WO2018172172A1 - Polymères fluorés et leurs utilisations - Google Patents

Polymères fluorés et leurs utilisations Download PDF

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WO2018172172A1
WO2018172172A1 PCT/EP2018/056493 EP2018056493W WO2018172172A1 WO 2018172172 A1 WO2018172172 A1 WO 2018172172A1 EP 2018056493 W EP2018056493 W EP 2018056493W WO 2018172172 A1 WO2018172172 A1 WO 2018172172A1
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group
polymer
chain
formula
different
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PCT/EP2018/056493
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Claudio Adolfo Pietro Tonelli
Ivan Diego WLASSICS
Giuseppe Marchionni
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2018172172A1 publication Critical patent/WO2018172172A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33379—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group
    • C08G65/33386—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic
    • C08G65/33389—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present invention relates to fluorinated polymers, in particular to
  • Lubricating oils and greases based on (per)fluoropolyethers are usually endowed with high thermal stability; however, when they are heated for prolonged times at temperatures higher than 230°C, partial or total degradation of the polymer chain and formation of volatile compounds occurs; this degradation is usually accompanied by the formation of Lewis acids, due to corrosion of the metallic parts in contact with the lubricant and Lewis acids further increase lubricant degradation.
  • additives may be used, which are typically chosen from fluorinated polymers bearing at one or both ends of the polymer chain non fluorinated aromatic groups that may contain heteroatoms, such as nitrogen and phosphorus.
  • non-fluorinated end groups are linked to the polymer chain through moieties like -CH2OCH2-, -CH2(OCH2CH2)mO-, - C(0)O- and -C(O)N(R), which undergo degradation under severe conditions.
  • these additives undergo phase separation upon storage at room temperature.
  • compositions to be used as lubricants or lubricant additives which comprise mono- and/or ⁇ /-functional aryl perfluoropolyethers.
  • Rf and Rf 1 are respectively a monovalent or divalent straight or branched (per)fluoropolyether chain having formula weight from about 400 to 15,000:
  • Y is a divalent radical selected from a group which comprises, inter alia, - CH2O- and -CF2-;
  • a is 0 or 1 ;
  • (O-CtR 1 ( U +v))b is a divalent aryloxy group
  • R is selected from a group comprising hydrogen and nitro groups, but it cannot be solely hydrogen or nitro or combinations thereof;
  • each R 1 is selected from a group which comprises hydrogen and nitro groups
  • t is equal to 6 + u
  • u is any combinations of 0, 2, 4, 6, 8, 10, 12, 14, 16;
  • v is independently 2 or 4;
  • b is 0-5.
  • All eighteen examples of this prior art document relate to the synthesis of monofunctional aryl derivatives of branched (per)fluoropolyethers comprising (OCF(CF3)CF2) units wherein an aryl group (namely a phenyl group) or an aryloxyaryl (namely a phenoxyphenyl) group is linked to the Rf chain via a -CF2- moiety.
  • Examples 7 and 8 relate to phenoxyphenyl derivatives and example 8 in particular discloses the preparation of a nitrodiphenyl ether derivative by nitration of the diphenylether derivative of example 7, whereby a nitro group is inserted on the phenoxy group.
  • R 1 is, inter alia, perfluoroalkoxy
  • Rf is a perfluoroalkyl chain from 2 to 10 carbon atoms
  • Ar is, inter alia, a biphenyl radical and R 2 is, inter alia, a nitro group.
  • the lubricants of formula R 1 -Rf-O-Ar-R 2 can be manufactured according to a procedure comprising the base-catalysed addition of hydroxy-substituted aryl compounds to terminal perfluoroolefins. This document does not contain any hint or suggestion that would have prompted a skilled person to replace the perfluoroalkyl chain Rf with a (per)fluoropolyether chain and to select aromatic moieties comprising two aromatic rings linked together via a ketone or sulfone group.
  • R is a perfluoroalkyl radical or Z-(Y) n -CFX-;
  • Q is a perfluoroalkyl polyether chain or a fluoroalkyl polyether chain
  • X is fluorine or trifluoromethyl
  • Y is a linking divalent radical which comprises -CH2O- and -CF2-;
  • n 0 or 1 ;
  • Z can be an aromatic radical containing 6 to 10 carbon atoms and optionally substituted with one or more nitro groups.
  • the sole specifically disclosed compound wherein Z bears a nitro group are those of examples 1 and 3, in which Z is p-nitrophenyl.
  • WO 2013/120827 discloses (per)fluoropolyether compounds comprising a (per)fluoropolyether chain (Rf) having two chain ends, wherein at least one of said chain ends have a bh ' or fer-phenyl group bearing at least one nitro group and, optionally, one or more further substituents, wherein the two or three phenyl groups are linked each other via a sigma bond.
  • polymer (P) according to the present invention can be manufactured via a very convenient and easy synthetic process that comprises a step [step (I)] of contacting
  • Mw weight average molecular weight
  • polymers (P*) comprising one (per)fluoropolyether chain (R P f) and at least one group (A) as defined above.
  • said polymer (P*) can be used as additives for fluorinated oils and greases, notably as stabilizers against thermooxidation.
  • polymers (P**) comprising at least two (per)fluoropolyether chains (R P f) and at least three groups (A) as defined above.
  • said polymer (P**) can be used as oil, without the need of being added with additives, such as notably thermal-stabilizers, anti-corrosion or anti rust additives, which could give raise to separation after exposure at harsh environment, at high temperatures and in the presence of metals and Lewis acids.
  • additives such as notably thermal-stabilizers, anti-corrosion or anti rust additives, which could give raise to separation after exposure at harsh environment, at high temperatures and in the presence of metals and Lewis acids.
  • said polymer (P**) can be also used as additive for fluorinated oils and greases having different chemical formula, notably for perfluoropolyether polymers.
  • group(s) (A) is(are) responsible for the stabilizing properties, in particular due to the presence of the electro-withdrawing substituent (i.e., the nitro group).
  • PFPE perfluoropolyether
  • (per)fluoropolyether is intended to indicate fully or partially fluorinated polymer
  • strong non-nucleophilic base is intended to indicate a base that does not act as a nucleophile, for example because of its steric hindrance (also referred to as steric bulky);
  • said chain (R pf ) is a chain of formula -(CFX) a O(Rf)(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 -CF3,
  • Rf comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
  • a and b equal or different from each other, are from 1 to 10, even more preferably from 1 to 3.
  • chain (Rf) complies with the following formula:
  • - X 1 is independently selected from -F and -CF3,
  • - X 2 , X 3 are independently -F, -CF3, 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 along the chain.
  • chain (Rf) is selected from chains of formula:
  • - 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 (as determined by NMR).; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10;
  • 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 (as determined by NMR); preferably b1 is 0, b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1 ; (Rf-IIC) -[(CF2CF2O)ci (CF2O)c2(CF2(CF2)cwCF 2 O)c3]- wherein:
  • c1 , c2, and c3 are independently integers ⁇ 0 chosen so that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000 (as determined by NMR); preferably d , c2 and c3 are all > 0, with the ratio c3/(c1 +c2) being generally lower than 0.2;
  • d is an integer > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000 (as determined by NMR);
  • Hal * is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
  • chain (Rf) complies with formula (Rf-lll) here below:
  • - a1 , and a2 are integers > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000 (as determined by NMR), with the ratio a1/a2 being generally comprised between 0.1 and 10, more preferably between 0.2 and 5.
  • said chain (R P f) is linked to said at least one group (A) via a linking group [group (L)].
  • said group (L) is a divalent alkyl chain comprising from 1 to 20, more preferably from 1 to 10, carbon atoms and at least one oxygen atom.
  • said group (L) is a chain of formula -CH2O- or -
  • Said at least one group (A) can be a monovalent group or a divalent group. Without being bounded by any theory, monovalent group (A) is typically a group located at the end of the polymeric chain, while divalent group (A) typically links two chains (R P f).
  • said monovalent group (A) complies with the following formula
  • SN is selected from halogen atom, triflate, nonaflate and group -OR1 , wherein R1 is an optionally halogenated, more preferably optionally fluorinated, alkyl chain comprising from 1 to 6 carbon atoms;
  • w and x are, each independently, zero or 1 ;
  • LN is halogen atom selected from fluorine or chlorine, even more preferably fluorine, or -OR1 , wherein R1 is a partially fluorinated alkyl chain comprising from 1 to 3 carbon atoms.
  • said monovalent group (A) complies with the following formulae (A-l-i) to (A-l-vi):
  • said divalent group (A) complies with the following formula (A- II):
  • T and w have the same meanings as in formula (A-l) and
  • each symbol * indicates the bond with one group (L) as defined above.
  • said divalent group (A) complies with the following
  • polymer (P * ) is mono-functional, i.e. it comprises one chain (R P f) having two chain ends, wherein one chain end comprises said monovalent group (A-l) as defined above, and the other chain end comprises a (per)fluorinated alkyl group comprising from 1 to 3 carbon atoms.
  • polymer (P*) is bi-functional, i.e. it comprises one chain one chain (R P f) having two chain ends, wherein both chain ends comprise said monovalent group (A-l) as defined above.
  • said polymer (P**) comprises at least two chains (R P f) each having two chain ends, wherein said chains (R P f) are linked together at one chain ends by one divalent group (A) as defined above and said chains (R P f) bear on the other chain end one monovalent group (A) as defined above.
  • said polymer (P**) complies with the following general formula:
  • each (A*) is a group of formula (A-l) as defined above,
  • each L corresponds to group (L) as defined above,
  • z is an integer from 1 to 10.
  • polymer (POH) is a (per)fluoropolyether polymer comprising one chain (R P f) as defined above for polymer (P) having two chain ends, wherein at least one chain end bears one hydroxy group.
  • said polymer (POH) comprises one chain (R P f) as described above for polymer (P).
  • said polymer (POH) comprises one chain (R P f) having two chain ends, wherein at least one chain end bears one hydroxy group.
  • both chain ends of said chain (R P f) bear one hydroxy group.
  • said at least one group (LN) is selected from halogen atom, triflate and nonaflate. More preferably, said group (LN) is a halogen atom selected from fluorine or chlorine. Fluorine is particularly preferred.
  • said compound (A) bears two groups (LN), as defined above.
  • said compound (A) complies with the following chemical formula ( ⁇ ⁇ ):
  • LN has the same meanings defined above for group (LN);
  • w and x are, each independently, zero or 1.
  • Said compound (A) can be contacted with said polymer (POH) as such, or it can be first dissolved in an optionally fluorinated inorganic aprotic solvent
  • Said solvent (S) is preferably selected in the group comprising
  • halogenated solvents such as fluorinated solvents.
  • Suitable examples of fluorinated solvents are halogenated
  • hydrocarbons hexafluoroxylene, chlorotrifluorotoluene, trifluorotoluene, hexafluorobenzene and mixtures thereof.
  • step (I) is performed in the
  • a strong non-nucleophilic base which is preferably selected from elements belonging to Group la of the periodic table, such as sodium and potassium metals; bulky alcoholates, such as potassium tert- butanolate and potassium neopentanolate; and bulky amines, such as 1 ,8- diazabiciclo[5.4.0]undec-7-ene (DBU).
  • a strong non-nucleophilic base which is preferably selected from elements belonging to Group la of the periodic table, such as sodium and potassium metals; bulky alcoholates, such as potassium tert- butanolate and potassium neopentanolate; and bulky amines, such as 1 ,8- diazabiciclo[5.4.0]undec-7-ene (DBU).
  • said step (I) is performed in the presence of a molar excess of said base compared to the molar amount of the polymer (POH).
  • said step (I) is performed under heating. More preferably, heating is performed at a temperature of from 40°C up to the reflux temperature of the base used in the reaction.
  • Polymers (P) of the present invention are endowed with lubricant
  • a further object of the present invention is represented by lubricant compositions in the form of greases or oils comprising at least one polymer (P) according to the present invention.
  • oils are compounds having kinematic
  • viscosity ASTM D445
  • suitable thickeners such as polytetrafluoroethylene (PTFE) or inorganic compounds, e.g. talc.
  • the lubricant compositions according to the present invention will have a kinematic viscosity in the above mentioned conditions of 30 to 3,000 cSt, preferably from 50 to 500 cSt, when determined at 20°C according to ASTM D445.
  • compositions (C1 )] containing at least one polymer (P), even more preferably at least one polymer (P * ) as defined above, as thermal stabilizers, comprise (preferably consist of):
  • Said composition (C1 ) can optionally contain further ingredients.
  • Suitable further ingredients are selected from thickening agents, preferably in an amount ranging from 1 % to 30% wt. based on the total weight of said composition (C1 ) and further additives, each additive being used in an amount ranging from 1 % to 5% wt based on the total weight of said composition (C1 ).
  • Base oils may be fluorinated or non-fluorinated (hydrogenated) oils or mixtures thereof.
  • fluorinated oils are (per)fluoropolyether oils; examples of (per)fluoropolyether oils (iii) suitable for the preparation of the compositions (C1) are those identified as formulae (1 a) - (8a) in EP 2089443 A (SOVLAY SOELXIS S.P.A.) or as formulae (1 ) - (8) in WO 2009/141284 (SOLVAY SOLEXIS S.P.A.) or as formulae (1 ) to (9) in WO 201 1/042374 (SOLVAY SOLEXIS S.P.A.) . More preferably, the
  • (per)fluoropolyether oils are those commercially available under the trade name FOMBLIN ® (type Y, M, W, or Z) from Solvay Specialty Polymers Italy S.p.A.; such oils generally comprise at least one oil (i.e. only one or mixture of more than one oil) complying with either of formulae herein after:
  • One or more polymer (P ** ) according to the present invention different from the one using as ingredient (i) can also be used as fluorinated base oil (ii) in compositions (C1 ); for example, if one polymer (P * ) is used as ingredient (i), one or more polymer (P ** ) can be used as ingredient (ii).
  • Suitable non fluorinated oils to be used as base oils in compositions (C1 ) are preferably selected from mineral, paraffinic, aromatic oils,
  • polyalphaolefins alkyl esters, silicone esters, naphthalene derivatives, polyalkylated cycloalkanes, polyphenylethers.
  • compositions in the form of greases [compositions (C2)] containing at least one polymer (P) according to the invention comprise (preferably consists of):
  • thickening agents examples include PTFE, talc, silica, boron
  • PTFE nitride, polyurea, alkali or alkali-earth metals terephthalate, calcium and lithium soaps and complexes thereof; among them, PTFE is preferred.
  • suitable additives are antirust agents, antioxidants, thermal stabilizers, pour point depressants, anti-wear agents, including those for high pressures, dispersants, tracers, dyestuffs, talc and inorganic fillers.
  • dispersants are, for example, surfactants, preferably non- ionic surfactants, more preferably (per)fluoropolyether surfactants and (per)fluoroalkyl surfactants.
  • anti-wear additives are examples of suitable additives.
  • the present invention relates to a method for thermo-stabilizing fluorinated oils and greases, said method comprising contacting said fluorinated oil and grease with at least one polymer (P) as defined in the present invention.
  • the mechanical stirrer was turned on to about 300 rpm, the (PFPE-I) was heated to 45°C and a 9,56 w/v solution of tBuOK tBuOH (795 ml; 677 mmol tBuOK) was dripped at a rate of 300 mmol/h. The temperature was raised to about 57°C and kept with stirring for 2 hours. The solution thus obtained was stripped with 90% v/v of tBuOH to obtain a clear to yellowish oil.
  • the crude reaction mixture was first cooled to room temperature and then centrifuged (10000 rpm; 25°C; 60 min) in order to separate the residual solid particulates, comprising mainly unreacted t-BuOK and starting 3- nitro-4-fluorobenzophenone.
  • Isolated yield 85 mol% of a dark viscous liquid
  • Isolated yield 90 mol% of a dark viscous liquid
  • Isolated yield 90 mol% of a dark viscous liquid
  • Isolated yield 85 mol% of a dark viscous liquid
  • Isolated yield 90 mol% of a dark viscous liquid
  • Isolated yield 90 mol% of a dark viscous liquid
  • Isolated yield 86 mol% of a dark viscous liquid
  • the crystalline solid obtained after the second nitration reaction was a 75/25 molar mixture of 3,3'-dinitro-4-fluorobenzosulphone/3-nitro-4- fluorobenzosulphone.
  • the mixture was is dissolved in the minimal amount of hot (95°C) hexafluoroxilene. The hot solution was let slowly cool to room temperature overnight.
  • the 3-nitro-4-fluorobenzosulphone remains enriched in the mother liquor.
  • the crude reaction mixture was first cooled to room temperature and then centrifuged (10000 rpm; 25°C; 60 min) in order to separate the residual solid particulates, comprising mainly unreacted t-BuOK and slightly excess of starting 3-nitro-4,4'-difluorobenzophenone.
  • Isolated yield 85 mol% of a dark viscous liquid
  • Isolated yield 85 mol% of a dark viscous liquid
  • Isolated yield 85 mol% of a dark viscous liquid
  • Isolated yield 88 mol% of a dark viscous liquid
  • Isolated yield 88 mol% of a dark viscous liquid
  • Polymer (P ** ) 21 was obtained by treating polymer (P ** ) 14 with an excess of trifluoroethanol, in the presence of ter-BuOK as the organic base, until complete conversion of the fluorine atom to groups -OCH2CF3.
  • thermooxidation test was carried out using the equipment described in: SNYDER, Carl E., et al. Development of Polyperfluoroalkylethers as High Temperature Lubricants and Hydraulic Fluids. ASLE Transactions. 1975, vol.3, no.13, p.171 -180.
  • the operating conditions were as follows: - Test temperature: 270 °C for oils and 250°C for greases;
  • Reference 1 is a Fomblin ® M30 PFPE oil without additive.
  • sample 1 A sample (sample 1 ) containing only PTFE and Fomblin ® PFPE M30 was used as reference.
  • sample 2 was added with 2 wt.% of the compound
  • a third sample (sample 3) was added with 2wt.% of the compound (la) of example 7 prepared as disclosed in WO 2013/120827 (SOLVAY
  • Thermostability test is carried out on neat sample placed in a close NMR tube and monitoring, as a function of time and temperature, the extent of degradation.
  • the diagnostic pre-terminal signal of the PFPE chain i.e. Rf-CF -Ch O-
  • Rf-CF -Ch O- gave a direct measure of the degradation.
  • Plotting the degradation as a function of time a first order kinetics was observed for all samples, and consequently a t1/2 for all samples was obtained.
  • the data represent, for each explored temperature, the time necessary (in hour) to degrade half of the product.
  • the tribometer allows the user to record the evolution of the coefficient of friction (CoF) during the steady-state tests.
  • the results are expressed in terms of:
  • CoF end - final friction coefficient
  • mm wear (mm) on the sphere: the value is calculated as the average of the two perpendicular diameters (d1 and d2), the sign of wear on the ball being measured through an optical microscope (Motic).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne des polymères fluorés, en particulier des (per)fluoropolyéthers destinés à être utilisés en tant que lubrifiants ou en tant qu'additifs pour des huiles ou graisses (per)fluorées.
PCT/EP2018/056493 2017-03-20 2018-03-15 Polymères fluorés et leurs utilisations WO2018172172A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022158501A1 (fr) * 2021-01-20 2022-07-28 株式会社Moresco Composé perfluoropolyéther, lubrifiant et disque magnétique

Citations (10)

* Cited by examiner, † Cited by third party
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