(Per)fluoropolyether polymer

Abstract

The present invention relates to polymers obtained by copolymerization of (per)fluoropolyethers (PFPE), tetrafluoroethylene (TFE) and at least one non-homopolymerizable olefin.

Description

[Technical Field]

[0001] Cross-reference to related patent applications This application claims priority to European Patent Application No. 20159010.6, filed February 24, 2020, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel polymers obtained by copolymerization of (per)fluoropolyethers (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) disclosed 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] Applicants have surprisingly found that by reacting a perfluoropolyether (PFPE) peroxide polymer with tetrafluoroethylene (TFE) and at least one specific non-homopolymerizable olefin under UV light, a PFPE-based polymer can be provided in the form of a rubbery polymer.

[0010] Advantageously, the PFPE-based polymers can be used as lubricants without the need for the addition of viscosity modifiers, such as the solid particles described in the above-mentioned WO 2016 / 150941.

[0011] Advantageously, the photochemical method described above allows the synthesis of PFPE-based rubbery polymers characterized by a narrow dispersity of molecular weights.

[0012] Thus, in a first aspect, the present invention provides a compound of formula (I): TO-[AB] z -[A-B'] z’ -A-T' (I) [In the formula, 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, -C3F6Cl, -CF2Br; and 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 an integer of 1 to 500; below: (1)-(CF2CF2) c -and-(CF2CFR X ) d - is statistically distributed within B and B'; and (2) Formula - (CF2CF2) c - the repeating units make up at least 11% by weight of the polymer (P) based on 100% by weight of the polymer (P). characterized by] The polymer (P) satisfies the following formula:

[0013] The Applicant has surprisingly discovered that compounds of the formula -(CFCF) c- is in an amount of at least 11% by weight of the polymer (P), based on 100% by weight of the polymer (P), the polymer is no longer in the form of an oil (i.e. a viscous liquid), but rather in the form of a rubbery polymer, thereby broadening its industrial applications. DETAILED DESCRIPTION OF THE INVENTION

[0014] 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.

[0015] The number average molecular weight of the polymer (P) is 19 When determined by F-NMR spectroscopy, it is preferably in the range of about 5,000 to 150,000 g / mol, more preferably 10,000 to 100,000 g / mol.

[0016] The polymer (P) preferably contains a compound of 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

[0017] The polymer (P) preferably contains a compound represented by the formula -(CF2CFR X )d -Contains repeating units of

[0018] According to one preferred embodiment, said polymer (P) is characterized in that: (2a) in an amount of at least 11% by weight, based on 100% by weight of said polymer (P), of the formula -(CFCF) c -, and 4 to 20% by weight of repeating units of the formula -(CF2CFR X ) d - or (2b) a compound of formula -(CF2CF2) in an amount of 15 to 28% by weight c -, and the repeating unit of the formula -(CF2CFR X ) d In the repeating unit of X is -CF3.

[0019] Preferably, according to one embodiment, the polymer (P) is: - in an amount of 11 to 30% by weight of the formula -(CF2CF2) c -, and - Formula -(CF2CFR X ) d In the repeating unit of X are independently -OCF3, -OC2F5, and -OC3F7, and combinations thereof; -OCF2OR f2 (In the formula, R f2 is selected from a linear or branched C1 to C6 perfluoroalkyl group, a cyclic C5 to C6 perfluoroalkyl group, and a linear or branched C2 to C6 perfluorooxyalkyl group; and d is an integer of 1 to 500.

[0020] Preferably, according to this embodiment, the polymer (P) is a compound of the formula -(CF2CFR X ) d -Contains repeating units of

[0021] Preferably, according to another embodiment, the polymer (P) is in an amount of 15 to 28% by weight, of the formula -(CF2CF2) c -, and - Formula -(CF2CFR X ) d In the repeating unit of -, R X is —CF3, and d is an integer of 1 to 500.

[0022] Preferably, the chain (R f ) comprises, or preferably consists of, repeat units R°, said repeat units independently (i) -CFXO- (where X is F or CF3); (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:

[0023] 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 3O) 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.

[0024] In a preferred embodiment, the chain (R f ) is the above formula (R f -I) is satisfied.

[0025] Preferably, X and X' are equal to or different from each other and are selected from -CF2- and -CF2CF2-.

[0026] 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.

[0027] 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.

[0028] Alternatively, the polymer (P) is prepared by contacting, under heat, at least one peroxide perfluoropolyether polymer, at least tetrafluoroethylene and at least one second comonomer.

[0029] The peroxide perfluoropolyether polymers are prepared according to methods known in the art, for example as disclosed in US Pat. No. 8,258,090 (Solvay Solexis SpA).

[0030] 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 f2is selected from the group consisting of -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2), or -CF3(MOVE3).

[0031] Advantageously, the polymer (P) is in the form of a rubbery polymer.

[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 become 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 (wherein 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] 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.

[0038] Peroxide content (PO) determination: Analysis of peroxide 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%.

[0039] 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.

[0040] 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.

[0041] Differential scanning calorimetry (DSC): Thermal transitions were determined on a PerkinElmer Pyris apparatus.

[0042] Thermogravimetric analysis (TGA): TGA was performed using a TA Instruments TGA5500 analyzer at a heating rate of 10°C / min in a N2 atmosphere.

[0043] Example 1 - Preparation of Polymer PFPE-TFE-PMVE (Polymer 1) Polymer 1 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.

[0044] 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%).

[0045] 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 PMVE and 53 g of TFE were fed into the reaction mixture at constant flow rates over a period of 6 hours.

[0046] 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.

[0047] 195.7 g of rubbery polymer was detected.

[0048] Acidity and PO were below the detection limit of the analytical method.

[0049] The resulting polymer 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).

[0050] The number average molecular weight was 29000 g / mol; the ratio of g2 / g1 was 0.9; g3 was 1.4 and g4 was 1.0.

[0051] of block B in the polymer 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 -CF (97%), -CF Cl (2%), and -CF CF Cl (1%).

[0052] DSC analysis showed the appearance of a single glass transition at -103°C.

[0053] TGA analysis detected the product to be stable at high temperatures (1% loss at 362°C).

[0054] Comparative Example 2 - Preparation of Polymer PFPE-PMVE (Polymer 2C) The synthesis of polymers 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 was 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. The 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.

[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 was obtained and characterized.

[0059] Acidity and PO were below the detection limit of the analytical method.

[0060] 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 36000 g / mol, the ratio g2 / g1 was 0.9, g3 was 2.0, and g4 was 2.5.

[0061] 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%).

[0062] Comparative Example 3 - Preparation of Polymer PFPE-TFE-PMVE (Polymer 3C) 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%), with a number average molecular weight (Mn) of 41,500, s / r = 1.09 and PO = 1.26%). was introduced into the reactor together with 100 g of peroxide perfluoropolyether (PFPE).

[0063] 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).

[0064] The mixture was then maintained under these conditions for 6 hours. Then 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.

[0065] 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.

[0066] After vacuum distillation of the solvent (Galden® HT230), 106 g of a viscous oil was recovered.

[0067] Acidity and PO measurements were performed on the product and were below the detection limit of the method.

[0068] 19 F-NMR analysis confirmed the following structure: 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 -(CF2CFX) y -wherein X is -F and -OCF3, and the average length of y was 27.0; q is 5.0; -(BO) in the final polymer q - 19.2% by weight (from TFE (10.8 w / w%) and PMVE (8.4 w / w%)) based on the total weight of the polymer; T and T' are -CF3 (81%), the remainder (19%) is -CF2Cl and -CF2CF2Cl).

[0069] The number average molecular weight (Mn) was 42800 g / mol.

Claims

1. A polymer [polymer (P)] having the formula (I): T-O-[A-B] ｚ -[A-B’] ｚ’ -A-T’ (I) [In the formula, 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; and 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 of 1 to 500; below: (1)-(CF ２ CF ２ ) ｃ - and - (CF ２ CFR Ｘ ) ｄ is statistically distributed within B and B'; and (2a) Based on 100% by weight of the polymer (P), a compound of the formula -(CF ２ CF ２ ) ｃ The repeating unit of the formula -(CF) is present in an amount of 11 to 30% by weight of the amount of the polymer (P), ２ CFR Ｘ ) ｄ The repeating units of the formula - are 4 to 20% by weight, and in the repeating units of the formula -(CF 2 CFR X ) d -, R x is independently -OCF 3 , -OC 2 F 5 , and -OC 3 F 7 and combinations thereof; OCF 2 OR f2 (wherein R f2 is a linear or branched C 1 -C 6 perfluoroalkyl group, a cyclic C 5 -C 6 perfluoroalkyl group, a linear or branched C 2 -C 6 perfluorooxyalkyl group); and d is an integer from 1 to 500; or (2b) Formula - (CF ２ CF ２ ) ｃ - repeat units of the formula -(CF ２ CFR Ｘ ) ｄ In the repeating unit of -, R Ｘ is -CF ３ Being characterized by A polymer (P) that satisfies the above formula.

2. The polymer (P) is in the range of 5000 to 150000 g / mol １９ The polymer (P) according to claim 1, having a number average molecular weight determined by F-NMR spectroscopy.

3. Formula - (CF ２ CFR Ｘ ) ｄ 2. The polymer (P) according to claim 1, wherein the repeating units of - are present in an amount of 6 to 18% by weight, based on 100% by weight of the polymer (P).

4. Formula - (CF ２ CF ２ ) ｃ - repeating units of the formula -(CF ２ CFR Ｘ ) ｄ In the repeating unit of -, R Ｘ But, -CF ３ and d is an integer of 1 to 500.

5. 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 -OR （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 polymer (P) according to claim 1, independently selected from the group consisting of:

6. 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 (CF ２ CF ２ CF ２ O) ｇ３ (CF ２ CF ２ CF ２ CF ２ O) ｇ４ ]- (In the formula, -X １ is -F and -CF ３ are independently selected from - X's equal or different from each other and for each occurrence ２ , X ３ are independently -F, -CF ３ with the proviso that at least one 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; when at least two of g1, g2, g3, and g4 are different from zero, the different repeat units are generally statistically distributed along the chain; () ｆ .)) -[(CFX １ O) ｇ１ (CFX ２ CFX ３ O) ｇ２ (CF ２ CF ２ CF ２ O) ｇ３ (CF ２ CF ２ CF ２ CF ２ O) ｇ４ -(CF(CF ３ )O) ｇ５ (CF ２ CF(CF ３ )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 independently ≧0 such that g1+g2+g3+g4+g5+g6 ranges from 2 to 300, provided that at least one of g5 and g6 is not 0. The polymer (P) according to claim 5, which satisfies the following:

7. The polymer (P) according to any one of claims 1 to 6, wherein the polymer (P) is in the form of a rubbery polymer.

8. 8. A method for producing the polymer (P) of any one of claims 1 to 7, comprising contacting at least one peroxide perfluoropolyether polymer, at least tetrafluoroethylene, and at least one second comonomer under heat or in the presence of ultraviolet light.

9. 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 fluoromethyl vinyl ethers of the general formula CF ２ = CFOCF ２ OR ｆ２ perfluoromethoxyvinyl ether (MOVE) of the formula (wherein 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 9. The method of claim 8, wherein the alkyl group is selected from the group consisting of alkyl groups, alkyl ethers ... containing alkyl groups, and alkyl ethers containing alkyl groups.