WO2017012909A1 - Agents anti-mousse - Google Patents

Agents anti-mousse Download PDF

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Publication number
WO2017012909A1
WO2017012909A1 PCT/EP2016/066486 EP2016066486W WO2017012909A1 WO 2017012909 A1 WO2017012909 A1 WO 2017012909A1 EP 2016066486 W EP2016066486 W EP 2016066486W WO 2017012909 A1 WO2017012909 A1 WO 2017012909A1
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group
chain
composition
polymer
equal
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Sara Rovinetti
Ugo De Patto
Marco Beltramin
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Solvay Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0418—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing P-atoms
    • 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
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/004—Foam inhibited 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/18—Anti-foaming property

Definitions

  • the present invention relates to the use of certain (per)fluoropolyether polymers as anti-foam agents in compositions based on hydrogenated or fluorinated oils.
  • PFPE Perfluoropolyether
  • foam control additives are conventionally used in industrial processes where foaming occurs.
  • Foam control additives include both anti-foams, i.e. chemical agents that are typically dispersed into the foaming solution to prevent the formation of excessive foam, and defoamers, i.e. substances that are sprayed over and rapidly collapse the existing foam.
  • PFPE polymer derivatives are known in the art.
  • US 2011/0015420 relates to a perfluoropolyether-modified polysiloxane, which attains a good defoaming effect for organic solvents.
  • PFPE comprising salified carboxylate chain ends
  • EP 0382224 A AUSIMONT S.R.L. discloses perfluoropolyethers having anti-rust properties, suitable for being used as components for lubricating greases or as antirust additives for lubricating oils and greases based on perfluoropolyethers.
  • this patent application only discloses PFPE comprising carboxylate chain ends salified with organic amine, notably morpholine, isobutylamine and triethanolamine.
  • metal salts of perfluorinated polyethers having at least one carboxylic acid end group have been disclosed in US 6638622 HITACHI GLOBAL STORAGE TECHNOLOGIES as anti-wetting and corrosion-protective agents for magnetic recording disks and magnetic recording heads.
  • said compounds are also referred to as ‘PFPE-COO - M + ’ wherein the PFPE is a perfluorinated polyether comprising monomers units having the structure -CF 2 O-, -CF 2 CF 2 O-, CF 2 CF 2 CF 2 O-, -CF(CF 3 )O-, -CF(CF 3 )CF 2 O- or a combination thereof and M + is the metal atom of the salt, preferably an alkali metal, e.g. sodium.
  • phase behaviour of perfluoropolyether carboxylates having sodium, potassium or ammonium counter-ions in water to examine the effect of the aqueous binary systems, in terms of hydration and counter-ion binding has been investigated by CABOI, F., et al, Counterion effect on the phase behaviour of perfluoropolyether carboxylates: micelles and liquid crystals in water, Colloids and Surface, 1999, 160, 47-56
  • Modern mechanical equipment such as a transmission, hydraulic, engine or gear all require a functional fluid to possess a number of different properties. These properties allow the equipment to operate in different harsh environments, including various regimes of soot/sludge formation, friction, corrosion, thermal decomposition, oxidation, extreme pressure and wear.
  • the different properties of the functional fluids are unique to a component of the mechanical equipment. This unique properties may depend on chemical interactions between additives, component design, as well as the materials used. Consequently, a number of functional fluids are required to lubricate various components within the mechanical equipment.
  • Functional fluids are known in the art as compositions comprising at least one oil in admixture with a further ingredient that is selected on the basis of the use intended for the specific functional fluid.
  • functional fluids suffer of a number of disadvantages, including notably the formation of foam, which has become more important in the last years, because of the diffusion of functional fluids having low and very low viscosity for energy saving.
  • US 7098173 GENERAL MOTORS CORPORATION relates to an anti-foam composition to be used in automatic transmission fluids (ATF), said composition comprising perfluoropolyether compounds.
  • ATF automatic transmission fluids
  • US 2004/0121921 GENERAL MOTORS CORPORATION relates to a functional fluid comprising (a) a lubricating oil, (b) an antiwear agent and (c) an antifoam composition comprising a perfluoropolyether compound.
  • suitable PFPE compounds have the following formulae: R 1 -(CF(CF 3 )-CF 2 -O-) n -R 2 R 1 -(CF 2 -CF 2 -CF 2 -O-) n -R 2 R 1 -(CF 2 -CF 2 -O-) n -(CF 2 -O-) m -R 2 R 1 -(CF 2 -CF(CF 3 )-O-) n -(CF 2 -O-) m -R 2 wherein R 1 and R 2 are functional or non-functional end groups. Among functional end groups, amide, alkoxy, silane, phosphate, carboxyl and -CF 2 -CH 2 (OCH 2 CH 2 ) p OH wherein p is from about 1 to about 20 are listed.
  • compositions containing (per)fluoropolyether polymers having two chain ends and comprising at one or both chain ends a carboxylic group in its acid form or in its salt form with monovalent organic and/or inorganic cations have been disclosed in EP 1681339 A SOLVAY SOLEXIS S.P.A. , EP 2025731 A SOLVAY SOLEXIS S.P.A. , EP 0435062 A AUSIMONT S.P.A. and US 5211861 AUSIMONT S.P.A. .
  • (per)fluoropolyether polymers comprising at least one acid end group salified with organic or inorganic counter-ions can be used as anti-foam additives in neutral PFPE and functional fluids.
  • the present invention relates to the use of a (per)fluoropolyether polymer [polymer (P)] as anti-foam agent, said polymer (P) comprising a (per)fluoropolyether chain [chain (R pf )] having two chain ends, wherein at least one chain end comprises at least one anionic group [group -A - ] selected from the group comprising, preferably consisting of, carboxylate, sulphate and phosphate, and a cationic group [group C + ] selected from the group comprising, preferably consisting of, monovalent and divalent inorganic cations and onium compounds.
  • said polymer (P) is used as anti-foam agent for neutral (per)fluoropolyether polymers [neutral PFPE].
  • said polymer (P) is used as anti-foam agent in a functional fluid composition comprising at least one hydrogenated oil.
  • the present invention relates to a method for reducing the formation of foam in a composition comprising at least one neutral PFPE [composition (C)] or in a functional fluid composition [composition (C*)], said method comprising - providing a composition (C) comprising at least on neutral PFPE and adding at least one polymer (P) to said composition (C), wherein said polymer (P 1 ) comprises chain (R pf ) as defined above for polymer (P) having two chain ends, wherein at least one chain end comprises at least one group (-A - ) as defined above for polymer (P), and a cationic group [group C + ] selected from the group comprising, preferably consisting of, monovalent inorganic cations and onium compounds; or - providing a composition (C*) comprising at least one hydrogenated oil, and adding at least one polymer (P) to said composition (C*), wherein said polymer (P 2 ) comprises a chain (R pf ) as defined
  • PFPE perfluoropolyether
  • (per)fluoropolyether is intended to indicate (per)fluoropolyether and, when used as substantive, is intended to mean either the singular or the plural from, depending on the context
  • (per)fluoropolyether is intended to indicate a fully or partially fluorinated polyether and the prefix "(per)” means that the polyether can be fully or partially fluorinated
  • neutral PFPE is intended to indicate PFPE having chain ends comprising neutral groups, such as groups comprising for example (perhalo)alkyl chains
  • - the expression “functional fluid composition” is intended to indicate a fluid composition comprising at least one hydrogenated oil in admixture with a further ingredient that is selected on the basis of the intended use, such as for example metal working fluids, such as cutting oils and coolants; engine oils; gear lubricants; hydraulic fluids; automatic transmission fluids; paint
  • said chain (R pf ) is a chain of formula -(CFX) a O(R f )(CFX') b - wherein a and b, equal or different from each other, are equal to or higher than 1, preferably from 1 to 10, more preferably from 1 to 3; X and X', equal or different from each other, are -F or -CF 3 , provided that when a and/or b are higher than 1, X and X’ are -F; (R f ) comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of: (i) -CFXO-, wherein X is F or CF 3 ; (ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is –F; (iii) -CF 2 CF 2 CW 2 O-
  • chain (R f ) complies with the following formula: (R f -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF 2 CF 2 CF 2 O) g3 (CF 2 CF 2 CF 2 O) g4 ]- wherein - X 1 is independently selected from -F and -CF 3 , - X 2 , X 3 , equal or different from each other and at each occurrence, are independently -F, -CF 3 , with the proviso that at least one of X is -F; - g1, g2 , g3, and g4, equal or different from each other, are independently integers ⁇ 0, such that g1+g2+g3+g4 is in the range from 2 to 300, preferably from 2 to 100; should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed
  • chain (R f ) is selected from chains of formula: (R f -IIA) -[(CF 2 CF 2 O) a1 (CF 2 O) a2 ]- wherein: - a1 and a2 are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10; (R f -IIB) -[(CF 2 CF 2 O) b1 (CF 2 O) b2 (CF(CF 3 )O) b3 (CF 2 CF(CF 3 )O) b4 ]- wherein: b1, b2, b3, b4, are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably b1 is 0, b2, b3, b4 are
  • chain (R f ) complies with formula (R f -III): (R f -III) -[(CF 2 O) f1 (CF(CF 3 )O) f2 (CF 2 CF(CF 3 )O) f3 ]- wherein: f1, f2 and f3 are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000.
  • said group (A - ) is selected from carboxylate and phosphate. More preferably, said group (A - ) is carboxylate.
  • said monovalent inorganic counter-ion is an alkaline metal, more preferably Li + , Na + , K + , Cs + .
  • said divalent cations are selected in the group comprising, more preferably consisting of, alkaline earth metals such as Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ; and transition metals such as Zn 2+ , Cu 2+ , Mn 2+ , Ni 2+ . More preferably, said divalent cations are selected from Mg 2+ , Ca 2+ , Zn 2+ and Cu 2+.
  • said onium compounds are selected in the group comprising, preferably consisting of, quaternary ammonium cations, quaternary pyridinium cations and quaternary phosphonium cations.
  • said onium compound is an ammonium cation, even more preferably an alkyl-ammonium cation. More preferably, it is selected in the group comprising tetrabutylammonium, tetrapropylammonium, tetraethylammonium, tetramethylammonium.
  • said group (A - ) is bonded to said chain (R pf ) through a bridging group [group (B)], said group (B) being a sigma bond or a linear or branched alkylene chain comprising from 1 to 6 carbon atoms, optionally interrupted by at least one heteroatom, preferably an oxygen atom. More preferably, said group (B) is a sigma bond or a linear or branched alkylene chain comprising from 1 to 3 carbon atom and interrupted by at least one oxygen atom. Even more preferably, said group (B) is a sigma bond or a chain of formula -CH 2 -O-CH 2 -.
  • said polymer (P) comprises one chain end comprising said group (A - ) and said group (C + ), the other chain end bearing a neutral terminal group (T).
  • said group (T) is selected in the group comprising -H, -F, -Cl, -(O)CF 3 , a straight or branched (perhalo)alkyl group, more preferably perfluoroalkyl group, comprising from 1 to 3 carbon atoms.
  • the abovementioned polymer (P) allows to reduce entrained air and hence bubbles formation, thus improving the air release properties of the neutral PFPE or of the functional fluid.
  • Polymer (P) according to the present invention can be advantageously prepared according to methods known in the art, for example as disclosed in US 4814372 AUSIMONT S.P.A. and in EP 2004722 A SOLVAY SOLEXIS S.P.A. .
  • polymer (P 1 ) comprising chain (R pf ) as defined above for polymer (P) having two chain ends, wherein at least one chain end comprises at least one group (-A - ) as defined above for polymer (P), and a cationic group [group C + ] selected from the group consisting of, monovalent inorganic cations and onium compounds is particularly useful as anti-foam agent in oils based on neutral PFPEs.
  • said neutral PFPE oils have a kinematic viscosity equal to or higher than 10 cSt at 20°C, more preferably of from 30 to 5000 cSt at 20°C, and even more preferably of from 50 to 1000 cSt at 20°C, measured according to ASTM D445.
  • Neutral PFPE oils are preferably selected from the following groups: (1) B-O-[CF(CF 3 )CF 2 O] b1' (CFXO) b2' -B' wherein: - X is equal to -F or -CF 3 ; - B and B', equal to or different from each other, are selected from -CF 3 , -C 2 F 5 or -C 3 F 7 ; - b1' and b2', equal or different from each other, are independently integers ⁇ 0 selected such that the b1'/b2' ratio is comprised between 20 and 1,000 and b1’+b2’ is in the range 5 to 250; should b1’ and b2’ be both different from zero, the different recurring units are generally statistically distributed along the chain.
  • Said products can be obtained by photooxidation of the hexafluoropropylene as described in CA 786877 MONTEDISON S.P.A. 19680406 , and by subsequent conversion of the end groups as described in GB 1226566 MONTECATINI EDISON S.P.A.
  • compositions (C) suitable for the purposes of the invention are lubricant compositions comprising PFPE oils of formulae (1), (4) and (5) cited above.
  • compositions (C) suitable for the purposes of the invention comprise notably: - lubricants commercially available under the trade name FOMBLIN ® (type Y, M, W, or Z) from Solvay Specialty Polymers Italy, S.p.A..
  • Lubricants of this family generally comprise at least one oil (i.e. only one or mixture of more than one oil) complying with either of formulae here below: wherein m/n is preferably from 20 to 10000, more preferably from 30 to 5000; and p/q is preferably 0.1/10, more preferably 0.2/5 and even more preferably 0.5/1.5.
  • said composition (C) or said composition (C*) is a lubricant composition, which can be used for example as metal working fluids, such as cutting oils and coolants; engine oils; gear lubricants; hydraulic fluids; automatic transmission fluids; paints coating and inks; compositions for paper industry, oil recovery, construction industry, jet dyeing of textiles, leather processing, chemical processing.
  • metal working fluids such as cutting oils and coolants; engine oils; gear lubricants; hydraulic fluids; automatic transmission fluids; paints coating and inks; compositions for paper industry, oil recovery, construction industry, jet dyeing of textiles, leather processing, chemical processing.
  • said composition (C) comprises the neutral PFPE as the main component, preferably in an amount of at least 60 wt.%, more preferably at least 80 wt %, even more preferably at least 85 wt % based on the total weight of the composition.
  • polymer (P 2 ) comprising a chain (R pf ) as defined above for polymer (P) having two chain ends, wherein at least one chain end comprises at least one group (-A - ) as defined above for polymer (P), and a cationic group [group C + ] selected from the group comprising, preferably consisting of, monovalent and divalent inorganic cations and onium compounds, is particularly useful as anti-foam agent in hydrogenated oils and notably functional fluids.
  • said composition (C*) comprises at least one hydrogenated base oil, which is preferably a mineral oil or a synthetic oil, such as polyalphaolefins (PAO) and PAGs; esters; silicon oils; polyphenylethers; etc.
  • a hydrogenated base oil which is preferably a mineral oil or a synthetic oil, such as polyalphaolefins (PAO) and PAGs; esters; silicon oils; polyphenylethers; etc.
  • Said at least one hydrogenated base oil can be in admixture with different hydrogenated base oils or with water.
  • the composition (C*) is in the form of a water-in-oil emulsion.
  • said composition (C*) comprises the hydrogenated base oil(s) as the main component, preferably in an amount of at least 60 wt.%, more preferably at least 80 wt %, even more preferably at least 85 wt % based on the total weight of the composition.
  • composition (C) and said composition (C*) can comprise further additives, such as for example antirust agents, antioxidants, thermal stabilizers, pour-point depressants, antiwear agents, including those for high pressures, dispersants, tracers, dyestuffs and fillers.
  • additives such as for example antirust agents, antioxidants, thermal stabilizers, pour-point depressants, antiwear agents, including those for high pressures, dispersants, tracers, dyestuffs and fillers.
  • dispersants are for example surfactants, preferably non-ionic surfactants, more preferably (per)fluoropolyether surfactants and (per)fluoroalkyl surfactants.
  • fillers examples include organic fillers such as polytetrafluoroethylene (PTFE) and inorganic fillers such as silica and talc.
  • PTFE polytetrafluoroethylene
  • inorganic fillers such as silica and talc.
  • compositions (C) or the composition (C*) are essentially made of the said neutral PFPE in combination with an amount of up to 1 % wt of any of the additives listed above are also encompassed by the present invention.
  • polymer (P) according to the present invention can be added to said composition (C) or to said composition (C*) in an amount of from 0.0001 wt.% (1ppm) to 10 wt.% based on the total weight of said composition,
  • polymer (P 1 ) is added to composition (C) in an amount of from 0.05 to 8 wt.% and even more preferably from 1 to 5.5 wt.%.
  • polymer (P 2 ) is added to composition (C*) in an amount of from 0.0001 wt.% (1 ppm) to 10 wt.% based on the total weight of said composition (C), more preferably, from 0.0005 wt.% (5 ppm) to 5 wt.% and even more preferably from 0.001 wt.% (10 ppm) to 1 wt.%.
  • polymer (P) is added to said composition (C) or to said composition (C*) and then a mixing step is performed, for example by high shear mixing.
  • composition (C # ) comprising at least one neutral PFPE oil, at least one polymer (P 1 ) as defined above and optionally further additives, as defined above.
  • said composition (C # ) comprises the neutral PFPE as the main component, i.e. from 60 to 99.9999 wt.% based on the total weight of the composition, more preferably from 70 to 99.95 wt.% and even more preferably from 90 to 99 wt.%.
  • said composition (C # ) comprises polymer (P 1 ) in an amount of from 0.0001 wt.% (1ppm) to 10 wt.% based on the total weight of said composition, more preferably from 0.05 to 8 wt.% and even more preferably from 1 to 5.5 wt.%.
  • said composition (C # ) comprises the further additives in an amount of from 0.1 to 30 wt.% based on the total weight of the composition.
  • composition (C $ ) comprising at least one hydrogenated base oil as defined above, at least one polymer (P 2 ) as defined above and optionally further additives.
  • said composition (C $ ) comprises the hydrogenated base oil(s) as the main component, i.e. from 60 to 99.9999 wt.% based on the total weight of the composition, more preferably from 70 to 99.9995 wt.% and even more preferably from 90 to 99.999 wt.%.
  • said composition (C $ ) comprises said polymer (P 2 ) in an amount of from 0.0001 wt.% (1 ppm) to 10 wt.% based on the total weight of said composition (C), more preferably, from 0.0005 wt.% (5 ppm) to 5 wt.% and even more preferably from 0.001 wt.% (10 ppm) to 1 wt.%.
  • said composition (C $ ) comprises the further additives in an amount of from 0.1 to 30 wt.% based on the total weight of the composition.
  • Base oils 1 to 3 and polymers A to C were obtained by Solvay Specialty Polymers Italy S.p.A.
  • Base oil 1 Fomblin ® M30 PFPE – linear PFPE oil having chemical formula CF 3 -[(CF 2 CF 2 O) p -(CF 2 O) q ]-CF 3 with p/q between 0.9 and 1 average molecular weight about 16,000 Da kinematic viscosity (measured according to ASTM D445): 280 cSt at 20°C, 45 cSt at 100°C viscosity index (measured according to ASTM S2270): 338
  • Base oil 2 Fomblin ® M60 PFPE – linear PFPE oil having chemical formula CF 3 -[(CF 2 CF 2 O) p -(CF 2 O) q ]-CF 3 with p/q between 0.9 and 1 average molecular weight 18,700 Da kinematic viscosity (measured according to ASTM D445): 550 cSt at 20°C, 86 cSt at 100°C viscosity index (measured according to ASTM S2270): 343
  • Polymer A branched mono-carboxylic acid PFPE having general formula T(CF 2 O) m (CF 2 CF(CF 3 )O) s (CF(CF 3 )O) p CF 2 T’ and average molecular weight (Mn) about 3,300 Da.
  • Polymer B branched mono-carboxylic acid PFPE having general formula T(CF 2 O) m (CF 2 CF(CF 3 )O) s (CF(CF 3 )O) p CF 2 T’ and average molecular weight (Mn) about 2,200 Da.
  • Polymer C branched mono-carboxylic acid PFPE having general formula T(CF 2 O) m (CF 2 CF(CF 3 )O) s (CF(CF 3 )O) p CF 2 T’ and average molecular weight (Mn) about 1,300 Da.
  • Polymer P-I PFPE carboxylate monofunctional salt of potassium, having the following structure: CF 3 O(CF 2 CF(CF 3 )O) p (CF 2 O) q CF 2 COO - K + average molecular weight (Mn) about 3,500 Da by NMR analysis.
  • Polymer P-II Commercial Fomblin ® DA305 PFPE obtained from Solvay Specialty Polymers Italy S.p.A - monofunctional carboxylic acid having the following structure: CF 3 O(CF 2 CF(CF 3 )O) p (CF 2 O) q CF 2 COOH average molecular weight (Mn) about 3,500 Da by NMR analysis.
  • This test method is used to determine the foaming characteristics of lubricating oils at 24°C and 93.5°C.
  • the test consists of three sequences performed at different temperatures. A portion of lubricants is aerated by the use of a gas diffuser with air at a flow rate of 94 ⁇ 5 ml/minute (corresponding to 5.64 l /h) at the test temperature of 24°C (Sequence I). The sample is aerated for 5 minutes and the amount of foam generated after disconnecting the gas diffuser is reported. At the end of a 10 minutes settling time, the amount of foam left is recorded. The test is repeated for fresh sample at 93.5°C (Sequence II), and then, after collapsing the foam, at 24°C (Sequence III).
  • Formulations with good antifoaming performances show sequence foam results in the range of 0 ml/0 ml, and the maximum foam tolerated is 50 ml/0 ml.
  • Magnesium salts were prepared following a procedure similar to that described for calcium salts using MgO instead of CaO, in the same mol amount.
  • Triethanolamine (TEA) salts were prepared following the procedure disclosed in EP 0382224 cited above. TEA salts are representative of EP 0 382 224 cited above.
  • TSA tetrabutylammonium
  • Each base oil 1, 2 and 3 was added with a PFPE carboxylate comprising monovalent organic and inorganic counter-ions, in the concentration as listed in the following Table 1.
  • compositions were then submitted to the test for the evaluation of foam formation, according to ASTM D892.
  • Base oils 1, 2 and 3 were submitted to the test for the evaluation of foam formation, according to ASTM D892.
  • base oils 1 to 3 were added with PFPE carboxylate comprising divalent organic and inorganic counter-ions, in the concentrations listed in the following Table 1. These compositions were also submitted to the test for the evaluation of foam formation, according to ASTM D892.
  • RENOLIN was left aging for more than 2 years.
  • the antifoaming properties of the aged oil were evaluated according to ASTM D892 standard method Sequence I (at 24°C). This result are reported in Table 1.
  • the foam volume was 520/250 ml, indicating that probably the antifoaming agent was separated from the composition and loosed its effectiveness.
  • RENOLIN was formulated by adding 50 ppm of polymer P-I.
  • RENOLIN was formulated by adding 100 ppm of polymer P-II.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne l'utilisation de certains polymères de (per)fluoropolyéther comme agents anti-mousse dans des compositions à base d'huiles hydrogénées ou fluorées.
PCT/EP2016/066486 2015-07-17 2016-07-12 Agents anti-mousse Ceased WO2017012909A1 (fr)

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Application Number Priority Date Filing Date Title
EP15177367.8 2015-07-17
EP15177367 2015-07-17
EP15177365 2015-07-17
EP15177365.2 2015-07-17

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018185026A1 (fr) * 2017-04-03 2018-10-11 Solvay Specialty Polymers Italy S.P.A. Compositions de fluide de travail
CN110898467A (zh) * 2019-12-05 2020-03-24 浙江新安化工集团股份有限公司 消泡活性物、其制备方法及消泡剂
WO2024149801A1 (fr) * 2023-01-12 2024-07-18 Solvay Specialty Polymers Italy S.P.A. Composition comprenant des polymères de (per)fluoropolyéther
WO2024149802A1 (fr) * 2023-01-12 2024-07-18 Solvay Specialty Polymers Italy S.P.A. Polymères de perfluoropolyéther

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018185026A1 (fr) * 2017-04-03 2018-10-11 Solvay Specialty Polymers Italy S.P.A. Compositions de fluide de travail
JP2020515697A (ja) * 2017-04-03 2020-05-28 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． 作動流体組成物
CN110898467A (zh) * 2019-12-05 2020-03-24 浙江新安化工集团股份有限公司 消泡活性物、其制备方法及消泡剂
WO2024149801A1 (fr) * 2023-01-12 2024-07-18 Solvay Specialty Polymers Italy S.P.A. Composition comprenant des polymères de (per)fluoropolyéther
WO2024149802A1 (fr) * 2023-01-12 2024-07-18 Solvay Specialty Polymers Italy S.P.A. Polymères de perfluoropolyéther

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