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.
• 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 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.
• 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.) May 3, 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.
• branched perfluoropolyethers having formulae CF 3 (OCF(CF 3 )CF 2 ) m (OCF 2 ) m OCF 3 , wherein m/n is equal to or higher than 1000, and F(CF 2 CF(CF 3 )O) q CF 2 CF 3 .
• 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.) May 10, 2005 discloses linear perfluoropolyether oils comprising —CF 2 CF 2 O— and —CF 2 O— recurring units, statistically distributed along the perfluoropolyoxyalkylene chain, in a —CF 2 CF 2 O—/—CF 2 O— 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 —CF 2 CF 2 O—/—CF 2 O— 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.
• a lubricant composition comprising:
• 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.
• 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 R F ) of the non-functional (per)fluoropolyether oil (non-functional PFPE oil) of the invention typically comprises one or more recurring units R o 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 1 -C 6 (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 -C 6 (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.
• 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 R F ) 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 R F ) as defined above, wherein at least one of J, J′, K and K′ represents a C 1 -C 6 (per)fluoro(oxy)alkyl group.
• Suitable non-functional PFPE oils according to the invention include, notably, the followings:
• Said products can be produced as described in EP 1454938 B (SOLVAY SOLEXIS S.P.A.) Oct. 5, 2005.
• 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 U.S. Pat. No. 4,523,039 (THE UNIVERSITY OF TEXAS) Jun. 11, 1985.
• 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: —CH 2 CF 2 CF 2 O—, and optionally fluorinating and/or chlorinating said polyether, as detailed in EP 148482 B (DAIKIN INDUSTRIES LTD.) Mar. 25, 1992.
• Said products can be obtained by photooxidation of C 3 F 6 as described in CA 786877 (MONTEDISON S.P.A.) Jun. 4, 1968 and by subsequent conversion of the end groups as described in GB 1226566 (MONTECATINI EDISON S.P.A.) Mar. 31, 1971.
• Said products can be manufactured by photooxidation of a mixture of C 3 F 6 and C 2 F 4 and subsequent treatment with fluorine as described in U.S. Pat. No. 3,665,041 (MONTECATINI EDISON S.P.A.) May 23, 1972.
• Said products can be prepared by ionic hexafluoropropylene epoxide oligomerization and subsequent treatment with fluorine as described in U.S. Pat. No. 3,242,218 (E. I. DU PONT DE NEMOURS AND CO.) Mar. 22, 1966.
• Said products can be obtained by ionic telomerization of the hexafluoropropylene epoxide and subsequent photochemical dimerization as reported in U.S. Pat. No. 3,214,478 (E. I. DU PONT DE NEMOURS AND CO.) Oct. 26, 1965.
• 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.) Jan. 1, 1987.
• an 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:
• 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:
• n 10-60
• 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.
• 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 1 having general formula —(CF 2 ) j —CFK—O—, wherein K is selected from a fluorine atom and a C 1 -C 5 (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.
• the compound (P) complies with formula (I-A), (I-A bis) or (II-A) here below:
• the compound (P) complies with formula (I-B) or (II-B) here below:
• said recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain;
• the compound (P) of this second embodiment of the invention preferably complies with formula (I-B) or (II-B) here above, wherein R′′ f O— and R′′′ f O— are selected from:
• the compound (P) of this second embodiment of the invention more preferably complies with formula (I-B*) or (II-B*) here below:
• the compound (P) typically complies with formula (IV-C) here below:
• 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.
• compositions of the invention comprise one or more compounds (P) complying with either of formulae (III-B) or (III-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:
• the functional PFPE derivative of the invention more preferably complies with formula (VI) here below:
• Preferred lubricant compositions of the invention comprise one or more functional PFPE derivatives selected from:
• 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:
• 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;
• 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.
• 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.
• 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.
• 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 notably including one or more anti-rust additives, oxidation inhibitors, antifoam agents, anti-wear additives and anti-scuff additives.
• 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.
• 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.
• the non-functional PFPE oil (1) is a linear non-functional PFPE oil having formula CF 3 O—(CF 2 O) n (CF 2 CF 2 O) m (CF 2 CF 2 CF 2 O) r (CF 2 CF 2 CF 2 CF 2 O) s —CF 3 , wherein m, n, r and s are integers such that the number average molecular weight is about 11000, 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 CF 3 O—(CF 2 CF 2 O) m (CF 2 O) n —CF 3 , 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 CF 3 O—(CF 2 CF 2 O) m (CF 2 O) n —CF 3 , 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.
• the functional PFPE derivative (1) has formula (1)
• 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 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.
• V ( d ⁇ ⁇ 1 ) 2 ⁇ ( d ⁇ ⁇ 2 ) 2 ⁇ 3.14 64 ⁇ ⁇ R
• 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 0.5% by weight of non-functional PFPE oil (3) of compound (P1).
• 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).
• 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 1C 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 (1).
• 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).
• 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).
• a composition was prepared by mixing non-functional PFPE oil (2) with 3% by weight of non-functional PFPE oil (2) of compound (P1).
• 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 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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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

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• 2010
  • 2010-10-01 CN CN2010800450732A patent/CN102762706A/zh active Pending
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  • 2010-10-01 JP JP2012532553A patent/JP5705860B2/ja not_active Expired - Fee Related
  • 2010-10-01 US US13/499,976 patent/US20120196780A1/en not_active Abandoned
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