EP2486114A1 - Lubricant compositions for vacuum pumps - Google Patents
Lubricant compositions for vacuum pumpsInfo
- Publication number
- EP2486114A1 EP2486114A1 EP10759933A EP10759933A EP2486114A1 EP 2486114 A1 EP2486114 A1 EP 2486114A1 EP 10759933 A EP10759933 A EP 10759933A EP 10759933 A EP10759933 A EP 10759933A EP 2486114 A1 EP2486114 A1 EP 2486114A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- different
- equal
- comprised
- group
- functional
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000000314 lubricant Substances 0.000 title claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 28
- 125000001424 substituent group Chemical group 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- -1 cyclic phosphazene compound Chemical class 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 6
- 125000003367 polycyclic group Chemical group 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 125000001153 fluoro group Chemical group F* 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 230000001050 lubricating effect Effects 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical group C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 74
- 238000001704 evaporation Methods 0.000 description 10
- 230000001588 bifunctional effect Effects 0.000 description 9
- 239000010702 perfluoropolyether Substances 0.000 description 9
- 238000013112 stability test Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005461 lubrication Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910020813 Sn-C Inorganic materials 0.000 description 2
- 229910018732 Sn—C Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- 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
-
- 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
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
-
- 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
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
- C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen 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
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
-
- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/44—Super vacuum or supercritical use
Definitions
- the present invention relates to (per)fluoropolyether lubricant
- compositions and use thereof for lubricating vacuum pumps are provided.
- Fluoropolyether lubricants are known in the art for being used in vacuum pumps in highly demanding applications, e.g. in the semiconductor industry, in particular for lubricating compressors and pumps handling reactive and hazardous gases, typically in rotary pumps, turbomolecular pumps, roots pumps and diffusion pumps.
- Fluoropolyether oils substantially free from volatile fractions are typically used for lubricating vacuum pumps so that back migration of the volatile oil fractions into the vacuum chamber, which is commonly due to heat generated by friction among the moving metallic parts while operating, is generally reduced.
- EP 0553768 B (AUSIMONT S.P.A.) 03.05.2000 discloses use in vacuum pumps of perfluoropolyethers having at most 0.1 % by weight of fractions exhibiting a molecular weight lower than or equal to 1500 and at most 1.3% by weight of fractions exhibiting a molecular weight lower than or equal to 1800, said perfluoropolyethers being typically endowed with a viscosity ranging from about 140 cSt to about 270 cSt at 20°C and preferably complying with branched perfluoropolyethers having formulae CF 3 (OCF(CF3)CF2)m(OCF 2 )nOCF3, wherein m/n is equal to or higher than 1000, and F(CF 2 CF(CF3)O) q CF 2 CF3.
- fluoropolyether oils of the prior art in particular linear fluoropolyether oils generally suffer from low thermal-oxidative stability in the presence of metals to be advantageously used as lubricants in high vacuum and ultra-high vacuum pumps.
- EP 1454938 B (SOLVAY SOLEXIS S.P.A.) 05.10.2005 discloses linear perfluoropolyether oils comprising -CF2CF2O- and -CF2O- recurring units, statistically distributed along the perfluoropolyoxyalkylene chain, in a -CF2 CF2O-/-CF2O- ratio comprised between 2 and 20, which exhibit improved thermal-oxidative stability in the presence of metals with respect to known linear perfluoropolyether oils having a lower -CF2CF2O-/-CF2O- ratio, typically comprised between 0.1 and 10, while maintaining a high viscosity index and a low pour point value as compared with known linear perfluoropolyether oils.
- the stability of the novel linear perfluoropolyether oils when used as lubricants may be further increased by the addition of perfluoropolyether-based thermal stabilizers comprising functional groups like, e.g., phosphines, phosphates, phosphazenes, benzothiazoles, triazines, amines, substituted amines, nitroderivative compounds.
- perfluoropolyether-based thermal stabilizers comprising functional groups like, e.g., phosphines, phosphates, phosphazenes, benzothiazoles, triazines, amines, substituted amines, nitroderivative compounds.
- non-functional PFPE oil comprising at least one (per)fluoropolyoxyalkylene chain (chain F);
- (B) at least one cyclic phosphazene compound [compound (P)] comprising one or more cyclic moieties having formula (I) or (II) here below: said cyclic moieties comprising, bound to one or more phosphorus atoms, at least one substituent comprising at least one (per)fluoropolyoxyalkylene chain (chain R'F);
- chain R'F (per)fluoropolyoxyalkylene chain (chain R'F) and at least one functional group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
- the lubricant composition of the invention advantageously exhibits improved thermal-oxidative stability in the presence of metals while maintaining low evaporation weight loss and high lubrication performances to be successfully used for high vacuum and ultra-high vacuum applications.
- (per)fluoropolyether is intended to denote either a fully fluorinated perfluoropolyether or a partially fluorinated fluoropolyether.
- (per)fluoropolyoxyalkylene chain is intended to denote either a fully fluorinated perfluoropolyoxyalkylene chain or a partially fluorinated fluoropolyoxyalkylene chain.
- the (per)fluoropolyoxyalkylene chain (chain Rp) of the non-functional (per)fluoropolyether oil (non-functional PFPE oil) of the invention typically comprises one or more recurring units R° having general formula -(CJJ')j -CKK'-O-, wherein J and J', equal to or different from each other, independently represent a fluorine atom or a C-
- the non-functional PFPE oil of the invention may be a linear
- non-functional PFPE oil or a branched non-functional PFPE oil.
- linear non-functional PFPE oil it is meant a non-functional PFPE oil comprising at least one (per)fluoropolyoxyalkylene chain (chain Rp) as defined above, wherein J and J' both represent a fluorine atom and K and K', equal to or different from each other, independently represent a hydrogen atom, a fluorine atom or a chlorine atom.
- branched non-functional PFPE oil it is meant a non-functional PFPE oil comprising at least one (per)fluoropolyoxyalkylene chain (chain Rp) as defined above, wherein at least one of J, J', K and K' represents a C1 -C6 (per)fluoro(oxy)alkyl group.
- Suitable non-functional PFPE oils according to the invention include, notably, the followings:
- - T and T are independently selected from -CF3, -C2F5 and -C3F7 groups;
- - b1 ' and b2' are independently integers ⁇ 0 such that the b17b2' ratio is comprised between 0.1 and 5 and the (b1 '+b2') sum is comprised between 5 and 250; should b1 ' and b2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
- Said products can be produced by photooxidation of C2F4 as reported in US 3715378 (MONTECATINI EDISON S.P.A.) 06.02.1973 and
- - T 2 and T 2 are independently selected from -CF 3 , -C 2 F 5 , -C3F7, -C4F9, -CF 2 CI, -CF 2 CF 2 CI groups;
- the c27c1 ' ratio is comprised between 2 and 20;
- the c17(c1 '+c2'+c3'+c4') ratio is comprised between 0.05 and 0.4;
- the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
- Said products can be produced as described in EP 1454938 B (SOLVAY SOLEXIS S.P.A.) 05.10.2005 .
- - T 3 and T 3 ' are independently selected from -C 2 Fs and -C3F7 groups;
- - d' is an integer comprised between 5 and 250.
- Said products can be obtained by a method comprising fluorinating a polyethyleneoxide, e.g. with elemental fluorine, and optionally thermally fragmentating the so-obtained fluorinated polyethyleneoxide as reported in US 4523039 (THE UNIVERSITY OF TEXAS) 1 1.06.1985 .
- Hal is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
- - e1 ', e2', and e3' are independently integers ⁇ 0 such that the (e1 '+e2'+e3') sum is comprised between 5 and 250; should at least two of e1 ', e2' and e3' be different from zero, the different recurring units are generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
- Said products may be prepared by ring-opening polymerizing
- - Y is selected from a fluorine atom or a -CF3 group
- - f1 ' and f2' are independently integers ⁇ 0 such that the f17f2' ratio is comprised between 20 and 1000 and the (f1 '+f2') sum is comprised between 5 and 250; should f1 ' and f2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
- Said products can be obtained by photooxidation of C3F6 as described in CA 786877 (MONTEDISON S.P.A.) 04.06.1968 and by subsequent conversion of the end groups as described in GB 1226566
- - g1 ', g2' and g3' are independently integers ⁇ 0 such that the (g1 '+g2'+g3') sum is comprised between 5 and 250; should at least two of g1 ', g2' and g3' be different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
- Said products can be manufactured by photooxidation of a mixture of C3F6 and C2F4 and subsequent treatment with fluorine as described in US 3665041 (MONTECATINI EDISON SPA) 23.05.1972 .
- - h' is an integer comprised between 5 and 250.
- Said products can be prepared by ionic hexafluoropropylene epoxide oligomerization and subsequent treatment with fluorine as described in US 3242218 (E. I. DU PONT DE NEMOURS AND CO.) 22.03.1966 .
- - i' is an integer comprised between 2 and 250.
- Said products can be obtained by ionic telomerization of the
- R 1 f is a C1-C6 perfluoroalkyl group
- R 2 f is selected from a fluorine atom and a C1-C6 perfluoroalkyl group
- - j1 ' is equal to 1 or 2;
- - j2' is an integer comprised between 5 and 250.
- Said products can be produced by the copolymerization of
- hexafluoroacetone with an oxygen-containing cyclic comonomer selected from ethylene oxide, propylene oxide, epoxy-butane and/or trimethylene oxide (oxethane) or substituted derivatives thereof and subsequent perfluorination of the resulting copolymer, as detailed in patent application WO 87/00538 (LAGOW ET AL.) 29.01.1987 .
- oxygen-containing cyclic comonomer selected from ethylene oxide, propylene oxide, epoxy-butane and/or trimethylene oxide (oxethane) or substituted derivatives thereof
- Preferred non-functional PFPE oils suitable for the purpose of the invention include, notably, the followings:
- T 2 and T 2 ' are -CF3 groups
- the c27c1 ' ratio is comprised between 2 and 5;
- the c17(c1 '+c2'+c3'+c4') ratio is comprised between 0.1 and 0.3;
- the different recurring units being generally statistically distributed along the perfluoropolyoxyalkylene chain;
- non-functional PFPE oils commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® (type M, Z or Y), said oils generally comprising at least one oil complying with either of formulae here below:
- non-functional PFPE oils commercially available from Daikin under the trade name DEMNUM®, said oils generally comprising at least one oil complying with formula here below:
- non-functional PFPE oils commercially available from Du Pont de Nemours under the trade name KRYTOX®, said oils generally comprising at least one low-molecular weight, fluorine end-capped, homopolymer of hexafluoropropylene epoxide complying with formula here below:
- non-functional PFPE oils suitable for the purpose of the invention include, notably, non-functional PFPE oils complying with formula (2) as described hereinabove and non-functional PFPE oils commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® (type M, Z or Y) as described hereinabove.
- a mixture of more than one non-functional PFPE oil as defined above may also be used in the lubricant composition of the invention.
- Preferred mixtures of more than one non-functional PFPE oil as defined above include, notably, mixtures of at least one linear non-functional PFPE oil as defined above with at least one branched non-functional PFPE oil as defined above.
- suitable mixtures of at least one linear non-functional PFPE oil as defined above with at least one branched non-functional PFPE oil as defined above include, notably, those commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® W.
- phosphazene compound [compound (P)] of the invention typically comprises one or more recurring units R having general formula -(CF2)j -CFK-O-, wherein K is selected from a fluorine atom and a C1-C5
- (per)fluoro(oxy)alkyl group and j is an integer comprised between 0 and 3, said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
- - Rf is a (per)fluoropolyoxyalkylene chain comprising one or more recurring units having formula -CF2O(CF2CF2O) P '(CF2O) q 'CF2-, wherein p' and q' are integers such that the number average molecular weight of the chain is comprised between 1000 and 2000, the q'/p' ratio being comprised between 0.2 and 2;
- R'f is a (per)fluoropolyoxyalkylene chain comprising one or more recurring units having formula -(C3F6O) q (CF(CF3)O) r -, wherein q and r are integers such that the number average molecular weight of the chain is comprised between 500 and 700, the q/r ratio being > 2.
- EP 1336614 A SOLVAY SOLEXIS S.P.A. 20.08.2003 .
- the compound (P) complies with formula l-B) or (ll-B) here below:
- R"f and R"'f independently represent a (per)fluoropolyoxyalkylene chain comprising one or more recurring units selected from:
- said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain;
- - Z and Z' equal to or different from each other, independently represent a polar group of formula -O " M + , wherein M is selected from hydrogen, a monovalent metal, preferably an alkaline metal, and an ammonium radical having formula -NR-1 R2R3R4, wherein each of R-
- - n is an integer comprised between 1 and 3, preferably equal to 1 ;
- - z is an integer comprised between 1 and 4, preferably equal to 1 ;
- n + nf is equal to 6;
- nz' + nf is equal to 8.
- the compound (P) of this second embodiment of the invention preferably complies with formula (l-B) or (ll-B) here above, wherein R"fO- and R"'fO- are selected from:
- - T 4 is selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -(CF 2 )f-CF 2 (T 1 ) and -(CF2)f-CF(T-
- - J is selected from groups having formulae -CE'(Y)CE2O(CH2CH2O) s i- and -CE'YO(CH2CH2O)s2-, wherein E and E', equal to or different from each other, are independently selected from a fluorine atom, a hydrogen atom and a -CF3 group, E being preferably a hydrogen atom and E' being preferably selected from a fluorine atom and a -CF3 group, Y is selected from a fluorine atom and a -CF3 group, s1 and s2, equal to or different from each other, are integers comprised between 0 and 5;
- - T 5 is selected from -CF 3 , -CFYCF3, -CF(Y)CF(Y)CF 3 , -(CFY)f-CFY(T'i) and -(CFY ⁇ -CYCT-iXT ⁇ ), wherein f is 0 or 1 , T'i and T 2 , equal to or different from each other, are independently selected from chlorine, bromine and hydrogen atoms;
- - r', s' and t' are numbers such that the (r'+ s'+ t') sum is comprised between 1 and 100, the t'/(r'+ s') ratio being comprised between 0.01 and 0.1 ;
- R * f is a C-i-Ce perfluoroalkylene group
- - 11 ", u1 ", t2", u2" are numbers such that the (t1 "+ u1 "+ t2"+ u2") sum is comprised between 1 and 100, the (t1 "+ t2") /(u1 "+ u2") ratio being comprised between 0.01 and 0.1 ;
- - v' is a number comprised between 1 and 100; (e) T 4 -CF2CH2-(OCF2CF2CH2)w'-OR * fO-(CH2CF2CF 2 O)w'-J- wherein:
- - w' is a number comprised between 1 and 100.
- the compound (P) of this second embodiment of the invention more preferably complies with formula (l-B * ) or (ll-B * ) here below:
- - T * is selected from -CF3, -CF2CF3 and -CF2CF2CF3 groups;
- - s * is a number comprised between 0 and 5.
- M being preferably an alkaline metal selected from Li, Na and K or an ammonium radical having formula -NR-1 R2R3R4, wherein each of R-
- - A is selected from: (i) -QR groups, wherein Q is a divalent group selected from -O-, -S-, -NR-
- - m is equal to 3 or 4;
- Preferred lubricant compositions of the invention comprise one or more compounds (P) according to the first and/or the second embodiment of the invention as detailed above.
- More preferred lubricant compositions of the invention comprise one or more compounds (P) according to the second embodiment of the invention as detailed above.
- Most preferred lubricant compositions of the invention comprise one or more compounds (P) complying with either of formulae (lll-B) or (lll-B bis) as described above.
- the functional (per)fluoropolyether derivative (functional PFPE derivative) of the invention comprises at least one (per)fluoropolyoxyalkylene chain (chain R'F) as defined above and at least one functional group typically comprising at least one ether, thioether, ester or amine group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
- the functional (per)fluoropolyether derivative (functional PFPE derivative) of the invention preferably complies with formula (V) here below:
- - Rp is a (per)fluoropolyoxyalkylene chain (chain R'F) as defined above;
- non-functional end-groups selected from a fluorine atom, a chlorine atom and a C1-C3 (per)fluoroalkyl group optionally containing one or more chlorine atoms,
- - Wi and W2 equal to or different from each other, independently represent a fluorine atom or a -CF3 group
- - p1 and pV are independently integers comprised between 1 and 3, preferably being equal to 1 when Wi and/or W2 are -CF3 groups.
- the functional PFPE derivative of the invention more preferably complies with formula (VI) here below:
- (a') A is selected from oxygen and sulphur atoms
- (b') B is selected from an oxygen atom, a sulphur atom and a -NH group,
- (c') W is selected from a hydrogen atom and a -CF3 group
- Y is selected from phenyl, pyridine, triazine, benzoxazole,
- benzothiazole and benzopyrazine groups optionally substituted with one or more substituents different from hydrogen atoms,
- non-functional end-groups selected from a fluorine atom, a chlorine atom, a -CF3 group, a -C2F5 group and a -(CF2) n CI group, wherein n is an integer comprised between 1 and 3,
- n * are integers such that the number average molecular weight of the functional PFPE derivative is comprised between 400 and 10000, the m * /n * ratio being comprised between 0.1 and 10.
- Preferred lubricant compositions of the invention comprise one or more functional PFPE derivatives selected from:
- Most preferred lubricant compositions of the invention comprise one or more functional PFPE derivatives complying with formula (VI) as described above wherein both T" and T" are functional end-groups as defined above (bifunctional PFPE derivatives).
- Non-limitative examples of suitable bifunctional PFPE derivatives include, notably, the followings:
- - bifunctional PFPE derivatives complying with formula here below: wherein m * and n * are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and 6000, preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5;
- bifunctional PFPE derivatives commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® DA 410, said bifunctional PFPE derivatives complying with formula here below: wherein m * and n * are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and
- 6000 preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5.
- lubricant compositions comprising one or more bifunctional PFPE derivatives complying with formula here below: wherein m * and n * are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and 6000, preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5.
- the lubricant composition of the invention typically comprises at least one cyclic phosphazene compound [compound (P)] as defined above in an amount of at least 0.1 % by weight, preferably at least 0.2% by weight, more preferably at least 0.3% by weight with respect to the weight of the non-functional PFPE oil.
- the lubricant composition of the invention typically comprises at least one cyclic phosphazene compound [compound (P)] as defined above in an amount of at most 15% by weight, preferably at most 10% by weight, more preferably at most 5% by weight with respect to the weight of the non-functional PFPE oil.
- the lubricant composition of the invention typically comprises at least one functional PFPE derivative different from compound (P) as defined above in an amount of at least 0.5% by weight, preferably at least 1 % by weight, more preferably at least 2% by weight with respect to the weight of the non-functional PFPE oil.
- the lubricant composition of the invention typically comprises at least one functional PFPE derivative different from compound (P) as defined above in an amount of at most 15 % by weight, preferably at most 10% by weight, more preferably at most 6% by weight with respect to the weight of the non-functional PFPE oil.
- compound (P) comprising at least one cyclic phosphazene compound [compound (P)] in an amount ranging from 0.3% to 5% by weight with respect to the weight of the non-functional PFPE oil and at least one functional PFPE derivative different from compound (P) as defined above in an amount ranging from 2% to 6% by weight with respect to the weight of the non-functional PFPE oil.
- the lubricant composition of the invention typically has a kinematic
- ⁇ viscosity ( ⁇ ) ranging from 100 to 350, preferably from 120 to 300, as measured at 20°C by ASTM D445.
- the lubricant composition can also further comprise other additives
- anti-rust additives notably including one or more anti-rust additives, oxidation inhibitors, antifoam agents, anti-wear additives and anti-scuff additives.
- lubricant composition of the invention include, notably, functional PFPEs commercially available from Solvay Solexis S.p.A. under the trade names FOMBLIN® DA305, FOMBLIN® DA306 and FOMBLIN® DA308.
- Another object of the invention is use of the lubricant composition as
- the non-functional PFPE oil (1 ) is a linear non-functional PFPE oil having formula CF3O-(CF2O)n(CF2CF2O) m (CF2CF2CF2O) r (CF2CF2CF2CF 2 O)s -CF3, wherein m, n, r and s are integers such that the number average molecular weight is about 1 1000, the m/n ratio being about 2.7.
- the non-functional PFPE oil (2) is a FOMBLIN® M15 linear non-functional PFPE oil having formula CF3O-(CF2CF 2 O) m (CF 2 O)n-CF3, wherein m and n are integers such that the number average molecular weight is about 10600, the m/n ratio being about 0.9.
- the non-functional PFPE oil (3) is a FOMBLIN® M30 linear non-functional PFPE oil having formula CF3O-(CF2CF 2 O) m (CF 2 O)n-CF3, wherein m and n are integers such that the number average molecular weight is about 13000, the m/n ratio being about 0.9.
- the non-functional PFPE oil (4) is a FOMBLIN ® Y25/6 branched non-functional PFPE oil having formula
- the compound (P1) is a cyclic phosphazene compound having formula
- indexes are integers such that the number average molecular weight is about 8300.
- m and n are integers such that the number average molecular weight is about 3800, the m/n ratio being about 0.9.
- the sintered metal bearing of Fe-Cu-Sn-C type was impregnated with the lubricant composition of the invention at 30°C, under vacuum (7 mbar), for
- the sintered metal bearing so treated was then allowed to drain for about 15 minutes, so that the amount of lubricant composition impregnated in the sintered metal bearing was about 0.05 g.
- the sintered metal bearing so impregnated was placed in a ventilated oven set at 200°C and weighted every 48-72 hours.
- Weight loss of the lubricant composition was checked as a function of time.
- Tribological test method Sliding wear tests were conducted with a ball-on-disk tribometer at 140°C during 6 hours under the following operating conditions:
- a lubricant composition was prepared by mixing non-functional PFPE oil (3) with 0.5% by weight of non-functional PFPE oil (3) of compound (P1 ) and 5% by weight of non-functional PFPE oil (3) of functional PFPE derivative (1 ).
- a composition was prepared by mixing non-functional PFPE oil (3) with
- a composition was prepared by mixing non-functional PFPE oil (3) with
- composition of Example 1 of the invention showed a substantial increase of the induction time to degradation with respect to compositions of comparative Examples 1 C and 2C, that is to say that the lubricant composition of the invention showed improved thermal-oxidative stability with respect to compositions comprising at least one non-functional PFPE oil as defined above and either at least one compound (P) as defined above or at least one functional PFPE derivative as defined above.
- a lubricant composition was prepared by mixing non-functional PFPE oil (1 ) with 3% by weight of non-functional PFPE oil (1 ) of compound (P1 ) and 3% by weight of non-functional PFPE oil (1) of functional PFPE derivative
- a lubricant composition was prepared by mixing non-functional PFPE oil
- a lubricant composition was prepared by mixing non-functional PFPE oil (4) with 3% by weight of non-functional PFPE oil (4) of compound (P1 ) and 3% by weight of non-functional PFPE oil (4) of functional PFPE derivative
- a composition was prepared by mixing non-functional PFPE oil (2) with
- Example 3C showed a substantial decrease of the induction time to degradation with respect to the lubricant composition of Example 4 of the invention.
- a composition was prepared by mixing non-functional PFPE oil (2) with 3% by weight of non-functional PFPE oil (2) of functional PFPE derivative
- Example 4C showed a substantial decrease of the induction time to degradation with respect to the lubricant composition of Example 4 of the invention.
- the tribological tests performed with the lubricant composition of Example 3 of the invention showed that substantially low or even slightly decreased wear volumes were measured with respect to compositions of comparative Examples 3C and 4C, that is to say that the lubricant composition of the invention showed good or slightly improved anti-wear properties with respect to compositions comprising at least one non-functional PFPE oil as defined above and either at least one compound (P) as defined above or at least one functional PFPE derivative as defined above.
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Abstract
The invention pertains to a lubricant composition comprising: (A) at least one non-functional (per)fluoropolyether oil (PFPE oil) comprising at least one (per)fluoropolyoxyalkylene chain (chain RF); (B) at least one cyclic phosphazene compound [compound (P)] comprising one or more cyclic moieties having formula (I) or (II) here below: said cyclic moieties comprising, bound to one or more phosphorus atoms, at least one substituent comprising at least one (per)fluoropolyoxyalkylene chain (chain R' F); (C) at least one functional (per)fluoropolyether derivative (functional PFPE derivative) different from compound (P) comprising at least one (per)fluoropolyoxyalkylene chain (chain R'F) and at least one functional group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
Description
Description
Lubricant compositions for vacuum pumps
[0001] This application claims priority to European application No. 09172280.1 filed 06.10.2009, the whole content of this application being incorporated herein by reference for all purposes.
Technical Field
[0002] The present invention relates to (per)fluoropolyether lubricant
compositions and use thereof for lubricating vacuum pumps.
Background Art
[0003] Fluoropolyether lubricants are known in the art for being used in vacuum pumps in highly demanding applications, e.g. in the semiconductor industry, in particular for lubricating compressors and pumps handling reactive and hazardous gases, typically in rotary pumps, turbomolecular pumps, roots pumps and diffusion pumps.
[0004] Actually, major requirements for fluoropolyether lubricants to be employed for high vacuum and ultra-high vacuum applications include high
thermal-oxidative stability in the presence of metals, low evaporation weight loss and high lubrication performances.
[0005] Fluoropolyether oils substantially free from volatile fractions are typically used for lubricating vacuum pumps so that back migration of the volatile oil fractions into the vacuum chamber, which is commonly due to heat generated by friction among the moving metallic parts while operating, is generally reduced.
[0006] Thus, EP 0553768 B (AUSIMONT S.P.A.) 03.05.2000 discloses use in vacuum pumps of perfluoropolyethers having at most 0.1 % by weight of fractions exhibiting a molecular weight lower than or equal to 1500 and at most 1.3% by weight of fractions exhibiting a molecular weight lower than or equal to 1800, said perfluoropolyethers being typically endowed with a viscosity ranging from about 140 cSt to about 270 cSt at 20°C and preferably complying with branched perfluoropolyethers having formulae CF3(OCF(CF3)CF2)m(OCF2)nOCF3, wherein m/n is equal to or higher than 1000, and F(CF2CF(CF3)O)qCF2CF3.
[0007] Nevertheless, fluoropolyether oils of the prior art, in particular linear
fluoropolyether oils generally suffer from low thermal-oxidative stability in the presence of metals to be advantageously used as lubricants in high vacuum and ultra-high vacuum pumps.
[0008] EP 1454938 B (SOLVAY SOLEXIS S.P.A.) 05.10.2005 discloses linear perfluoropolyether oils comprising -CF2CF2O- and -CF2O- recurring units, statistically distributed along the perfluoropolyoxyalkylene chain, in a -CF2 CF2O-/-CF2O- ratio comprised between 2 and 20, which exhibit improved thermal-oxidative stability in the presence of metals with respect to known linear perfluoropolyether oils having a lower -CF2CF2O-/-CF2O- ratio, typically comprised between 0.1 and 10, while maintaining a high viscosity index and a low pour point value as compared with known linear perfluoropolyether oils. The stability of the novel linear perfluoropolyether oils when used as lubricants may be further increased by the addition of perfluoropolyether-based thermal stabilizers comprising functional groups like, e.g., phosphines, phosphates, phosphazenes, benzothiazoles, triazines, amines, substituted amines, nitroderivative compounds.
[0009] The need was thus felt to provide for (per)fluoropolyether lubricants having improved thermal-oxidative stability in the presence of metals while maintaining low evaporation weight loss and high lubrication performances in terms of suitable kinematic viscosity and anti-wear and anti-rust properties, so as to be successfully used in high vacuum and ultra-high vacuum pumps by ensuring lower maintenance costs of the pumps due to a longer life-time of the lubricants and lower consumptions due to their high lubrication performances.
Disclosure of Invention
[0010] It is thus an object of the invention a lubricant composition comprising:
(A) at least one non-functional (per)fluoropolyether oil (non-functional PFPE oil) comprising at least one (per)fluoropolyoxyalkylene chain (chain F);
(B) at least one cyclic phosphazene compound [compound (P)] comprising one or more cyclic moieties having formula (I) or (II) here below:
said cyclic moieties comprising, bound to one or more phosphorus atoms, at least one substituent comprising at least one (per)fluoropolyoxyalkylene chain (chain R'F);
(C) at least one functional (per)fluoropolyether derivative (functional PFPE derivative) different from compound (P) comprising at least one
(per)fluoropolyoxyalkylene chain (chain R'F) and at least one functional group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
[001 1 ] The Applicant has surprisingly found that the lubricant composition of the invention advantageously exhibits improved thermal-oxidative stability in the presence of metals while maintaining low evaporation weight loss and high lubrication performances to be successfully used for high vacuum and ultra-high vacuum applications.
[0012] To the purpose of the present invention, "(per)fluoropolyether" is intended to denote either a fully fluorinated perfluoropolyether or a partially fluorinated fluoropolyether.
[0013] To the purpose of the present invention, "(per)fluoropolyoxyalkylene chain" is intended to denote either a fully fluorinated perfluoropolyoxyalkylene chain or a partially fluorinated fluoropolyoxyalkylene chain.
[0014] The (per)fluoropolyoxyalkylene chain (chain Rp) of the non-functional (per)fluoropolyether oil (non-functional PFPE oil) of the invention typically comprises one or more recurring units R° having general formula -(CJJ')j -CKK'-O-, wherein J and J', equal to or different from each other, independently represent a fluorine atom or a C-|-C6 (per)fluoro(oxy)alkyl group, K and K', equal to or different from each other, independently
represent a hydrogen atom, a fluorine atom, a chlorine atom or a C-1-C6 (per)fluoro(oxy)alkyl group and j is an integer comprised between 0 and 3, said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
[0015] The non-functional PFPE oil of the invention may be a linear
non-functional PFPE oil or a branched non-functional PFPE oil.
[0016] By "linear non-functional PFPE oil" it is meant a non-functional PFPE oil comprising at least one (per)fluoropolyoxyalkylene chain (chain Rp) as defined above, wherein J and J' both represent a fluorine atom and K and K', equal to or different from each other, independently represent a hydrogen atom, a fluorine atom or a chlorine atom.
[0017] By "branched non-functional PFPE oil" it is meant a non-functional PFPE oil comprising at least one (per)fluoropolyoxyalkylene chain (chain Rp) as defined above, wherein at least one of J, J', K and K' represents a C1 -C6 (per)fluoro(oxy)alkyl group.
[0018] Representative examples of suitable non-functional PFPE oils according to the invention include, notably, the followings:
(1 ) T1-O-(C2F4O)br(CF2O)b -T1 '
wherein:
- T and T , equal to or different from each other, are independently selected from -CF3, -C2F5 and -C3F7 groups;
- b1 ' and b2', equal to or different from each other, are independently integers≥ 0 such that the b17b2' ratio is comprised between 0.1 and 5 and the (b1 '+b2') sum is comprised between 5 and 250; should b1 ' and b2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
Said products can be produced by photooxidation of C2F4 as reported in US 3715378 (MONTECATINI EDISON S.P.A.) 06.02.1973 and
subsequent treatment with fluorine as described in US 3665041
(MONTECATINI EDISON S.P.A.) 23.05.1972 .
(2) T2-O-(CF2O)c (CF2CF2O)c2'(CF2CF2CF2O)c3'(CF2CF2CF2CF2O)c4'-T
2'
wherein:
- T2 and T2 , equal to or different from each other, are independently selected from -CF3, -C2F5, -C3F7, -C4F9, -CF2CI, -CF2CF2CI groups;
- c1 \ c2', c3' and c4', equal to or different from each other, are
independently integers≥ 0 such that the number average molecular weight is comprised between 700 and 100000;
- the c27c1 ' ratio is comprised between 2 and 20;
- the (c3'+c4')/(c1 '+c2'+c3'+c4') ratio is comprised between 0.05 and 0.2;
- the c17(c1 '+c2'+c3'+c4') ratio is comprised between 0.05 and 0.4;
should at least two of c1 ', c2', c3' and c4' be different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
Said products can be produced as described in EP 1454938 B (SOLVAY SOLEXIS S.P.A.) 05.10.2005 .
(3) T3-O-(CF2CF2O)d-T3'
wherein:
- T3 and T3', equal to or different from each other, are independently selected from -C2Fs and -C3F7 groups;
- d' is an integer comprised between 5 and 250.
Said products can be obtained by a method comprising fluorinating a polyethyleneoxide, e.g. with elemental fluorine, and optionally thermally fragmentating the so-obtained fluorinated polyethyleneoxide as reported in US 4523039 (THE UNIVERSITY OF TEXAS) 1 1.06.1985 .
(4) T1-O-(CF2CF2C(Hal)2O)er-(CF2CF2CH2O)e2'-(CF2CF2CH(Hal)O)e3'-T V
wherein:
- T and T , equal to or different from each other, have the same meaning as defined above;
- Hal, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
- e1 ', e2', and e3', equal to or different from each other, are independently integers≥ 0 such that the (e1 '+e2'+e3') sum is comprised between 5 and 250; should at least two of e1 ', e2' and e3' be different from zero, the different recurring units are generally statistically distributed along the
(per)fluoropolyoxyalkylene chain.
Said products may be prepared by ring-opening polymerizing
2,2,3,3-tetrafluorooxethane in the presence of a polymerization initiator to give a polyether comprising repeating units of the formula: -CH2CF2CF2 O-, and optionally fluorinating and/or chlorinating said polyether, as detailed in EP 148482 B (DAIKIN INDUSTRIES LTD.) 25.03.1992 .
(5) T1-O-[CF(CF3)CF2O]fr(CFYO)f2'-T1 '
wherein:
- T and T , equal to or different from each other, have the same meaning as defined above;
- Y, equal or different at each occurrence, is selected from a fluorine atom or a -CF3 group;
- f1 ' and f2', equal to or different from each other, are independently integers≥ 0 such that the f17f2' ratio is comprised between 20 and 1000 and the (f1 '+f2') sum is comprised between 5 and 250; should f1 ' and f2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
Said products can be obtained by photooxidation of C3F6 as described in CA 786877 (MONTEDISON S.P.A.) 04.06.1968 and by subsequent conversion of the end groups as described in GB 1226566
(MONTECATINI EDISON S.P.A.) 31.03.1971 .
(6) T1-O-[CF(CF3)CF2O]gr(C2F4O)g (CFYO)g3-T1'
wherein:
- T and T ', equal to or different from each other, have the same meaning as defined above;
- Y, equal or different at each occurrence, has the same meaning as defined above;
- g1 ', g2' and g3', equal to or different from each other, are independently integers≥ 0 such that the (g1 '+g2'+g3') sum is comprised between 5 and 250; should at least two of g1 ', g2' and g3' be different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
Said products can be manufactured by photooxidation of a mixture of C3F6
and C2F4 and subsequent treatment with fluorine as described in US 3665041 (MONTECATINI EDISON SPA) 23.05.1972 .
(7) C3F7O-[CF(CF3)CF2O]h.-T3
wherein:
- T3 has the same meaning as defined above;
- h' is an integer comprised between 5 and 250.
Said products can be prepared by ionic hexafluoropropylene epoxide oligomerization and subsequent treatment with fluorine as described in US 3242218 (E. I. DU PONT DE NEMOURS AND CO.) 22.03.1966 .
(8) {C3F7O-[CF(CF3)CF2O]i-CF(CF3)-}2
wherein:
- i' is an integer comprised between 2 and 250.
Said products can be obtained by ionic telomerization of the
hexafluoropropylene epoxide and subsequent photochemical dimerization as reported in US 3214478 (E. I. DU PONT DE NEMOURS AND CO.) 26.10.1965 .
(9) R1f-{C(CF3)2-O-[C(R2f)2]j C(R2f)2-O}j -R1f
wherein:
- R1f, equal or different at each occurrence, is a C1-C6 perfluoroalkyl group;
- R2f, equal or different at each occurrence, is selected from a fluorine atom and a C1-C6 perfluoroalkyl group;
- j1 ' is equal to 1 or 2;
- j2' is an integer comprised between 5 and 250.
Said products can be produced by the copolymerization of
hexafluoroacetone with an oxygen-containing cyclic comonomer selected from ethylene oxide, propylene oxide, epoxy-butane and/or trimethylene oxide (oxethane) or substituted derivatives thereof and subsequent perfluorination of the resulting copolymer, as detailed in patent application WO 87/00538 (LAGOW ET AL.) 29.01.1987 .
Preferred non-functional PFPE oils suitable for the purpose of the invention include, notably, the followings:
(i) non-functional PFPE oils complying with formula (2) as described
above, wherein:
- T2 and T2' are -CF3 groups;
- cV, c2', c3' and c4', equal to or different from each other, are
independently integers > 0 such that the number average molecular weight is comprised between 1000 and 20000;
- the c27c1 ' ratio is comprised between 2 and 5;
- the (c3'+c4')/(c1 '+c2'+c3'+c4') ratio is comprised between 0.07 and 0.2;
- the c17(c1 '+c2'+c3'+c4') ratio is comprised between 0.1 and 0.3;
the different recurring units being generally statistically distributed along the perfluoropolyoxyalkylene chain;
(ii) non-functional PFPE oils commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® (type M, Z or Y), said oils generally comprising at least one oil complying with either of formulae here below:
CF3-[(OCF2CF2)m-(OCF2)n]-OCF3 m+n = 40 -180; m/n = 0.5 - 2
CF3-[(OCF(CF3)CF2)p-(OCF2)q]-OCF3 p+q = 8 - 45; p/q = 20 - 1000
(iii) non-functional PFPE oils commercially available from Daikin under the trade name DEMNUM®, said oils generally comprising at least one oil complying with formula here below:
F-(CF2CF2CF20)n-(CF2CF2CH20)rCF2CF3 j = 0 or integer > 0; n+j = 10 - 150
(iv) non-functional PFPE oils commercially available from Du Pont de Nemours under the trade name KRYTOX®, said oils generally comprising at least one low-molecular weight, fluorine end-capped, homopolymer of hexafluoropropylene epoxide complying with formula here below:
F-(CF(CF3)CF2O)n-CF2CF3
n = 10 - 60
[0020] More preferred non-functional PFPE oils suitable for the purpose of the invention include, notably, non-functional PFPE oils complying with formula (2) as described hereinabove and non-functional PFPE oils commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® (type M, Z or Y) as described hereinabove.
[0021] A mixture of more than one non-functional PFPE oil as defined above may also be used in the lubricant composition of the invention.
[0022] Preferred mixtures of more than one non-functional PFPE oil as defined above include, notably, mixtures of at least one linear non-functional PFPE oil as defined above with at least one branched non-functional PFPE oil as defined above. Representative examples of suitable mixtures of at least one linear non-functional PFPE oil as defined above with at least one branched non-functional PFPE oil as defined above include, notably, those commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® W.
[0023] The (per)fluoropolyoxyalkylene chain (chain R'F) of the cyclic
phosphazene compound [compound (P)] of the invention typically comprises one or more recurring units R having general formula -(CF2)j -CFK-O-, wherein K is selected from a fluorine atom and a C1-C5
(per)fluoro(oxy)alkyl group and j is an integer comprised between 0 and 3, said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
[0024] According to a first embodiment of the invention, the compound (P)
complies with formula (l-A), (l-A bis) or (ll-A) here below:
wherein:
- Rf is a (per)fluoropolyoxyalkylene chain comprising one or more recurring units having formula -CF2O(CF2CF2O)P'(CF2O)q'CF2-, wherein p' and q' are integers such that the number average molecular weight of the chain is comprised between 1000 and 2000, the q'/p' ratio being comprised between 0.2 and 2;
- R'f is a (per)fluoropolyoxyalkylene chain comprising one or more recurring units having formula -(C3F6O)q(CF(CF3)O)r-, wherein q and r are integers such that the number average molecular weight of the chain is comprised between 500 and 700, the q/r ratio being > 2.
[0025] Compounds (P) complying with formula (l-A), (l-A bis) or (ll-A) as
described in this first embodiment of the invention are notably disclosed in EP 1336614 A (SOLVAY SOLEXIS S.P.A.) 20.08.2003 .
[0026] According to a second embodiment of the invention, the compound (P) complies with formula l-B) or (ll-B) here below:
wherein:
- R"f and R"'f, equal to or different from each other, independently represent a (per)fluoropolyoxyalkylene chain comprising one or more recurring units selected from:
(i) -CFYO-, wherein Y is a fluorine atom or a -CF3 group,
(ii) -CF2CFYO-, wherein Y has the same meaning as defined above,
(iii) -CF2CF2CF2O-,
(iv) -CF2CF2CF2CF2O-,
said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain;
- Z and Z', equal to or different from each other, independently represent a polar group of formula -O"M+, wherein M is selected from hydrogen, a monovalent metal, preferably an alkaline metal, and an ammonium radical having formula -NR-1 R2R3R4, wherein each of R-| , R2, R3, R4 is, independently, a hydrogen atom or a C1-C12 hydrocarbon group, optionally fluorinated, or a polar group of formula -O")2M'2+, wherein M' is a divalent metal, preferably an alkaline earth metal;
- n is an integer comprised between 1 and 3, preferably equal to 1 ;
- z is an integer comprised between 1 and 4, preferably equal to 1 ;
- nf is an integer such that n + nf is equal to 6;
- nf is an integer such that nz' + nf is equal to 8.
The compound (P) of this second embodiment of the invention preferably complies with formula (l-B) or (ll-B) here above, wherein R"fO- and R"'fO- are selected from:
(a) T4-O- (CF2CF2O)p.(CF2O)q.-J- wherein:
- T4 is selected from -CF3, -CF2CF3, -CF2CF2CF3, -(CF2)f-CF2(T1) and -(CF2)f-CF(T-|)(T2), wherein f is 0 or 1 , Ti and T2, equal to or different from each other, are independently selected from chlorine, bromine and hydrogen atoms;
- J is selected from groups having formulae -CE'(Y)CE2O(CH2CH2O)si- and -CE'YO(CH2CH2O)s2-, wherein E and E', equal to or different from each other, are independently selected from a fluorine atom, a hydrogen atom and a -CF3 group, E being preferably a hydrogen atom and E' being
preferably selected from a fluorine atom and a -CF3 group, Y is selected from a fluorine atom and a -CF3 group, s1 and s2, equal to or different from each other, are integers comprised between 0 and 5;
- p' and q' are numbers such that the (p'+q') sum is comprised between 1 and 100 and the q'/p' ratio is comprised between 0.1 and 10;
(b) T5-O- (CF2CF(CF3)OV-(CF2CF2O)s'-(CFYO)t-J- wherein:
- T5 is selected from -CF3, -CFYCF3, -CF(Y)CF(Y)CF3, -(CFY)f-CFY(T'i) and -(CFY^-CYCT-iXT^), wherein f is 0 or 1 , T'i and T2, equal to or different from each other, are independently selected from chlorine, bromine and hydrogen atoms;
- Y, equal or different at each occurrence, has the same meaning as defined above;
- J has the same meaning as defined above;
- r', s' and t' are numbers such that the (r'+ s'+ t') sum is comprised between 1 and 100, the t'/(r'+ s') ratio being comprised between 0.01 and 0.1 ;
(c) T5-(OCFY)t1"(OC3F6)u 1"-OR*fO-(C3F6O)U2"(CFYO)t2"-J- wherein:
- T5 has the same meaning as defined above;
- Y, equal or different at each occurrence, has the same meaning as defined above;
- J has the same meaning as defined above;
- R*f is a C-i-Ce perfluoroalkylene group;
- 11 ", u1 ", t2", u2" are numbers such that the (t1 "+ u1 "+ t2"+ u2") sum is comprised between 1 and 100, the (t1 "+ t2") /(u1 "+ u2") ratio being comprised between 0.01 and 0.1 ;
(d) T4-CF2CF2O-(CF2-(CF2)x'CF2O)v'-J- wherein:
- T4 has the same meaning as defined above;
- J has the same meaning as defined above;
- x' is equal to 1 or 2;
- v' is a number comprised between 1 and 100;
(e) T4-CF2CH2-(OCF2CF2CH2)w'-OR*fO-(CH2CF2CF2O)w'-J- wherein:
- T4 has the same meaning as defined above;
- J has the same meaning as defined above;
- R*f has the same meaning as defined above;
- w' is a number comprised between 1 and 100.
The compound (P) of this second embodiment of the invention more preferably complies with formula (l-B*) or (ll-B*) here below:
wherein:
- Z, Z', nz, nZ', rif and rif have the same meaning as defined above;
- R"*f O- and R"'*f 0-, equal to or different from each other, represent a fluoropolyoxyalkylene chain having formula:
T*-O-(CF2CF2O)p*(CF2O)q*-CF2-CH2O(CH2CH2O)s*- wherein:
- T* is selected from -CF3, -CF2CF3 and -CF2CF2CF3 groups;
- p* and q* are numbers such that the (p*+q*) sum is comprised between 1 and 50 and the q*/p* ratio is comprised between 0.1 and 10;
- s* is a number comprised between 0 and 5.
The compound (P) of this second embodiment of the invention most preferably complies with formula (lll-B) or (lll-B bis) here below:
wherein:
- M and M' have the same meaning as defined above, M being preferably an alkaline metal selected from Li, Na and K or an ammonium radical having formula -NR-1 R2R3R4, wherein each of R-| , R2, R3, R4 is, independently, a hydrogen atom or a C1 -C12 hydrocarbon group, preferably Ri = R2 = R3 = R4 = n-butyl, and M' being preferably an alkaline earth metal selected from Ca and Mg, more preferably M' being Ca;
- each of p*i (i = 1 to 5) and q*i (i = 1 to 5) is independently an integer > 0 such that the (p*i+q*i) sum is comprised between 2 and 25 and the q*i/p*i ratio is comprised between 0.1 and 10.
[0030] Compounds (P) complying with formula (l-B) or (ll-B) as described in this second embodiment of the invention are notably disclosed in WO
2008/000706 (SOLVAY SOLEXIS S.P.A.) 03.01.2008 .
[0031] According to a third embodiment of the invention, the compound (P)
typically complies with formula (IV-C) here below:
wherein:
- A, equal or different at each occurrence, is selected from:
(i) -QR groups, wherein Q is a divalent group selected from -O-, -S-, -NR-|- and -NH-NH-, wherein Ri is a hydrogen atom or a C1-C4 alkyl group, and R is a C6-C-12 aryl group, preferably a phenyl group, optionally substituted by one or more, preferably 1 or 2 groups selected from C 1-C4 alkyl groups, -OR2-, -NR3R4, -NO2, fluorine and chlorine atoms, wherein R2, R3 and R4 are hydrogen atoms or C1-C4 alkyl groups;
(ii) RFCH2O(CH2CH2O)s-, wherein Rp is a (per)fluoropolyoxyalkylene chain (chain R'F) as defined above and s is equal to 0, 1 or 2;
- m is equal to 3 or 4;
- n is equal to 0.
[0032] Compounds (P) complying with formula (IV-C) as described in this third embodiment of the invention are notably disclosed in EP 0597369 A
(AUSIMONT S.P.A.) 16.09.1998 .
[0033] Preferred lubricant compositions of the invention comprise one or more compounds (P) according to the first and/or the second embodiment of the invention as detailed above.
[0034] More preferred lubricant compositions of the invention comprise one or more compounds (P) according to the second embodiment of the invention as detailed above.
[0035] Most preferred lubricant compositions of the invention comprise one or more compounds (P) complying with either of formulae (lll-B) or (lll-B bis) as described above.
[0036] The functional (per)fluoropolyether derivative (functional PFPE derivative) of the invention comprises at least one (per)fluoropolyoxyalkylene chain (chain R'F) as defined above and at least one functional group typically comprising at least one ether, thioether, ester or amine group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
[0037] The functional (per)fluoropolyether derivative (functional PFPE derivative) of the invention preferably complies with formula (V) here below:
T-(CFW1)p1-0-RF-(CFW2)pi-T (V)
wherein:
- Rp is a (per)fluoropolyoxyalkylene chain (chain R'F) as defined above;
- T and T, equal to or different from each other, are selected from:
i) functional end-groups comprising at least one ether, thioether, ester or amine group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms,
ii) non-functional end-groups selected from a fluorine atom, a chlorine atom and a C1-C3 (per)fluoroalkyl group optionally containing one or more chlorine atoms,
with the proviso that at least one of T and T is a functional end-group as defined hereinabove;
- Wi and W2, equal to or different from each other, independently represent a fluorine atom or a -CF3 group;
- p1 and pV, equal to or different from each other, are independently integers comprised between 1 and 3, preferably being equal to 1 when Wi and/or W2 are -CF3 groups.
The functional PFPE derivative of the invention more preferably complies with formula (VI) here below:
T"-CF2O(CF2CF2O)m*(CF2O)n*CF2-T" (VI)
wherein:
- T" and T"\ equal to or different from each other, are selected from:
i) functional end-groups selected from those having formulae -CH2-A-Y, -CH(CF3)-A-Y, -CHW'-B-(CH2CH2O)m'-Y and -COOY, wherein:
(a') A is selected from oxygen and sulphur atoms,
(b') B is selected from an oxygen atom, a sulphur atom and a -NH group,
(c') W is selected from a hydrogen atom and a -CF3 group,
(d') m' is an integer comprised between 0 and 6,
(e') Y is selected from phenyl, pyridine, triazine, benzoxazole,
benzothiazole and benzopyrazine groups optionally substituted with one or more substituents different from hydrogen atoms,
ii) non-functional end-groups selected from a fluorine atom, a chlorine atom, a -CF3 group, a -C2F5 group and a -(CF2)nCI group, wherein n is an
integer comprised between 1 and 3,
with the proviso that at least one of T" and T" is a functional end-group as defined hereinabove;
- m* and n* are integers such that the number average molecular weight of the functional PFPE derivative is comprised between 400 and 10000, the m*/n* ratio being comprised between 0.1 and 10.
[0039] Preferred lubricant compositions of the invention comprise one or more functional PFPE derivatives selected from:
- functional PFPE derivatives complying with formula (V) as described above wherein at least one of T and T is a functional end-group
comprising at least one ether or thiether group comprising at least one pyridine group optionally substituted with one or more substituents different from hydrogen atoms, notably disclosed in EP 1479753 A
(SOLVAY SOLEXIS S.P.A.) 24.1 1.2004 ;
- functional PFPE derivatives complying with formula (V) as described above wherein at least one of T and T is a functional end-group
comprising at least one ether or ester group comprising at least one phenyl group optionally substituted with one or more substituents different from hydrogen atoms, notably disclosed in EP 1354932 B (SOLVAY SOLEXIS S.P.A.) 14.06.2006 ;
- functional PFPE derivatives complying with formula (V) as described above wherein at least one of T and T is a functional end-group
comprising at least one ether, thioether or amine group comprising at least one 1 ,3,5-triazine group optionally substituted with one or more
substituents different from hydrogen atoms, notably disclosed in EP 1712580 B (SOLVAY SOLEXIS S.P.A.) 10.12.2008 ;
- functional PFPE derivatives complying with formula (V) as described above wherein at least one of T and T is a functional end-group
comprising at least one ether or thioether group comprising at least one benzoxazole, benzothiazole or benzopyrazine group optionally substituted with one or more substituents different from hydrogen atoms, notably disclosed in EP 1659164 A (SOLVAY SOLEXIS S.P.A.) 24.05.2006 .
[0040] Most preferred lubricant compositions of the invention comprise one or
more functional PFPE derivatives complying with formula (VI) as described above wherein both T" and T" are functional end-groups as defined above (bifunctional PFPE derivatives).
Non-limitative examples of suitable bifunctional PFPE derivatives include, notably, the followings:
- bifunctional PFPE derivatives complying with formula here below:
wherein m* and n* are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and 6000, preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5;
- bifunctional PFPE derivatives commercially available from Solvay Solexis S.p.A. under the trade name FOMBLIN® DA 410, said bifunctional PFPE derivatives complying with formula here below:
wherein m* and n* are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and
6000, preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5.
Very good results have been obtained with lubricant compositions comprising one or more bifunctional PFPE derivatives complying with formula here below:
wherein m* and n* are integers such that the number average molecular weight of the bifunctional PFPE derivative is comprised between 1000 and 6000, preferably between 2000 and 4000, the m/n ratio being comprised between 0.1 and 5.
[0043] The lubricant composition of the invention typically comprises at least one cyclic phosphazene compound [compound (P)] as defined above in an amount of at least 0.1 % by weight, preferably at least 0.2% by weight, more preferably at least 0.3% by weight with respect to the weight of the non-functional PFPE oil.
[0044] The lubricant composition of the invention typically comprises at least one cyclic phosphazene compound [compound (P)] as defined above in an amount of at most 15% by weight, preferably at most 10% by weight, more preferably at most 5% by weight with respect to the weight of the non-functional PFPE oil.
[0045] The lubricant composition of the invention typically comprises at least one functional PFPE derivative different from compound (P) as defined above in an amount of at least 0.5% by weight, preferably at least 1 % by weight, more preferably at least 2% by weight with respect to the weight of the non-functional PFPE oil.
[0046] The lubricant composition of the invention typically comprises at least one functional PFPE derivative different from compound (P) as defined above in an amount of at most 15 % by weight, preferably at most 10% by weight, more preferably at most 6% by weight with respect to the weight of the non-functional PFPE oil.
[0047] Very good results have been obtained with lubricant compositions
comprising at least one cyclic phosphazene compound [compound (P)] in an amount ranging from 0.3% to 5% by weight with respect to the weight of the non-functional PFPE oil and at least one functional PFPE derivative different from compound (P) as defined above in an amount ranging from 2% to 6% by weight with respect to the weight of the non-functional PFPE oil.
[0048] The lubricant composition of the invention typically has a kinematic
viscosity (η) ranging from 100 to 350, preferably from 120 to 300, as
measured at 20°C by ASTM D445.
[0049] The lubricant composition can also further comprise other additives
notably including one or more anti-rust additives, oxidation inhibitors, antifoam agents, anti-wear additives and anti-scuff additives.
Representative examples of anti-rust additives which can be
advantageously added to the lubricant composition of the invention include, notably, functional PFPEs commercially available from Solvay Solexis S.p.A. under the trade names FOMBLIN® DA305, FOMBLIN® DA306 and FOMBLIN® DA308.
[0050] Another object of the invention is use of the lubricant composition as
described above for lubricating vacuum pumps, in particular high vacuum and ultra-high vacuum pumps, especially in the semiconductor industry where high-purity lubricants are typically required.
[0051] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[0052] The invention will be now described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention.
[0053] Raw materials
[0054] The non-functional PFPE oil (1 ) is a linear non-functional PFPE oil having formula CF3O-(CF2O)n(CF2CF2O)m(CF2CF2CF2O)r(CF2CF2CF2CF2O)s -CF3, wherein m, n, r and s are integers such that the number average molecular weight is about 1 1000, the m/n ratio being about 2.7.
[0055] The non-functional PFPE oil (2) is a FOMBLIN® M15 linear non-functional PFPE oil having formula CF3O-(CF2CF2O)m(CF2O)n-CF3, wherein m and n are integers such that the number average molecular weight is about 10600, the m/n ratio being about 0.9.
[0056] The non-functional PFPE oil (3) is a FOMBLIN® M30 linear non-functional PFPE oil having formula CF3O-(CF2CF2O)m(CF2O)n-CF3, wherein m and n are integers such that the number average molecular weight is about 13000, the m/n ratio being about 0.9.
[0057] The non-functional PFPE oil (4) is a FOMBLIN® Y25/6 branched non-functional PFPE oil having formula
CF3O-(CF(CF3)CF2O)p(CF2O)q-CF3, wherein p and q are integers such that the number average molecular weight is about 3800.
[0058] The compound (P1) is a cyclic phosphazene compound having formula
wherein p*i (i = 1 to 5) and q*i (i = 1 to 5) indexes are integers such that the number average molecular weight is about 8300.
[0059] The functional PFPE derivative (1 ) has formula
wherein m and n are integers such that the number average molecular weight is about 3800, the m/n ratio being about 0.9.
[0060] Thermal-oxidative stability test method
Thermal-oxidative stability tests were conducted on a sintered metal bearing of Fe-Cu-Sn-C type.
The sintered metal bearing of Fe-Cu-Sn-C type was impregnated with the lubricant composition of the invention at 30°C, under vacuum (7 mbar), for
25 minutes. The sintered metal bearing so treated was then allowed to drain for about 15 minutes, so that the amount of lubricant composition impregnated in the sintered metal bearing was about 0.05 g.
The sintered metal bearing so impregnated was placed in a ventilated oven set at 200°C and weighted every 48-72 hours.
Weight loss of the lubricant composition was checked as a function of time.
An induction time was measured until complete degradation of the lubricant composition.
[0061] Tribological test method
Sliding wear tests were conducted with a ball-on-disk tribometer at 140°C during 6 hours under the following operating conditions:
- ball diameter: 10 mm;
- applied load: 200 N;
- amplitude of oscillation: 1 mm;
- frequency of oscillation: 50 Hz.
The wear volume (V) on the disk [mm3] has been calculated as follows:
wherein:
- d1 represents the diagonal of the disk wear parallel to the oscillating motion;
- d2 represents the diagonal of the disk wear perpendicular to the oscillating motion;
- R represents the ball radius (5 mm).
[0062] Example 1
A lubricant composition was prepared by mixing non-functional PFPE oil (3) with 0.5% by weight of non-functional PFPE oil (3) of compound (P1 ) and 5% by weight of non-functional PFPE oil (3) of functional PFPE derivative (1 ).
The results for the thermal-oxidative stability test of said lubricant composition are set forth in Table 1 here below.
[0063] Example 1 C (comparative)
A composition was prepared by mixing non-functional PFPE oil (3) with
0.5% by weight of non-functional PFPE oil (3) of compound (P1 ).
The results for the thermal-oxidative stability test of said composition are set forth in Table 1 here below.
[0064] Example 2C (comparative)
A composition was prepared by mixing non-functional PFPE oil (3) with
5% by weight of non-functional PFPE oil (3) of functional PFPE derivative
(1 ).
The results for the thermal-oxidative stability test of said composition are set forth in Table 1 here below.
Table 1
[0065] The thermal-oxidative stability tests performed with the lubricant
composition of Example 1 of the invention showed a substantial increase of the induction time to degradation with respect to compositions of comparative Examples 1 C and 2C, that is to say that the lubricant composition of the invention showed improved thermal-oxidative stability with respect to compositions comprising at least one non-functional PFPE oil as defined above and either at least one compound (P) as defined above or at least one functional PFPE derivative as defined above.
[0066] Example 2
A lubricant composition was prepared by mixing non-functional PFPE oil (1 ) with 3% by weight of non-functional PFPE oil (1 ) of compound (P1 ) and 3% by weight of non-functional PFPE oil (1) of functional PFPE derivative
(1 ) .
The results for the tribological test and the evaporating constant at 150°C [(mm3 of evaporated lubricant / mm2 of exposed surface area)■ h] ([*]) of said lubricant composition are set forth in Table 2 here below.
[0067] Example 3
A lubricant composition was prepared by mixing non-functional PFPE oil
(2) with 3% by weight of non-functional PFPE oil (2) of compound (P1 ) and 3% by weight of non-functional PFPE oil (2) of functional PFPE derivative
(1 ).
The results for the tribological test and the evaporating constant at 150°C [(mm3 of evaporated lubricant / mm2 of exposed surface area)■ h] ([*]) of said lubricant composition are set forth in Table 2 here below.
[0068] Example 4
A lubricant composition was prepared by mixing non-functional PFPE oil
(4) with 3% by weight of non-functional PFPE oil (4) of compound (P1 ) and 3% by weight of non-functional PFPE oil (4) of functional PFPE derivative
(1 ).
The results for the tribological test and the evaporating constant at 150°C [(mm3 of evaporated lubricant / mm2 of exposed surface area)■ h] ([*]) of said lubricant composition are set forth in Table 2 here below.
[0069] Example 3C (comparative)
A composition was prepared by mixing non-functional PFPE oil (2) with
3% by weight of non-functional PFPE oil (2) of compound (P1).
The results for the tribological test and the evaporating constant at 150°C
[(mm3 of evaporated lubricant / mm2 of exposed surface area)■ h] ([*]) of said composition are set forth in Table 2 here below.
The thermal-oxidative stability tests performed with the composition of
Example 3C showed a substantial decrease of the induction time to degradation with respect to the lubricant composition of Example 4 of the invention.
[0070] Example 4C (comparative)
A composition was prepared by mixing non-functional PFPE oil (2) with 3% by weight of non-functional PFPE oil (2) of functional PFPE derivative
(1 ).
The results for the tribological test and the evaporating constant at 150°C
[(mm3 of evaporated lubricant / mm2 of exposed surface area)■ h] ([*]) of said composition are set forth in Table 2 here below.
The thermal-oxidative stability tests performed with the composition of
Example 4C showed a substantial decrease of the induction time to degradation with respect to the lubricant composition of Example 4 of the invention.
Substantially low wear volumes and low evaporating constants were measured for the lubricant compositions of Examples 2, 3 and 4 of the invention, that is to say that the lubricant compositions of the invention exhibited substantially high lubrication performances in terms of anti-wear properties and low evaporation weight loss. In particular, the tribological tests performed with the lubricant composition of Example 3 of the invention showed that substantially low or even slightly decreased wear volumes were measured with respect to compositions of comparative Examples 3C and 4C, that is to say that the lubricant composition of the invention showed good or slightly improved anti-wear properties with respect to compositions comprising at least one non-functional PFPE oil as defined above and either at least one compound (P) as defined above or at least one functional PFPE derivative as defined above.
Claims
1. A lubricant composition comprising:
(A) at least one non-functional (per)fluoropolyether oil (non-functional PFPE oil) comprising at least one (per)fluoropolyoxyalkylene chain (chain Rp);
(B) at least one cyclic phosphazene compound [compound (P)] comprising one or more cyclic moieties having formula (I) or (II) here below:
said cyclic moieties comprising, bound to one or more phosphorus atoms, at least one substituent comprising at least one (per)fluoropolyoxyalkylene chain (chain R'F);
(C) at least one functional (per)fluoropolyether derivative (functional PFPE derivative) different from compound (P) comprising at least one
(per)fluoropolyoxyalkylene chain (chain R'F) and at least one functional group comprising at least one monocyclic or polycyclic aromatic ring, said aromatic ring optionally containing one or more heteroatoms selected from N, O and S and one or more substituents different from hydrogen atoms.
2. The lubricant composition of claim 1 , wherein the non-functional PFPE oil is selected from the followings:
(1) T1-O-(C2F4O)br(CF2O)b -T1 '
wherein:
- T and T , equal to or different from each other, are independently selected from -CF3, -C2F5 and -C3F7 groups;
- bV and b2', equal to or different from each other, are independently integers
≥ 0 such that the b17b2' ratio is comprised between 0.1 and 5 and the
(b1 '+b2') sum is comprised between 5 and 250; should bV and b2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
(2) T2-O-(CF2O)c (CF2CF2O)c2'(CF2CF2CF2O)c3'(CF2CF2CF2CF2O)c4'-T2' wherein:
- T2 and T2 , equal to or different from each other, are independently selected from -CF3, -C2F5, -C3F7, -C4F9, -CF2CI, -CF2CF2CI groups;
- cV, c2', c3' and c4', equal to or different from each other, are independently integers≥ 0 such that the number average molecular weight is comprised between 700 and 100000;
- the c27c1 ' ratio is comprised between 2 and 20;
- the (c3'+c4')/(c1 '+c2'+c3'+c4') ratio is comprised between 0.05 and 0.2;
- the c17(c1 '+c2'+c3'+c4') ratio is comprised between 0.05 and 0.4;
should at least two of c1 ', c2', c3' and c4' be different from zero, the different recurring units are generally statistically distributed along the
perfluoropolyoxyalkylene chain.
(3) T3-O-(CF2CF2O)d-T3'
wherein:
- T3 and T3', equal to or different from each other, are independently selected from -C2F5 and -C3F7 groups;
- d' is an integer comprised between 5 and 250.
(4) T1-O-(CF2CF2C(Hal)2O)e -(CF2CF2CH2O)e2'-(CF2CF2CH(Hal)O)e3'-T1 ' wherein:
- T and T , equal to or different from each other, have the same meaning as defined above;
- Hal, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
- e1 ', e2', and e3', equal to or different from each other, are independently integers≥ 0 such that the (e1 '+e2'+e3') sum is comprised between 5 and 250; should at least two of e1 ', e2' and e3' be different from zero, the different recurring units are generally statistically distributed along the
(per)fluoropolyoxyalkylene chain.
(5) T1 -O-[CF(CF3)CF2O]fr(CFYO)f2'-T1'
wherein:
- T and T , equal to or different from each other, have the same meaning as defined above;
- Y, equal or different at each occurrence, is selected from a fluorine atom or a -CF3 group;
- fV and f2', equal to or different from each other, are independently integers≥ 0 such that the f17f2' ratio is comprised between 20 and 1000 and the (f1 '+f2') sum is comprised between 5 and 250; should f1 ' and f2' be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.
(6) T -O-[CF(CF3)CF2O]gr(C2F4O)g (CFYO)g3-T1 '
wherein:
- T and T ', equal to or different from each other, have the same meaning as defined above;
- Y, equal or different at each occurrence, has the same meaning as defined above;
- g1 ', g2' and g3', equal to or different from each other, are independently integers≥ 0 such that the (g1 '+g2'+g3') sum is comprised between 5 and 250; should at least two of g1 ', g2' and g3' be different from zero, the different recurring units are generally statistically distributed along the
perfluoropolyoxyalkylene chain.
(7) C3F7O-[CF(CF3)CF2O]h.-T3
wherein:
- T3 has the same meaning as defined above;
- h' is an integer comprised between 5 and 250.
(8) {C3F7O-[CF(CF3)CF2O]r-CF(CF3)-}2
wherein:
- i' is an integer comprised between 2 and 250.
(9) R1f-{C(CF3)2-O-[C(R2f)2]jrC(R2f)2-O}j2-R1f
wherein:
- R1f, equal or different at each occurrence, is a C-|-C6 perfluoroalkyl group;
- R2f, equal or different at each occurrence, is selected from a fluorine atom
and a C-1-C6 perfluoroalkyl group;
- jV is equal to 1 or 2;
- j2' is an integer comprised between 5 and 250.
The lubricant composition of claims 1 and 2, wherein a mixture of more than one non-functional PFPE oil is used.
The lubricant composition of anyone of claims 1 to 3, wherein the cyclic phosphazene compound [compound (P)] complies with formula (l-B) or (ll-B) here below:
wherein:
- R"f and R"'f, equal to or different from each other, independently represent a (per)fluoropolyoxyalkylene chain comprising one or more recurring units selected from:
(i) -CFYO-, wherein Y is a fluorine atom or a -CF3 group,
(ii) -CF2CFYO-, wherein Y has the same meaning as defined above,
(iii) -CF2CF2CF2O-,
(iv) -CF2CF2CF2CF2O-,
said recurring units being generally statistically distributed along the
(per)fluoropolyoxyalkylene chain;
- Z and Z', equal to or different from each other, independently represent a polar group of formula -O"M+, wherein M is selected from hydrogen, a monovalent metal, preferably an alkaline metal, and an ammonium radical having formula -NR-1 R2R3R4, wherein each of R-| , R2, R3, R4 is,
independently, a hydrogen atom or a C1-C12 hydrocarbon group, optionally
fluorinated, or a polar group of formula -0")2Μ' , wherein M' is a divalent metal, preferably an alkaline earth metal;
- n is an integer comprised between 1 and 3, preferably equal to 1 ;
- n ' is an integer comprised between 1 and 4, preferably equal to 1 ;
- nf is an integer such that nz + nf is equal to 6;
- n is an integer such that nz' + rif is equal to 8.
5. The lubricant composition of claim 4, wherein the cyclic phosphazene
compound [compound (P)] complies with formula (l-B*) or (ll-B*) here below:
wherein:
- Z, Z', nz, nz% nf and n have the same meaning as defined in claim 4;
- R"*f O- and R"'*f O-, equal to or different from each other, represent a (per)fluoropolyoxyalkylene chain having formula:
T*-O-(CF2CF2O)p*(CF2O)q*-CF2-CH2O(CH2CH2O)s*- wherein:
- T* is selected from -CF3, -CF2CF3 and -CF2CF2CF3 groups;
- p* and q* are numbers such that the (p*+q*) sum is comprised between 1 and 50 and the q*/p* ratio is comprised between 0.1 and 10;
- s* is a number comprised between 0 and 5.
6. The lubricant composition of claims 4 and 5, wherein the cyclic phosphazene compound [compound (P)] complies with formula (lll-B) or (lll-B bis) here below:
wherein:
- M and M' have the same meaning as defined in claim 4, M being preferably an alkaline metal selected from Li, Na and K or an ammonium radical having formula -NR1 R2R3R4, wherein each of Ri , R2, R3, R4 is, independently, a hydrogen atom or a C1 -C12 hydrocarbon group, preferably Ri = R2 = R3 = R4 = n-butyl, and M' being preferably an alkaline earth metal selected from Ca and Mg, more preferably M' being Ca;
- each of p*i (i = 1 to 5) and q*i (i = 1 to 5) is independently an integer > 0 such that the (p*i+q*i) sum is comprised between 2 and 25 and the q*i/p*i ratio is comprised between 0.1 and 10.
7. The lubricant composition of anyone of claims 1 to 6, wherein the functional PFPE derivative complies with formula (V) here below:
T-(CFW1)p1-O-RF-(CFW2)pr-T' (V)
wherein:
- RF is a (per)fluoropolyoxyalkylene chain (chain R»;
- T and T, equal to or different from each other, are selected from:
i) functional end-groups comprising at least one ether, thioether, ester or amine group comprising at least one monocyclic or polycyclic aromatic ring, said
aromatic ring optionally containing one or more heteroatoms selected from N,
O and S and one or more substituents different from hydrogen atoms, ii) non-functional end-groups selected from a fluorine atom, a chlorine atom and a C1-C3 (per)fluoroalkyl group optionally containing one or more chlorine atoms,
with the proviso that at least one of T and T is a functional end-group as defined hereinabove;
- Wi and W2, equal to or different from each other, independently represent a fluorine atom or a -CF3 group;
- p1 and pV, equal to or different from each other, are independently integers comprised between 1 and 3, preferably being equal to 1 when Wi and/or W2 are -CF3 groups.
8. The lubricant composition of claim 7, wherein the functional PFPE derivative complies with formula (VI) here below:
T"-CF2O(CF2CF2O)m*(CF2O)n*CF2-T" (VI)
wherein:
- T" and T", equal to or different from each other, are selected from:
i) functional end-groups selected from those having formulae -CH2-A-Y, -CH(CF3)-A-Y, -CHW'-B-(CH2CH2O)m'-Y and -COOY, wherein:
(a') A is selected from oxygen and sulphur atoms,
(b') B is selected from an oxygen atom, a sulphur atom and a -NH group,
(c') W is selected from a hydrogen atom and a -CF3 group,
(d') m' is an integer comprised between 0 and 6,
(e') Y is selected from phenyl, pyridine, triazine, benzoxazole, benzothiazole and benzopyrazine groups optionally substituted with one or more substituents different from hydrogen atoms,
ii) non-functional end-groups selected from a fluorine atom, a chlorine atom, a -CF3 group, a -C2F5 group and a -(CF2)nCI group, wherein n is an integer comprised between 1 and 3,
with the proviso that at least one of T" and T" is a functional end-group as defined hereinabove;
- m* and n* are integers such that the number average molecular weight of the functional PFPE derivative is comprised between 400 and 10000, the m*/n*
ratio being comprised between 0.1 and 10.
9. The lubricant composition of anyone of claims 1 to 8, wherein at least one cyclic phosphazene compound [compound (P)] is comprised in an amount ranging from 0.3% to 5% by weight with respect to the weight of the non-functional PFPE oil and at least one functional PFPE derivative different from compound (P) is comprised in an amount ranging from 2% to 6% by weight with respect to the weight of the non-functional PFPE oil.
10. Use of the lubricant composition of anyone of claims 1 to 9 for lubricating vacuum pumps.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10759933A EP2486114A1 (en) | 2009-10-06 | 2010-10-01 | Lubricant compositions for vacuum pumps |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09172280 | 2009-10-06 | ||
PCT/EP2010/064686 WO2011042374A1 (en) | 2009-10-06 | 2010-10-01 | Lubricant compositions for vacuum pumps |
EP10759933A EP2486114A1 (en) | 2009-10-06 | 2010-10-01 | Lubricant compositions for vacuum pumps |
Publications (1)
Publication Number | Publication Date |
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EP2486114A1 true EP2486114A1 (en) | 2012-08-15 |
Family
ID=42061075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP10759933A Withdrawn EP2486114A1 (en) | 2009-10-06 | 2010-10-01 | Lubricant compositions for vacuum pumps |
Country Status (6)
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US (1) | US20120196780A1 (en) |
EP (1) | EP2486114A1 (en) |
JP (1) | JP5705860B2 (en) |
CN (1) | CN102762706A (en) |
TW (1) | TW201124523A (en) |
WO (1) | WO2011042374A1 (en) |
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CN103781819B (en) * | 2011-06-24 | 2016-11-16 | 索尔维特殊聚合物意大利有限公司 | (entirely) perfluoroalkyl polyether block copolymer |
JP6214566B2 (en) | 2012-02-17 | 2017-10-18 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | (Per) fluoropolyethers having bi- or ter-phenyl end groups |
SG11201500680SA (en) | 2012-08-08 | 2015-02-27 | Agency Science Tech & Res | Lubricants for magnetic recording media |
WO2018172172A1 (en) | 2017-03-20 | 2018-09-27 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated polymers and uses thereof |
CN108893176A (en) * | 2018-06-12 | 2018-11-27 | 天津大学 | A kind of perfluoro polyether oil and preparation method thereof |
WO2022123431A1 (en) | 2020-12-07 | 2022-06-16 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA786877A (en) | 1968-06-04 | Pasetti Adolfo | Fluorinated oxygen-containing products and process for their preparation | |
US3242218A (en) | 1961-03-29 | 1966-03-22 | Du Pont | Process for preparing fluorocarbon polyethers |
DE1249247B (en) | 1961-04-25 | 1967-09-07 | E. I. Du Pont De Nemours And Company, Wilmington, Del. (V. St. A.) | Process for the preparation of perfluoroolefin polyethers |
DE1745169B2 (en) | 1967-02-09 | 1977-04-21 | Montecatini Edison S.P.A., Mailand (Italien) | FLUORINATED LINEAR POLYAETERS AND THE PROCESS FOR THEIR PRODUCTION |
US3665041A (en) | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
GB1226566A (en) | 1967-04-04 | 1971-03-31 | ||
US4523039A (en) | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
DE3485616D1 (en) | 1983-12-26 | 1992-05-07 | Daikin Ind Ltd | METHOD FOR PRODUCING HALOGEN-CONTAINING POLYATHERS |
JPS61233088A (en) * | 1985-04-08 | 1986-10-17 | Nippon Mektron Ltd | Synthetic oil composition |
US4675452A (en) | 1985-07-18 | 1987-06-23 | Lagow Richard J | Perfluorinated polyether fluids |
IT1214640B (en) * | 1985-11-20 | 1990-01-18 | Ausimont Spa | USE OF PERFLUOROPOLYETERS IN MECHANICAL PUMPS. |
JP2614740B2 (en) * | 1988-04-15 | 1997-05-28 | 日本メクトロン株式会社 | Stabilized perfluoropolyether composition |
IT1258831B (en) | 1992-01-30 | 1996-02-29 | Ausimont Spa | PROCESS TO REDUCE THE RE-BROADCASTING IN MECHANICAL PUMPS FOR THE GENERATION OF VACUUM, WORKING WITH PERFLUOROPOLYETHERIC OILS |
IT1256304B (en) | 1992-11-10 | 1995-11-30 | Ausimont Spa | PHOSPHAZEN DERIVATIVES AND THEIR USE AS PERFLUOROPOLETER-BASED STABILIZERS FOR OILS AND FATS |
ITMI20020281A1 (en) | 2002-02-14 | 2003-08-14 | Ausimont Spa | CYCLIC PHOSFAZENIC COMPOUNDS AND THEIR USE AS ADDITIVES OF PERFLUOROPOLYEREAL OILS |
ITMI20020804A1 (en) | 2002-04-17 | 2003-10-17 | Ausimont Spa | ADDITIVES FOR PERFLUOROPOLYEREAL OILS |
ITMI20030372A1 (en) | 2003-03-03 | 2004-09-04 | Solvay Solexis Spa | LINEAR PERFLUOROPOLYTERS WITH IMPROVED THERMO-OXIDATIVE STABILITY. |
ITMI20030992A1 (en) * | 2003-05-20 | 2004-11-21 | Solvay Solexis Spa | PERFLUOROPOLITEREI ADDITIVES. |
ITMI20042239A1 (en) * | 2004-11-19 | 2005-02-19 | Solvay Solexis Spa | ADDITIVES FOR FLUOROPOLIETERES |
ITMI20042238A1 (en) * | 2004-11-19 | 2005-02-19 | Solvay Solexis Spa | COMPOUNDS FOR FLUOROPOLIRTEREI |
ITMI20050646A1 (en) | 2005-04-14 | 2006-10-15 | Solvay Solexis Spa | ADDITIVES FOR FLUORINE OILS |
EP1873162A1 (en) * | 2006-06-29 | 2008-01-02 | Solvay Solexis S.p.A. | Cyclic phosphazene compounds |
-
2010
- 2010-10-01 CN CN2010800450732A patent/CN102762706A/en active Pending
- 2010-10-01 WO PCT/EP2010/064686 patent/WO2011042374A1/en active Application Filing
- 2010-10-01 JP JP2012532553A patent/JP5705860B2/en not_active Expired - Fee Related
- 2010-10-01 US US13/499,976 patent/US20120196780A1/en not_active Abandoned
- 2010-10-01 EP EP10759933A patent/EP2486114A1/en not_active Withdrawn
- 2010-10-05 TW TW099133876A patent/TW201124523A/en unknown
Non-Patent Citations (1)
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---|
See references of WO2011042374A1 * |
Also Published As
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JP5705860B2 (en) | 2015-04-22 |
CN102762706A (en) | 2012-10-31 |
TW201124523A (en) | 2011-07-16 |
JP2013506747A (en) | 2013-02-28 |
US20120196780A1 (en) | 2012-08-02 |
WO2011042374A1 (en) | 2011-04-14 |
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