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WO2024068676A1 - Polymères de perfluoropolyéther - Google Patents

Polymères de perfluoropolyéther Download PDF

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Publication number
WO2024068676A1
WO2024068676A1 PCT/EP2023/076610 EP2023076610W WO2024068676A1 WO 2024068676 A1 WO2024068676 A1 WO 2024068676A1 EP 2023076610 W EP2023076610 W EP 2023076610W WO 2024068676 A1 WO2024068676 A1 WO 2024068676A1
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chain
formula
group
block
carbon atoms
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Andrea LOTIERZO
Ugo De Patto
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Solvay Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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Priority to CN202380069347.9A priority Critical patent/CN119948070A/zh
Priority to EP23777272.8A priority patent/EP4594373A1/fr
Priority to JP2025518177A priority patent/JP2025536121A/ja
Publication of WO2024068676A1 publication Critical patent/WO2024068676A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/24—Monomers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/28—Monomers containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/30—Monomers containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458—Monomers containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur 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
    • 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
    • C08G65/33365—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group
    • C08G65/33368—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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 new copolymers comprising (per)fluoropolyether chains and functional groups.
  • PFPE polymers have been long known as base oils or as additives in several lubricant applications.
  • US 4,500,739 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 Ci-e 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:
  • R1 to Rs are halogen, H, Ci-e (per)haloalkyl, Ci-e alkyl, Ci-e 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 500-500 000;
  • B’ is (la) but at least one of R1 to Rs has a meaning different from that in B.
  • US 6,403,539 discloses perfluoro-polyether polymers containing sulphonyl fluoride groups pending along the backbone.
  • This patent application discloses a process wherein the sulphonyl fluoride-containing monomer is contemporaneously fed with an O2 flow in a liquid reaction medium, thus obtaining perfluoropolyethers containing in the chain peroxidic groups.
  • the presence of the peroxidic groups is not desired for safety concerns.
  • this patent application discloses that to obtain non peroxidic products without chain scission, the peroxidic perfluoropolyethers are subjected to a thermal treatment at temperatures generally in the range from 150°C to 250°C or to a photochemical treatment, optionally in the presence of a solvent.
  • the process herein disclosed - in which the functionalized monomer is added at the beginning of the polymerization - does not allow the synthesis of a polymer having segregated blocks from the functionalized monomer but rather it allows for the synthesis of a PFPE polymer having randomly distributed functional groups.
  • US 2011/0230631 (Solvay Solexis S.p.A, September 22, 2011) discloses (per)fluoropolyethers comprising at least one (per)fluoropolyoxyalkylene chain comprising at least one recurring unit of formula -CF2-CF(CF2O-SC>2F)-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.
  • CN 103724559 discloses a method comprising placing the perfluoropolyether peroxide prepared by a photo-oxidation method in an inert fluorine-containing solvent, introducing perfluoro-olefin under an ultraviolet irradiation condition, and reacting the perfluoro-olefin with the peroxide to form a stable perfluoropolyether compound.
  • WO 2019/048394 Solvay Specialty Polymers Italy S.p.A., March 14, 2019 discloses polyfunctional perfluoropolyether derivatives including a plurality of ionisable groups selected from the group consisting of -SOsXa, -PChXa and - COOXa, wherein Xa is H, ammonium group or a monovalent metal.
  • the Applicant faced the problem of providing new functional PFPE copolymers characterised by an increased viscosity (as measured by complex viscosity at 0.1 rad/s at 25°C), while maintaining low glass transition temperature (Tg) and still being in the liquid state at room temperature.
  • the new functional PFPE copolymers according to the present invention are characterised by an increased viscosity index, notably between 40°C and 100°C.
  • the new functional PFPE copolymers according to the present invention are characterised by an increased thermal stability (as shown in the examples via TGA analysis), which makes them suitable for use in harsh environments and applications.
  • the new PFPE copolymers comprising functional groups are suitable for use as additives in different technical fields, including as anti-rust, anti-wear, to increase compatibility among base oils and thickeners and other ingredients dispersed in such base oils.
  • the functional groups can be further reacted or derivatized to provide further functionalized derivatives.
  • 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.
  • At least one first block [block (1)] complying with formula (I): wherein m is 0 or an integer from 1 to 5, preferably from 1 to 2;
  • 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 (II):
  • 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 a functional group, preferably selected from: -SO2F, -SO3H, -COOH, -COF, - CN, -Br and -CONH2; and y is an integer equal to 1 or 2; with the proviso that in formula (I), at least one, preferably one, of Rs to Rs is group of formula (II);
  • n is an integer from 1 to 3;
  • Ri 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 (IV):
  • 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 (V): -[(A) a -(B) b -(F) f ] u -(A)-T (V) wherein u is zero or an integer from 1 to 50;
  • T is a perfluorinated alkyl group; a is zero or 1 , each A is a PFPE chain; b is zero or an integer from 1 to 3,
  • RIA to R4A each independently has the meaning defined above for each of R1 to R4, respectively; f is 0 or an integer from 1 to 5, preferably from 1 to 2;
  • At least one third block [block (3)] comprising a PFPE chain; with the proviso that, in copolymer (P): the sum of (m+f) is at least 1 , preferably from 1 to 100; the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11, even more preferably from 1 to 9; and said at least one block (1), said at least one block (2), and when present said at least one block (3) 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 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 as determined via NMR, 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-I 11) here below: (Rf-lll)-[(CF2CF2O) a i(CF 2 O) a 2]- wherein:
  • - a1 , and a2 are integers > 0 such that the number average molecular weight is between 400 and 100,000 as determined via NMR, 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.
  • m is 0 or an integer from 1 to 2.
  • one of Rs to Rs is a group of formula (II).
  • R20 is a sigma bond or a group selected from those of formula (R2o-i) to (R2o-iv) as represented 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 6, preferably from 1 to 3, carbon atoms, and more preferably complying with formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF 2 CF(CF 3 )-; 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 in formula (II).
  • R complies with one of the following formulae:
  • RCF is either a perfluoroalkyl chain comprising from 1 to 12, preferably from 1 to 8 carbon atoms, optionally interrupted by one or more oxygen atoms
  • 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 a 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, X and y are as defined above for formula (II);
  • 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. Accordingly, the PFPE peroxy, the compound of formula (X-p) and the compound of formula (XX-p) can be supplied to the reaction environment in any order.
  • the PFPE peroxy can be subjected to partial reduction ofthe 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-IIC) or (Rf-lll) as defined above.
  • 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: (R20-D
  • 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-, -CF 2 CF(CF 3 )-; 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 )-;
  • R500 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 :
  • CF2 CFCF 2 OCF2CF 2 COF
  • CF2 CFOCF 2 CF(CF 3 )OCF2CF 2 CN
  • CF2 CFCF 2 OCF2CF 2 CN
  • CF2 CFCF 2 OCF2CF 2 Br
  • CF2 CFOCF 2 CF(CF 3 )OCF2CF 2 Br
  • CF 2 CFOCF 2 CF 2 SO 2 F
  • CF 2 CFOCF 2 CF(SO 2 F) 2
  • CF 2 CFOCF 2 CF(CF 2 OCF2CF2SO 2 F)(OCF 2 CF 2 SO 2 F)
  • CF 2 CFOCF 2 CF(CF 2 CF 2 SO 2 F)(OCF 2 CF 2 SO 2 F)
  • CF 2 CFOCF 2 OCF 2 CF(CF 2 OCF 2 CF 2 SO 2 F)(SO 2 F).
  • 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 compound (XX-p) is not limited.
  • 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) of process (P) can be advantageously performed by contacting said PFPE peroxy with one compound of formula (XX-p).
  • step (a) can be performed by contacting said PFPE peroxy with two or more compounds of formula (XX-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, hydrofluoropolyethers.
  • 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.
  • said process (P) comprises after step (b), step (c) of removal of the solvent and/or step (d) of fractionation.
  • Said step (c) of removal of the solvent can be carried out by evaporation, for example by distillation under vacuum.
  • Said step (d) of fractionation can be performed via solvent extraction, using supercritical CO 2 , hexafluoroxylene or hydrofluorocarbons as solvents, and mixtures thereof when the fractionation step is performed via precipitation fractionation.
  • Supercritical CO 2 is preferred.
  • the present invention relates to copolymer (P) obtained via process (P) as described above.
  • the functional groups introduced as pendant groups in block (1) of copolymer (P), such as notably -SO 2 F, -SO 3 H, -COOH, -COF, -CN, -Br and - CONH 2 , as well as the functional groups at the chain ends of copolymer (P), such as notably -COF and -OC(O)F, can be properly reacted to obtain other different functional groups.
  • copolymer (PF) according to the present invention is obtained from process (P) as described above, which further comprises after said step (b) , at least one step (c) comprising at least one of salification, hydrolyzation, oxidation, reduction or another chemical reaction capable of providing functional group(s) of interest.
  • the present invention further encompasses copolymer (PF) obtained at the end of step (c) of process (P).
  • the present invention encompasses a block copolymer [copolymer (F»] comprising a first and a second perfluoropolyether chain [PFPE chain] each having two chain ends, wherein the first chain end of each one of said firstand second PFPE chain is a chain end of copolymer (P) and each one comprises a group selected from a perfluorinated linear or branched alkyl chain comprising from 1 to 6 carbon atoms, -COOH and salts thereof with an organic cation, preferably onium cation, more preferably ammonium, or an inorganic cation, preferably an alkaline metal, more preferably Na + , K + ; -COOR wherein R is a linear or branched alkyl chain comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably 1 carbon atoms; -COF; -CONH2; - CON(R 3 OO)(R3
  • At least one third block [block (3)] comprising a PFPE chain; with the proviso that, in copolymer (PF): the sum of (m+f) is at least 1 , preferably from 1 to 100; the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11 , even more preferably from 1 to 9; and said at least one block (1), said at least one block (2), and, when present, said at least one block (3) are statistically distributed.
  • the present invention relates to a mixture [mixture (PF)] comprising two or more copolymers (PF) as defined above.
  • the present invention relates to a mixture [mixture (P)] comprising two or more copolymers (P) as defined above.
  • mixture (P) is obtained via process (P) as described above.
  • said mixture (P) can be subjected to one or more purification steps (also referred to as “fractionation” steps) as disclosed above, thus obtaining separate copolymers (P) characterised by different viscosities and/or number average molecular weights as measured by 19 F-NMR and/or functionality (F), preferably from 3 to 102.
  • purification steps also referred to as “fractionation” steps
  • F functionality
  • Said mixtures can further contain the PFPE peroxy used as starting material and/or mixtures of copolymers (P) containing peroxy groups [copolymer (Po-o)] and/or mixtures of copolymers (PF) containing peroxy groups [copolymers (PF-O-O)] can be obtained.
  • copolymer (Po-o) and/or copolymer (PF-O-O) can be isolated and used as intermediate in other processes.
  • the amount of peroxy groups that can be present in the mixture containing copolymer (P) or copolymer (PF) of the present invention can be up to 99% based on the amount of the starting peroxy groups in the PFPE peroxy, depending on the final application the amount of said peroxy groups can be properly adjusted for example up to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5%.
  • the amount of said peroxy groups is up to 1 , even more preferably up to 0.5 % and still more preferably up to 0.1%.
  • At least one third block [block (3)] comprising a PFPE chain as defined above; with the proviso that
  • n+b the sum of (n+b) is at least 1 , preferably from 1 to 15, more preferably from 1 to 11 , even more preferably from 1 to 9;
  • At least one third block [block (3)] comprising a PFPE chain as defined above; with the proviso that
  • the present invention related to a mixture [mixture (M1)] comprising at least one copolymer (P) as defined above, and at least one of said PFPE peroxy used as starting material and/or one or more of copolymers (Po-o).
  • the present invention relates to a mixture [mixture (M2)] comprising at least one copolymer (PF) as defined above, and at least one of at least one of copolymer (P) as defined above, said PFPE peroxy used as starting material, said one or more copolymers (Po-o), and/or said one or more copolymers (PF-O-O).
  • M2 mixture [mixture (M2)] comprising at least one copolymer (PF) as defined above, and at least one of at least one of copolymer (P) as defined above, said PFPE peroxy used as starting material, said one or more copolymers (Po-o), and/or said one or more copolymers (PF-O-O).
  • Copolymer (P) and/or copolymer (PF) according to the present invention can be used for different applications in several industries, wherein outstanding resistance and durability at high temperature and harsh environments is required.
  • copolymer (P) and/or copolymer (PF) can be used as base oils as lubricants.
  • copolymer (P) and/or copolymer (PF) can be used as additives in halogenated oils and/or greases.
  • the copolymers according to the present invention as well as the mixtures described herein, are in the liquid state at room temperature, or even at temperatures lower than room temperature, with advantages in handling and storage of the copolymers.
  • copolymer (P) is in the liquid state at room temperature.
  • copolymer (PF) is in the liquid state at room temperature.
  • each of copolymer (Po-o) and copolymer (PF-O-O) as well as each of mixture (M1) and mixture (M2) is in the liquid state at room temperature.
  • each of copolymer (Po-o) and copolymer (PF-O-O) as well as each of mixture (M1) and mixture (M2) is in the liquid state at room temperature.
  • 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
  • Perfluorinated solvents Galden(R) HT200 and Galden(R) D100, as well as tetrafluoroethylene (TFE) and perfluoro-methylvinyl-ether (PMVE), and perfluorinated sulfonyl vinyl ether (VEFS) CF 2 CFOCF 2 CF 2 SO 2 F were obtained by Solvay Specialty Polymers Italy S.p.A..
  • 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 CFC 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 complex viscosity was measured by means of frequency sweep tests, using an MCR502 Anton-Paar rheometer with parallel plate geometry (25mm diameter). The viscosity was measured in this way at 25°C and 100°C and its value at 0.1 rad/s of oscillation is reported.
  • Viscosity index was calculated according to ASTM D2270 measuring viscosity at about 40°C and about 100°C.
  • TGA analysis was performed with a TGA 5500 analyzer from TA Instruments with a heating rate of 10°C/min in an oxygen-containing atmosphere (air), measuring the temperatures at which a loss of 10% and 50% of the weight of the samples occurred.
  • FT-IR spectra were acquired on a Thermo Fisher IS10 Spectrometer on liquid samples as thin films on KBr.
  • Example 1 PFPE copolymers with 8CNVE, PBVE
  • the oil was diluted with 1876 g of Galden(R) D100. Next, 19.4 g of 8CNVE and 2.5 g of PBVE were added to the reactor. The mixture was then purged with nitrogen under stirring, and the UV lamp was switched on for 42 hours at 20°C. After this time, the lamp was switched off and the reaction mixture was transferred into a 2-L round bottom flask. The mixture was stripped at 120°C for 6h under reduced pressure (0.1 mbar).
  • X and X’ -CF 3 , -CF 2 COF and -OCOF.
  • Example 2 - PFPE copolymers with VEFS and PBVE
  • the obtained solution was distilled at 240°C for 4h in a round bottom flask equipped with a magnetic stirrer in order to remove the solvent and unreacted monomer traces.
  • the distillation was conducted first at atmospheric pressure, then under reduced pressure (0.1 mbar) until complete removal of the solvent.
  • the oil was diluted with 1876 g of Galden(R) HT200 and then 23.0 g of VEFS and 1.1 g of PBVE were added to the reactor.
  • Example 2 The polymers of Example 2 and Comparative Example 2a were also subjected to TGA analysis to determine their weight loss under heating conditions. The results are reported in the following Table 2.

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Abstract

La présente invention concerne de nouveaux copolymères comprenant des chaînes (per)fluoropolyéther et des groupes fonctionnels.
PCT/EP2023/076610 2022-09-28 2023-09-26 Polymères de perfluoropolyéther Ceased WO2024068676A1 (fr)

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CN202380069347.9A CN119948070A (zh) 2022-09-28 2023-09-26 全氟聚醚聚合物
EP23777272.8A EP4594373A1 (fr) 2022-09-28 2023-09-26 Polymères de perfluoropolyéther
JP2025518177A JP2025536121A (ja) 2022-09-28 2023-09-26 ペルフルオロポリエーテルポリマー

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Citations (16)

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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
US5585449A (en) * 1993-12-29 1996-12-17 Ausimont S.P.A. Fluoroelastomers comprising monomeric units deriving from a bis-olefin
US5719259A (en) 1995-08-14 1998-02-17 E. I. Du Pont De Nemours And Company Perfluoroalkylene oxide copolymer composition containing functional groups
US5877264A (en) * 1996-11-25 1999-03-02 E. I. Du Pont De Nemours And Company Fast-curing perfluoroelastomer composition
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
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
WO2012007374A1 (fr) * 2010-07-14 2012-01-19 Solvay Solexis S.P.A. Composition de fluoroélastomère
US8258090B2 (en) 2006-11-30 2012-09-04 Solvay Solexis S.P.A. Fluorinated lubricants
CN103724559A (zh) 2013-12-17 2014-04-16 中昊晨光化工研究院有限公司 一种由全氟聚醚过氧化物合成全氟聚醚的方法
US20140114009A1 (en) * 2011-06-09 2014-04-24 Solvay Specialty Polymers Italy S.P.A. Hyperbranched fluoroelastomer additive
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

Patent Citations (16)

* 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
US5585449A (en) * 1993-12-29 1996-12-17 Ausimont S.P.A. Fluoroelastomers comprising monomeric units deriving from a bis-olefin
US5719259A (en) 1995-08-14 1998-02-17 E. I. Du Pont De Nemours And Company Perfluoroalkylene oxide copolymer composition containing functional groups
US5877264A (en) * 1996-11-25 1999-03-02 E. I. Du Pont De Nemours And Company Fast-curing perfluoroelastomer composition
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
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
WO2012007374A1 (fr) * 2010-07-14 2012-01-19 Solvay Solexis S.P.A. Composition de fluoroélastomère
US20140114009A1 (en) * 2011-06-09 2014-04-24 Solvay Specialty Polymers Italy S.P.A. Hyperbranched fluoroelastomer additive
CN103724559A (zh) 2013-12-17 2014-04-16 中昊晨光化工研究院有限公司 一种由全氟聚醚过氧化物合成全氟聚醚的方法
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

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