WO2024149802A1 - Polymères de perfluoropolyéther - Google Patents

Polymères de perfluoropolyéther Download PDF

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WO2024149802A1
WO2024149802A1 PCT/EP2024/050486 EP2024050486W WO2024149802A1 WO 2024149802 A1 WO2024149802 A1 WO 2024149802A1 EP 2024050486 W EP2024050486 W EP 2024050486W WO 2024149802 A1 WO2024149802 A1 WO 2024149802A1
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group
formula
chain
carbon atoms
block
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Andrea LOTIERZO
Roberto Valsecchi
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Syensqo Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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Priority to EP24700726.3A priority Critical patent/EP4649105A1/fr
Priority to JP2025540787A priority patent/JP2026503102A/ja
Priority to CN202480018094.7A priority patent/CN120958062A/zh
Publication of WO2024149802A1 publication Critical patent/WO2024149802A1/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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material 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
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • C10M2211/063—Perfluorinated compounds 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes

Definitions

  • the present invention relates to a copolymer comprising (per)fluoro- polyether chains and functional groups that confer discharging properties to the copolymer itself.
  • PFPE polymers have been long known as base oils or as additives in several lubricant applications.
  • US 4500739 discloses the reaction of a peroxidic PFPE with - among the others - perfluoro butadiene (Group II of fluoroolefins).
  • Example 4 discloses the reaction with perfluoro butadiene, with a large excess of perfluorinated bis-olefin, resulting in pendant unsaturated groups along the macromolecular chain such that the reaction can further proceed in the presence of hexamethylenediamine.
  • T and T’ are C1-3 perfluoroalkyl or C1-6 alkyl, A and A are a perfluoropolyether chain, B derives from two different olefins, of which at least one homopolymerizable by radical route, of formula: (la) -[(CRiR 2 -CR3R4)j-(CR5R6-CR7R8)j]- wherein j is from 1 to 5, j’ is from 0 to 4 and the sum of j+j’ is between 2 and 5;
  • R1 to Rs are halogen, H, C1-6 (per)haloalkyl, C1-6 alkyl, C1-6 oxy(per)fluoroalkyl; z is higher than or equal to 2, z’ is an integer and the sum of z and z’ is such that the number average molecular weight of the polymer of formula (I) is in the range 500-500000;
  • B’ is (la) but at least one of R1 to R8 has a meaning different from that in B.
  • This patent discloses block copolymers characterised by a linear backbone, without any branching. Indeed, no branching is obtained within B, notably comprising (per)fluoropolyether chains.
  • PFPE polymers comprising functional groups along the backbone have been disclosed in the art, being useful as reactive intermediate compounds and as additives.
  • US 2011/0230631 discloses (per)fluoropolyethers comprising at least one (per)fluoropolyoxyalkylene chain comprising at least one recurring unit of formula -CF2-CF(CF2O-SO2F)-O-, wherein fluorosulfate group in brackets is a pendant group, which is subsequently reacted with a nucleophilic agent to provide functional groups, such as notably carboxylic acid, acyl fluoride, amide and esters.
  • WO 2019/048394 (Solvay Specialty Polymers Italy S.p.A.) discloses polyfunctional perfluoropolyether derivatives including a block (with sub “n2”) comprising a plurality of ionisable groups selected from the group consisting of -SOsXa, -POsXa and -COOXa, wherein Xa is H, ammonium group or a monovalent metal; and a block (with sub “n1”) comprising PFPE chain(s).
  • Such polyfunctional PFPE is then used as a dispersant in the synthesis of TFE-based elastomers.
  • the Applicant is aware that lubricants based on PFPE-polymers are currently used to lubricate electric and electronic components, including for example electrical connectors. However, the Applicant is also aware that such lubricants are provided in the form of greases and often comprise solid particles as thickeners. When thickeners in the form of solid particles are used, issues in the stability can arise and for example separation of the solid particles can be observed.
  • the Applicant also faced the problem of developing lubricants that can be used to lubricate electric and electronic components with the aim of decreasing the static discharge that can be generated in electric and electronic equipment.
  • the Applicant developed copolymers that can be used as oils for such applications, such oils showing inherent reduced electrical resistivity without the need of adding conductive additives.
  • copolymers can be used as oils without the need of adding thickeners in the form of solid particles, thus simplifying the manufacturing process and the storage of the same. Also, no compatibility issues arose with the additive and no phase separation occurred.
  • the copolymer according to the present invention also showed low-to-zero weight loss when used at high temperatures
  • PFPE perfluoropolyether
  • the term “functionality (F)” is intended to indicate the amount of functional groups in the copolymer according to the present invention as measured via NMR or titration.
  • L A is 0 or an integer from 1 to 250;
  • R100, R101, R102 and R103 are each independently selected from hydrogen atom, halogen atom, more preferably fluorine or chlorine atom; linear or branched alkyl chain comprising from 1 to 6 carbon atoms; -OR200 wherein R200 is a linear or branched perfluorinated chain comprising from 1 to 6 carbon atoms or a group of formula -CF2OR201 in which R201 is a perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or one of R100 and R101 and one of R102 and R103 are a fluorine atom and the other of R100 and R101 and the other of R102 and R103 together form a perhalogenated cyclic ring having from 4 to 6 members, optionally comprising heteroatoms, such as oxygen atoms; L is 0 or an integer from 1 to 250, and
  • D is a group of formula -(CRioo*Rior-CRio2*Rio3*)- wherein at least one of R o* , R101* R102* and R103* is different from R100, R101 , R102, and R103, such that (D) is different from -[CRIOORIOI -CRIO2R-I O3]L A -; with the proviso that, when L A and L are both different from 0, the recurring units are statistically distributed;
  • Rs to Rs each independently, is selected in the group comprising, preferably consisting of, -F, perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms, and group of formula (III):
  • R20 is a sigma bond, or linear or branched perfluoroalkyl chain comprising from 1 to 12 carbon atoms, preferably comprising and/or interrupted by at least one oxygen atom,
  • X is an anionic functional group selected from: each being salified with at least one inorganic metal salt or with at least one organic group preferably selected from ammonium or phosphonium, and y is an integer equal to 1 or 2; with the proviso that in formula (II), at least one, preferably one, of Rs to Rs is group of formula (III);
  • R1 to R4 each independently, is selected in the group comprising, preferably consisting of, fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms, group of formula (V):
  • R10 is an oxygen atom, or a bi-/tri-/tetravalent perfluorinated alkyl chain comprising from 1 to 24 carbon atoms and being optionally interrupted by at least one oxygen atom, t is zero or 1 , z is an integer from 1 to 3,
  • Ri 1 to R15 each independently, is selected in the group comprising, preferably consisting of: fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms and group of formula (VI): -[(A)a-(B) b -(E)c-(F)f]u-(A)-T (VI) wherein u is zero or an integer from 1 to 50;
  • RIA to R4 A each independently has the meaning defined above for each of Ri to R4, respectively; c is 0 or an integer from 1 to 50,
  • D* has the same meaning provided above for D, with the proviso that, when e A and e* are both different from 0, the recurring units are statistically distributed;
  • f is 0 or an integer from 1 to 5, preferably from 1 to 2;
  • RS A to RS A each independently, has the meaning provided above for each of Rs to Rs, respectively; with the proviso that :
  • At least one of Ri to R4 is a group of formula (V),
  • one of R11 or R12 and one of R13 to R15 is a group of formula (VI),
  • said at least one block (1 ), said at least one block (2), said at least one block (3) and, when present, said at least one block (4) are statistically distributed.
  • first chain end of said first and second PFPE chain correspond to the two chain ends of copolymer (P).
  • each of said PFPE chain is a fully fluorinated chain [chain (Rf)] comprising, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
  • 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 100,000, preferably between 400 and 50,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably comprised between 0.1 and 10;
  • 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 100,000, preferably between 400 and 50,000, with the ratio a1/a2 being generally between 0.1 and 10, more preferably between 0.2 and 5.
  • At least one of L A and L, preferably both L A and L, is different from 0.
  • R100, R101, R 2 and R103 each independently, is a halogen atom, such as fluorine atom or chlorine atom.
  • m is an integer from 1 to 2.
  • one of Rs to Rs is a group of formula (V).
  • R 2 o is a sigma bond or a group selected from those of formula (R 2 o-i) to (R 2 o-iv) as defined hereinafter:
  • each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3;
  • s3 is an integer from 1 to 6, preferably from 1 to 5;
  • R400 is a linear or branched perfluorinated alkyl chain comprising from 1 to
  • R401 is a linear or branched perfluorinated alkyl chain comprising from 1 to 3 carbon atoms, more preferably complying with formula -CF 2 -, - CF 2 CF 2 -, -CF(CF 3 )-;
  • Rsoo is a linear perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms and optionally interrupted by at least one oxygen atom;
  • R501 is a chain of formula -OR503 wherein R503 is a linear perfluorinated alkyl chain comprising from 1 to 3 carbon atoms; Rso2 is a linear perfluorinated alkyl chain comprising from 1 to 4 carbon atoms and optionally interrupted by at least one oxygen atom; each of R501 and R502 bonding a group X as defined above.
  • R10 complies with one of the following formulae:
  • the present invention relates to a process [process (P)] for the manufacture of copolymer (P) as defined above.
  • the process according to the present invention can be easily scaled up from laboratory scale to pilot and industrial scale.
  • copolymer (P) of the present invention is prepared via process (P) comprising at least the following steps :
  • each of R21 to R23 is independently -F or perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms,
  • R20 and y are as defined above for formula (III) and
  • X is selected from :
  • Rf is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 ; a group C1-C12 [(per)fluoro]-oxyalkyl comprising catenary oxygen atoms, preferably perfluoro-2-propoxypropyl group;
  • Rt2 is selected from the group consisting of C-i-Ce perfluoro-alkyls; Cs-Ce cyclic perfluoro-alkyls, and C2-C6 perfluoro-oxy-alkyls, comprising at least one catenary oxygen atom, preferably Fta is -CF2CF3, -CF2CF2OCF3, or - CF 3 ;
  • Rfz is selected from the group consisting of C-i-Ce perfluoro-alkyls, Cs-Ce cyclic perfluoro-alkyls, and C2-C6 perfluoro-oxy-alkyls, comprising at least one catenary oxygen atom;
  • each of Rf3, Rf4, Rts, Rf6, equal to or different from each other, is independently selected from the group consisting of fluorine atom and C1- Ce perfluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; and/or
  • each of R21 to R23 are as defined above in formula (X-p)
  • each of R31 to R33 is independently -F or perfluorinated alkyl group having from 1 to 6 carbon atoms
  • R10 is an oxygen atom, a perfluorinated alkyl chain comprising from 1 to 24 carbon atoms, optionally interrupted by at least one oxygen atom, t is zero or 1 ; each of z* and z** is independently 1 or 2; and
  • step (a) the order in which the reactants are added is not limited.
  • the PFPE peroxy, the compound of formula (X-p), and when used both or either or the compound of formula (XX-p) and at least one compound (0), can be supplied to the reaction environment in any order.
  • the PFPE peroxy can be subjected to partial reduction of the peroxide bonds, for example by chemical reduction or UV treatment or thermal treatment.
  • chain (Rf) complies with formulae (Rf-I), or (Rf-IIA), (Rf-IIB), (Rf-I IC) or (Rf-lll) as defined above.
  • step (a) of the process of the present invention is performed with at least one compound (O).
  • said at least one compound (O) is selected in the group comprising, preferably consisting of:
  • olefin comprising from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms. More preferably, it is selected in the group comprising: tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE). TFE and HFP being particularly preferred.
  • the first compound (O) is selected from those defined in (i) above and a second compound (0) is selected in the group comprising, more preferably consisting of:
  • Rf is a Ci-C 6 (per)fluoroalkyl group, preferably -CFs, -C2F5, -C3F7 ; a group C1-C12 [(per)fluoro]-oxyalkyl comprising catenary oxygen atoms, preferably perfluoro-2-propoxypropyl group;
  • Rf2 is selected from the group consisting of C-i-Ce perfluoro-alkyls; Cs-Ce cyclic perfluoro-alkyls, and C2-C6 perfluoro-oxy-alkyls, comprising at least one catenary oxygen atom, preferably Rf 2 is -CF2CF3, -CF2CF2OCF3, or - CF 3 ;
  • Rf? is selected from the group consisting of Ci-Ce perfluoro-alkyls, Cs-Ce cyclic perfluoro-alkyls, and C2-C6 perfluoro-oxy-alkyls, comprising at least one catenary oxygen atom;
  • each of Fta, Rf4, Rfs, Rf6, equal to or different from each other, is independently selected from the group consisting of fluorine atom and C-i- Ce perfluoroalkyl groups, optionally comprising one or more than one oxygen atom, such as notably -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3 .
  • each of R21 , R22 and R23 is -F.
  • R20 is a sigma bond or a group selected from those of formula (R2o-i) to (R2o-iv) as defined hereinafter: (R 2 o-i)
  • each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3;
  • s3 is an integer from 1 to 6, preferably from 1 to 5;
  • R400 is a linear or branched perfluorinated alkyl chain comprising from 1 to 6, preferably from 1 to 3, carbon atoms, and more preferably complying with formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CFs)-; and R401 is a linear or branched perfluorinated alkyl chain comprising from 1 to 3 carbon atoms, more preferably complying with formula -CF2-, - CF2CF2-, -CF(CF 2 )-;
  • Rsoo is a linear perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms and optionally interrupted by at least one oxygen atom;
  • R501 is a chain of formula -OR503 wherein R503 is a linear perfluorinated alkyl chain comprising from 1 to 3 carbon atoms;
  • R502 is a linear perfluorinated alkyl chain comprising from 1 to 4 carbon atoms and optionally interrupted by at least one oxygen atom; each of R501 and R502 bonding a group X as defined above.
  • said at least one compound of formula (X-p) is selected in the group comprising, more preferably consisting of :
  • said at least one compound of formula (XX-p) complies with the following formula:
  • RCF is a linear perfluoroalkyl chain comprising from 1 to 10, preferably from 1 to 8 carbon atoms.
  • the amount of each of said at least one compound (X-p), and when used compound (XX-p) and/or at least one compound (0) is not limited. As explained above, the amount of each of the above mentioned compounds can advantageously be selected based on both the amount of the PFPE peroxy, as well as its peroxidic content, and the properties desired in the final copolymer (P).
  • the equivalents of double bonds of said compound (X-p) to the equivalents of peroxidic groups preferably range from 1 :100 to 5000:100.
  • the equivalents of double bonds of said compound (XX-p) to the equivalents of peroxidic groups preferably range from 1 :100 to 100:100.
  • Step (a) of process (P) can be advantageously performed by contacting said PFPE peroxy with one compound of formula (X-p).
  • step (a) can be performed by contacting said PFPE peroxy with two or more compounds of formula (X-p).
  • Step (a) and step (b) can be performed in the presence of a fluorinated solvent.
  • said fluorinated solvent is selected in the group comprising: perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, hydrofluoro- polyethers.
  • step (b) is performed in the presence of UV radiation for a time from 2 to 150 hours, more preferably from 5 to 100 hours.
  • step (b) is performed in the presence of UV radiation at a temperature from -60°C to +150°C, more preferably from -20°C to +100°C and even more preferably from 0°C to 60°C.
  • step (b) can be performed under thermal treatment, preferably by heating at a temperature from 150 °C to 250 °C.
  • said step (b) is performed in an inert atmosphere.
  • a fluorination step can be performed after step (b) and before step (c1 ) or (c2).
  • a fluorination step allows neutralising the end groups -COF at the chain end(s) of the PFPE peroxy.
  • said step (c1 ) of salifying is performed with at least one inorganic metal salt, which is preferably an alkaline metal.
  • said alkaline metal is selected in the group comprising: sodium, potassium, cesium, lithium, magnesium and calcium.
  • said step (c2) of hydrolysis is performed in the presence of an alkaline compound.
  • such step can be performed using metal hydroxide, such as a solution of sodium or potassium hydroxide in water.
  • metal hydroxide such as a solution of sodium or potassium hydroxide in water.
  • step (c2) is performed at 20-100°C.
  • step (c2) is performed for a time from 1 hour to 10 hours.
  • the copolymer (P) as obtained at the end of step (c2) can be further reacted in order to obtain the organic salt with a compound containing the ammonium group or the phosphonium group.
  • the compound comprising the ammonium group complies with formula:
  • each of R21 , R22, R23 is selected from: linear or branched C1-C20 aliphatic chain, optionally containing at least one heteroatom, preferably - O-; or two of R21 , R22, R23 together form a 5- or 6- membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and/or being optionally substituted by at least one linear or branched alkyl chain comprising from 1 to 10 carbon atoms and optionally containing at least one heteroatom, preferably selected from -O- and -N-, and the third of R21 , R22, R23 is as defined above.
  • said compound comprising the ammonium group is selected from triethanol ammonium, triethyl ammonium, pyridinium, trimethyl ammonium, tributyl ammonium, 1 -methyl imidazolium, di(ethyl)cyclohexyl-ammonium, benzimidazolium, 1 -benzyl imidazolium.
  • the compound comprising the phosphonium group complies with formula:
  • each of R211 , R221 , R231 is selected from: linear or branched C1-C20 aliphatic chain, optionally containing at least one heteroatom, preferably - O-; or two of R211 , R221 , R231 together form a 5- or 6- membered aliphatic or aromatic ring, said ring optionally containing at least one heteroatom and/or being optionally substituted by at least one linear or branched alkyl chain comprising from 1 to 10 carbon atoms and optionally containing at least one heteroatom, preferably selected from O and N, and the third of R211 , R221 , R231 is as defined above.
  • said compound comprising the organic phosphonium salt is selected from triethyl phosphine, tri propyl phosphine, tributylphosphine, triethylphosphine, trioctylphosphine.
  • the present invention relates to copolymer (P) obtained via process (P) as described above.
  • L A is 0 or an integer from 1 to 250;
  • R100, R101 , R102 and R103 are each independently selected from hydrogen atom, halogen atom, more preferably fluorine or chlorine atom; linear or branched alkyl chain comprising from 1 to 6 carbon atoms; -OR200 wherein R200 is a linear or branched perfluorinated chain comprising from 1 to 6 carbon atoms or a group of formula -CF2OR201 in which R201 is a perfluorinated alkyl chain comprising from 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms; or one of R100 and R101 and one of R102 and R103 are a fluorine atom and the other of R100 and R101 and the other of R102 and R103 together form a perhalogenated cyclic ring having from 4 to 6 members, optionally comprising heteroatoms, such as oxygen atoms;
  • L is 0 or an integer from 1 to 250
  • D is a group of formula -(CRioo*Rior-CRio2*Rio3*)- wherein at least one of R100* , R101* R102* and R103* is different from R100, R101 , R102, and R103, such that (D) is different from -[CRIOORIOI -CRIO2R-I O3]L A -; with the proviso that, when L A and L are both different from 0, the recurring units are statistically distributed;
  • Rs to Rs each independently, is selected in the group comprising, preferably consisting of, -F, perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms, and group of formula (III):
  • R20 is a sigma bond, or linear or branched perfluoroalkyl chain comprising from 1 to 12 carbon atoms, preferably comprising and/or interrupted by at least one oxygen atom
  • R1 to R4 each independently, is selected in the group comprising, preferably consisting of, fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms, group of formula (V):
  • R10 is an oxygen atom, or a bi-/tri-/tetravalent perfluorinated alkyl chain comprising from 1 to 24 carbon atoms and being optionally interrupted by at least one oxygen atom, t is zero or 1 , z is an integer from 1 to 3,
  • R11 to R15 each independently, is selected in the group comprising, preferably consisting of: fluorine atom, perfluorinated linear or branched alkyl group having from 1 to 6 carbon atoms and group of formula (VI): -[(A) a -(B)b-(E)c-(F) f ]u-(A)-T (VI) wherein u is zero or an integer from 1 to 50;
  • RIA to R4 A each independently has the meaning defined above for each of Ri to R4, respectively; c is 0 or an integer from 1 to 50,
  • E is a block of formula
  • D* has the same meaning provided above for D, with the proviso that, when e A and e* are both different from 0, the recurring units are statistically distributed;
  • f is 0 or an integer from 1 to 5, preferably from 1 to 2;
  • RS A to RS A each independently, has the meaning provided above for each of Rs to Rs, respectively; with the proviso that :
  • At least one of Ri to R4 is a group of formula (V),
  • one of R11 or R12 and one of R13 to R15 is a group of formula (VI),
  • said at least one block (1 ), said at least one block (2), said at least one block (3) and said at least one block (4) are statistically distributed.
  • the PFPE chain of copolymer (P°) is as defined above for copolymer (P).
  • block (1 ) of copolymer (P°) is as defined above for copolymer (P).
  • block (3) of copolymer (P°) is as defined above for copolymer (P).
  • each of m, Rs to Rs and R20 in block (2) of copolymer (P°) have the same meanings defined above for copolymer (P).
  • X in block (2) of copolymer (P°) is selected from :
  • X is an anionic group of formula copolymer (P°) is prepared via a process [process (P°)], said process (P°) comprising the same steps (a), (b) and (cl ) or (c2) as defined for process (P).
  • copolymer (P°°) is prepared via process (P°°) comprising in step (a) contacting:
  • each of R21 to R23 is independently -F or perfluorinated linear or branched alkyl chain having from 1 to 6 carbon atoms,
  • R20 and y are as defined above for formula (III) and
  • X is selected from :
  • process (P°) of the present invention comprises after step (b), at least one of the following steps:
  • CF2 CFCF2OCF2CF 2 COF
  • CF2 CFO(CF2)3OCF(CF 3 )COF
  • CF2 CFOCF2CF(CF3)OCF2CF 2 CN
  • CF2 CFCF2OCF2CF 2 CN.
  • copolymer (P) and copolymer (P°) according to the present invention is advantageously used to lubricate electric and electronic components, in particular with the aim of decreasing the static discharge that can be generated in electric and electronic equipment.
  • the element in the electric, electronic or mechanical device to be lubricated with copolymer (P) or copolymer (P°) according to the present invention is preferably selected from electrical connectors, sensors, switchgears, circuit breakers, battery terminals, or ball bearings.
  • Peroxidic perfluoropolyether oil was obtained by Solvay Specialty Polymers Italy S.p.A., complying with formula XO-(CF 2 CF 2 O)ai (CF 2 O)a2(O)h-X’ wherein
  • 19 F-NMR-Varian Mercury 300 MHz spectrometer working for the 19 F nucleus was used to obtain the structure, molecular weight, chain end composition of the perfluoropolyether oils.
  • the 19 F-NMR spectrum was obtained on pure samples using CFCI3 as internal reference.
  • the peroxidic content (PO) was expressed as grams of peroxidic oxygen per 100 g of polymer.
  • the analysis of the peroxide content was carried out by iodometric titration using a Mettler DL40 device equipped with platinum electrode.
  • the sensitivity limit for the PO determination was 0.0002%.
  • the mixture was transferred into a second glass photochemical reactor and treated with UV light and 1 NL/h of fluorine gas at 60°C for 8 hours.
  • the UV lamp was switched off and the mixture was thoroughly flushed with nitrogen.
  • the reactor content then was transferred in a round bottom flask equipped with a magnetic stirrer and treated at 240°C for 6h to remove solvent and residual P.O.
  • the distillation was conducted first at atmospheric pressure, then under reduced pressure (0.1 mbar) until complete removal of the solvent. Iodometric titration confirmed the complete removal of the peroxide units.
  • the number average molecular weight (M n ) was 24 530 g/mol.
  • Example 1 - Copolymer (P) salified with triethyl amine
  • Example 2 - Copolymer (P) salified with 1 -butylimidazole
  • Example 1 The procedure disclosed for Example 1 was followed, with the difference that 0.6 g of 1 -butyl Imidazole were used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un copolymère comprenant des chaînes (per)fluoropolyéther et des groupes fonctionnels qui confèrent des propriétés de décharge au copolymère lui-même.
PCT/EP2024/050486 2023-01-12 2024-01-10 Polymères de perfluoropolyéther Ceased WO2024149802A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP24700726.3A EP4649105A1 (fr) 2023-01-12 2024-01-10 Polymères de perfluoropolyéther
JP2025540787A JP2026503102A (ja) 2023-01-12 2024-01-10 パーフルオロポリエーテルポリマー
CN202480018094.7A CN120958062A (zh) 2023-01-12 2024-01-10 全氟聚醚聚合物

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EP23151335 2023-01-12

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Citations (14)

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Publication number Priority date Publication date Assignee Title
US4500739A (en) 1982-03-19 1985-02-19 Montedison S.P.A. Process for the insertion of perfluoroolefines on perfluoropolyethers and corresponding products
US4853097A (en) 1986-05-07 1989-08-01 Ausimont S.P.A. Perfluoropolyethers free from peroxidic oxygen and containing perfluoroepoxy groups positioned along the perfluoropolyether chain, and their derivatives
US5104911A (en) 1988-04-11 1992-04-14 Ausimont S.R.L. Cross-linked products with the structure of perfluoropolyethers having functional groups
US5719259A (en) 1995-08-14 1998-02-17 E. I. Du Pont De Nemours And Company Perfluoroalkylene oxide copolymer composition containing functional groups
US6403539B1 (en) * 1999-08-04 2002-06-11 Ausimont S.P.A. Perfluoropolyether lubricant containing sulphonylfluoride groups
WO2003106515A1 (fr) 2002-06-14 2003-12-24 ダイキン工業株式会社 Monomere fluore possedant un groupe fonctionnel sulfonate, copolymere fluore comprenant celui-ci et membrane echangeuse d'ions
US6896996B2 (en) * 2001-01-03 2005-05-24 Austmont S.P.A. Perfluoropolyether additives for electrochemical applications
US20080138685A1 (en) 2005-07-27 2008-06-12 Asahi Glass Company, Limited Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane/electrode assembly
US20110230631A1 (en) 2008-12-05 2011-09-22 Solvay Solexis S.P.A. Polyfunctional (per)fluoropolyethers
US8258090B2 (en) 2006-11-30 2012-09-04 Solvay Solexis S.P.A. Fluorinated lubricants
WO2017012909A1 (fr) * 2015-07-17 2017-01-26 Solvay Specialty Polymers Italy S.P.A. Agents anti-mousse
JP2017025242A (ja) 2015-07-27 2017-02-02 旭硝子株式会社 フルオロスルホニル基含有モノマー、フルオロスルホニル基含有ポリマー、スルホン酸基含有ポリマー、液状組成物、膜電極接合体およびそれらの製造方法
WO2019048394A1 (fr) 2017-09-08 2019-03-14 Solvay Specialty Polymers Italy S.P.A. Procédé pour la fabrication de polymères fluorés
WO2022078766A1 (fr) * 2020-10-14 2022-04-21 Solvay Specialty Polymers Italy S.P.A. Nouveaux polymères de (per)fluoropolyéther et leur utilisation

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500739A (en) 1982-03-19 1985-02-19 Montedison S.P.A. Process for the insertion of perfluoroolefines on perfluoropolyethers and corresponding products
US4853097A (en) 1986-05-07 1989-08-01 Ausimont S.P.A. Perfluoropolyethers free from peroxidic oxygen and containing perfluoroepoxy groups positioned along the perfluoropolyether chain, and their derivatives
US5104911A (en) 1988-04-11 1992-04-14 Ausimont S.R.L. Cross-linked products with the structure of perfluoropolyethers having functional groups
US5719259A (en) 1995-08-14 1998-02-17 E. I. Du Pont De Nemours And Company Perfluoroalkylene oxide copolymer composition containing functional groups
US6403539B1 (en) * 1999-08-04 2002-06-11 Ausimont S.P.A. Perfluoropolyether lubricant containing sulphonylfluoride groups
US6896996B2 (en) * 2001-01-03 2005-05-24 Austmont S.P.A. Perfluoropolyether additives for electrochemical applications
WO2003106515A1 (fr) 2002-06-14 2003-12-24 ダイキン工業株式会社 Monomere fluore possedant un groupe fonctionnel sulfonate, copolymere fluore comprenant celui-ci et membrane echangeuse d'ions
US20080138685A1 (en) 2005-07-27 2008-06-12 Asahi Glass Company, Limited Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane/electrode assembly
US8258090B2 (en) 2006-11-30 2012-09-04 Solvay Solexis S.P.A. Fluorinated lubricants
US20110230631A1 (en) 2008-12-05 2011-09-22 Solvay Solexis S.P.A. Polyfunctional (per)fluoropolyethers
WO2017012909A1 (fr) * 2015-07-17 2017-01-26 Solvay Specialty Polymers Italy S.P.A. Agents anti-mousse
JP2017025242A (ja) 2015-07-27 2017-02-02 旭硝子株式会社 フルオロスルホニル基含有モノマー、フルオロスルホニル基含有ポリマー、スルホン酸基含有ポリマー、液状組成物、膜電極接合体およびそれらの製造方法
WO2019048394A1 (fr) 2017-09-08 2019-03-14 Solvay Specialty Polymers Italy S.P.A. Procédé pour la fabrication de polymères fluorés
WO2022078766A1 (fr) * 2020-10-14 2022-04-21 Solvay Specialty Polymers Italy S.P.A. Nouveaux polymères de (per)fluoropolyéther et leur utilisation

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