WO2024068677A1 - Polymères de perfluoropolyéther - Google Patents

Polymères de perfluoropolyéther Download PDF

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Publication number
WO2024068677A1
WO2024068677A1 PCT/EP2023/076612 EP2023076612W WO2024068677A1 WO 2024068677 A1 WO2024068677 A1 WO 2024068677A1 EP 2023076612 W EP2023076612 W EP 2023076612W WO 2024068677 A1 WO2024068677 A1 WO 2024068677A1
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chain
block
formula
group
carbon atoms
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PCT/EP2023/076612
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English (en)
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Andrea LOTIERZO
Ugo De Patto
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2024068677A1 publication Critical patent/WO2024068677A1/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
    • 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
    • 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

  • 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.
  • 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 O 2 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.
  • Polyfunctional (per)fluoropolyether polymers have been further disclosed in US 5,719,259 (E.I.
  • 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 -CF 2 -CF(CF 2 O-SO 2 F)-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.
  • 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 -SO3Xa, -PO3Xa and – COOXa, wherein Xa is H, ammonium group or a monovalent metal.
  • Xa is H, ammonium group or a monovalent metal.
  • the Applicant developed new co-polymers comprising (per)fluoropolyether chains and (per)fluorinated co-monomers, whose properties - for example with respect to their viscosity and/or physical appearance - can be properly tuned based on their intended final use.
  • the Applicant faced the problem of preparing new co-polymers comprising (per)fluoropolyether chains characterised by increased viscosity (as measured by complex viscosity at 0.1 rad/s at 25°C).
  • the new copolymers according to the present invention show a low glass transition temperature (T g ) and are in the liquid state at room temperature.
  • T g glass transition temperature
  • the new copolymers according to the present invention can be provided in a solid form, such as in particular as rubbers, or in a semi-solid form.
  • the Applicant developed new copolymers comprising functional groups, which can be advantageously introduced as pendant groups along the main backbone of the PFPE copolymers to make them suitable for use as SSPI 2022/021 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.
  • copolymer (P) according to the invention can be provided in liquid form or in semi-solid form. However, when required by the final use, copolymer (P) can also be provided in the form of solid, such as a rubber.
  • copolymer (P) is characterised by a complex viscosity, measured at 0.1 rad/s and at 25°C, varying in a large range, such as from 10 Pa*s to more than 2000 Pa*s.
  • said 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: (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) -CF2CF2CF2O-; (iv) -CF 2 CF 2 CF 2 O-; (v) -(CF 2 ) j -CFZ-O- wherein j is an integer from 0 to 3 and Z is a group of general formula -O-R(f-a)-T, wherein R(f-a) is a fluoropolyoxyalkene chain
  • chain (Rf) complies with the following formula: (Rf-I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF 2 CF 2 CF 2 O) g3 (CF 2 CF 2 CF 2 O) g4 ]- wherein - X 1 is independently selected from -F and -CF3, SSPI 2022/021 - X 2 , X 3 , equal or different from each other and at each occurrence, 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
  • chain (R f ) is selected from chains of formula: (Rf-IIA) -[(CF2CF2O)a1(CF2O)a2]- wherein: - 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; (Rf-IIB) -[(CF2CF2O)b1(CF2O)b2(CF(CF3)O)b3(CF2CF(CF3)O)b4]- wherein: b1, b2, b3, b4, 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; preferably each of b1, b2, b3, b4 are > 0; (Rf-IIA)
  • chain (R f ) complies with formula (R f -III) here below: (R f -III) -[(CF 2 CF 2 O) a1 (CF 2 O) a2 ]- 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.
  • at least one of L ⁇ and L is different from 0.
  • both L ⁇ and L are different from 0.
  • R 100 , R 101 , R 102 and R 103 are a halogen atom, such as fluorine atom or chlorine atom.
  • m is 0 or an integer from 1 to 2.
  • one of R 5 to R 8 is a group of formula (V).
  • R20 is a sigma bond or a group selected from those of formula (R20-i) to (R20-iv) as defined hereinafter: (R 20 -i) -(CF2)s1-O-(CF2)s2- wherein each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3; (R20-ii) -O-(CF 2 ) s3 - wherein s3 is an integer from 1 to 6, preferably from 1 to 5; (R20-iii) -O-R 400 -O-R 401 - wherein 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(CF3)-; and R401 is a linear or branched perfluorinated alkyl chain comprising from 1 to 6, preferably
  • 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
  • An advantage of the process for the manufacture of copolymer (P) according to the present invention is that the amounts of the reactants providing each of block (1), block (2) and block (3) can be tuned and selected a priori based on the desired properties of the final copolymer (P). This is advantageous as selecting a priori the amount of the reactants allows to tune the number of each block (1), block (2) and block (3) in copolymer (P).
  • step (a) the order in which the reactants are added is not limited. Accordingly, the PFPE peroxy, the compound of formula (X-p), the compound of formula (XX- p) and the compound (O) 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) comprising, preferably consisting of, repeating units (R°) being independently selected from the group consisting of formulae (i)
  • 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: (i) fully halogenated olefin comprising from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms.
  • each of R21, R22 and R23 is -F.
  • SSPI 2022/021 R 20 is a sigma bond or a group selected from those of formula (R20-i) to (R20-iv) as defined hereinafter: (R20-i) -(CF2)s1-O-(CF2)s2- wherein each of s1 and s2 is independently an integer from 1 to 6, preferably from 1 to 3; (R 20 -ii) -O-(CF2)s3- wherein s3 is an integer from 1 to 6, preferably from 1 to 5; (R 20 -iii) -O-R400-O-R401- wherein 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 -CF 2 -
  • the amount of each of said at least one compound (X-p), compound (XX-p) and compound (O) 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). [0054] For example, the equivalents of double bonds of said compound (X-p) to the equivalents of peroxidic groups preferably range from 1:100 to 5000:100. Also, 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).
  • said 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).
  • said 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, 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.
  • step (b) is performed in an inert atmosphere.
  • the present invention relates to copolymer (P) obtained via process (P) as described above.
  • the functional groups introduced as pendant groups in block (3) of copolymer (P), such as notably -SO2F, -SO3H, -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).
  • PFPE chain perfluoropolyether chain
  • 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 atom
  • the present invention relates to a mixture [mixture (PF)] comprising two or more copolymers (P F ) as defined above.
  • mixtures of copolymers (P) or copolymers (PF) according to the present invention are typically obtained.
  • 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), 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.
  • Said mixtures can further contain the PFPE peroxy used as starting material and/or mixtures of copolymers (P) containing peroxy groups [copolymer (P O-O )] and/or mixtures of copolymers (P F ) containing peroxy groups [copolymers (P F-O-O )] can be obtained.
  • 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).
  • M1 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 (P O-O ), and/or said one or more copolymers (PF-O-O).
  • copolymer (PO-O) and/or copolymer (PF-O-O) can be isolated and used as intermediate in other processes.
  • 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%.
  • Copolymer (P) and/or copolymer (P F ) 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.
  • copolymers according to the present invention 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 (P F ) 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.
  • Example 1 - PFPE copolymer with VEFS, TFE, PMVE and PBVE 250.3 g of the peroxidic perfluoropolyether oil described above were charged in a 1500 mL stirred cylindrical photochemical reactor equipped with a high pressure mercury lamp model HANAU TQ150, a thermocouple, a condenser and a mechanical stirrer. [00102] 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 – PFPE copolymers with 8CNVE, PBVE, TFE and PMVE 251.8 g of the peroxidic perfluoropolyether oil described above were charged in the same reactor as Example 1. The oil was diluted with 1873 g of Galden(R) D100. Next, 29.2 g of 8CNVE and 2.5 g of PBVE were added to the reactor. [00111] The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor, at a rate of 17.1 and 9.3 g/h, respectively. After the flow started, the UV lamp was switched on and the reaction was conducted at 20°C for 6h.
  • the introduction of the -CN functional groups was also confirmed by FT-IR spectroscopy measurements, confirming the presence of the peak at 2269 cm -1 .
  • Comparative Example 1 - PFPE copolymers with VEFS, TFE and PMVE 251 g of the peroxidic perfluoropolyether oil described above were charged in a the same reactor as Example 1.
  • the oil was diluted with 1876 g of a SSPI 2022/021 perfluorinated solvent, Galden(R) HT200, and 14.0 g of VEFS were added to the reactor. [00119] The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor, at a rate of 14.6 and 8.0 g/h, respectively. After the flow started, the UV lamp was switched on and the reaction was conducted at 20°C for 7h.
  • the oil was diluted with 1875 g of a perfluorinated solvent, Galden(R) D100, and 29.2 g of 8CNVE were added to the reactor. [00126] The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor, at a rate of 17.1 and 9.3 g/h, respectively. After the flow started, the UV lamp was switched on and the reaction was conducted at 20°C for 6h. After this time the olefin flows were interrupted and the UV lamp was kept on for further 35 hours at 20°C.

Abstract

La présente invention concerne de nouveaux copolymères comprenant des chaînes (per)fluoropolyéther et des groupes fonctionnels.
PCT/EP2023/076612 2022-09-28 2023-09-26 Polymères de perfluoropolyéther WO2024068677A1 (fr)

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EP22198270.5 2022-09-28

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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
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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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* Cited by examiner, † Cited by third party
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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
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