Perfluoropolyether Polymer

Abstract

The present invention relates to novel copolymers comprising (per)fluoropolyether chains and functional groups.

Description

[Technical Field]

[0001] Cross-reference to related patent applications This patent application claims priority to European Patent Application No. 22198267.1, filed September 28, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel copolymers comprising (per)fluoropolyether chains and functional groups. [Background technology]

[0003] (Per)fluoropolyethers (hereinafter referred to as "PFPE polymers") have long been known as base oils or as additives in several lubricating applications.

[0004] Several syntheses of PFPE polymers have been disclosed in the art. The first synthesis of an unspecified fully fluorinated polyether mixture was reported in 1953, in which an oily product was obtained during the photo-oligomerization of hexafluoropropene. Since then, many different fully fluorinated polyethers have been synthesized and described in the literature.

[0005] U.S. Patent No. 4,500,739 (Montedison) discloses the reaction of peroxide PFPE with, inter alia, perfluorobutadiene (a Group II fluoroolefin). Example 4 discloses the reaction of a large excess of a fully fluorinated bis-olefin with perfluorobutadiene, resulting in pendant unsaturated groups along the polymer chain so that the reaction can proceed further in the presence of hexamethylenediamine.

[0006] U.S. Patent No. 8,258,090 (in the name of Solvay Solexis SpA) discloses a compound of the formula: (I) TO-[AB] z -[A'-B'] z’ -A-T' The present invention discloses a fluorinated lubricant of the formula: T and T' are C 1~3 Perfluoroalkyl or C 1~6 is alkyl, A and A are perfluoropolyether chains, B is derived from two different olefins, at least one of which has the formula: (Ia) -[(CR1R2-CR3R4) j -(CR5R6-CR7R8) j’ ]- (where, j is 1 to 5, j' is 0 to 4, and the sum of j+j' is 2 to 5, R1 to R8 are halogen, H, C 1~6 (Per)haloalkyl, C 1~6 Alkyl, C 1~6 oxy(per)fluoroalkyl, z is 2 or more, 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 of 500 to 500,000. which are homopolymerizable by a radical route; B' is (Ia), but at least one of R1 to R8 has a different meaning from B.

[0007] This patent discloses block copolymers characterized by a linear backbone without branching: in fact, no branching is obtained within B, which in particular contains (per)fluoropolyether chains.

[0008] PFPE polymers containing functional groups along the backbone have been disclosed in the art and are useful as reactive intermediate compounds and additives.

[0009] Perfluoropolyether polymers obtained from the reaction of polyperoxide perfluoropolyethers with fluorinated olefins in the presence of ultraviolet radiation are disclosed in US Pat. No. 4,500,739 (Montedison SpA, February 19, 1985).

[0010] U.S. Patent No. 6,403,539 (Ausimont SpA, June 11, 2002) discloses perfluoropolyether polymers containing sulfonyl fluoride groups as pendant groups along the main chain. This patent application describes a method in which sulfonyl fluoride-containing monomers are co-fed with an O2 stream in a liquid reaction medium to obtain perfluoropolyethers containing peroxide groups in the chain. However, the presence of peroxide groups is undesirable due to safety concerns. Therefore, this patent application discloses that peroxide perfluoropolyethers are thermally treated, typically at temperatures ranging from 150°C to 250°C, or optionally photochemically treated in the presence of a solvent, to obtain non-peroxide products without chain scission. The process disclosed therein (adding the functionalized monomer at the beginning of polymerization) does not allow for the synthesis of polymers with blocks isolated from the functionalized monomer, but allows for the synthesis of PFPE polymers with randomly distributed functional groups.

[0011] Multifunctional (per)fluoropolyether polymers are further disclosed in U.S. Pat. No. 5,719,259 (EI Du Pont de Nemours and Company, February 17, 1998), U.S. Pat. No. 4,853,097 (Ausimont Srl, August 1, 1989), and U.S. Pat. No. 5,104,911 (Ausimont Srl, April 14, 1992).

[0012] US Patent Application Publication No. 2011 / 0230631 (Solvay Solexis SpA, September 22, 2011) discloses (per)fluoropolyethers comprising at least one (per)fluoropolyoxyalkylene chain containing at least one repeating unit of the formula -CF2-CF(CF2O-SO2F)-O-, where the fluorosulfate group in parentheses is a pendant group that subsequently reacts with a nucleophile to provide functional groups such as carboxylic acids, acyl fluorides, amides, and esters, among others.

[0013] Chinese Patent No. 103724559 (Zhonghao Chengguang Res Inst Chemical Ind, April 16, 2014) discloses a method for forming a stable perfluoropolyether compound by placing a perfluoropolyether peroxide prepared by a photooxidation method in an inert fluorine-containing solvent, introducing a perfluoroolefin under ultraviolet irradiation conditions, and reacting the perfluoroolefin with the peroxide.

[0014] WO 2019 / 048394 (Solvay Specialty Polymers Italy SpA, March 14, 2019) discloses polyfunctional perfluoropolyether derivatives containing multiple ionizable groups selected from the group consisting of -SO3Xa, -PO3Xa, and -COOXa, where Xa is H, an ammonium group, or a monovalent metal. Summary of the Invention

[0015] Applicants were faced with the challenge of providing new functionalized PFPE copolymers characterized by an increased viscosity (measured by complex viscosity at 0.1 rad / s at 25° C.) while maintaining a low glass transition temperature (Tg) and remaining in a liquid state at room temperature.

[0016] Furthermore, the novel functionalized PFPE copolymers of the present invention are characterized by an increased viscosity index, especially between 40°C and 100°C.

[0017] Additionally, and even more surprisingly, the novel functionalized PFPE copolymers according to the present invention are characterized by increased thermal stability (as shown in the examples by TGA analysis), making them suitable for use in harsh environments and applications.

[0018] Furthermore, the novel PFPE copolymers containing functional groups are suitable for use as additives in various technical fields such as rust prevention and antiwear, and for use in enhancing compatibility between base oils and thickeners and other components dispersed in such base oils. Furthermore, as explained in more detail in the detailed description, the functional groups can be further reacted or derivatized to provide even more functionalized derivatives. DETAILED DESCRIPTION OF THE INVENTION

[0019] For purposes of this description 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 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 term "functionality number (F)" is intended to indicate the amount of functional groups in the copolymer according to the invention, as determined by NMR or titration.

[0020] In a first aspect, the present invention provides a block copolymer [copolymer (P)] comprising first and second perfluoropolyether chains [PFPE chains], each having two chain ends, wherein the first chain ends of each of the first and second PFPE chains are chain ends of the copolymer (P) and each comprise a group selected from a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F, and -OC(=O)F, and the second chain ends of the first and second PFPE chains are selected from the following blocks: - at least one first block [block (1)] according to formula (I): [ka] (In the formula, m is 0 or an integer of 1 to 5, preferably 1 or 2; R5 to R8 are each independently selected from -F, a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and a group represented by formula (II): (II) -R 20 -(X) y and in formula (II), R 20 is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing 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; y is an integer of 1 or 2, In formula (I), at least one, preferably one, of R5 to R8 is a group of formula (II); - at least one second block [block (2)] according to formula (III): [ka] (In the formula, n is an integer from 1 to 3; R1 to R4 each independently represent a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, or a group represented by formula (IV): (IV) -(R 10 ) t [C(R 11 )(R 12 )-C(R 13 )(R 14 )(R 15 )] z and in formula (IV), R 10 is an oxygen atom or a divalent / trivalent / tetravalent fully fluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by at least one oxygen atom; t is zero or one, z is an integer from 1 to 3, R 11 ~R 15 are each independently a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and a group represented by the formula (V): -[(A) a -(B) b -(F) f ] u -(A)-T (V) and in formula (V), u is 0 or an integer of 1 to 50, T is a fully fluorinated alkyl group; a is zero or one, each A is a PFPE chain; b is zero or an integer from 1 to 3; B is a block of formula (III*): -[C(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- (III*) and in formula (III*): R 1^ ~R 4^ each independently has the meaning defined above for each of R1 to R4, f is 0 or an integer of 1 to 5, preferably 1 or 2; F is a block of formula (I*): -[C(R 5^ )(R 6^ )-C(R 7^ )(R 8^ )]- In formula (I*), R 5^ ~R 8^ each independently has the meaning given above for each of R5 to R8, In the formula (III), at least one of R1 to R4 is a group of the formula (IV), In the formula (III*), R 1^ ~R 4^at least one of which is a group of formula (IV), In the formula (IV), R 11 or R 12 One of the following and R 13 ~R 15 one of which is a group of formula (V) In the formula (V), the repeating units (A), (B), and (F) are statistically distributed; and - optionally, at least one third block comprising a PFPE chain [block (3)]; In the copolymer (P), the sum of (m+f) is at least 1, preferably 1 to 100; The sum of (n+b) is at least 1, preferably 1 to 15, more preferably 1 to 11, and even more preferably 1 to 9; the at least one type of block (1), the at least one type of block (2), and, if present, the at least one type of block (3), are statistically distributed; Regarding the block copolymer [copolymer (P)].

[0021] It will be understood by those skilled in the art that the first chain ends of the first and second PFPE chains correspond to two chain ends of copolymer (P).

[0022] Preferably, in the copolymer (P), each of the PFPE chains is a fully fluorinated chain [chain (R f )], wherein the repeat units are independently selected from the group consisting of: (i) -CFXO- (wherein X is -F or -CF3), (ii) -CF₂C₂X₅O₂-, where X is the same or different in each occurrence and is -F or CF₃, provided that at least one of X is -F; (iii) -CF2CF2CF2O-; (iv) -CF2CF2CF2CF2O-; (v)-(CF2) j -CFZ-O- (wherein j is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -T is a group, and R (f-a) is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, said repeating units being selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, each X is independently -F or -CF3, and T is a C1 to C3 perfluoroalkylalkyl chain.

[0023] Preferably, the chain (R f ) follows the formula: (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 2 , X 3 are the same or different and, in each occurrence, 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 represent integers greater than or equal to 0 such that g1+g2+g3+g4 ranges from 2 to 300, preferably from 2 to 100; at least two of g1, g2, g3, and g4 must be different from zero, the different repeat units being generally statistically distributed along the chain).

[0024] More preferably, the chain (R f ) is a chain of the following expressions: (R f -IIA) -[(CF2CF2O) a1 (CF2O) a2]- (In the formula: a1 and a2 are independently integers equal to or greater than 0 such that the number average molecular weight, determined by NMR, is between 400 and 100,000, preferably between 400 and 50,000, a1 and a2 are preferably not both equal to 0, and the ratio a1 / a2 is preferably comprised between 0.1 and 10; (R f -IIB) -[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]- (In the formula: b1, b2, b3, and b4 are independently integers of 0 or greater such that the number average molecular weight determined by NMR is 400 to 100,000, preferably 400 to 50,000, and preferably each of b1, b2, b3, and b4 is greater than 0; (R f -IIC) -[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]- (In the formula: cw is 1 or 2; c1, c2, and c3 are independently integers greater than or equal to 0 selected to provide a number average molecular weight, as determined by NMR, of 400 to 100,000, preferably 400 to 50,000, and preferably c1, c2, and c3 are all greater than 0 and the ratio c3 / (c1+c2) is generally less than 0.2; is selected from.

[0025] More preferably, the chain (R f ) is herein represented by the following formula (R f -III): (R f -III) -[(CF2CF2O) a1 (CF2O) a2 ]- (In the formula, a1 and a2 are integers greater than 0 such that the number average molecular weight determined by NMR is 400 to 100,000, preferably 400 to 50,000, and the ratio a1 / a2 is generally 0.1 to 10, more preferably 0.2 to 5. Follow.

[0026] Preferably, m is 0 or an integer of 1-2 in block (1).

[0027] Preferably, in block (1), at least one of R5 to R8 is a group of formula (II).

[0028] Preferably, in block (1), R 20 is a sigma bond or a bond represented by the formula (R 20 -i)~(R 20 -iv) is a group selected from: (R 20 -i) -(CF2) s1 -O-(CF2) s2 - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3); (R 20 -ii) -O-(CF2) s3 - (wherein s3 is an integer of 1 to 6, preferably 1 to 5); (R 20 -iii) -OR 400 -OR 401 - (In the formula, R 400 is a linear or branched fully fluorinated alkyl chain containing 1 to 6, preferably 1 to 3, carbon atoms, more preferably a fully fluorinated alkyl chain according to the formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-; R401 is a linear or branched fully fluorinated alkyl chain containing 1 to 3 carbon atoms, more preferably a fully fluorinated alkyl chain according to the formula -CF2-, -CF2CF2-, -CF(CF2)-; (R 20 -iv) [ka] (In the formula, R 500 is a linear, fully fluorinated alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 is an expression - OR 503 is a chain of R 503 is a linear, fully fluorinated alkyl chain containing 1 to 3 carbon atoms; R 502 is a linear, fully fluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 and R 502 each of which bonds to a group X as defined above in formula (II).

[0029] Preferably, in block (2) and formula (IV), R 10 follows one of the following formulas: (R 10 -i) -(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, each of d, d*, e, e*, f, and f* is independently zero or 1; R CF is a perfluoroalkyl chain containing 1 to 12, preferably 1 to 8, carbon atoms, optionally interrupted by one or more oxygen atoms; (R10 -ii) -O-(C3F6O) h -(CF2) i -(C3F6O) j -O- (wherein h=j, h+j is 2 to 6, and i is 2 to 6).

[0030] In a second aspect, the present invention relates to a process for the preparation of the copolymer (P) defined above [Process (P)]. The process according to the invention can be easily scaled up from laboratory scale to pilot scale and industrial scale.

[0031] Advantageously, the copolymer (P) of the invention is prepared by a process (P) comprising at least the following steps: (a) · at least one perfluoropolyether polymer containing at least one peroxide group [PFPEperoxy]; at least one fully fluorinated compound of formula (Xp): [ka] (In the formula, R 21 ~R 23 each is independently -F or a fully fluorinated straight or branched alkyl chain having 1 to 6 carbon atoms; R 20 , X, and y are as defined above for formula (II); at least one fully fluorinated compound of formula (XX-p): [ka] (In the formula, R 21 ~R 23 are as defined above in formula (Xp), R 31 ~R 33 each is independently —F or a fully fluorinated alkyl group having 1 to 6 carbon atoms; R 10 is an oxygen atom or a fully fluorinated alkyl chain containing 1 to 24 carbon atoms, optionally interrupted by at least one oxygen atom; t is zero or one, each of z* and z** is independently 1 or 2); contacting the (b) reacting said PFPE peroxy with at least one compound of formula (Xp) and at least one compound of formula (XX-p) in the presence of UV irradiation or with heating.

[0032] In step (a), the order in which the reactants are added is not limited. Thus, the PFPE peroxy, the compound of formula (Xp), and the compound of formula (XX-p) can be added to the reaction environment in any order.

[0033] Step (a) can be preceded by partial reduction of the peroxy bonds of the PFPE peroxy, for example by chemical reduction or UV or heat treatment.

[0034] Preferably, the PFPE peroxy is a peroxide perfluoropolyether polymer having two chain ends each comprising a group selected from a linear or branched fully fluorinated alkyl chain containing 1 to 6 carbon atoms or —C(═O)F, wherein the two chain ends comprise, or preferably consist of, a perfluoropolyether chain [chain (R°)] independently selected from the group consisting of formulas (i) to (v) as defined above. f )] and has a peroxide content (PO), defined as grams of active oxygen (Mw=16) in 100 g of PFPE peroxy, between 0.1 and 4, preferably between 0.1 and 3.5.

[0035] Preferably, in the PFPE peroxy, the chain (R f) conforms to the formula (Rf-I), or (Rf-IIA), (Rf-IIB), (Rf-IIC), or (Rf-III), as defined above.

[0036] Preferably, in said at least one compound of formula (Xp), R 21 , R 22 , and R 23 Each of these is -F.

[0037] Preferably, in the compound (Xp), R 20 is a sigma bond or a bond of the formula (R 20 -i)~(R 20 -iv) is a group selected from: (R 20 -i) -(CF2) s1 -O-(CF2) s2 - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3); (R 20 -ii) -O-(CF2) s3 - (wherein s3 is an integer of 1 to 6, preferably 1 to 5); (R 20 -iii) -OR 400 -OR 401 - (In the formula, R 400 is a linear or branched fully fluorinated alkyl chain containing 1 to 6, preferably 1 to 3, carbon atoms, more preferably a fully fluorinated alkyl chain according to the formula -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-; R401 is a linear or branched fully fluorinated alkyl chain containing 1 to 3 carbon atoms, more preferably a fully fluorinated alkyl chain according to the formula -CF2-, -CF2CF2-, -CF(CF2)-; (R 20 -iv) [ka] (In the formula, R 500 is a linear, fully fluorinated alkyl chain containing 1 to 6, preferably 1 to 3, carbon atoms optionally interrupted by at least one oxygen atom; R 501 is an expression -OR 503 is a chain of R 503 is a linear, fully fluorinated alkyl chain containing 1 to 3 carbon atoms; R 502 is a linear, fully fluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 and R 502 each of which bonds to a group X as defined above).

[0038] Preferably, said at least one compound of formula (Xp) is selected from the group comprising, more preferably consisting of: CF2=CFCF2OCF2CF2COOH, CF2=CFOCF2COOH, CF2=CFO(CF2)5COOH, CF2=CFOCF2CF2OCF2COOH, CF2=CFOCF2CF2COOH, CF2 = CFCF2OCF2CF2COF, CF2=CFOCF2COF, CF2 = CFO(CF2)3OCF(CF3)COF, CF2 = CFO(CF2)5COF, CF2 = CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CN, CF2 = CFO(CF2)5CN, CF2 = CFO(CF2)3OCF(CF3)CN, CF2=CFCF2OCF2CF2CN, CF2=CFOCF2CF2Br, CF2 = CFCF2OCF2CF2Br, CF2=CFOCF2CF(CF3)OCF2CF2Br, CF2=CFCF2OCF2CF2CONH2, CF2=CFOCF2CONH2, CF2=CFOCF2CF2CONH2, CF2=CFOCF2CF2SO2F, CF2=CFSO2F, CF2 = CFOCF2CF(SO2F)2, CF2=CFOCF2CF(CF2OCF2CF2SO2F)(OCF2CF2SO2F), CF2=CFOCF2CF(CF2CF2SO2F)(OCF2CF2SO2F), CF2=CFOCF2OCF2CF(CF2OCF2CF2SO2F)(SO2F).

[0039] Some exemplary compounds of formula (Xp) and their preparation are described in WO 03 / 106515 (Daikin Ind.), JP 2017-025242 (ASAHI GLASS CO., LTD.), and U.S. Patent Application Publication No. 2008 / 138685 (AGC Inc.).

[0040] Preferably, in said compound of formula (XX-p), when t is 1, 1, 2, 3, or 4 unsaturated moieties are R 10 are bonded to the same or different atoms, preferably carbon atoms, belonging to

[0041] Preferably, said at least one compound of formula (XX-p) conforms to the following formula: CF2=CF(R 10 ) t CF=CF2 (wherein t is 0 or 1, R 10 follows one of the following formulas: (R 10 -i) -(CF2) d (O) e (CF2O)f R CF (O) e* (CF2) d* (CF2O) f* (In the formula, each of d, d*, e, e*, f, and f* is independently zero or 1; R CF is a perfluoroalkyl chain containing 1 to 12, preferably 1 to 8, carbon atoms, optionally interrupted by one or more oxygen atoms; (R 10 -ii) -O-(C3F6O) h -(CF2) i -(C3F6O) j -O- (wherein h=j, h+j is 2 to 6, and i is 2 to 6).

[0042] According to a particularly preferred embodiment, said at least one compound of formula (XX-p) conforms to the following formula: CF2=CF(R 10 ) t CF=CF2 (wherein t is 1, R 10 is expressed as follows: (R 10 -i) -(CF2) d (O) e (CF2O) f R CF (O) e* (CF2) d* (CF2O) f* In accordance with the formula: d, f, d* and f* are zero; e and e* are 1, R CF is a linear perfluoroalkyl chain containing 1 to 10, preferably 1 to 8, carbon atoms).

[0043] Preferably, the compound of formula (XX-p) is selected from the group comprising, more preferably consisting of: CF2=CFCF=CF2 CF2=CFOCF=CF2 CF2=CFCF2OCF2CF=CF2 CF2=CFO-(CF2)3CF=CF2 CF2=CFCF2O(CF2)3OCF2-CF=CF2 CF2=CFCF2CF=CF2 CF2=CF(CF2)2CF=CF2 CF2=CF(CF2)3CF=CF2 CF2=CF(CF2)4CF=CF2 CF2=CFOCF2OCF=CF2 CF2=CFO(CF2)2OCF=CF2 CF2=CFO(CF2)3OCF=CF2 CF2=CFO(CF2)4OCF=CF2 CF2=CF(CF2)2OCF=CF2 CF2=CF(CF2)3OCF=CF2 CF2=CF(CF2)4OCF=CF2 CF2=CFCF2O(CF2)2OCF2O-CF=CF2 CF2=CFCF2O(CF2)3OCF2O-CF=CF2 CF2=CFCF2O(CF2)4OCF2OCF=CF2 CF2=CFCF2O(CF2)6OCF2CF=CF2 CF2=CFO-CF2O-(CF2)2O-CF2O-CF=CF2 CF2=CFO-CF2O-(CF2)3O-CF2O-CF=CF2 CF2=CFO-CF2O-(CF2)4O-CF2O-CF=CF2 CF2=CFO-(CF2O)6-CF=CF2 CF2=CFO-(CF2CF2O)2-CF=CF2 CF2=CFO-(CF2CF2O)2-CF2OCF=CF2 CF2=CFO(C3F6O) h -(CF2) i -(C3F6O) j -OCF=CF2 (In these formulas, h and j are the same, The sum of these is 2 to 6, and i is 2 to 6).

[0044] The amount of each of the at least one compound (Xp) and the compound (XX-p) is not limited.

[0045] For example, the ratio of the equivalent of the double bond of the compound (Xp) to the equivalent of the peroxide group is preferably in the range of 1:100 to 5000:100.

[0046] Similarly, the ratio of the equivalent of the double bond in the compound (XX-p) to the equivalent of the peroxide group is preferably in the range of 1:100 to 100:100.

[0047] Step (a) of process (P) can be advantageously carried out by contacting said PFPE peroxy with a compound of one of formula (Xp).

[0048] Alternatively, step (a) can be carried out by contacting the PFPE peroxy with two or more compounds of formula (Xp).

[0049] Step (a) of process (P) can be advantageously carried out by contacting said PFPE peroxy with a compound of one of formulas (XX-p).

[0050] Alternatively, step (a) can be carried out by contacting the PFPE peroxy with two or more compounds of formula (XX-p).

[0051] Steps (a) and (b) may be carried out in the presence of a fluorinated solvent.

[0052] Preferably, the fluorinated solvent is selected in the group comprising perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, hydrofluoropolyethers.

[0053] Preferably, step (b) is carried out in the presence of UV radiation for a period of 2 to 150 hours, preferably 5 to 100 hours.

[0054] Preferably, step (b) is carried out at a temperature of from −60° C. to +150° C., more preferably from −20° C. to +100° C., even more preferably from 0° C. to 60° C., in the presence of UV radiation.

[0055] Alternatively, step (b) can be carried out under heat treatment, preferably by heating at a temperature of 150°C to 250°C.

[0056] Preferably, step (b) is carried out in an inert atmosphere.

[0057] Preferably, the process (P) comprises, after step (b), a step (c) of solvent removal and / or a step (d) of fractionation.

[0058] The step (c) of removing the solvent may be carried out by evaporation, for example vacuum distillation.

[0059] Said step (d) of fractionation can be carried out by solvent extraction using supercritical CO2, hexafluoroxylene or hydrofluorocarbons, and mixtures thereof as solvents when the fractionation step is carried out by precipitation fractionation. Supercritical CO2 is preferred.

[0060] In a third aspect, the present invention relates to a copolymer (P) obtainable by the process (P) described above.

[0061] Advantageously, the functional groups introduced as pendant groups in the block (1) of the copolymer (P), such as, in particular, -SO2F, -SO3H, -COOH, -COF, -CN, -Br, and -CONH2, as well as the functional groups at the chain ends of the copolymer (P), such as, in particular, -COF and -OC(O)F, can be reacted appropriately to obtain other different functional groups.

[0062] The expression "capable of reacting" is intended to indicate that such functional groups can be, for example, in the form of salts, hydrolyzed, reduced, oxidized or subjected to different chemical reactions to obtain functional groups with the desired reactivity, taking into account the final use of the copolymer (P).

[0063] Advantageously, the copolymer (P F ) is obtained from the above method (P), which further comprises, after step (b), at least one step (c) of converting to a salt form, hydrolyzing, oxidizing, reducing, or subjecting to another chemical reaction capable of obtaining the desired functional group.

[0064] The present invention further relates to the copolymer (P) obtained at the end of step (c) of the method (P). F ) is included.

[0065] Accordingly, the present invention provides a block copolymer [copolymer (P F ) wherein the first chain end of each of the first and second PFPE chains is a chain end of a copolymer (P), each of which is a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, an organic cation of -COOH and COOH, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal, more preferably Na + , K. + -COOR (wherein R is a linear or branched alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom); -COF; -CONH; -CON(R 300 )(R 301 )(wherein, R 300 and R 301 each of which has the same meaning as defined for R);-(R) c-OH, where c is 0 or 1 and R is as defined above; -C(O)-OC(O)R, where R is as defined above, provided that (i) at least one chain end of the first and second PFPE chains comprises a group other than a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and (ii) when one chain end comprises the group -COF, the other chain end does not comprise a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms or -COF; The second chain ends of the first and second PFPE chains are each formed from a block of: - at least one first block [block (1)] according to formula (I): [ka] (In the formula, m, R5 to R8 have the meanings defined above); - at least one second block [block (2)] according to formula (III): [ka] (In the formula, n, R1 to R4 have the meanings defined above); and - optionally, at least one third block comprising a PFPE chain [block (3)]; Although they are bonded to each other via F ) in the sum of (m+f) is at least 1, preferably 1 to 100; The sum of (n+b) is at least 1, preferably 1 to 15, more preferably 1 to 11, and even more preferably 1 to 9; the at least one type of block (1), the at least one type of block (2), and, if present, the at least one type of block (3), are statistically distributed; Regarding block copolymers [copolymer (PF)].

[0066] In another aspect, the present invention provides a copolymer of two or more copolymers (P F ), mixture [mixture (P F )].

[0067] The purification step can be carried out after either step (b) and / or step (c) of the method (P), but typically is carried out after the copolymer (P) or copolymer (P) according to the invention. F ) mixture is obtained.

[0068] Therefore, in a further aspect, the present invention relates to a mixture [mixture (P)] comprising two or more copolymers (P) as defined above.

[0069] It will be clear to those skilled in the art that the mixture (P) can be obtained via the above method (P).

[0070] Advantageously, said mixture (P) can be subjected to one or more purification steps (also called "fractionation" steps) as disclosed above, resulting in the production of different viscosities and / or 19 Separate copolymers (P) can be obtained, characterized by their number average molecular weights, measured by F-NMR, and / or by their functionality (F), preferably between 3 and 102.

[0071] The mixture may further contain PFPE peroxy used as starting material and / or a mixture of copolymers (P) containing peroxy groups [copolymers (P O-O )], and / or copolymers containing peroxy groups (P F ) mixture [copolymer (P F-O-O )] can be obtained.

[0072] Advantageously, the copolymer (P O-O ) and / or copolymer (P F-O-O ) can be isolated and used as an intermediate in other processes.

[0073] The copolymer (P) or copolymer (P F The amount of peroxy groups that may be present in a mixture containing PFPE peroxy can be up to 99% based on the amount of starting peroxy groups in the PFPE peroxy, but depending on the end use, the amount of peroxy groups can be appropriately adjusted, for example, to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5%.

[0074] More preferably, the amount of peroxy groups is at most 1, even more preferably at most 0.5%, even more preferably at most 0.1%.

[0075] In another aspect, the present invention provides a block copolymer [copolymer (P O-O )], wherein each of the first and second PFPE chains is a chain (Rf) as defined above, or (Rf O-O ) is a repeating unit according to any one of the formulas (i) to (v) defined above for (R°) O-O ), having a peroxide content (PO), defined as grams of active oxygen (Mw=16) in 100 g of PFPE peroxide, between 0.1 and 4, preferably between 0.1 and 3.5, wherein each of the first and second PFPE chains has two chain ends, the first chain ends of each of the first and second PFPE chains are chain ends of a copolymer (P), each comprising a group selected from a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —C(═O)F, and —OC(═O)F, and the second chain ends of the first and second PFPE chains are each a block of the following: - at least one first block [block (1)] according to formula (I) defined above: - at least one second block [block (2)] according to formula (III) defined above: and / or - optionally at least one third block comprising a PFPE chain as defined above [block (3)]; are connected to each other via *Copolymer (P O-O ) in the blocks (1), (2), and, if present, the blocks (3), are statistically distributed; The sum of (n+b) is at least 1, preferably 1 to 15, more preferably 1 to 11, and even more preferably 1 to 9; · the sum of (m+f) is at least 1, preferably 1 to 100; Regarding block copolymers [copolymer (PO-O)].

[0076] In yet another embodiment, the present invention provides a block copolymer [copolymer (P F-O-O )], wherein each of the first and second PFPE chains is a chain (Rf) as defined above, or a chain (Rf O-O ) is a repeating unit according to any one of the formulas (i) to (v) defined above for (R°) O-O ), and has a peroxide content (PO), defined as grams of active oxygen (Mw=16) in 100 g of PFPE peroxide, between 0.1 and 4, preferably between 0.1 and 3.5, and each of the first and second PFPE chains has two chain ends, and the first chain end of each of the first and second PFPE chains is a chain end of a copolymer (P), each of which is a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, an organic cation of -COOH and COOH, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal, more preferably Na + , K. + -COOR (wherein R is as defined above); -COF; CON(R 300 )(R 301 )(wherein, R 300 and R 301each of which is a hydrogen atom or has the same meaning as defined for R; -(R)cOH (wherein c is 0 or 1 and R is as defined above); -C(O)-OC(O)R (wherein R is as defined above); -Br; -CN; and the second chain ends of the first and second PFPE chains comprise a group selected from: - at least one first block [block (1)] according to formula (I) defined above: - at least one second block [block (2)] according to formula (III) defined above: and / or - optionally at least one third block comprising a PFPE chain as defined above [block (3)]; are connected to each other via *Copolymer (P F-O-O ) in the blocks (1), (2), and, if present, the blocks (3), are statistically distributed; The sum of (n+b) is at least 1, preferably 1 to 15, more preferably 1 to 11, and even more preferably 1 to 9; · the sum of (m+f) is at least 1, preferably 1 to 100; Regarding block copolymers [copolymer (PF-OO)].

[0077] In yet another aspect, the present invention provides a process for the preparation of at least one copolymer (P) as defined above, at least one of said PFPE peroxys used as starting materials, and / or one or more copolymers (P O-O ) [Mixture (M1)].

[0078] In yet another aspect, the present invention provides a polymerizable composition comprising at least one copolymer (P F ), at least one copolymer (P) as defined above, said PFPE peroxy used as starting material, said one or more copolymers (P O-O ), and / or one or more copolymers thereof (P F-O-O) [Mixture (M2)].

[0079] The copolymer (P) and / or copolymer (P F ) can be used for a variety of applications in several industries where excellent resistance and durability at high temperatures and in harsh environments are required. For example, copolymer (P) and / or copolymer (P F ) can be used as a base oil for lubricants. Alternatively, copolymer (P) and / or copolymer (P F ) can be used as an additive in halogenated oils and / or greases.

[0080] For this purpose and advantageously, the copolymers according to the invention and the mixtures described herein are in a liquid state at room temperature and even below room temperature, which has advantages with regard to handling and storage of the copolymers.

[0081] Advantageously, therefore, the copolymer (P) is in the liquid state at room temperature.

[0082] Also advantageously, copolymers (P F ) is in a liquid state at room temperature.

[0083] In addition, copolymer (P O-O ) and copolymer (P F-O-O ), and each of the mixtures (M1) and (M2) are in a liquid state at room temperature.

[0084] In addition, copolymer (P O-O ) and copolymer (P F-O-O ), and each of the mixtures (M1) and (M2) are in a liquid state at room temperature.

[0085] 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 a term may be unclear, the statements of this application shall control.

[0086] The present invention is hereinafter illustrated in more detail by the examples contained in the experimental section below, which are illustrative only and should not be construed as limiting the scope of the invention in any way. [Example]

[0087] material Peroxide perfluoropolyether oil was obtained from Solvay Specialty Polymers Italy SpA and has the following formula: XO-(CF2CF2O) a1 (CF2O) a2 (O) h -X' (In the formula, X and X' are -CF3, -CF2COF, -COF) and have the following properties: Mn=31990g / mol;PO=1.61%;a1 / a2=1.0

[0088] The following were purchased from Anles LTD and used as received: (8CNVE) CF2=CFOCF2CF(CF3)OCF2CF2CN (PBVE) CF2=CFOCF2CF2CF2OCF=CF2

[0089] The perfluorosolvents Galden® HT200 and Galden® D100, as well as tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE), and perfluorosulfonyl vinyl ether (VEFS) CF2=CFOCF2CF2SO2F were obtained from Solvay Specialty Polymers Italy SpA.

[0090] method: 19 Works for F nuclides 19 F-NMR-Varian Mercury 300 MHz spectrometer was used to obtain the structure, molecular weight, and chain end composition of perfluoropolyether oils. 19F-NMR spectra were obtained on pure samples using CFCl3 as an internal standard.

[0091] The peroxide content (PO) is expressed as grams of peroxide oxygen per 100 g of polymer. Analysis of the peroxide content was performed by iodometric titration using a Mettler DL40 device equipped with a platinum electrode. The sensitivity limit for PO measurement was 0.0002%.

[0092] Complex viscosity was measured by a frequency sweep test using an MCR502 Anton-Paar rheometer (25 mm diameter) in parallel plate geometry. Viscosity was measured by this method at 25°C and 100°C, and values ​​are reported at an oscillation of 0.1 rad / s.

[0093] Viscosity index was calculated according to ASTM D2270, which measures viscosity at about 40°C and about 100°C.

[0094] TGA analysis was performed using a TA Instruments TGA5500 analyzer in an oxygen-containing atmosphere (air) at a heating rate of 10°C / min to determine the temperatures at which 10% and 50% loss in sample weight occurred.

[0095] FT-IR spectra were acquired on a Thermo Fisher IS10 Spectrometer with liquid samples as thin films on KBr.

[0096] GPC analyses to determine average molecular weights (Mw and Mn) were performed on a Waters GPC equipped with an RI detector and operated at 35° C. All average molecular weight results are reported relative to a perfluoropolyether linear neutral internal standard.

[0097] Example 1 - PFPE Copolymer Containing 8CNVE and PBVE 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, 249.2 g of the above-described peroxide perfluoropolyether oil was placed.

[0098] The oil was diluted with 1876 g of Galden® D100. 19.4 g of 8CNVE and 2.5 g of PBVE were then added to the reactor. The mixture was then purged with nitrogen while stirring, and the UV lamp was turned on at 20°C for 42 hours. After this time, the lamp was turned off, and the reaction mixture was transferred to a 2 L round-bottom flask. The mixture was stripped under reduced pressure (0.1 mbar) at 120°C for 6 hours.

[0099] 265 g of copolymer in the form of a clear, viscous oil was obtained as residue.

[0100] 19 F-NMR analysis confirmed that 8CNVE was incorporated into the copolymer at a concentration of 8.1 wt %.

[0101] In this copolymer, a2 / a1 was 0.9, and X and X' were -CF3, -CF2COF, and -OCOF.

[0102] The introduction of the –CN functional group was also confirmed by FT-IR spectroscopy, which showed a peak at 2269 cm -1 The presence of a peak was confirmed.

[0103] Comparative Example 1 - PFPE Copolymer with 8CNVE 252.1 g of the above-described peroxide perfluoropolyether oil was placed in the same reactor as in Example 1. The oil was diluted with 1873 g of Galden® HT200. 19.45 g of 8CNVE was then added to the reactor, and the mixture was purged with nitrogen. The mixture was then purged with nitrogen while stirring, and the UV lamp was turned on at 20°C for 41 hours.

[0104] After this time, the lamp was switched off and the reaction mixture was transferred to a 2 L round-bottom flask. The mixture was stripped under reduced pressure (0.1 mbar) at 120° C. for 6 hours.

[0105] 224.5 g of copolymer in the form of a clear, viscous oil was obtained as residue.

[0106] Product 19 F-NMR analysis confirmed the following copolymer structure containing 8CNVE at a concentration of 8.0 wt %: XO-(CF2CF2O) a2 (CF2O) a1 (CF2CFO(CF2CF(CF3)OCF2CF2CN)) m -X' (wherein a2 / a1=0.9, m=6.4, where X and X' = -CF3, -CF2COF, and -OCOF).

[0107] Number average molecular weight (M n ) is 31100 g / mol.

[0108] The introduction of the –CN functional group was also confirmed by FT-IR spectroscopy, which showed a peak at 2269 cm -1 The presence of a peak was confirmed.

[0109] Example 2 - PFPE Copolymers Containing VEFS and PBVE 250.5 g of the above-described peroxide perfluoropolyether oil was placed in the same reactor as in Example 1. The oil was diluted with 1877 g of Galden® HT200. 14.0 g of VEFS and 2.5 g of PBVE were then added to the reactor, and the mixture was purged with nitrogen. The UV lamp was then turned on, and the reaction was carried out at 20°C for 7 hours. After this time, the UV lamp was turned off.

[0110] To remove the solvent and traces of unreacted monomer, the resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240° C. for 4 hours, first at atmospheric pressure and then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[0111] 220.3 g of copolymer in the form of a clear, viscous oil was obtained as residue.

[0112] 19 F-NMR analysis confirmed the absence of residual peroxide units and that VEFS was incorporated into the copolymer at a concentration of 5.8 wt %.

[0113] In this copolymer, a2 / a1 was 1.0, and X and X' were -CF3, -CF2COF, and -OCOF.

[0114] Comparative Example 2a - PFPE Copolymer with VEFS 250 g of the above-described peroxide perfluoropolyether oil was placed in the same reactor as in Example 1. The oil was diluted with 1875 g of Galden® HT200. 14.0 g of VEFS was then added to the reactor, and the mixture was purged with nitrogen. The UV lamp was then turned on, and the reaction was carried out at 20°C for 7 hours. After this time, the UV lamp was turned off.

[0115] To remove the solvent and traces of unreacted monomer, the resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240° C. for 4 hours, first at atmospheric pressure and then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[0116] 215.9 g of copolymer in the form of a clear oil was obtained as residue.

[0117] Product 19 F-NMR analysis confirmed the absence of residual peroxide, the incorporation of VEFS into the copolymer at a concentration of 6.0 wt %, and the following structure: XO-(CF2CF2O) a2 (CF2O) a2 (CF2CFO(CF2CF2SO2F)) m -X' (In the formula, a2 / a1=1.0, m = average 5.6, X and X' = -CF3, -CF2COF, and -OCOF, The number average molecular weight (Mn) is 30,400 g / mol).

[0118] Comparative Example 2b - PFPE Copolymer with VEFS, TFE, PMVE, and PBVE 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, 250.3 g of the above-described peroxide perfluoropolyether oil was placed.

[0119] The oil was diluted with 1876 g of Galden® HT200, then 23.0 g of VEFS and 1.1 g of PBVE were added to the reactor.

[0120] The mixture was then purged with nitrogen while stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 14.6 g / h and 8.0 g / h, respectively. After the start of the flow, the UV lamp was switched on and the reaction was carried out for 7 hours at 20° C. After this time, the flow of olefins was interrupted and the UV lamp was switched off.

[0121] To remove the solvent and traces of unreacted monomer, the resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240° C. for 4 hours, first at atmospheric pressure and then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[0122] 298.0 g of copolymer in the form of a clear, viscous oil was obtained as residue, which was analyzed by iodometric titration, confirming the complete removal of the peroxide units.

[0123] 19 F-NMR analysis confirmed the absence of residual peroxide.

[0124] The incorporation of VEFS, TFE, and MVE into the copolymer was at concentrations of 5.3 wt%, 13.9 wt%, and 9.8 wt%, respectively.

[0125] In this copolymer, a2 / a1 was 0.9, and X and X' were -CF3, -CF2COF, and -OCOF.

[0126] The properties of the copolymers according to the invention and the comparative copolymers are summarized in Table 1 below.

[0127] [Table 1]

[0128] The polymers of Example 2 and Comparative Example 2a were also subjected to TGA analysis to determine weight loss under heating conditions, the results of which are reported in Table 2 below.

[0129] [Table 2]

Claims

1. A block copolymer [copolymer(P)] comprising first and second perfluoropolyether chains [PFPE chains], each having two chain ends, wherein the first chain end of each of the first and second PFPE chains is the chain end of copolymer(P), and each comprises a group selected from a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F, and -OC(=O)F, and the second chain ends of the first and second PFPE chains are the following block: - At least one first block [block (1)] according to formula (I): 【Chemistry 1】 (In the formula, m is an integer from 0 to 5; R ５ ~R ８ Each of these is independently -F, a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and formula (II): (_). ２０ ()) ｙ Selected from the group containing the base, in formula (II), R ２０ This is a sigma bond, or a straight or branched perfluoroalkyl chain containing 1 to 12 carbon atoms, preferably containing at least one oxygen atom and / or having oxygen atoms sandwiched between them. X is a functional group, preferably -SO ２ F, -SO ３ H, -COOH, -COF, -CN, -Br, and -CONH ２ Selected from, y is an integer of 1 or 2, In formula (I), R ５ to R ８ , at least one, preferably one, of which is a group of formula (II)); - At least one second block [block (2)] following formula (III): 【Chemistry 2】 (In the formula, n is an integer between 1 and 3; R １ ~R ４ Each of these independently comprises a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, formula (IV): (IV) -(R １０ ) ｔ [C(R) １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ Selected from the group containing the base, in formula (IV), R １０ This is a divalent / trivalent / tetravalent fully fluorinated alkyl chain containing 1 to 24 carbon atoms, which may be oxygen atoms or optionally have at least one oxygen atom sandwiched between them. t is either zero or 1. z is an integer between 1 and 3. R １１ ~R １５ Each of these independently comprises a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and formula (V): -[(A) ａ -(B) ｂ -(F) ｆ ] ｕ -(A)-T (V) Selected from the group containing the base, in formula (V), u is an integer from 0 to 50. T is a fully fluorinated alkyl group, a is either zero or 1, Each A is a PFPE chain, b is zero or an integer between 1 and 3. B is the block of equation (III*): ____ １＾ () ２＾ )?|() ３＾ () ４＾ ) ) (__|) And in equation (III*), R １＾ ~R ４＾ Each of them is independent of R １ ~R ４ Each of these has the meaning defined above, f is 0 or an integer from 1 to 5. F is the block of expression (I*): -[C(R ５＾ )(R ６＾ )-C(R ７＾ )(R ８＾ )]- And in equation (I*), R ５＾ ~R ８＾ Each of them is independent of R ５ ~R ８ Each of these has the meaning shown above, - In the above formula (III), R １ ~R ４ At least one of them is a base of formula (IV), - In the above formula (III *), R １＾ ~R ４＾ At least one of them is a base of formula (IV), - In the above formula (IV), R １１ or R １２ one of the and R １３ ~R １５ One of them is the basis of equation (V), (In formula (V), the repeating units (A), (B), and (F) are statistically distributed); and - At least one optional third block [block (3)] containing a PFPE chain; They are bonded to each other via a link, but in copolymer (P), The sum of (m + f) is at least 1, preferably 1 to 100; The sum of (n+b) is at least 1, preferably 1 to 15; - The at least one type of block (1), the at least one type of block (2), and the at least one type of block (3) if present are statistically distributed. Block copolymer [Copolymer (P)].

2. Each of the PFPE chains is a fully fluorinated chain containing repeating units R° [chain (R ｆ The copolymer (P) according to claim 1, wherein the repeating unit is independently selected from the group consisting of the following: (i) -CFXO-(wherein X is -F or -CF) ３ (It is) (ii) -CFXCFXO- (wherein X is the same or different in each existence, -F or CF ３ However, this is subject to the condition that at least one of X is -F). (iii)-CF ２ CF ２ CF ２ O-; (iv)-CF ２ 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 the general formula -O-R) （ｆ－ａ） -T is the base, R （ｆ－ａ） This is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are: -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ Selected from O-, each of X independently becomes -F or -CF ３ And T is C １ ~C ３ (It is a perfluoroalkylalkyl chain.)

3. In block (1), - m is 0 or an integer between 1 and 2, and / or ・R ５ ~R ８ At least one of them is a base of formula (II), and / or ・R ２０ However, it is either a sigma combination or an equation represented by the following (R ２０ -i) ~ (R ２０ -v): (R ２０ -i) -(CF ２ ) ｓ１ -O-(CF ２ ) ｓ２ - (In the formula, s1 and s2 are independently integers between 1 and 6); () ２０ )) -O-(CF ２ ) ｓ３ - (In the formula, s3 is an integer between 1 and 6); () ２０ )) -O-R ４００ -O-R ４０１ - (In the formula, R ４００ is a linear or branched fully fluorinated alkyl chain containing 1 to 6, preferably 1 to 3 carbon atoms, more preferably of the formula -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF(CF ３ )- which is a fully fluorinated alkyl chain; R401 is a linear or branched fully fluorinated alkyl chain containing 1 to 3 carbon atoms, more preferably of formula -CF ２ -, -CF ２ CF ２ -, -CF (CF ２ (A fully fluorinated alkyl chain according to the following rules); (R) ２０ (-iv) 【Transformation 3】 (In the formula, R ５００ This is a straight, fully fluorinated alkyl chain containing 1 to 6 carbon atoms, which may optionally have at least one oxygen atom sandwiched between them; R ５０１ is the formula - OR ５０３ It is a chain of R ５０３ It is a straight, fully fluorinated alkyl chain containing 1 to 3 carbon atoms; R ５０２ This is a straight, fully fluorinated alkyl chain containing 1 to 4 carbon atoms, and optionally having at least one oxygen atom sandwiched between them. R ５０１ and R ５０２ Each of these combines the base X defined above in formula (II) of claim 1; The copolymer (P) according to claim 1, wherein the group is selected from among those.

4. In block (2) and equation (IV), R １０ The formula is as follows: (R) １０ -i) -(CF ２ ) ｄ (O) ｅ (CF) ２ O) ｆ R ＣＦ (O) ｅ＊ (CF) ２ ) ｄ＊ (CF2O) ｆ＊ (In the formula, Each of d, d*, e, e*, f, and f* is independently either zero or one. R ＣＦ (This is any of the perfluoroalkyl chains containing 1 to 12 atoms, which may optionally have one or more oxygen atoms sandwiched between them.) (R １０ -ii) -O-(C ３ F ６ O) ｈ -(CF ２ ) ｉ -(C ３ F ６ O) ｊ -O- (In the equation, h = j, h + j is between 2 and 6, and i is between 2 and 6.) The copolymer (P) according to claim 1, wherein the copolymer (P) conforms to one of the following.

5. at least, (a) - At least one perfluoropolyether polymer [PFPEperoxy] containing at least one peroxide group; • At least one fully fluorinated compound of formula (X-p): 【Chemistry 4】 (In the formula, R ２１ ~R ２３ Each of these is independently a -F, or a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms. R ２０ X and y are as defined in claim 1 for equation (II); • At least one fully fluorinated compound of formula (XX-p): 【Transformation 5】 (In the formula, R ２１ ~R ２３ Each of them is independently a -F, or a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms. R ３１ ~R ３３ Each of them is independently -F, or a fully fluorinated alkyl group having 1 to 6 carbon atoms. R １０ This is a fully fluorinated alkyl chain containing 1 to 24 carbon atoms, which may be oxygen atoms or optionally have at least one oxygen atom sandwiched between them. t is either zero or 1. (Each of z* and z** is independently 1 or 2) and; The process of bringing them into contact; and b) A step of reacting the PFPE peroxy with at least one compound of formula (X-p) and at least one compound of formula (XX-p) in the presence of UV irradiation or while heating; Method (P), including.

6. - A step prior to step (a) in which the peroxy bond of the PFPE peroxy is partially reduced by chemical reduction, UV treatment, or heat treatment; and / or - After step (b), a step (c) to remove the solvent and / or a step (d) to separate the materials. The method according to claim 5 (P), including the method according to claim 5.

7. The PFPE peroxy is a peroxide perfluoropolyether polymer having two chain ends, each containing a linear or branched fully fluorinated alkyl chain containing 1 to 6 carbon atoms, or a group selected from -C(=O)F, wherein the two chain ends are of formulas (i) to (v): (i) -CFXO-(wherein X is -F or -CF) ３ (It is) (ii) -CFXCFXO- (wherein X is the same or different in each existence, -F or CF ３ However, this is subject to the condition that at least one of X is -F). (iii)-CF ２ CF ２ CF ２ O-; (iv)-CF ２ 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 the general formula -O-R) （ｆ－ａ） -T is the base, R （ｆ－ａ） This is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being: -CFXO-, -CFCFFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ Selected from O-, each of X independently becomes -F or -CF ３ And T is C １ ~C ３ The method according to claim 5 (P), wherein a peroxide content (PO), independently selected from the group consisting of perfluoroalkyl alkyl chains, is between 0.1 and 4, and is defined as the gram amount of reactive oxygen species in 100 g of PFPE peroxy.

8. In the above-mentioned compound of at least one formula (X-p), ・R ２１ , R ２２ , and R ２３ Each of them is -F, and / or ・R ２０ However, it is either a sigma combination or an expression defined below (R ２０ -i) ~ (R ２０ -iv): (R ２０ -i) -(CF ２ ) ｓ１ -O-(CF ２ ) ｓ２ - (In the formula, s1 and s2 are independently integers between 1 and 6); () ２０ )) -O-(CF ２ ) ｓ３ - (In the formula, s3 is an integer between 1 and 6); () ２０ )) -O-R ４００ -O-R ４０１ - (In the formula, R ４００ This is a linear or branched, fully fluorinated alkyl chain containing 1 to 6, preferably 1 to 3, carbon atoms, more preferably of formula -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ A fully fluorinated alkyl chain according to )-; R ４０１ This is a linear or branched, fully fluorinated alkyl chain containing 1 to 3 carbon atoms, preferably of the formula -CF ２ -, -CF ２ CF ２ -, -CF (CF ２ (A fully fluorinated alkyl chain according to the following rules); (R) ２０ (-iv) 【Transformation 6】 (In the formula, R ５００ This is a straight, fully fluorinated alkyl chain containing 1 to 6 carbon atoms, which may optionally have at least one oxygen atom sandwiched between them; R ５０１ is the formula - OR ５０３ It is a chain of, and in the formula, R ５０３ It is a straight, fully fluorinated alkyl chain containing 1 to 3 carbon atoms; R ５０２ This is a straight, fully fluorinated alkyl chain containing 1 to 4 carbon atoms, which may optionally have at least one oxygen atom sandwiched between them. R ５０１ and R ５０２ Each of these combines the base X defined above in formula (II) of claim 1. The method according to claim 5 (P), wherein the base is selected from among those.

9. In the compound of the above formula (XX-p), - When t is 1, the 1, 2, 3, or 4 unsaturated parts are R １０ The method according to claim 5 (P), wherein the same or different atoms belonging to the same group, preferably carbon atoms, are bonded to the same or different atoms, preferably carbon atoms.

10. The above-mentioned compound of formula (XX-p) is the following: CF ２ =CF(R １０ ) ｔ CF=CF ２ (In the formula, t is 0 or 1, R １０ The formula is as follows: (R) １０ -i) -(CF ２ ) ｄ (O) ｅ (CF) ２ O) ｆ R ＣＦ (O) ｅ＊ (CF) ２ ) ｄ＊ (CF2O) ｆ＊ Accordingly, in the formula, Each of d, d*, e, e*, f, and f* is independently either zero or one. R ＣＦ (wherein it is any of the perfluoroalkyl chains containing 1 to 12, which may optionally have one or more oxygen atoms sandwiched between them); (R １０ -ii) -O-(C ３ F ６ O) ｈ -(CF ２ ) ｉ -(C ３ F ６ O) ｊ -O- (In the equation, h = j, h + j is between 2 and 6, and i is between 2 and 6); The method according to claim 5 (P).

11. Steps (a) and (b) are carried out in the presence of a fluorinated solvent; and / or - Step (b) is carried out in an inert atmosphere; - Step (b) is carried out for 2 to 150 hours and / or at a temperature of -60°C to +150°C in the presence of UV radiation; or Step (b) is preferably carried out under heat treatment by heating at a temperature of 150°C to 250°C; The method according to claim 5.

12. A block copolymer [copolymer (P Ｆ )] wherein the first chain ends of the first and second PFPE chains are each chain ends of copolymer (P), and each is a salt with a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, an organic cation of -COOH and COOH, preferably an onium cation, or an inorganic cation, preferably an alkali metal; -COOR (wherein R is a linear or branched alkyl chain containing 1 to 6 carbon atoms); -COF; -CONH ２ ;-CON(R ３００ ) (Caution ３０１ ) (wherein, R ３００ and R ３０１ Each of these has the same meaning as defined for R; -(R) ｃ It contains a group selected from OH (wherein c is 0 or 1 and R is as defined above); -C(O)-O-C(O)R (wherein R is as defined above), However, (i) at least one chain end of the first and second PFPE chains contains a group different from a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and (ii) if one chain end contains the group -COF, the other chain end does not contain a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, or -COF. The second end of the first and second PFPE chains is the following block: - At least one first block [block (1)] according to formula (I): 【Transformation 7】 (In the formula, m is an integer from 0 to 5; R ５ ~R ８ Each of these is independently -F, a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and formula (II): (_). ２０ ()) ｙ Selected from the group containing the base, in formula (II), R ２０ This is a sigma bond, or a straight or branched perfluoroalkyl chain containing 1 to 12 carbon atoms, preferably containing at least one oxygen atom and / or having oxygen atoms sandwiched between them. X is a functional group, preferably -SO ２ F, -SO ３ H, -COOH, -COF, -CN, -Br, and -CONH ２ Selected from, y is an integer of 1 or 2, In equation (I), R ５ ~R ８ (At least one of these, preferably one, is a base of formula (II); - At least one second block [block (2)] following formula (III): 【Transformation 8】 (In the formula, n is an integer between 1 and 3; R １ ~R ４ Each of these independently comprises a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, formula (IV): (IV) -(R １０ ) ｔ [C(R) １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ Selected from the group containing the base, in formula (IV), R １０ This is a divalent / trivalent / tetravalent fully fluorinated alkyl chain containing 1 to 24 carbon atoms, which may be oxygen atoms or optionally have at least one oxygen atom sandwiched between them. t is either zero or 1. z is an integer between 1 and 3. R １１ ~R １５ Each of these is independently selected from the group comprising a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and a group of formula (V) as described in claim 1); and - At least one optional third block [block (3)] containing a PFPE chain; They are bonded to each other via a copolymer (P Ｆ ) in The sum of (m + f) is at least 1, preferably 1 to 100; The sum of (n+b) is at least 1, preferably 1 to 15; - The at least one type of block (1), the at least one type of block (2), and the at least one type of block (3) if present are statistically distributed. Block copolymer [Copolymer (PF)].

13. Block copolymer containing first and second perfluoropolyether chains [PFPE chains] [Copolymer (P Ｏ－Ｏ )] and each of the first and second PFPE chains is a chain (Rf) as defined in claim 2, or (Rf Ｏ－Ｏ ) is a repeating unit of a chain (Rf) that follows any one of the formulas (i) to (v) defined in claim 2 for (R°). Ｏ－Ｏ ) and having a peroxide content (PO) between 0.1 and 4, defined as the grams of reactive oxygen species (Mw=16) in 100 g of PFPE peroxy, wherein each of the first and second PFPE chains has two chain ends, the first chain end of each of the first and second PFPE chains is a copolymer (P) chain end, each containing a group selected from a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F, and -OC(=O)F, and the second chain ends of the first and second PFPE chains are the following blocks: - At least one first block [block (1)] according to formula (I): 【Chemistry 9】 (In the formula, m is an integer from 0 to 5; R ５ ~R ８ Each of these is independently -F, a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and formula (II): (_). ２０ ()) ｙ Selected from the group containing the base, in formula (II), R ２０ This is a sigma bond, or a straight or branched perfluoroalkyl chain containing 1 to 12 carbon atoms, preferably containing at least one oxygen atom and / or having oxygen atoms sandwiched between them. X is a functional group, preferably -SO ２ F, -SO ３ H, -COOH, -COF, -CN, -Br, and -CONH ２ Selected from, y is an integer of 1 or 2, In equation (I), R ５ ~R ８ (At least one of these, preferably one, is a base of formula (II); - At least one second block [block (2)] following formula (III): 【Chemistry 10】 (In the formula, n is an integer between 1 and 3; R １ ~R ４ Each of these independently comprises a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, formula (IV): (IV) -(R １０ ) ｔ [C(R) １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ Selected from the group containing the base, in formula (IV), R １０ This is a divalent / trivalent / tetravalent fully fluorinated alkyl chain containing 1 to 24 carbon atoms, which may be oxygen atoms or optionally have at least one oxygen atom sandwiched between them. t is either zero or 1. z is an integer between 1 and 3. R １１ ~R １５ Each of these is independently selected from the group comprising a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and a group of formula (V) as defined in claim 1); and / or - At least one optional third block [block (3)] comprising the PFPE chain as defined in claim 2; They are connected to each other via, * Copolymer (P Ｏ－Ｏ ) in - The aforementioned block (1), the aforementioned block (2), and the aforementioned block (3) if present are statistically distributed, The sum of (n+b) is at least 1, preferably 1 to 15; The sum of (m + f) is at least 1, preferably 1 to 100; Block copolymer [copolymer (PO-O)].

14. Block copolymer containing first and second perfluoropolyether chains [PFPE chains] [Copolymer (P Ｆ－Ｏ－Ｏ )] and each of the first and second PFPE chains is a chain (Rf) as defined in claim 2, or (Rf Ｏ－Ｏ ) is a repeating unit of a chain (Rf) that follows any one of the formulas (i) to (v) defined in claim 2 for (R°). Ｏ－Ｏ ), and having a peroxide content (PO) between 0.1 and 4, defined as the number of grams of reactive oxygen species (Mw=16) in 100 g of PFPE peroxy, wherein each of the first and second PFPE chains has two chain ends, and the first chain end of each of the first and second PFPE chains is a copolymer (P) chain end, each being a salt with a fully fluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, an organic cation of -COOH and COOH, preferably an onium cation, or an inorganic cation, preferably an alkali metal; -COOR (wherein R is as defined above); -COF; CON (R ３００ ) (Caution ３０１ ) (wherein, R ３００ and R ３０１ Each of these is either a hydrogen atom or has the same meaning as defined for R); -(R)cOH (wherein c is 0 or 1 and R is as defined above); -C(O)-O-C(O)R (wherein R is as defined above); -Br; -CN2 comprising a group selected from these; the second chain ends of the first and second PFPE chains are - At least one first block [block (1)] according to formula (I): 【Chemistry 11】 (In the formula, m is an integer from 0 to 5; R ５ ~R ８ Each of these is independently -F, a fully fluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and formula (II): (_). ２０ ()) ｙ Selected from the group containing the base, in formula (II), R ２０ This is a sigma bond, or a straight or branched perfluoroalkyl chain containing 1 to 12 carbon atoms, preferably containing at least one oxygen atom and / or having oxygen atoms sandwiched between them. X is a functional group, preferably -SO ２ F, -SO ３ H, -COOH, -COF, -CN, -Br, and -CONH ２ Selected from, y is an integer of 1 or 2, In equation (I), R ５ ~R ８ (At least one of these, preferably one, is a base of formula (II); - At least one second block [block (2)] following formula (III): 【Chemistry 12】 (In the formula, n is an integer between 1 and 3; R １ ~R ４ Each of these independently comprises a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, formula (IV): (IV) -(R １０ ) ｔ [C(R) １１ )(R １２ )-C(R １３ )(R １４ )(R １５ )] ｚ Selected from the group containing the base, in formula (IV), R １０ This is a divalent / trivalent / tetravalent fully fluorinated alkyl chain containing 1 to 24 carbon atoms, which may be oxygen atoms or optionally have at least one oxygen atom sandwiched between them. t is either zero or 1. z is an integer between 1 and 3. R １１ ~R １５ Each of these is independently selected from the group comprising a fluorine atom, a fully fluorinated linear or branched alkyl group having 1 to 6 carbon atoms, and a group of formula (V) as defined in claim 1); and / or - At least one optional third block [block (3)] comprising the PFPE chain as defined in claim 2; They are connected to each other via, * Copolymer (P Ｆ－Ｏ－Ｏ ) in - The aforementioned block (1), the aforementioned block (2), and the aforementioned block (3) if present are statistically distributed, The sum of (n+b) is at least 1, preferably 1 to 15; The sum of (m + f) is at least 1, preferably 1 to 100; Block copolymer [copolymer (PF-O-O)].

15. At least one copolymer (P) according to any one of claims 1 to 4, at least one of the PFPE peroxy used as a starting material, and / or one or more copolymers (P) according to claim 13 Ｏ－Ｏ A mixture containing ) [Mixture (M1)].

16. At least one copolymer (P) according to claim 12 Ｆ ), at least one copolymer (P) according to any one of claims 1 to 4, at least one PFPE peroxy used as a starting material, one or more copolymers (P) according to claim 13 Ｏ－Ｏ ), and / or the one or more copolymers (P) described in claim 14. Ｆ－Ｏ－Ｏ ) [Mixture (M2)].

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