(Per)fluoropolyether polymer composition

Abstract

The present invention relates to a composition comprising at least one (per)fluoropolyether base oil and at least one polymer obtained by copolymerizing a (per)fluoropolyether (PFPE), tetrafluoroethylene (TFE) and at least one non-homopolymerizable olefin.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to European Patent Application No. 20159015.5, filed February 24, 2020, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a composition comprising at least one (per)fluoropolyether base oil and at least one polymer obtained by copolymerizing a (per)fluoropolyether (PFPE), tetrafluoroethylene (TFE) and at least one non-homopolymerizable olefin. [Background technology]

[0003] It is known in the art that the polymerization of perfluorinated olefins in the presence of perfluorinated polyperoxides can produce polymers in the form of greases.

[0004] For example, U.S. Patent No. 3,493,530 (Montecatini Edison SpA) discloses a process for polymerizing halogenated olefins with polymeric perfluorinated polyperoxides to form polymer mixtures in a wide range of ratios during the reaction, depending on the initial amounts of monomer and polyperoxide. Such a reaction makes it possible to obtain homogeneous greases that can be used as lubricants. According to this document, polymerization can be carried out under heat or at room temperature in the presence of ultraviolet light.

[0005] US Patent No. 4,500,739 (Montedison SpA) discloses perfluoropolyethers which, in addition to the -CF2 and -C2F4- repeating units, also contain third fluoroalkylene units containing three or more carbon atoms, said units being linked to one another via -O-ether bridges, and the process for obtaining said polyethers consists in reacting a mixture of polyperoxide perfluoropolyethers with fluorinated olefins in the presence of ultraviolet light.

[0006] More recently, U.S. Pat. No. 8,258,090 (Solvay Solexis SpA) discloses fluorinated lubricants of formula (I): TO-[AB] z -[A-B'] z’ -A-T' (I) where A represents a perfluoropolyether chain and B represents a block formed of units derived from one or more olefins, at least one of which is polymerizable via a radical pathway. The patent provides a very long list of suitable olefins, and synthesis via a thermal process is the preferred synthetic route.

[0007] WO 2016 / 150941 (Solvay Specialty Polymers Italy SpA) discloses highly viscous fluids suitable for use as damping fluids. In other words, these polymers are highly viscous fluids that can be provided in damper devices to absorb and attenuate impact impulses. In particular, Example 10 of this patent application describes the synthesis by a photochemical route of polymers containing segments from PFPE, TFE, and perfluoromethylvinylether (PMVE), such that the polymers thus obtained have the formula -(BO) q - (where B is derived from TFE (10.8 w / w%) and PMVE (8.4 w / w%)) in a ratio of 19.2 wt. % (wt. % based on the total weight of the polymer). Despite its high viscosity, this polymer is provided in the form of an oil.

[0008] WO 2018 / 185026 (Solvay Specialty Polymers Italy SpA) discloses a liquid composition comprising a physical mixture of at least one (per)fluoropolyether polymer and at least one amorphous polymer. Summary of the Invention

[0009] The Applicant has surprisingly found that it is possible to provide a composition having an optimized dynamic viscosity compared to known compositions from the prior art by mixing two PFPE-based polymers.

[0010] Advantageously, the composition can be used as a lubricant without the need to add viscosity modifiers, such as the solid particles described in the above-mentioned WO 2016 / 150941.

[0011] Thus, in a first aspect, the present invention relates to a composition [composition (C)] comprising (I) and (II) below: (I) at least one polymer [polymer (P)] satisfying chemical formula (I); TO-[AB] z -[A-B'] z’ -A-T' (I) A is -(X) a -O-(R f )-(X') b - in which (R f ) is a fully or partially fluorinated polyoxyalkylene chain, X and X' are equal to or different from each other and are selected from -CF2-, -CF2CF2-, and -CF(CF3)-; a and b are equal to or different from each other and are integers equal to 0 or 1; provided that the block A attached to the terminal group TO- has a=1 and the block A attached to the terminal group T' has b=0; z is an integer greater than or equal to 2; z' is an integer of 0 or 1 or greater; T and T' are equal to or different from each other and are a hydrogen atom or a group selected from -CF2H, -CF2CF2H, -CF3, -CF2CF3, -CF2CF2CF3, -CF2Cl, -CF2CF2Cl, -CF3F6Cl, -CF2Br, B and B' are the same or different and have the formula -[(CF2CF2) c -(CF2CFR X ) d ] e - (In the formula, R X is, independently, -CF3, -OCF3, -OC2F5, and -OC3F7 and combinations thereof; -OCF2OR f2 (In the formula, R f2 is a linear or branched C1 to C6 perfluoroalkyl group, a cyclic C5 to C6 perfluoroalkyl group, or a linear or branched C2 to C6 perfluorooxyalkyl group; preferably, R f2 is selected from -CF2CF3, -CF2CF2OCF3 or -CF3; c, d, and e are independently integers of 1 to 500; (1) The repeating unit -(CFCF) c -and-(CF2CFR X ) d - is statistically distributed within B and B'; and (2) the formula -(CF2CF2) c - recurring units amount to at least 11% by weight of the weight of said polymer (P), based on 100% by weight of said polymer (P); (II) at least one (per)fluoropolyether polymer [polymer PFPE] comprising: - at least one (per)fluoropolyether chain [chain (R pf )]and, - Said chain (R pf ) and two chain ends [chain (R e )], wherein both said chains (Re ) has two chain ends [chain (R e )].

[0012] Advantageously, said composition (C) is characterized by a dynamic viscosity measured at 25° C. and 0.1 rad / s of greater than or equal to 60 Pa*s.

[0013] Advantageously, said composition (C) can be obtained by contacting at least one polymer (P) as defined above with at least one polymeric PFPE as defined above, optionally in the presence of a fluorinated solvent and / or a fluorinated additive selected from the group comprising fluorescent agents, anticorrosive agents, etc.

[0014] The applicant has surprisingly found that by contacting the at least one polymer (P) with the polymeric PFPE, a homogeneous composition is obtained having a semi-liquid consistency and dynamic viscosity such that the composition (C) can be used as a lubricant in industrial applications even under harsh environments. DETAILED DESCRIPTION OF THE INVENTION

[0015] For purposes of this specification and the claims that follow: - the use of parentheses around symbols or numbers specifying a formula, such as in expressions like "polymer (P)", has the sole purpose of better distinguishing the symbols or numbers from the rest of the text, and therefore said parentheses may also be omitted; - the acronym "PFPE" stands for "(per)fluoropolyether" and, when used as a noun, is intended to mean either the singular or the plural, depending on the context; - the prefix "(per)" in the term "(per)fluoropolyether" means that the polyether can be fully or partially fluorinated; - the term "olefin" is intended to mean an unsaturated hydrocarbon containing at least one carbon-carbon double bond.

[0016] The number average molecular weight of the polymer (P) is 19 When determined by F-NMR spectroscopy, it is preferably in the range of 5,000 to 150,000 g / mol, more preferably 10,000 to 100,000 g / mol.

[0017] The polymer (P) is preferably a compound represented by the formula -(CFCF) in an amount of 11 to 30% by weight, more preferably 15 to 28% by weight, based on 100% by weight of the polymer (P). c -Contains repeating units of

[0018] The polymer (P) is preferably a compound represented by the formula -(CF2CFR X ) d -Contains repeating units of

[0019] Preferably, the chain (R f ) comprises or preferably consists of a repeating unit R°, said repeating unit being (i) -CFXO- (wherein X is F or CF); (ii) -CFXCFXO- (wherein X, equal or different at each occurrence, is F or CF3, provided that at least one of X is -F); (iii) -CFCFCWO- (wherein each W is equal to or different from one another and is F, Cl, or H); (iv) -CF2CF2CF2CF2O-; (v)-(CF2) w -CFZ-O- (wherein w is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -Y group, where R (f-a)is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, said repeat units being selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (wherein each X is independently F or CF3), and Y is a C1 to C3 perfluoroalkyl group). are independently selected from the group consisting of:

[0020] Preferably, the chain (R f ) is expressed by the following formula (R f -I) and (R f -II): (R f -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- (In the formula, - X 1 is independently selected from -F and -CF3; - X's that are equal or different from each other and from each occurrence 2 , X 3 are independently -F, -CF3, provided that at least one of X is -F; - g1, g2, g3 and g4 are equal to or different from one another and independently ≧0 such that g1+g2+g3+g4 ranges from 2 to 300, preferably from 10 to 250, and even more preferably from 15 to 200; if at least two of g1, g2, g3 and g4 are different from zero, the different repeat units are generally statistically distributed along the chain; (R f -II) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4-(CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]- (In the formula, - X 1 , X 2 , X 3 is as defined above; g1, g2, g3, g4, g5, and g6 are equal to or different from one another and are independently ≧0 such that g1+g2+g3+g4+g5+g6 ranges from 2 to 300, preferably 10 to 250, provided that at least one of g5 and g6 is not 0. Meet the following.

[0021] In a preferred embodiment, the chain (R f ) is the above formula (R f -I) is satisfied.

[0022] Preferably, X and X' are equal to or different from each other and are selected from -CF2- and -CF2CF2-.

[0023] Preferably, T and T' are equal to or different from each other and are a hydrogen atom or a group selected from -CF3, -CF2CF3, -CF2CF2CF3, -CF2Cl, -CF2CF2Cl.

[0024] Preferably, said polymer (P) is prepared by contacting at least one peroxide perfluoropolyether polymer, at least tetrafluoroethylene and at least one second comonomer in the presence of ultraviolet light.

[0025] Alternatively, the polymer (P) is prepared by contacting, under heating, at least one peroxide perfluoropolyether polymer, at least tetrafluoroethylene and at least one second comonomer.

[0026] The peroxide perfluoropolyether polymers are prepared by methods known in the art.

[0027] According to one preferred embodiment, the at least one second comonomer is selected from the group consisting of hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), and copolymers of the general formula CF2=CFOCF2OR. f2 perfluoromethoxyvinyl ether (MOVE) (wherein R f2 is a linear or branched C1 to C6 perfluoroalkyl group, a cyclic C5 to C6 perfluoroalkyl group, or a linear or branched C2 to C6 perfluorooxyalkyl group; preferably, R f2 is selected from the group consisting of -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2), or -CF3(MOVE3).

[0028] Advantageously, the polymer (P) is in the form of a rubbery polymer.

[0029] Preferably, the polymeric PFPE has the formula -(X) a -O-(R f )-(X') b -(In the formula, X, X', a, b and R f is as defined above for the polymer (P)) pf ) is included.

[0030] Alternatively, the polymeric PFPE may have the formula (II): TO-[AB] z -[A-B'] z’ -A-T' (II) wherein T, A, B, B', T', z and z' are as defined above for polymer (P), except that the polymer (P) has the formula -(CFCF) c - is up to 11 wt % by weight of said polymeric PFPE, based on 100 wt % of said polymeric PFPE.

[0031] Preferably, the composition (C) contains the polymer (P) in an amount of 0.5 to 85% by weight, based on the total weight of the composition (C), and the polymer PFPE in an amount of 15 to 99.5% by weight, based on the total weight of the composition (C).

[0032] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that the term may be unclear, the statements of this application shall control.

[0033] The present invention is exemplified herein below in more detail by the Examples contained in the Experimental Section below; however, the Examples are illustrative only and should not be construed as limiting the scope of the invention in any way. [Example]

[0034] Experimental section material: formula TO-(CF2CF2O) m (CF2O) n (O) h -T' Peroxide perfluoropolyether oils having the formula: where T and T' are chain ends selected from -CF, -CFCOF, -COF, -CFCOOH, -CFCl, -CFCFCl were obtained from Solvay Specialty Polymers Italy SpA.

[0035] Tetrafluoroethylene (TFE) and perfluoro(methyl vinyl ether) (PMVE) were obtained from Solvay Specialty Polymers Italy SpA.

[0036] The perfluorinated solvents Galden® D02 and Galden® HT200 are commercially available from Solvay Specialty Polymers Italy SpA.

[0037] Polymer (C): Tecnoflon® PFR LT Low Temperature Perfluoroelastomer

[0038] Polymer (D): Hyflon® AD40L An amorphous perfluorinated copolymer of 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxide (TTD) and tetrafluoroethylene (TFE) having a glass transition temperature of 95°C (measured according to ASTM D3418) and an intrinsic viscosity of 0.40 dL / g at 30°C (measured according to ASTM D2857).

[0039] Characterization Methods: 19 F-NMR spectroscopy: A Varian Mercury 200 MHz spectrometer acting on fluorine nuclei was used to obtain the structures, number average molecular weights and compositions of the PFPE oils reported in the examples below. 19 F-NMR spectra were obtained on pure samples using CFCl as an internal standard. Hexafluorobenzene was also used as the solvent.

[0040] Determination of Peroxide Content (PO): Analysis of peroxygen content was performed by iodometric titration using a Mettler DL40 instrument equipped with a platinum electrode. The detection limit for PO determination was 0.0002%.

[0041] Residual acidity measurement: Acidity was measured by potentiometric titration using a Mettler DL40 instrument equipped with a DG115-SC type electrode. Titrations were performed using 0.01 M aqueous NaOH as the titrant. The detection limit for acidity measurement was 0.4 meq / kg.

[0042] Dynamic viscosity measurement: Dynamic viscosity was measured in a frequency sweep test using an MCR502 Anton-Paar rheometer (25 mm diameter) in parallel plate geometry.

[0043] Differential scanning calorimetry (DSC): Thermal transitions were determined on a PerkinElmer Pyris apparatus.

[0044] Thermogravimetric analysis (TGA): TGA was performed using a TA TGA5500 analyzer at a heating rate of 10°C / min in a N2 atmosphere.

[0045] Example 1 - Preparation of Polymer (A) Polymer A was prepared using a 1000 mL cylindrical photochemical reactor equipped with a high-pressure mercury lamp (HANAU TQ150), a magnetic stirrer, a thermocouple, and a condenser.

[0046] The peroxide perfluoropolyether used had a number average molecular weight of 26700 g / mol; PO = 1.51%; m / n = 1.0; chain ends T and T' were -CF (90%), -CF COF (5%), -COF (2%), -CF Cl (2%), -CF CF Cl (1%).

[0047] 150.6 g of the peroxide perfluoropolyether having the above formula and 1555 g of Galden® D02 were added to a reactor. They were mixed thoroughly to obtain a clear, homogeneous solution. The reactor was maintained at 20°C under a nitrogen atmosphere during the synthesis. With the UV lamp on, 89 g of MVE and 53 g of TFE were fed into the reaction mixture at constant flow rates over a period of 6 hours.

[0048] After this reaction time, the lamp was turned off, the olefin flow was discontinued, and the reaction mixture was flushed with nitrogen. The mixture was transferred to a second glass photochemical reactor and treated with UV light and 1 NL / h of fluorine gas at 60°C for 7 hours. The contents of the reactor were transferred to a round-bottom flask equipped with a magnetic stir bar, and the solvent and residual PO (150°C-230°C) were removed.

[0049] 195.7 g of rubbery polymer was detected.

[0050] Acidity and PO were below the detection limit of the analytical method.

[0051] The resulting polymer [polymer (A)] had the following structure: TO-(CF2O) g1 (CF2CF2O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 (BO) g5 -T' where B is a block copolymer containing randomly distributed TFE and PMVE units.

[0052] The number average molecular weight was 29000 g / mol; the g2 / g1 ratio was 0.9. 19 The total weight calculated by F-NMR analysis was 34% (24% w / w from TFE and 10% w / w from PMVE). The chain ends T and T' were -CF3 (97%), -CF2Cl (2%), -CF2CF2Cl (1%).

[0053] DSC analysis showed the appearance of a single glass transition at −103° C. TGA analysis detected the product to be stable at high temperatures (1% loss at 362° C.).

[0054] Comparative Example 2 - Preparation of Copolymer PFPE-PMVE (Polymer B1-C) The synthesis of polymer B1-C containing PMVE units was carried out in a 1000 mL cylindrical photochemical reactor equipped with a high-pressure mercury lamp (HANAU TQ150), a magnetic stirrer, a thermocouple, and a condenser.

[0055] 1260 g of Galden® HT200 were introduced into the reactor together with 272 g of peroxide perfluoropolyether having the above formula, Mn=32900 g / mol, PO=1.50%, m / n=1.0; chain ends T and T′ were -CF3 (55%), -CF2COF (27%), -COF (10%), -CF2Cl (5%), -CF2CF2Cl (3%).

[0056] The reactor was cooled under nitrogen and stirring to about 10° C. Once the mixture was homogeneous and up to temperature, the UV lamp was turned on and PMVE was fed in.

[0057] The reaction was carried out for 6 hours, during which 111 g of PMVE was flushed in a constant stream. Finally, the UV lamp was turned off and the PMVE feed was interrupted. The reaction mixture was analyzed to determine 0.16% residual PO, referenced to PFPE. The mixture was transferred to a second glass photochemical reactor and treated with UV light and 1 NL / h fluorine gas at 60 °C for 13 hours. The reaction mixture was then transferred to a round-bottom flask equipped with a porcelain stir bar and subjected to vacuum distillation (150 °C to 230 °C) to remove the solvent and residual PO.

[0058] 262 g of oil (polymer B1-C) was obtained and characterized. Acidity and PO were below the detection limit of the analytical method. 19 F-NMR analysis confirmed the following structure: TO-(CF2O) g1 (CF2CF2O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 (CF2CF(OCF3)O) g5 -T' Here, the number average molecular weight was 36,000, the ratio of g2 / g1 was 0.9, g3 was 2.0, and g4 was 2.5.

[0059] The proportion of (CF2CF(OCF3)O) units in the polymer is 19 The calculated value by F-NMR analysis was 12.3%. T and T' were -CF3 (92%), -CF2Cl (5%), and -CF2CF2Cl (3%).

[0060] Comparative Example 3 - Preparation of Copolymer PFPE-TFE-PMVE (Polymer B2-C) 420 g of Galden® HT230 was dissolved in a solution of 100 ml of a 100% aqueous ethanol solution of the formula: TO-(CF2O) r (CF2CF2O) s (O) t -T' (wherein T and T' are -CF3 (45%), -CF2Cl (13%), -CF2CF2Cl (7%), and -CF2COF (35%), the number average molecular weight (Mn) was 41,500, s / r = 1.09, and PO was 1.26%). was introduced into the reactor along with 100 g of peroxide perfluoropolyether (PFPE).

[0061] The reactor was cooled to about 10° C. under nitrogen and under stirring. Once at temperature, the UV lamp was switched on and the fluorinated monomers (PMVE and TFE) were fed through the same inlet (the flow rate of TFE was 1.8 Nl / h and that of PMVE was 1.0 Nl / h).

[0062] The mixture was then maintained under these conditions for 6 hours, after which the UV lamp was turned off, the TFE and PMVE feeds were interrupted, and the temperature was allowed to rise to room temperature under a nitrogen stream.

[0063] The resulting mixture was transferred to a second glass reactor and treated at 230° C. for 5 hours, and then fluorinated with 1 Nl / h of fluorine gas at 180° C. for a total of 24 hours.

[0064] After vacuum distillation of the solvent (Galden® HT230), 106 g of a viscous oil was recovered.

[0065] The product was subjected to acidity and PO measurements, which were below the detection limits of the method.

[0066] 19 F-NMR analysis confirms the structure of polymer B2-C as follows: TO-(CF2O) g1 (CF2CF2O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 (BO) q-T' where: The ratio g2 / g1 is 0.91; g3 and g4 are 2.4 and 2.3, respectively; B is -(CFX) y -, X is -F and -CF3, and the average length of y is 27.0; q was 5.0.

[0067] -(BO) in the final polymer q The proportion of - was 19.2 wt% (derived from TFE (10.8% w / w) and PMVE (8.4% w / w)) based on the total weight of the polymer; T and T' were -CF3 (81%), and the remaining portion (19%) was -CF2Cl and -CF2CF2Cl.

[0068] The number average molecular weight (Mn) was 42,800.

[0069] Example 4 - Preparation of base oil The base oil was obtained using a 1000 mL cylindrical photochemical reactor equipped with a high-pressure mercury lamp (HANAU TQ150), a magnetic stirrer, a thermocouple, and a cooler.

[0070] The peroxide perfluoropolyether used had a number average molecular weight of 42700 g / mol; PO = 1.54%; m / n = 0.9. The chain ends T and T' were -CF3 (79%), -CF2COF (14%), -COF (3%), -CF2Cl (2%), and -CF2CF2Cl (2%).

[0071] A reactor was charged with 271.6 g of peroxide perfluoropolyether and 1250 g of Galden® HT200. They were mixed thoroughly to obtain a clear, homogeneous solution. The reactor was maintained at 20°C under a nitrogen atmosphere during the synthesis. With the UV lamp on, 64 g of PMVE and 44.4 g of TFE were fed to the reaction mixture and mixed together at constant flow rates over a period of 4 hours.

[0072] After this reaction time, the lamp was turned off, the olefin flow was discontinued, and the reaction mixture was flushed with nitrogen. The mixture was transferred to a second glass photochemical reactor and treated with UV light and 1 NL / h of fluorine gas at 60°C for 7 hours. The contents of the reactor were transferred to a round-bottom flask equipped with a magnetic stir bar, and the solvent and residual PO (150°C-230°C) were removed. 259.2 g of viscous oil was detected. The acidity and PO were below the detection limits of the analytical method.

[0073] The resulting base oil has the following structure: TO-(CF2O) g1 (CF2CF2O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 (BO) g5 -T' where B was a block copolymer containing randomly distributed TFE and PMVE units.

[0074] The number average molecular weight was 40000 g / mol; the ratio of g2 / g1 was 0.9; g3=4.2; g4=4.4.

[0075] of block B in the polymer 19 The total mass determined by F-NMR analysis was 17.3% (9.5% w / w from TFE and 7.8% w / w from PMVE). The chain ends T and T' were -CF3 (96%), -CF2Cl (2%), -CF2CF2Cl (2%).

[0076] The dynamic viscosity value at 0.1 rad / s and 25°C was 46.9 Pa*s.

[0077] Example 5 - Preparation of a composition in the presence of a solvent Polymer A, Polymer C, and Polymer D were each weighed out in an amount of 5 g or 10 g, and dissolved in 100 g of Galden® HT55 as a solvent in a glass flask.

[0078] Each mixture was heated to the solvent reflux temperature and stirred for 1 hour, at which point the solution was homogeneous.

[0079] Next, 90 g of base oil (prepared as described in Example 4) was weighed and dissolved in 100 g of Galden® HT55 as a solvent in a glass flask. The mixture was heated to the solvent reflux temperature and continued to stir for 1 hour. At the end of the stirring period, the mixture was analyzed by visual inspection. The solution was homogeneous.

[0080] The solutions obtained from Polymer A, Polymer C and Polymer D were each combined with the base oil solution and the solvent was removed under vacuum at 150°C.

[0081] The final compositions were visually analyzed for appearance and their dynamic viscosities were measured at 25°C.

[0082] The results are reported in Table 1 below.

[0083] [Table 1]

[0084] Example 6 - Preparation of a composition without solvent 5 g of Polymer A was weighed and mixed with 95 g of the base oil prepared above.

[0085] The mixture was heated to 130° C. and stirred for 2 hours.

[0086] The solution thus obtained (composition 9) was homogeneous.

Claims

1. A composition [composition (C)] comprising the following (I) and (II): (I) At least one polymer [polymer (P)] satisfying chemical formula (I): T-O-[A-B] ｚ -[A-B’] ｚ’ -A-T’ (I) A is -(X) ａ -O-(R ｆ )-(X') ｂ -, wherein (R ｆ ) is a polyoxyalkylene chain which is fully or partially fluorinated, X and X' are equal to or different from each other, and are -CF ２ -, -CF ２ CF ２ -, and -CF (CF ３ )—selected from; a and b are equal to or different from each other and are integers equal to 0 or 1; provided that the block A attached to the terminal group TO-- has a=1, and the block A attached to the terminal group T' has b=0; z is an integer of 2 or greater; z' is an integer of 0 or 1 or greater; T and T' are equal to or different from each other and are a hydrogen atom or -CF ２ H, -CF ２ CF ２ H, -CF ３ , -CF ２ CF ３ , -CF ２ CF ２ CF ３ , -CF ２ Cl, —CF ２ CF ２ Cl, -C ３ F ６ Cl, —CF ２ Br, B and B' are the same or different and have the formula -[(CF ２ CF ２ ) ｃ -(CF ２ CFR Ｘ ) ｄ ] ｅ - [In the formula, R Ｘ is, independently, -CF ３ , -OCF ３ , -OC ２ F ５ , and -OC ３ F ７ and combinations thereof; -OCF ２ OR ｆ２ (In the formula, R ｆ２ is a linear or branched C １ ~C ６ Perfluoroalkyl group, cyclic C ５ ~C ６ Perfluoroalkyl group, linear or branched C ２ ~C ６ perfluorooxyalkyl groups; c, d, and e are independently integers from 1 to 500; (1) The repeating unit -(CF ２ CF ２ ) ｃ - and - (CF ２ CFR Ｘ ) ｄ is statistically distributed within B and B'; and (2) Formula - (CF ２ CF ２ ) ｃ - repeating units in an amount of 15 to 28% by weight of the weight of said polymer (P), based on 100% by weight of said polymer (P); (II) at least one (per)fluoropolyether polymer [polymer PFPE] comprising: at least one (per)fluoropolyether chain [chain (R ｐｆ )]and, - the chain (R ｐｆ ) and two chain ends [chain (R ｅ ) )], wherein both said chains (R ｅ ) has two chain ends [chain (R ｅ ) ].

2. The composition (C) according to claim 1, wherein the composition (C) has a dynamic viscosity measured at 25°C and 0.1 rad / s of 60 Pa*s or more.

3. The composition (C) according to claim 1, wherein the composition (C) is obtainable by contacting at least one polymer (P) according to claim 1 with at least one polymer PFPE according to claim 1, optionally in the presence of at least one fluorinated solvent and / or at least one fluorinated additive.

4. The polymer (P) １９ 2. The composition (C) of claim 1, having a number average molecular weight of 5,000 to 150,000 g / mol as determined by F-NMR spectroscopy.

5. The polymer (P) is a compound of the formula -(CF) in an amount of 4 to 20% by weight, based on 100% by weight of said polymer (P). ２ CFR Ｘ ) ｄ The composition (C) according to claim 1, comprising a repeating unit of the formula:

6. The polymer (P) is a compound of the formula -(CF) in an amount of 6 to 18% by weight, based on 100% by weight of said polymer (P). ２ CFR Ｘ ) ｄ The composition (C) according to claim 1, comprising a repeating unit of the formula:

7. The chain (R ｆ ) comprises a repeat unit R°, said repeat unit being (i) -CFXO- (wherein X is F or CF ３ ); (ii) -CFXCFXO-, where X, equal or different at each occurrence, is F or CF ３ with the proviso that at least one of X is -F; (iii)-CF ２ CF ２ CW ２ O- (wherein each W is equal to or different from one another and is F, Cl, or H); (iv)-CF ２ CF ２ CF ２ CF ２ O-; (v)-(CF ２ ) ｗ -CFZ-O- (wherein w is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -Y group, where R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being as follows: -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O—, where each X is independently F or CF ３ and Y is selected from C １ ~C ３ perfluoroalkyl group) The composition (C) of claim 1, independently selected from the group consisting of:

8. The polymer PFPE has the formula -(X) ａ -O-(R ｆ )-(X’) ｂ - (In the formula, X, X', a, b and R ｆ is as defined in claim 1 for the polymer (P)) ｐｆ The composition (C) according to claim 1, comprising:

9. The polymer PFPE is represented by the formula (II): T-O-[A-B] ｚ -[A-B'] ｚ’ -A-T' (II) wherein T, A, B, B', T', z and z' are as defined in claim 1, provided that the formula -(CF ２ CF ２ ) ｃ 2. The composition (C) according to claim 1, wherein the repeating units of - are up to 11% by weight of the polymer PFPE, based on 100% by weight of the polymer PFPE.

10. The composition (C) according to any one of claims 1 to 9, wherein the polymer (P) is present in an amount of 0.5 to 85 wt% based on the total weight of the composition (C), and the polymer PFPE is present in an amount of 15 to 99.5 wt% based on the total weight of the composition (C).

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