WO2016020232A1 - Lubrication method with alkoxylated perfluoropolyether - Google Patents
Lubrication method with alkoxylated perfluoropolyether Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
- C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
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- 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
- C10M169/06—Mixtures of thickeners and additives
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
- C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Abstract
Description
HO-(CH2CH2O)r(CH2CH(OH)CH2O)p-CH2CF2O(CF2CF2O)mCF2CH2O-(CH2CH(OH)CH2O)q(CH2CH2O)s-H (I)
wherein:
m is an integer of from 3 to 200,
each of r and s, which are independent of each other, and is an integer of from 0 to 100, and each of p and q, which are independent of each other and, is an integer of from 0 to 100.
HO(CH2CH2O)rCH2CF2O(CF2CF2O)mCF2CH2O(CH2CH2O)sH (Ic)
wherein r and s are simultaneously 1
and a compound of formula:
HO(CH2CH(OH)CH2O)pCH2CF2O(CF2CF2O)mCF2CH2O(CH2CH(OH)CH2O)qH (Id)
wherein p and q are simultaneously 1. Examples 6-1, 6-2 and 7 illustrate the synthesis of certain compounds complying with formulae (Ic) and (Id) above. Nevertheless, this prior art does not teach to prepare compounds complying formula (I) having r and s higher than 1.
(A) (X-)xY(-Z)z
wherein:
- X is a group represented by the following formula (X):
HO-(CH2CH2O)a(CH2CH(OH)CH2O)b-(CH2)c-CF2O(CF2CF2O)d- (X)
wherein a is an integer of from 0 to 100, b is an integer of from 0 to 100, c is an integer of from 1 to 100, and d is an integer of from 1 to 200;
- Z is a group represented by the following formula (Z):
RFO(CF2CF2O)g- (Z)
wherein RF is a C1-20 perfluoroalkyl group or a group having an etheric oxygen atom inserted between carbon-carbon atoms of such a perfluoroalkyl group (the group has no -OCF2O- structure), and g is an integer of from 3 to 200;
- Y is a (x+z) valent perfluorinated saturated hydrocarbon group, or a (x+z) valent perfluorinated saturated hydrocarbon group having an etheric oxygen atom inserted between carbon-carbon atoms, having no -OCF2O- structure;
- X, Z: x is an integer of at least 2, z is an integer of at least 0, and (x+z) is an integer of from 3 to 20, provided that when x is at least 2, groups represented by the formula (X) may be the same or different, and when z is at least 2, groups represented by the formula (Z) may be the same or different (reference is made in particular to [0015] – [0019]). This document teaches that fluoropolyether compounds (A) are useful, inter alia, as lubricants, especially in the form of solutions with organic solvents (par. [0013] and [0024]), and that they are less subject to deterioration, as they do not contain -OCF2O- units in their molecular structure. Indeed, in formula (A), group Y is an at least trivalent group which does not contain -OCF2O- units. Thus, this document teaches away from PFPE lubricants comprising -CF2O- repeating units. In addition, this prior art does not teach to synthesise fluoropolyether compounds having more than one ethoxylated units in the chain ends.
(B-4)
HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d7(CF2O)g2CF2CH2OCH2CH(OH)CH2OH
(B-5)
HOCH2CH2OCH2CF2O(CF2CF2O)d8(CF2O)g3CF2CH2OCH2CH2OH.
A-[CF2-O-(CF2CF2O)m-(CF2O)n-CF2]A'
wherein A or A' could be -CH2OH, or -CH2OCH2CH(OH)CH2OH; and the ratio m/n is 0. 2/1 to 5/1, preferably 0. 5/1 to 2/1.
X-CF2-O(CF2-CF2-O)-(CF2O)q-CF2-X,
wherein X may be -CH2OH, CH2(O-CH2-CH2)nOH, CH2OCH2CH(OH)CH2OH or -CH2O-CH2-piperonyl (page 22, lines 4 – 8).
HO(CH2CH2O)pCH2CF2O(CF2CF2O)n(CF2O)mCF2CH2(OCH2CH2)pOH.
A-O-Rf-(CF2)x-CFZ-CH2-O-Ra (I)
wherein:
- Rf is a (per)fluoropolyoxyalkylene chain having an average number molecular weight Mn ranging from 100 to 8,000, preferably from 300 to 6,000, more preferably from 800 to 3,000, and comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from:
(i) -CFXO-, wherein X is F or CF3,
(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the provision that at least one of X is –F,
(iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F or H,
(iv) -CF2CF2CF2CF2O-,
(v) –(CF2)j-CFZ’-O- wherein j is an integer from 0 to 3 and Z’ is a group of general formula –ORf’T, wherein Rf’ is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the followings : -CFXO- , -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3 and T being a C1-C3 perfluoroalkyl group;
- Z is fluorine or CF3;
- x is 0 or 1, with the proviso that, when, x is 1, Z is F;
- A is -(CF2)x-CFZ-CH2-O-Ra, wherein x and Z are as defined above, or is a straight or branched C1-C4 perfluoroalkyl group wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups and
- Ra is a hydroxy-, alkoxy- or acyloxy- terminated polyoxyalkylene chain free from fluorine atoms (chain Ra), said chain comprising from 4 to 50 fluorine-free oxyalkylene units, said units being the same or different from one another and being selected from -CH2CH2O- and -CH2CH(J)O-, wherein J is as defined above
with the proviso that, if A is -(CF2)x-CFZ-CH2-Ra and chain Ra is hydroxy-terminated and comprises only -CH2CH2O- units, chain Rf does not consist only of -CF2CF2O- repeating units.
(a) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-
wherein m, n, p, q are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement, with the proviso that if, p and q are simultaneously 0, n is not 0; when m is other than 0, the m/n ratio is preferably between 0.1 and 20; when (m+n) is other than 0, (p+q)/(m+n) is preferably between 0 and 0.2;
(b) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-
wherein a, b, c, d are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; with the proviso that, at least one of a, c and d is not 0; when b is other than 0, a/b is preferably between 0.1 and 10; when (a+b) is different from 0 (c+d)/(a+b) preferably is between 0.01 and 0.5, more preferably between 0.01 and 0.2;
(c) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-
wherein e, f, g are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when e is other than 0, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.
(Ra-I) -(CH2CH2O)r(CH2CH(CH3)O)s(CH2CH(CH2CH3)O)t(CH2CH(Ph)O)uR1
wherein r, s, t and u are independently selected from 0 and a positive number, with r+s+t+u ranging from 4 to 50, preferably from 4 to 15, more preferably from 4 to 10, and R1 is selected from hydrogen, C1-C4 straight or branched alkyl, preferably methyl, and -C(O)R2, wherein R2 is C1-C4 straight or branched (halo)alkyl, with the proviso that, if chain Rf of compounds (I) comprises only -CF2CF2O- units and bears at both ends a chain (Ra-I) wherein s, t and u are 0, R1 is not hydrogen.
Ra-O-CH2-CF2-O-Rf-CF2-CH2-O-Ra (I-A)
wherein:
- Ra is as defined above and
- Rf complies with formula (a) as defined above.
A-O-Rf-CF2-CH2-O-Ra (I-B)
wherein:
- A is a straight or branched C1-C4 perfluoroalkyl group wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups,
- Ra is as defined above and
- Rf complies with formula (a) as defined above.
A-O-Rf-(CF2)x-CFZ-CH2-O-Ra (I*)
wherein:
- Rf is a (per)fluoropolyoxyalkylene chain having an average number molecular weight Mn ranging from 100 to 8,000, preferably from 300 to 6,000, more preferably from 800 to 3,000, and comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from
(i) -CFXO-, wherein X is F or CF3,
(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the proviso that at least one of X is –F,
(iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F or H,
(iv) -CF2CF2CF2CF2O-,
(v) –(CF2)j-CFZ’-O- wherein j is an integer from 0 to 3 and Z’ is a group of general formula –ORf’T, wherein Rf’ is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the followings : -CFXO- , -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3, and T being a C1-C3 perfluoroalkyl group;
- Z is fluorine or CF3;
- x is 0 or 1, with the proviso that, when, x is 1, Z is F;
- A is (CF2)x-CFZ-CH2-O-Ra, wherein x and Z are as defined above, or is selected from straight or branched C1-C4 perfluoroalkyl groups wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups and
- Ra complies with formula (Ra-I*) below:
-(CH2CH2O)r(CH2CH(CH3)O)s(CH2CH(CH2CH3)O)t(CH2CH(Ph)O)uR1 (Ra-I*)
wherein:
- r, s, t and u are independently selected from 0 and a positive number and r+s+t+u is a positive number ranging from 4 to 50, preferably from 4 to 15, more preferably from 4 to 10; and
- R1 is selected from hydrogen, C1-C4 straight or branched alkyl, and -C(O)R2, wherein R2 is C1-C4 straight or branched (halo)alkyl, with the proviso that, when R1 is hydrogen, at least one of s, t and u is not 0.
(a*) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-
wherein m, n, p, q are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when m is other than 0, the m/n ratio is preferably between 0.1 and 20; when (m+n) is other than 0, (p+q)/(m+n) is preferably between 0 and 0.2;
(b*) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-
wherein a, b, c, d are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; with the proviso that, at least one of a, c and d is not 0; when b is other than 0, a/b is preferably between 0.1 and 10; when (a+b) is different from 0 (c+d)/(a+b) preferably is between 0.01 and 0.5, more preferably between 0.01 and 0.2;
(c*) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-
wherein e, f, g are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when e is other than 0, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.
Ra-O-CH2-CF2-O-Rf-CF2-CH2-O-Ra (I*-A)
in which:
- Rf complies with formulae (a*) – (c*) as defined above; and
- Ra complies with formula (Ra-I*) as defined above.
A-O-Rf-CF2-CH2-O-Ra (I*-B)
in which:
- Rf complies with formulae (a*) – (c*) as defined above; and
- Ra complies with formula (Ra-I*) as defined above, and A is a straight or branched C1-C4 perfluoroalkyl group wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups.
Y-O-Rf-(CF2)x-CFZ-CH2-OH (II)
wherein:
- Rf, x and Z are as defined above;
- Y is (CF2)x-CFZ-CH2-OH, wherein x and Z are as defined above, or is selected from straight or branched C1-C4 perfluoroalkyl groups wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups and
the alkoxylating agent is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide and a mixture of two or more thereof.
HO-CH2-CF2-O-Rf-CF2-CH2-OH (II-A)
wherein Rf complies with formula (a) as defined above
with ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide or with a mixture of two or more thereof.
A-O-Rf-CF2-CH2-OH (II-B)
wherein Rf complies with formula (a) as defined above and A is a straight or branched C1-C4 perfluoroalkyl group wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups
with ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide or with a mixture of two or more thereof.
1) separately providing a mixture [M1], comprising a PFPE alcohol of formula (II) as defined above and a catalytic amount of the corresponding alkoxide (herein after “PFPE-alk”);
2) bringing into contact mixture [M1] with a boric acid triester of the same PFPE alcohol (herein after “PFPE-triBor)” in such an amount that the molar ratio PFPE-alk:PFPE-triBor is at least 1, to obtain a mixture [M2];
3) contacting mixture [M2] with a catalytic amount of an iodine source to obtain a mixture [M3];
4) treating mixture [M3] with ethylene oxide, propylene oxide, 1,2-butykene oxide or styrene oxide or a mixture thereof to provide a mixture [M4] containing a PFPE-PAG (I).
(a) a PFPE-PAG of formula (I) as defined above; in admixture of one or more of:
(b) a lubricant base oil;
(c) a thickening agent;
(d) an additive; and optionally
(e) a solvent.
(a1) a PFPE-PAG of formula (I) as defined above and
(a2) a PAG, preferably a PEG and, optionally
(a3) one or more additives.
H(OCH2CH2)OrCH2CF2O(CF2CF2O)m(CF2O)n-CF2CH2O(CH2CH2O)rH
with r=5, p/q~1 and an average molecular weight Mn=2050
was manufactured as indicated above. The product is a transparent liquid at room temperature and the pour point is -18°C.
at 20°C = 395 cSt;
at 40°C = 137 cSt and
at 100°C = 17.5 cSt
with a corresponding viscosity index equal to 141.
- both a PEG having the same molecular weight as the PFPE-PAG of Example 1 (Comparative example 2) and
- a PEG having the same molecular weight as the PAG moieties in the PFPE-PAG of Example 1 (Comparative example 3).
at 20°C = 274 cSt,
at 40°C = 98 cSt
and at 100°C = 13.7 cSt
with a corresponding viscosity index equal to 142.
- Temperature: 60°C (kinematic viscosity of the sample oil at this temperature was 43 cSt);
- Stroke: 2 mm
- Frequency: 50 Hz
- Pre-load: 50 N for 30’’
- Load: 100 N for 15’ and increase of 100 N each 2’ up to 2000 N.
at 20°C = 316 cSt;
at 40°C = 115 cSt and
at 100°C=20.8 cSt
with a corresponding viscosity index equal to 207.
Claims (13)
- A lubrication method comprising applying to a surface to be lubricated a polymer complying with formula (I) below:A-O-Rf-(CF2)x-CFZ-CH2-O-Ra (I)wherein:- Rf is a (per)fluoropolyoxyalkylene chain having an average number molecular weight Mn ranging from 100 to 8,000, preferably from 300 to 6,000, more preferably from 800 to 3,000, and comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from:(i) -CFXO-, wherein X is F or CF3,(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the proviso that at least one of X is –F,(iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F or H,(iv )-CF2CF2CF2CF2O-,(v) –(CF2)j-CFZ’-O- wherein j is an integer from 0 to 3 and Z’ is a group of general formula –ORf’T, wherein Rf’ is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the followings : -CFXO- , -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3 and T being a C1-C3 perfluoroalkyl group;- Z is fluorine or CF3;- x is 0 or 1, with the proviso that, when, x is 1, Z is F;- A is -(CF2)x-CFZ-CH2-O-Ra, wherein x and Z are as defined above, or is a straight or branched C1-C4 perfluoroalkyl group wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups and- Ra is a hydroxy-, alkoxy- or acyloxy- terminated polyoxyalkylene chain free from fluorine atoms (chain Ra), said chain comprising from 4 to 50 fluorine-free oxyalkylene units, said units being the same or different from one another and being selected from -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(CH2CH3)O- and -CH2CH(Ph)O-,with the proviso that, if A is -(CF2)x-CFZ-CH2-Ra and chain Ra is hydroxy-terminated and comprises only -CH2CH2O- units, chain Rf does not consist only of -CF2CF2O- repeating units.
- The method according to claim 1, wherein chain Rf in polymer (I) is selected from formulae (a) - (c) below:those selected from formulae (a) - (c) here below:(a) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-wherein m, n, p, q are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement, with the proviso that if, p and q are simultaneously 0, n is not 0; when m is other than 0, the m/n ratio is preferably between 0.1 and 20; when (m+n) is other than 0, (p+q)/(m+n) is preferably between 0 and 0.2;(b) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-wherein a, b, c, d are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; with the proviso that, at least one of a, c and d is not 0; when b is other than 0, a/b is preferably between 0.1 and 10; when (a+b) is different from 0 (c+d)/(a+b) preferably is between 0.01 and 0.5, more preferably between 0.01 and 0.2;(c) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-wherein e, f, g are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when e is other than 0, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.
- The method according to claim 1 or 2 wherein chain Ra in polymer (I) complies with formula (Ra-I) below:(Ra-I) -(CH2CH2O)r(CH2CH(CH3)O)s(CH2CH(CH2CH3)O)t(CH2CH(Ph)O)uR1wherein r, s, t and u are independently selected from 0 and a positive number, with r+s+t+u ranging from 4 to 50, and R1 is selected from hydrogen, C1-C4 straight or branched alkyl, and -C(O)R2, wherein R2 is C1-C4 straight or branched (halo)alkyl, with the proviso that , if chain Rf of compounds (I) comprises only -CF2CF2O- units and bears at both ends a chain (Ra-I) wherein s, t and u are 0, R1 is not hydrogen.
- The method according to claim 3 wherein in chain (Ra-I), r is a positive number ranging from 4 to 15, s, t and u are 0 and R1 is selected from hydrogen or methyl, with the proviso that, if chain Rf of compounds (I) comprises only -CF2CF2O- units and bears at both ends a chain (Ra-I), R1 is not hydrogen.
- The method according to claim 3 wherein, in chain (Ra-I), r, t and u are 0, s is a positive number ranging from 4 to 15 and R1 is selected from hydrogen or methyl.
- The method according to claim 3 wherein in chain (Ra-I), t and u are 0, r+s ranges from 4 to 15 and R1 is selected from hydrogen or methyl.
- The method according to any one of claims 1 to 6 wherein polymer (I) complies with formula (I-A) below:Ra-O-CH2-CF2-O-Rf-CF2-CH2-O-Ra (I-A)wherein Ra is as defined in any one of claims 1, 3, 4, or 6 and Rf complies with formula (a) as defined in claim 2.
- A polymer complying with formula (I*)A-O-Rf-(CF2)x-CFZ-CH2-O-Ra (I*)wherein:- Rf is a (per)fluoropolyoxyalkylene chain having an average number molecular weight Mn ranging from 100 to 8,000, preferably from 300 to 6,000, more preferably from 800 to 3,000, and comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from(i) -CFXO-, wherein X is F or CF3,(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the proviso that at least one of X is –F,(iii) -CF2CF2CW2O-, wherein each of W, equal or different from each other, are F or H,(iv) -CF2CF2CF2CF2O-,(v) -(CF2)j-CFZ’-O- wherein j is an integer from 0 to 3 and Z’ is a group of general formula –ORf’T, wherein Rf’ is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen among the followings : -CFXO- , -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3, and T being a C1-C3 perfluoroalkyl group;- Z is fluorine or CF3;- x is 0 or 1, with the proviso that, when, x is 1, Z is F;- A is (CF2)x-CFZ-CH2-O-Ra, wherein x and Z are as defined above, or is selected from straight or branched C1-C4 perfluoroalkyl groups wherein one fluorine atom can be substituted by one chlorine atom or one hydrogen atom, with the proviso that, if chlorine is present in group A, it is in a molar amount lower than 2% with respect to the overall amount of end groups and- Ra complies with formula (Ra-I*) below:-(CH2CH2O)r(CH2CH(CH3)O)s(CH2CH(CH2CH3)O)t(CH2CH(Ph)O)uR1 (Ra-I*)wherein:- r, s, t and u are independently selected from 0 and a positive number and r+s+t+u is a positive number ranging from 4 to 50;and R1 is selected from hydrogen, C1-C4 straight or branched alkyl, and -C(O)R2, wherein R2 is C1-C4 straight or branched (halo)alkyl, with the proviso that, when R1 is hydrogen, at least one of s, t and u is not 0.
- The polymer according to claim 8 wherein chain Rf is selected from formulae (a*) - (c*) here below:(a*) -(CF2O)n(CF2CF2O)m(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-wherein m, n, p, q are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when m is other than 0, the m/n ratio is preferably between 0.1 and 20; when (m+n) is other than 0, (p+q)/(m+n) is preferably between 0 and 0.2;(b*) -(CF2CF(CF3)O)a(CF2CF2O)b(CF2O)c(CF(CF3)O)d-wherein a, b, c, d are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; with the proviso that, at least one of a, c and d is not 0; when b is other than 0, a/b is preferably between 0.1 and 10; when (a+b) is different from 0 (c+d)/(a+b) preferably is between 0.01 and 0.5, more preferably between 0.01 and 0.2;(c*) -(CF2CF(CF3)O)e(CF2O)f(CF(CF3)O)g-wherein e, f, g are 0 or integers selected in such a way as chain Rf meets the above number average molecular weight requirement; when e is other than 0, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.
- The polymer according to claim 9 of formula (I*-A) belowRa-O-CH2-CF2-O-Rf-CF2-CH2-O-Ra (I*-A)in which:- Ra complies with formula (Ra-I*) as defined in claim 9 and- Rf complies with formula (a*) as defined in claim 10.
- The polymer according to claim 10 wherein r, t and u in formula (Ra-I*) are 0 and s is a positive number ranging from 4 to 15.
- The polymer according to claim 10 wherein in formula (Ra-I*) r+s is a positive number ranging from 4 to 15 and t and u are 0.
- A composition comprising:(a) a polymer as defined in any one of claims 8 to 12; in admixture of one or more of(b) a lubricant base oil;(c) a thickening agent;(d) an additive; and optionally(e) a solvent.
Priority Applications (4)
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US15/501,820 US20170240839A1 (en) | 2014-08-05 | 2015-07-29 | Lubrication method with alkoxylated perfluoropolyether |
JP2017506335A JP2017523292A (en) | 2014-08-05 | 2015-07-29 | Lubricating method with alkoxylated perfluoropolyether |
CN201580054088.8A CN107109283A (en) | 2014-08-05 | 2015-07-29 | Use the lubricating method of the PFPE of alkoxylate |
EP15750276.6A EP3177701B1 (en) | 2014-08-05 | 2015-07-29 | Lubrication method with alkoxylated perfluoropolyether |
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EP14179867 | 2014-08-05 | ||
EP14179867.8 | 2014-08-05 |
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WO2016020232A1 true WO2016020232A1 (en) | 2016-02-11 |
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PCT/EP2015/067354 WO2016020232A1 (en) | 2014-08-05 | 2015-07-29 | Lubrication method with alkoxylated perfluoropolyether |
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US (1) | US20170240839A1 (en) |
EP (1) | EP3177701B1 (en) |
JP (1) | JP2017523292A (en) |
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WO (1) | WO2016020232A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110072912A (en) * | 2016-12-14 | 2019-07-30 | 索尔维特殊聚合物意大利有限公司 | (complete) perfluoroalkyl polyether polymer |
WO2020084054A1 (en) | 2018-10-26 | 2020-04-30 | Solvay Specialty Polymers Italy S.P.A. | Polyacrylic pfpe derivatives |
Families Citing this family (2)
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US10213943B2 (en) * | 2015-09-11 | 2019-02-26 | Toyo Gosei Co., Ltd. | Composition |
CN109022105B (en) * | 2018-06-13 | 2021-09-17 | 权家(厦门)新材料有限公司 | Water-soluble fluorocarbon graphene engine oil and preparation method thereof |
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WO2020084054A1 (en) | 2018-10-26 | 2020-04-30 | Solvay Specialty Polymers Italy S.P.A. | Polyacrylic pfpe derivatives |
Also Published As
Publication number | Publication date |
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JP2017523292A (en) | 2017-08-17 |
EP3177701B1 (en) | 2018-07-25 |
EP3177701A1 (en) | 2017-06-14 |
US20170240839A1 (en) | 2017-08-24 |
CN107109283A (en) | 2017-08-29 |
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