those belonging to the following classes:
- (1) E-O-[CF2CF(CF3)O]m' (CFXO)n'-E'
wherein
X is equal to -F or -CF3;
E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;
m' and n' are integers such that the m'/n' ratio is between 20 and 1,000, n' being different from 0, and the viscosity of the product at 20°C is between 10 and 4.000 cSt; the units being statistically distributed along the backbone.
These polymers can be obtained by perfluoropropene photooxidation, as described inGB 1,104,432 GB 1,226,566 - (2) C3F7O-[CF(CF3)CF2O]o'-D
wherein
D is equal to -C2F5 or -C3F7;
o' is an integer such that the viscosity of the product is within the range indicated under (1).
These polymers can be prepared by ionic oligomerization of perfluoropropyleneoxide and subsequent treatment with fluorine as described inUSP 3,242,218 . - (3) {C3F7O-[CF(CF3)CF2O]p'-CF(CF3)-}2
wherein
p' is an integer such that the viscosity of the product is within the range indicated under (1).
These products can be obtained by ionic telomerization of perfluoropropyleneoxide and subsequent photochemical dimerization as reported inUSP 3,214,478 . - (4) E-O-[CF2CF(CF3)O]q' (C2F4O)r' (CFX)s'-E'
wherein
X is equal to -F or -CF3;
E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;
q', r' and s' are integers, including 0, so that the viscosity of the product is in the range indicated under (1) .
These polymers can be obtained by photooxidation of a mixture of C3F6 and C2F4 and subsequent treatment with fluorine as described inUSP 3,665,041 . - (5) E-O-(C2F4O)t' (CF2O)u'-E'
wherein
E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;
t' and u' are integers such that the t'/u' ratio is between 0.1 and 5, u' being different from 0, and the viscosity of the product is in the reported range under (1).
These polymers are obtained by photooxidation of C2F4 as reported inUSP 3,715,378 and subsequent treatment with fluorine as described inUSP 3,665,041 . - (6) E-O- (CF2CF2CF2O)v' -E'
wherein
E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;
v' is a number such that the viscosity of the product is in the above reported range under (1).
These polymers are obtained as reported inEP 148,482 - (7) D-O-(CF2CF2O)z'-D'
wherein
D and D', equal to or different from each other, are selected from -C2F5 or -C3F7;
z' is an integer such that the viscosity of the product is within the above reported range under (1).
These polymers can be obtained as reported inUSP 4,523,039 . - (8) E1-O (CF2O) n (CF2CF2O) m- (CF2CF2CF2O) p (CF2CF2CF2CF2O) q-E2
wherein
E1 and E2 are perfluoroalkyl end groups equal to or different from each other, having formula - (CF2)zCF3, wherein z is an integer from 0 to 3; n, m, p, q are integers such that the viscosity is as defined under (1) , m/n is between 2 and 20, n being different from 0, preferably between 2 and 10;
the ratio (p+q)/(m+n+p+q) is between 0.05 and 0.2, (m+n+p+q) being different from 0; n/(m+n+q+p) ranges between 0.05 and 0.4, (m+n+p+q) being different from 0. - These are obtained according to
EP 1,454,938 . - The preferred perfluoropolyether oils are those of the class (1), (4), (5) and (8).
- The above mentioned perfluoropolyethers of the classes from (1) to (8) have perfluoroalkyl end groups, are liquid with a very low vapour pressure value and have a viscosity, at 20°C, generally between 10 and 100,000 cSt, preferably between 40 and 2,000 cSt.
- The perfluoropolyethers usable for preparing oils and greases are available on the market as for example FOMBLIN® (Solvay Solexis).
- The lubricant compositions of the present invention have a high shelf life at room temperature and do not visually show any substantially phase separation for long periods of time.
- The compositions of the present invention can also contain other additives commonly used in perfluoropolyether lubricant formulations, as for example anti-wear additives.
- A further object of the present invention is a process to obtain the triazine compounds of formula (I) comprising the following stages:
-
- i) reaction of a perfluoropolyoxyalkylene derivative having formula
T"1-CFW1-O-Rf-CFW2-T"2 (II)
wherein
Rf, W1 and W2 have the above meaning;
T"1 and T"2 can be equal to or different from each other, having general formula equal to -CHAa-Ba(CH2CH2O)na-H, wherein Aa = H, CF3; Ba = O, S, NH; na is an integer from 0 to 6, extremes included; or selected from F, CF3, C2F5, (C2F4)Cl, with the proviso that at least one of the two end groups T"1 and T"2 is equal to -CHAa-Ba(CH2CH2O)na-H, preferably is selected from O-CH2OH, O-CH2SH, O-CH2NH2, CH(OH)CF3;
with
a trihalo-triazine of formula:
at a temperature between 0° and 10°C, wherein the ratio between the equivalents of the compound (II) and the moles of (III) is equal to 1:1, in the presence of a solvent inert under the reaction conditions, capable to solubilize the reactants, and in the presence of an organic or inorganic base, preferably maintaining the reaction mixture under stirring; - ii) reaction of the product obtained in i) with an equivalent of a derivative of formula:
Q-H (IV)
wherein Q has the above reported meaning for Q1 and Q2;
at a temperature in the range 25°-35°C; - iii) reaction of the product obtained in ii) with an equivalent of a compound of formula (IV), equal to or different from the one used in step ii), at a temperature in the range 65°C-100°C, preferably 70°C-90°C;
- separation of the organic phase of the reaction mixture obtained in A) from the aqueous phase and subsequent separation, preferably by filtration, of the organic phase to remove the residual organic or inorganic insoluble salts;
- several washings of the liquid organic phase with acid water and subsequent separation of the obtained compound of formula (I) from the organic solvent, for example by evaporation.
- In stage A) the inert solvent is preferably selected from toluene, xylene, hexafluoroxylene, acetone, diethyl-ketone, etc. The used solvent amount is depending on the reactant solubility in the solvent itself. In stage A) as inorganic base, NaOH, KOH, Na2CO3, K2CO3 can be used; as organic base, 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine (collidine) can be used. Preferably as base 2,4,6-trimethylpyridine is used.
- The ratio between the equivalents of the base and the sum of the equivalents of compounds (II) and (IV) used in the above mentioned three steps of stage (A) is in the range 1:1-2:1, preferably 1:1-1.5:1.
- The reaction times for each step are between 2 and 8 hours, preferably between 4 and 6 hours.
- The compounds of formula (II) are known in the prior art, for example from
USP 6,509,509 andUSP 5,124,058 . - The reactants having the structure (III), (IV) are known and commercially available.
- The process of the present invention results particularly advantageous as the selective substitution of only one halogen atom of the triazine ring (III) which takes place in each step i), ii), iii) of stage A) allows the highly selective substitution of the halogen atoms of the triazine reactant (III) obtaining additives having a predetermined chemical structure.
- Said selective process allows furthermore to obtain the triazine compounds of formula (I) with a yield higher than about 90%.
- As said, the additives of the present invention do not contain phosphor, are obtainable with a defined chemical structure in high yields by a simple and highly selective process. Said additives allow furthermore to broaden the application field of the perfluoropolyether lubricants in thermooxidative environment in the presence of metals, in particular at temperatures higher than 280°C, in combination with anti-rust properties and high shelf life at 25°C.
- The lubricating compositions comprising the additives of the present invention can be used in the presence of metals and in oxidative environment (in the presence of air and oxygen) at high temperatures, higher than 200°C, without any substantial lubricant degradation phenomenon. In particular the lubricating compositions containing the additives of the present invention can be used even at temperatures of about 300°C.
- Besides, as said, the compositions of the present invention have the advantage to be stable to storage at room temperature for long periods of time, thus overcoming the prior art drawbacks.
- The Applicant has surprisingly and unexpectedly found that the compounds of the present invention, although containing non fluorinated substituents as the phenol groups, are dispersible in fluorinated oils at room temperature and do not show any substantial phase separation, thus allowing stability to storage (i.e. high shelf life).
- As said, the additives of the present invention can be used in lubricating oils and greases. In particular the preferred greases are the fluorinated ones, more preferably perfluoropolyether base greases. In the case of perlfuoropolyether-based lubricating greases, the compositions contain, besides the additive of the present invention and the perfluoropolyether oil belonging to one or more of the above mentioned classes, as an essential component, a thickener, in the amounts used in the prior art, as for example PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea. Besides, said compositions can also contain other additives commonly used in grease technology, as talc, inorganic fillers, anti-wear additives. In the case of PTFE used as a thickener, the polymer primary particle sizes, measured by electronic scanning microscopy (SEM); are between 0.02 and 0.25 micron. Said particles can be obtained, for example, by known microemulsion, emulsion, suspension polymerization processes.
- The present invention will be better illustrated by the following Examples, which have a merely illustrative and not limitative purpose of the invention.
- The microoxidation test reported in the Examples has been carried out by using the equipment described in the following publication: Carl E. Snyder, Jr. and Ronald E. Dolle, Jr., ASLE Transactions, 13(3), 171-180 (1975) . The used operating conditions were the following:
- Test temperature :
- 300°C
- Air flow :
- 1 l/h
- Metals dipped in the fluid:
- stainless steel (AISI 304)
and Ti alloy (Al 6%, V 4%) - Test duration :
- 24, 48, 72 hours
- The lubricating composition to be tested is introduced in the glass test tube of the equipment shown in the reference Fig. 1, and the whole is weighed and brought to the test temperature. When 24, 48 or 72 hours have elapsed, depending on the test kind, the glass test tube, cooled at room temperture, is weighed again. The difference of weight before and after the heating determines the per cent weight loss of the composition under examination.
- After the test the surface aspect of the metals which have been dipped in the tested composition is visually evaluated.
- A series of carbon steel (C15) (UNI) sheets having 50x100x2 mm sizes are prepared by polishing with abrasive papers (400-800 mesh) followed by cleaning and degreasing with a cloth soaked in n-hexane, and then dried. These sheets are treated by dip-coating in the"test dispersion and then placed in the fog chamber. The fog chamber is formed of one sprayer, connected to a water reserve, which, by compressed air (P = 3 atm) is capable to saturate with moisture the chamber at the temperature of 35°C. The sheets are left in the chamber closed and saturated with moisture and are controlled at time regular intervals by visual inspection up to the appearance of stains on the surface. The test evaluation is expressed according to the following classification:
- (0) no rust stain;
- (1) one/three corrosion spots having a diameter lower than 1 mm;
- (2) three stains having a diameter higher than 1 mm or more stains having a diameter lower than 1 mm for a total of corroded surface lower than 1%;
- (3) four or five stains having a diameter higher than 1 mm or more stains having a diameter lower than 1 mm for a total of corroded surface between 1% and 5%;
- (4) corroded surface between 5% and 10%;
- (5) corroded surface higher than 10%.
- The kinematic viscosity has been measured by capillary viscometer Cannon-Fenske according to the ASTM D445 method.
-
- 300 g of hexafluoroxylene, 12.7 g (0.068 moles) of 2,4,6-trichlorotriazine and 9 g (0.074 moles) of collidine are introduced in a 1 litre glass flask, equipped with mechanical stirring, thermometer and dripper. The reaction mixture is cooled to 0°C and then 50 g (0.034 moles, 0,068 eq) of HOCH2CF2(OCF2)d(OCF2CF2)cOCF2CH2OH (MW = 1,466) are slowly dripped, under stirring, maintaining the temperature inside the flask between 0°C and 10°C.
- When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
- 9 g (0.074 moles) of collidine are then added and the temperature brought to 30°C. Under these conditions 42.8 g (0.068 eq) of Cl(C3F6O)aCF2OH (MW = 631) are added by dripping under stirring. When the addition is over, the reaction is allowed to continue for about 4 hours under stirring. Additional 9 g (0.074 moles) of collidine and 6.4 g (0.068 eq) of phenol are then added to the reaction mixture. After the addition, the temperature is brought to 80°C and the reaction is allowed to continue for about 6 hours.
- After cooling, the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- The liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 96.3 g of product with a yield equal to 92% are thus obtained.
- The IR and NMR analyses (1H, 13C and 19F) confirm the structure and thus the high selectivity of the synthesis.
-
- The Example 1 was repeated but by using 9.4 g (0.068 eq) of p-nitrophenol instead of phenol.
- 97.8 g of product with a yield equal to 91% are thus obtained. The IR and NMR analyses (1H, 13C and 19F) confirm the structure and thus the high selectivity of the synthesis.
-
- 300 g of hexafluoroxylene, 6.35 g (0.034 moles) of 2,4,6-trichlorotriazine and 4.5 g (0.036 moles) of collidine are introduced in a 1 litre glass flask, equipped with mechanical stirring, thermometer and dripper. The reaction mixture is cooled to 0°C and then 128 g (0.034 moles) of the compound (II) T1'-CFW1-O(C3F6O)a-CFW2-T2'-H (MW = 3,771), prepared according to the teaching of
USP 5,124,058 herein incorporated by reference, are slowly dripped, under stirring, maintaining the temperature inside the flask between 0°C and 10°C. - When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperture and left under these conditions for further 2 hours.
- 9 g (0.074 moles) of collidine and 9.4 g (0.068 eq) of p-nitrophenol are then added. After the addition, the temperature is brought to 80°C and the reaction is allowed to continue for about 6 hours.
- After cooling, the precipitated collidine hydrochloride is then removed from the reaction mxiture by filtration.
- The liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 133 g of product with a yield equal to 95% are thus obtained. The IR and NMR analyses (1H, 13C and 19F) confirm the structure and thus the high selectivity of the synthesis.
-
- 300 g of hexafluoroxylene, 7.1 g (0.038 moles) of 2,4,6-trichlorotriazine and 5 g (0.041 moles) of collidine are introduced in a 1 litre glass flask, equipped with mechanical stirring, thermometer and dripper.
- The reaction mixture is cooled to 0°C and then 50 g (0.038 moles) of the compound (II) T1'-CFW1-O(C3F6O)a-CFW2-T2'-H (MW = 1,296), prepared according to the teaching of
USP 5,124,058 herein incorporated by reference, are slowly dripped under stirring, maintaining the temperature inside the flask between 0°C and 10°C. - When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
- 5 g (0.041 moles) of collidine are then added and the temperature is brought to 30°C. Under these conditions, by dripping under stirring, additional 50 g (0.038 eq) of T1'-CFW1-O(C3F6O)a-CFW2-T2'-H are added. When the addition is over, the reaction is allowed to continue for about 4 hours. Additional 5 g (0.041 moles of collidine and 3.6 g (0.088 eq) of phenol are then added to the reaction mixture. After the addition, the temperature is brought to 80°C and the reaction is allowed to continue.for about 6 hours.
- After cooling, the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- The liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 98.2 g of product with a yield equal to 92% are thus obtained. The IR and NMR analyses (1H, 13C and 19F) confirm the structure and thus the high selectivity of the synthesis.
-
- 300 g of hexafluoroxylene, 6.35 g (0.034 moles) of 2,4,6-trichlorotriazine and 13.5 g (0.108 moles) of collidine are introduced in a 1 litre glass flask, equipped with mechanical stirring, thermometer and dripper.
- The reaction mixture is cooled to 0°C and then 384 g (0.102 moles) of the compound (II) T1'-CFW1-O(C3F6O)a-CFW2-T2'-H (MW = 3,771) are slowly dripped, under stirring, maintaining the temperature inside the flask between 0°C and 10°C.
- When the alcohol dripping is over, the reaction mixture temperature is slowly brought to 80°C and the reaction is allowed to continue for about 6 hours.
- After cooling, the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
- The liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by"weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 370 g of product with a yield equal to 93% are thus obtained. The IR and NMR analyses (1H, 13C and 19F) confirm the structure and thus the high selectivity of the synthesis.
- 50 g of a perfluoropolyether oil of the class (5), having kinematic viscosity at 20°C of 260 cSt, commercially known as Fomblin® Z25, are added with 0.5 g of the additive of the Example 4 and then introduced in the glass test tube for the microoxidation test, in the presence of metals. After 24 hours at 300°C under the indicated operating conditions, a weight loss of 1.1% was determined.
- The metals dipped in the fluid during the test (stainless steel and Ti, Al, V alloy) did not show oxidation/attack signs, but resulted comparable with those not exposed to the treatment.
- During the test the composition kept limpid and no development of smokes was observed.
- Furthermore the composition obtained by adding the perfluoropolyether oil with the additive of the Example 4 has resulted stable at room temperature and it does not visually show any separation after 168 hours.
- The Example 6 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.46% by weight was measured.
- The Example 6 was repeated by using 0.5 g of the additive of the Example 1. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.98% was measured. The metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
- The composition obtained by adding the perfluoropolyether oil with the additive of the Example 1 resulted stable at room temperature and it did not visually show any phase separation after 168 hours.
- The Example 8 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.6% by weight was measured.
- The Example 8 was repeated but increasing the time of the microoxidation test to 72 hours. At the end of the test a loss of 2.2% by weight was measured.
- The Example 6 was repeated by using 0.5 g of the additive of the Example 3. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.47% was measured. The metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack sings, but are comparable with those not exposed to the treatment.
- The composition obtained by adding the perfluoropolyether oil with the additive of the Example 3 resulted stable at room temperature and it did not visually show any separation after 168 hours.
- The Example 6 was repeated by using 0.5 g of the additive of the Example 2. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.82% was measured. The metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
- The composition obtained by adding the perfluoropolyether oil with the additive of the Example 2 resulted stable at room temperture and it did not visually show any separation after 168 hours.
- The Example 6 was repeated in the absence of stabilizing additives. During the test a development of white smokes was observed. After 24 hours at 300°C under the indicated operating conditions the oil was completely decomposed.
- The metals dipped into the oil during the test (stainless steel and Ti, Al, V alloy) show evident oxidation/attack signs and a remarkable darkening of the surface.
- The Example 6 was repeated but by using as stabilizing agent 0.5 g of a non triazine stabilizing additive of formula
EP 1, 354, 932 . - After 24 hours at 300°C under the indicated operating conditions a weight loss of 1.06% was measured. The metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) did not show oxidation/attack signs, but were comparable with those not exposed to the treatment.
- However the composition obtained by adding the perfluoropolyether oil with the additive having aryl end groups of
EP 1,354,932 and not containing triazine rings shows evident phase separation at room temperature already within 24 hours. - The Example 6 was repeated but by using as stabilizing agent 0.5 g of the compound of the Example 5 (comparative).
- After 24 hours at 300°C under the indicated operating conditions, a weight loss of 49% was measured.
- By comparing these data with those of stability of the Examples according to the invention, it results that the compounds containing triazine rings not substituted with aryl groups are not sufficient to guarantee a good stabilizing activity for perfluoropolyether oils in oxidative environment in the presence of metals at high temperatures.
- A lubricating composition is prepared containing 0,5 g of the additive of the Example 2, 9.5 g of a perfluoropolyether lubricant of structure (1), having kinematic viscosity at 20°C of 40 cSt, commercially known as Fomblin® Y04. Said composition is then diluted with 190 g of a fluorinated solvent commercially known as Galden® SV90.
- Then a metal sheet, cleaned according to what reported for the fog chamber test, is treated by dipping for 1 minute in said mixture. Said time elapsed, the sheet is taken and allowed to dry in a ventilated stove for 30 minutes at 60°C to remove the solvent. Then the sheet is placed in the fog chamber for the test.
- After 118 hours under the test conditions the sheet does not show corrosion signs.
- The Example 16 was repeated without adding the invention additive and by using a lubricating mixture formed of 10 g of Fomblin® Y04 oil and 190 g of fluorinated solvent Galden® SV90.
- After 118 h under the test conditions the sheet shows an extended corrosion between 5% and 10% of the total surface.
- The Example 16 was repeated without using the perfluoropolyether oil and by using a mixture formed of 0.5 g of the additive of the Example 2 and 199.5 g of fluorinated solvent Galden® SV90.
- After 118 ore under the test conditions the sheet does not show corrosion signs.
- The Example 16 was repeated by using only 200 g of fluorinated solvent Galden® SV90 (control test).
- After 118 hours under the test conditions the sheet shows an extended corrosion higher than 10% of the total surface.
Table 1: Microoxidation test Ex. Oil Additive Additive Conc. (%w/w oil) Dispersion Aspect(at room T) Duration test Loss (%w/w) 6 Fomblin Z 25 Ex. 4 1% Homogeneous after 168h 24 h 1.1 7 " " " " 48 h 1.46 8 " Ex. 1 " " 24 h 0.98 9 " " " " 48 h 1.6 10 " " " " 72 h 2.2 11 " Ex. 3 " " 24 h 0.47 12 " Ex. 2 " " 24 h 0.82 13 comp " --- --- ---- 24 h Decomposed 14 comp " EP 1354932 1% Phase Separation after 24h 24 h 1.06 15 comp " Triaz. without aryls 24 h 49 Table 2: Resistance test to corrosion (fog chamber) Ex. Oil Solvent Additive Concentration (%w/w of oil) Corrosion 16 Fomblin Y04 Galden SV 90 Ex. 2 5 NO 17 comp Fomblin Y04 Galden SV 90 - - 5-10% 18 - Galden SV 90 Ex. 2 - NO 19 comp - Galden SV 90 - - > 10%
with the proviso that at least one of Q1 and Q2 is equal to the group:
Claims (17)
- Compounds comprising perfluoropolyether chains and having at least one aryltriazine end group, of formula:- Rf is a (per)fluoropolyoxyalkylene chain formed of one or more repeating units, statistically placed along the chain, having the following structure: (CFXO), (CF2CF2O), (CF2CF2CF2O), (CF2CF2CF2CF2O), (CR6R7CF2CF2O), (CF(CF3)CF2O), (CF2CF(CF3)O), wherein X = F, CF3; R6 and R7, equal to or different from each other, are selected from H, Cl, or perfluoroalkyl from 1 to 4 carbon atoms, said Rf having a number average molecular weight in the range 500-10,000, preferably 500-5,000;- W1, W2, equal to or different from each other, are -F or -CF3;- T1 is equal to -CHAa-Ba(CH2CH2O)na- wherein Aa = H, CF3;
Ba = O, S, NH; na is an integer from 0 to 6, extremes included;- Q1, Q2, equal to or different from each other, are a perfluoropolyoxyalkylene chain of formula:wherein T'2 is equal to -F, -CF3, -C2F5,
-T1-CFW1-O-Rf-CFW2-T'2,
- (C2F4)Cl; T1, W1 and W2 have the above meaning; or a group of formula:with the proviso that at least one of Q1 and Q2 is equal to: - Compounds according to claim 1, wherein the perfluoropolyether chain Rf is selected from the following structures:(A) -(CF2CF(CF3)O)a(CFXO)b- or
-(CF2CF(CF3)O)a(CFXO)b-CF2(R'f)CF2-O-(CF2CF(CF3)O)a(CFXO)b-wherein R'f is a fluoroalkylene group from 1 to 4 C atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above range; a/b is between 10 and 100, b being different from 0;(B) -(CF2CF2O)c(CF2O)d(CF2(CF2)2O)h-
wherein c, d and h are integers such that the number average molecular weight is within the above range; c/d, d being different from 0, is between 0.1 and 10; h/(c+d), (c+d) being different from 0, is between 0 and 0.05; z is 2 or 3; h can also be equal to 0;(C) -(CF2CF(CF3)O)e(CF2CF2O)f(CFXO)g-
wherein X is F or CF3; e, f, g are integers such that the number average molecular weight is in the above range; e/(f+g) is between 0.1 and 10, (f+g) being different from 0; f/g is between 2 and 10;(D) -(CF2(CF2)2O)s-
wherein s is an integer such as to give the above molecular weight, z has the already defined meaning;(E) -(CR6R7CF2CF2O)j'- or
-(CR6R7CF2CF2O)p'-R'f-O-(CR6R7CF2CF2O)q'-
wherein R6 and R7 are equal to or different from each other and selected from H, C1 or perfluoroalkyl from 1 to 4 C atoms; R'f is a fluoroalkylene group from 1 to 4 C atoms; j', p' and q' are integers such as to have a molecular weight as the above mentioned one;(F) -(CF(CF3)CF2O)j"-
j" being an integer such as to give the above molecular weight. - Compounds according to claim 2, wherein the structures Rf are (A) or (B).
- Use of the compounds of claims 1-3 as thermal stabilizers for fluorinated oils and greases in thermooxidative conditions in the presence of metals.
- Use of the compounds of claims 1-3 as anti-rust additives for fluorinated oils and greases.
- Use according to claim 4 as anti-rust additives.
- Lubricating compositions comprising:- from 99.95 to 90% by weight, preferably from 99.5 to 95%, of a perfluoropolyether oil or a PFPE based grease on perfluoropolyether oils;- from 0.05 to 10% by weight, preferably from 0.5 to 5% by weight, of at least one of the triazine compounds of formula (I) of claims 1-3.
- Compositions according to claim 7, wherein the perfluoropolyether oil is selected from the following classes:(1) E-O-[CF2CF(CF3)O]m'-(CFXO)n'-E'
whereinX is equal to -F or -CF3;E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;m' and n' are integers such that the m'/n' ratio is between 20 and 1,000 , n' being different from 0, and the viscosity of the product at 20°C is between 10 and 4.000 cSt; the units being statistically distributed along the backbone.(2) C3F7O-[CF(CF3)CF2O]o'-D
whereinD is equal to -C2F5 or -C3F7;o' is an integer such that the viscosity of the product is within the range indicated under (1).(3) {C3F7O-[CF(CF3)CF2O]p'-CF(CF3)-}2
whereinp' is an integer such that the viscosity of the product is within the range indicated under (1).(4) E-O-[CF2CF(CF3)O]q'(C2F4O)r'(CFX)s'-E'
whereinX is equal to -F or -CF3;E and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;q', r' and s' are integers, including 0, so that the viscosity of the product is in the range indicated under (1).(5) E-O- (C2F4O)t'(CF2O)u'-E'
whereinE and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;t' and u' are integers such that the t'/u' ratio is between 0.1 and 5, u' being different from 0, and the viscosity of the product is in the above reported range under (1).(6) E-O-(CF2CF2CF2O)v'-E'
whereinE and E', equal to or different from each other, are selected from -CF3, -C2F5 or -C3F7;v' is a number such that the viscosity of the product is in the above reported range under (1).(7) D-O-(CF2CF2O)z'-D'
whereinD and D', equal to or different from each other, are selected between -C2F5 or -C3F7;z' is an integer such that the viscosity of the product is within the above reported range under (1).(8) E1-O(CF2O)n(CF2CF2O)m-(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-E2whereinE1 and E2 are perfluoroalkyl end groups equal to or different from each other, having formula -(CF2)2CF3, wherein z is an integer from 0 to 3; n, m, p, q are integers such that the viscosity is as defined under (1), m/n is between 2 and 20, n being different from 0, preferably between 2 and 10; the ratio (p+q)/(m+n+p+q) is between 0.05 and 0.2, (m+n+p+q) being different from 0; n/(m+n+q+p) ranges between 0.05 and 0.4, (m+n+p+q) being different from 0. - Compositions according to claim 8, wherein the perfluoropolyether oils are those of the classes (1), (4), (5) and (8).
- Compositions according to claims 7-9 comprising the additives commonly used in perfluoropolyether lubricant formulations, preferably anti-wear additives.
- A process for preparing triazine compounds of formula (I) of claims 1-3 comprising the following stages:STAGE A)i) reaction of a perfluoropolyoxyalkylene derivative having formula
T"1-CFW1-O-Rf-CFW2-T"2 (II)
whereinRf, W1 and W2 have the above meaning;T"1 and T"2 can be equal to or different from each other, having general formula equal to -CHAa-Ba(CH2CH2O)na-H, wherein Aa = H, CF3; Ba = O, S, NH; na is an integer from 0 to 6, extremes included; or selected from F, CF3, C2F5, (C2F4)Cl, with the proviso that at least one of the two end groups T"1 and T"2 is equal to -CHAa-Ba(CH2CH2O)na-H, preferably is selected from O-CH2OH, O-CH2SH, O-CH2NH2, CH(OH)CF3;with
a trihalo-triazine of formula:
at a temperature between 0° and 10°C, wherein the ratio between the equivalents of the compound (II) and the moles of (III) is equal to 1:1, in the presence of a solvent inert under the reaction conditions, capable to solubilize the reactants, and in the presence of an organic or inorganic base, preferably maintaining the reaction mixture under stirring;ii) reaction of the product obtained in i) with an equivalent of a derivative of formula:
Q-H (IV)
wherein Q has the above reported meaning for Q1 and Q2;
at a temperature in the range 25°-35°C;iii) reaction of the product obtained in ii) with an equivalent of a compound of formula (IV), equal to or different from the one used in step ii), at a temperature in the range 65°C-100°C, preferably 70°C-90°C;STAGE B)
separation of the organic phase of the reaction mixture obtained in A) from the aqueous phase and subsequent separation, preferably by filtration, of the organic phase to remove the residual organic or inorganic insoluble salts;STAGE C)
several washings of the liquid organic phase with acid water and subsequent separation of the obtained compound of formula (I) from the organic solvent, for example by evaporation. - A process according to claim 11, wherein in stage A) the inert solvent is selected from toluene, xylene, hexafluoroxylene, acetone, diethyl-ketone.
- A process according to claims 11-12, wherein in stage A) the inorganic base is selected from NaOH, KOH, Na2CO3, K2CO3; the organic base is selected from 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine (collidine).
- A process according to claims 11-13, wherein the base is 2,4,6-trimethylpyridine.
- A process according to claims 11-14, wherein the ratio between the equivalents of base and the sum of the equivalents of compounds (II) and (IV) used in the three steps of stage (A) is in the range 1:1-2:1, preferably 1:1-1.5:1.
- Lubricating greases having a perfluoropolyether base comprising the additive of claims 1-3, a perfluoropolyether oil and a thickener, preferably selected from PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea, more preferably PTFE.
- Greases according to claim 16 comprising talc, inorganic fillers, anti-wear additives.
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Application Number | Priority Date | Filing Date | Title |
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IT000646A ITMI20050646A1 (en) | 2005-04-14 | 2005-04-14 | ADDITIVES FOR FLUORINE OILS |
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EP1712580A1 EP1712580A1 (en) | 2006-10-18 |
EP1712580B1 true EP1712580B1 (en) | 2008-12-10 |
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EP (1) | EP1712580B1 (en) |
JP (1) | JP4975355B2 (en) |
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IT (1) | ITMI20050646A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011042374A1 (en) | 2009-10-06 | 2011-04-14 | Solvay Solexis S.P.A. | Lubricant compositions for vacuum pumps |
Families Citing this family (6)
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WO2009096570A1 (en) | 2008-02-01 | 2009-08-06 | Nok Klueber Co., Ltd. | Lubricant compositions |
GB0917450D0 (en) * | 2009-10-06 | 2009-11-18 | 3M Innovative Properties Co | Triazine containing fluoropolyether elastomers having very low glass transition temperatures, compositions containing them and methods of making them |
US8405929B2 (en) | 2009-12-29 | 2013-03-26 | HGST Netherlands B.V. | Inhibiting oxidation of organic contaminants in a hard disk drive (HDD) |
JP5940084B2 (en) * | 2010-12-03 | 2016-06-29 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | Triazine derivative |
US8685548B2 (en) | 2011-03-31 | 2014-04-01 | Seagate Technology Llc | Lubricant compositions |
WO2018159232A1 (en) * | 2017-03-02 | 2018-09-07 | 昭和電工株式会社 | Magnetic recording medium, fluoroether compound, and lubricant for magnetic recording medium |
Family Cites Families (4)
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JPS6050788B2 (en) * | 1980-11-20 | 1985-11-11 | ダイキン工業株式会社 | Cyanuric chloride derivatives of hexafluoroepoxypropane oligomers and their uses |
IT1231758B (en) * | 1989-04-20 | 1991-12-21 | Ausimont Srl | FUNCTIONALIZED FLUOROPOLITERS |
JP3392213B2 (en) * | 1994-04-19 | 2003-03-31 | 日本メクトロン株式会社 | Perfluoroalkylene ether triazine oligomer and method for producing the same |
JP4548761B2 (en) * | 2000-06-15 | 2010-09-22 | 富士フイルムホールディングス株式会社 | Lubricant composition |
-
2005
- 2005-04-14 IT IT000646A patent/ITMI20050646A1/en unknown
-
2006
- 2006-03-30 DE DE602006004099T patent/DE602006004099D1/en active Active
- 2006-03-30 EP EP06006673A patent/EP1712580B1/en not_active Not-in-force
- 2006-04-14 JP JP2006111734A patent/JP4975355B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011042374A1 (en) | 2009-10-06 | 2011-04-14 | Solvay Solexis S.P.A. | Lubricant compositions for vacuum pumps |
Also Published As
Publication number | Publication date |
---|---|
EP1712580A1 (en) | 2006-10-18 |
DE602006004099D1 (en) | 2009-01-22 |
JP2006290892A (en) | 2006-10-26 |
ITMI20050646A1 (en) | 2006-10-15 |
JP4975355B2 (en) | 2012-07-11 |
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