(Per)fluoropolyether (PFPE) polymers

Abstract

The present invention relates to novel (per)fluoropolyether polymers characterized by high molecular weight and high functionality, to the process for their preparation and to their use as intermediate compounds in the preparation of further polymers.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to European Patent Application No. 19156266.9, filed February 8, 2019, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel (per)fluoropolyether (PFPE) polymers characterized by high molecular weight and high functionality, to processes for their preparation and to their use as intermediate compounds in the preparation of further polymers. [Background technology]

[0003] Difunctional (per)fluoropolyether polymers (PFPEs) are known in the art for many applications, for example as lubricants, surfactants, coatings, or as macromonomers in polycondensation reactions. In all such applications, it is desirable to use difunctional PFPEs with as high a difunctionality content as possible. For example, in polycondensation reactions, the use of PFPEs with very high difunctionality content is necessary to avoid stochastic interruption of polymer chains, which is observed when significant amounts of monofunctional PFPEs are present.

[0004] However, bifunctional PFPEs are typically available in mixtures with monofunctional and neutral (or non-functional) PFPEs, due to the fact that the currently available synthetic methods for their production do not allow obtaining pure bifunctional polymers.Therefore, subsequent purification is required to separate bifunctional PFPEs from monofunctional and neutral PFPEs or to enrich the content of bifunctional PFPEs.For this purpose, purification processes have been developed and disclosed in the art, which typically involve the use of solid adsorbent stationary phases and eluents (for example, U.S. Patent Nos. 5,246,588 and 7,288,682 in the name of Solvay Solexis SpA; U.S. Patent No. 5,262,057 in the name of Ausimont SpA and European Patent No. 0822216 are mentioned).

[0005] More recently, a method for enhancing the content of difunctional PFPE polymers in a mixture of neutral, monofunctional and difunctional PFPE polymers has been disclosed in WO 2013 / 060658 (in the name of Solvay Specialty Polymers Italy SpA), which method comprises the use of an adsorbent stationary phase and a supercritical fluid as the mobile phase.

[0006] In addition to the above, another problem in the synthesis of PFPE polymers is the difficulty of obtaining PFPE polymers with high molecular weights. In fact, currently available synthesis methods make it possible to obtain PFPEs with number average molecular weights (Mn) usually in the range of 400 to 5,000.

[0007] In this context, US Patent No. 5,354,922 (in the name of Ausimont SpA) discloses that it is possible to obtain peroxyperfluoropolyoxyalkylenes with a viscosity at 20°C ranging from 300,000 to 8,000,000 cSt, which provides neutral perfluoropolyoxyalkylene polymers endowed with a functionality of more than 1.9 and at the same time a high molecular weight, by chemical reduction. More particularly, the perfluoropolyoxyalkylenes obtained by chemical reduction are said to have number-average molecular weights ranging from 400 to 20,000 and functionality ranging from 1.99 to 1.88, respectively. However, on the other hand, peroxyperfluoropolyoxyalkylenes with a viscosity at 20°C of more than 100,000 cSt are very difficult to handle on an industrial scale. For viscosities of more than 100,000 cSt at 20°C, the use of solvents is mandatory, which requires modifications of the industrial plant and then subsequent steps to process the solvent. On the other hand, this patent illustrates the synthesis of functional perfluoropolyoxyalkylene polymers having number average molecular weights of up to 3,200.

[0008] WO 2008 / 122639 (in the name of Solvay Solexis SpA) also discloses a method for preparing functionalized perfluoropolyether polymers. The polymers are said to have a number average molecular weight of 200 to 8,000. However, in the examples, only perfluoropolyether polymers having number average molecular weights of 1,080 and 1,270 are prepared.

[0009] The above mentioned documents demonstrate in fact that when high functionality is desired, the final perfluoropolyether polymer is characterized by a low number average molecular weight.

[0010] PFPEs with (Mn) in the range of 3,500-5,000 are usually isolated from mixtures containing lower molecular weight PFPEs. This problem and the isolation of high molecular weight monofunctional PFPEs was disclosed, for example, in WO 2016 / 083280 (in the name of Solvay Specialty Polymers Italy SpA).

[0011] WO 2016 / 083279 (in the name of Solvay Specialty Polymers Italy SpA) discloses in Example 4 the synthesis of a polymer obtained by reacting Fomblin® Z DOL PFPE with Fomblin® Z DOL PFPE containing nonaflate end groups, such that after thin-film distillation the polymer has a partially fluorinated backbone containing three perfluoropolyether segments linked together by hydrogen-containing chains of formula -CH2OCH2- and has a number average molecular weight of 8100 g / mol. The functionality of this polymer is not indicated. Summary of the Invention

[0012] The Applicant was now faced with the problem of providing (per)fluoropolyether polymers characterized by both a high number average molecular weight (i.e., a number average molecular weight of about 7,000 to 30,000) and a high functionality (i.e., of at least 1.80).

[0013] Although PFPE polymers having a number average molecular weight of 10,000 or less have been disclosed in the art, the applicant is well aware that when PFPE polymers are prepared by photooxidation of tetrafluoroethylene, it is necessary to find a balance between the desired molecular weight and the desired functionality. In fact, to obtain a mixture of PFPE polymers characterized by a high functionality (such as at least 1.80), the number average molecular weight of the final PFPE polymer will be 1,500 or less. On the other hand, if a higher number average molecular weight is desired, a starting material with a lower amount of peroxy oxygen (PO) should be used, thus adversely affecting the final functional value. Up to now, the applicant is not aware of any photooxidation process applied on an industrial scale that makes it possible to obtain a bifunctional PFPE polymer having a number average molecular weight of 7,000 or more.

[0014] The applicant also faced the problem of providing a (per)fluoropolyether polymer characterized by both a high number average molecular weight and a high functionality, without the step of purifying a mixture containing neutral, monofunctional and difunctional PFPE polymers.Indeed, as the number average molecular weight of the PFPE polymer increases, the difficulty of finding a separation technique that can efficiently separate neutral, monofunctional and difunctional polymers on an industrial scale also increases.

[0015] In addition, the applicant was faced with the problem of providing (per)fluoropolyether polymers characterized by both high number average molecular weight and high functionality, whose main chain still contains units of the formula -(CF2O)-. Indeed, the C1-repeating units provide the final PFPE polymer with unique low temperature properties compared to PFPE polymers whose main chain contains only repeating units of the formula -(CF2CF2CF2O)- or -[CF(CF3)CF2O]-.

[0016] Surprisingly, the applicant has found that the nucleotide sequence of at least 7,000 daltons ( 19It has been found that perfluoropolyether polymers characterized by a number average molecular weight (Mn) of at least 1.80 (as measured by F-NMR) and a functionality (F) of at least 1.80 can be prepared by a convenient method that can be easily carried out on an industrial scale and does not require a separate purification step.

[0017] Thus, in a first aspect, the present invention relates to a polymer (PFPE) as defined below: EST A method for producing the same [method (P)], The method comprises the steps of: (I) At least one perfluoropolyether diol [polymer (PFPE)] having a functionality of at least 1.90 is reacted with at least one perfluoro-bis-vinyl ether [compound (F)] to form two chain ends [chain (E HFPE providing at least one partially fluorinated polyether polymer [polymer (HFPE)] comprising said backbone having a chain (E HFPE At least one of the chains (E HFPE PFPE) comprises a group selected from -OH, -F, -CF3 or -COOH, wherein the equivalent ratio between the polymer (PFPE) and the compound (F) is greater than 1; (II) The at least one polymer (HFPE) obtained in step (I) is contacted with at least one compound selected from perfluorinated acid anhydrides, perfluorinated carboxylic acids, carbonyl difluoride, perfluoroacyl fluorides or perfluoroacyl chlorides to convert the two chain ends [chain(E HFPE-P At least one partially fluorinated polyether polymer [polymer(HFPE)] P ) , wherein the chain (E HFPE-P At least one of the chains (E HFPE-P ) comprises an ester group, a fluoroformate, or a group of formula -F, -CF3, or -COOH; (III) The at least one polymer (HFPE) obtained in step (II) P ) is contacted with at least one fluorine source to form two chain ends [chain(E PFPE-P at least one fully fluorinated polyether polymer [polymer(PFPE)] P ) , wherein the chain (E PFPE-P ) is at least one of the groups -OC(=O)R 3 (R 3 is a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms, optionally interrupted by -F, -CF3, or oxygen atoms), and other chains (E PFPE-P ) is a group of the formula -F, -CF3 or a group -OC(=O)R 3 (R 3 is as defined above; (IV) the at least one polymer (PFPE P ) is contacted with a compound containing at least one group capable of providing nucleophilic substitution to form two chain ends [chain(E PFPE-EST A perfluoropolyether polymer having the above-mentioned main chain [polymer (PFPE)] EST ) , wherein the chain (E PFPE-EST ) at least one of the formula -C(=O)X 1 (X 1 is an -OH or an alkoxy chain containing 1 to 6 carbon atoms) and the other chain (E PFPE-EST ) is of the formula -F, -CF3 or -C(=O)X 1 (X 1 is as defined above, and wherein the backbone has the following formula: -(CFX # ) z1 O(R f )(CFX * ) z2 D F * -[O-CF2CF2(CF2) z OR CF-O(CF2) z* CF2CF2-R pf-F ] t - {in formula: t is an integer of 1 to 30, preferably 1 to 25, and more preferably 1 to 20; z and z * each is independently 0 or 1; z1 is an integer equal to or greater than 1; z2 is an integer of 0 or 1 or more; Equal or different, X # and X * is -F or -CF3, provided that when z1 and / or z2 are greater than 1, X # and X * is -F; D F * is a perfluorinated alkylene chain containing 1 to 6, more preferably 1 to 3, carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R CF is a perfluoroalkyl chain containing 2 to 12, preferably 2 to 6, carbon atoms, optionally interrupted by one or more oxygen atoms; (R f ) comprises, and preferably consists of, repeat units R°, said repeat units being independently (i) -CFXO- (wherein X is F or CF3); (ii) -CFXCFXO- (wherein X, equal or different for each occurrence, 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(where R (f-a)is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, said repeat units being selected from among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (each X is independently F or CF3), and T is a C1 to C3 perfluoroalkyl group). selected from the group consisting of; R pf-F is the expression: -OD F -(CFX # ) z1 -O(R f )(CFX * ) z2 - (where: z1, z2, X # , X * and (R f ) is as defined above; DF is a perfluorinated alkylene chain containing 1 to 6, more preferably 1 to 3, carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. is a chain of The present invention relates to a method comprising the steps of:

[0018] The Applicant has surprisingly found that the process (P) described above makes it possible to obtain partially and fully fluorinated polyether polymers characterized by a novel chemical structure.

[0019] Thus, in a second aspect, the present invention provides a method for the preparation of a cyclic tether comprising the steps of: HFPE ) , wherein the polymer comprises a partially fluorinated polyether backbone (HFPE), The backbone has the following formula: -D(CFX # ) z1 O(R f )(CFX * ) z2 D * -[OCF2CFH(CF2) z OR CF-O(CF2) z* CFHCF2-R pf ] t - [In the formula, t is an integer from 1 to 30; z and z * each is independently 0 or 1; R CF is a perfluorinated alkyl chain containing 1 to 12, preferably 2 to 6, carbon atoms, optionally interrupted by one or more oxygen atoms; z1 and z2, which are equal to or different from each other, are integers equal to or greater than 1; Equal or different, X # and X * is -F or -CF3, provided that when z1 and / or z2 are greater than 1, X # and X * is -F; D and D, which are equal or different from each other * is a sigma bond or an alkylene chain containing 1 to 6, more preferably 1 to 3, carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R pf is the expression: -OD-(CFX # ) z1 -O(R f )(CFX * ) z2 -D * - (where z1, z2, X # , X * , D and D * is a chain of (as defined above), (R f ) comprises, preferably consists of, a repeating unit R° selected from the group consisting of formulae (i) to (v) as defined above. The present invention relates to a polymer according to the present invention.

[0020] Advantageously, in said polymer (HFPE), at least 90% of said chain ends contain one group of formula -OH. HFPE-OH ) is the equation reported above: F HFPE-OH =2×E f / (E f +E n ) (where: E f is the number of -OH end groups, E n is the number of -F, -CF3 and -COOH end groups) It is calculated according to:

[0021] Advantageously, the polymer (HFPE) has a molecular weight of at least 7,000 Daltons ( 19 Preferably, the polymer (HFPE) is characterized by a number average molecular weight (Mn) of at least 9,000 Daltons, more preferably at least 9,500 Daltons (as measured by F-NMR). Preferably, the polymer (HFPE) is characterized by a number average molecular weight (Mn) of 30,000 Daltons or less, more preferably 25,000 Daltons or less, even more preferably 20,000 Daltons or less.

[0022] Advantageously, said polymer (HFPE) is characterized by a functionality (F) of at least 1.80, more preferably at least 1.85, even more preferably at least 1.89, even more preferably at least 1.92. A preferred embodiment has a functionality of at least 1.95.

[0023] In a third aspect, the present invention provides a polymer (HFPE) comprising a partially fluorinated backbone as defined above for the polymer (HFPE). P ), wherein the main chain has two chain ends [chain(E HFPE-P )], and HFPE-P ) is at least one of the groups -OC(=O)R 3 (R 3is a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms optionally interrupted by -F, -CF3, or oxygen atoms), the other chain end containing a group -OC(=O)R3, where R3 is as defined above, or a group of formula -F, -CF3 or -COOH.

[0024] Polymer (HFPE P ) functionality (F HFPE-P ) is reported in the equation: F HFPE-P =2×E f / (E f +E n ) (where: E f is the group -OC(=O)R 3 (R 3 is the number of -F or -CF E n is the number of -F, -CF3 and -COOH end groups) It is calculated according to:

[0025] Advantageously, said polymer (HFPE P ) is at least 7,000 Daltons ( 19 Preferably, the polymer (HFPE) is characterized by a number average molecular weight (Mn) of at least 9,000 Daltons, more preferably at least 9,500 Daltons, as measured by F-NMR. P ) are characterized by a number average molecular weight (Mn) of less than or equal to 30,000 daltons, more preferably less than or equal to 25,000 daltons, and even more preferably less than or equal to 20,000 daltons.

[0026] Advantageously, said polymer (HFPE P ) is characterized by a functionality (F) of at least 1.80, more preferably at least 1.85, even more preferably at least 1.89, and even more preferably at least 1.92. Preferred embodiments have a functionality of at least 1.95.

[0027] In a fourth aspect, the present invention provides a method for the preparation of a medicament comprising the steps of: PFPE-P Polymers containing fully fluorinated polyether backbones (PFPEs) P ) where The backbone has the following formula: -(CFX # ) z1 O(R f )(CFX * ) z2 D F * -[O-CF2CF2(CF2) z OR CF -O(CF2) z* CF2CF2-R pf-F ] t - {In the formula, t is an integer from 1 to 30; z and z * each is independently 0 or 1; z1 is an integer equal to or greater than 1; z2 is an integer of 0 or 1 or more; Equal or different, X # and X * is -F or -CF3, provided that when z1 and / or z2 are greater than 1, X # and X * is -F; D F * is a perfluorinated alkylene chain containing 1 to 6, more preferably 1 to 3, carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R CF is a perfluoroalkyl chain containing 2 to 12, preferably 2 to 6, carbon atoms, optionally interrupted by one or more oxygen atoms, (R f ) comprises, and preferably consists of, repeat units R°, said repeat units being independently (i) -CFXO- (wherein X is F or CF3), (ii) -CFXCFXO- (wherein, equal or different for each occurrence, X is F or CF3, provided that at least one of X is -F); (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-, (v) -(CF2)j-CFZ-O-, where j is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -T(where R (f-a) is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, said repeat units being selected from among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (each X is independently F or CF3), and T is a C1 to C3 perfluoroalkyl group). selected from the group consisting of; R pf-F is the expression: -OD F -(CFX # ) z1 -O(R f )(CFX * ) z2 -D F * - (where: z1, z2, X # , X * and (R f ) is as defined above; Equal to or different from each other, D F and D. F * is a perfluorinated alkylene chain containing 1 to 6, more preferably 1 to 3, carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. is a chain of According to the polymer (PFPE P ) regarding.

[0028] Polymer (PFPE P ) functionality (F PFPE-P) is reported in the equation: F PFPE-P =2×E f / (E f +E n ) (where: E f is the group -OC(=O)R 3 (R 3 is the number of -F, -CF3, or a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms, optionally interrupted by oxygen atoms; E n is the number of groups -F, -CF3) It is calculated according to:

[0029] Advantageously, said polymer (PFPE P ) is at least 7,000 Daltons ( 19 Preferably, the polymer (PFPE) is characterized by a number average molecular weight (Mn) of at least 9,000 Daltons, more preferably at least 9,500 Daltons, as measured by F-NMR. P ) are characterized by a number average molecular weight (Mn) of less than or equal to 30,000 daltons, more preferably less than or equal to 25,000 daltons, and even more preferably less than or equal to 20,000 daltons.

[0030] Advantageously, said polymer (PFPE P ) has a functionality (F) of at least 1.80, more preferably at least 1.85, even more preferably at least 1.89, and even more preferably at least 1.92. PFPE-P ). Preferred embodiments have a functionality of at least 1.95.

[0031] In a fifth aspect, the present invention relates to a perfluoropolyether polymer [polymer (PFPE) as defined above. EST )].

[0032] Advantageously, said polymer (PFPE EST ) is at least 7,000 Daltons (19 Preferably, the polymer (PFPE) is characterized by a number average molecular weight (Mn) of at least 9,000 Daltons, more preferably at least 9,500 Daltons, as measured by F-NMR. EST ) are characterized by a number average molecular weight (Mn) of less than or equal to 30,000 daltons, more preferably less than or equal to 25,000 daltons, and even more preferably less than or equal to 20,000 daltons.

[0033] Polymer (PFPE EST ) functionality (F EST ) is reported in the equation: F EST =2×E f / (E f +E n ) (where: E f is the group -C(=O)X 1 (X 1 is the number of -OH or an alkoxy chain containing 1 to 6 carbon atoms, E n is the number of groups -F and -CF3) It is calculated according to:

[0034] Advantageously, said polymer (PFPE EST ) has a functionality (F) of at least 1.80, more preferably at least 1.85, even more preferably at least 1.89, and even more preferably at least 1.92. EST ). Preferred embodiments have a functionality of at least 1.95.

[0035] Advantageously, said polymer (PFPE EST ) can be further reacted to provide useful PFPE derivatives, such as PFPEs containing (poly)amide groups and hydroxy groups at their chain ends.

[0036] Hydroxy group-containing PFPEs are of particular interest within the present invention.

[0037] In a further aspect, the present invention relates to a polymer (PFPE P ) according to the formula provided above for the backbone, and two chain ends [chain(E PFPE-OHOH Perfluoropolyether polymer [polymer (PFPE)] OHOH )], wherein the chain (E PFPE-OHOH ) contains a group of formula -CHOH and the other chain end contains groups of formula -CHOH, -F, -CF.

[0038] Advantageously, said polymer (PFPE OHOH ), wherein the chain (E HWHF At least 90% of the polymer (PFPE) contains one group of the formula -OH, or in other words OHOH ) has a functionality (F OHOH ).

[0039] Polymer (PFPE OHOH ) functionality (F OHOH ) is reported in the equation: F OHOH =2×E f / (E f +E n ) (where: E f is the number of -OH end groups, E n is the number of -F, -CF3 end groups) It is calculated according to:

[0040] Advantageously, said polymer (PFPE OHOH ) is at least 7,000 Daltons ( 19 Preferably, the polymer (PFPE) is characterized by a number average molecular weight (Mn) of at least 9,000 Daltons, more preferably at least 9,500 Daltons, as measured by F-NMR. OHOH) are characterized by a number average molecular weight (Mn) of less than or equal to 30,000 daltons, more preferably less than or equal to 25,000 daltons, and even more preferably less than or equal to 20,000 daltons.

[0041] Advantageously, said polymer (PFPE OHOH ) is characterized by a functionality (F) of at least 1.80, more preferably at least 1.85, even more preferably at least 1.89, and even more preferably at least 1.92. Preferred embodiments have a functionality of at least 1.95. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] For purposes of this description and the following claims: - the use of parentheses around symbols or numbers specifying a formula, such as in expressions such as "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 term "(per)fluoropolyether" is intended to denote a fully or partially fluorinated polymer; The expression "functionality of the (per)fluoropolyether polymer" according to the present invention is defined as follows: F=2×E f / (E f +E n ) (where E f is the number of functional groups of interest, and E n is the number of perfluorinated end groups (including, inter alia, -F and -CF groups) plus E f (The number of functional end groups is different from that evaluated as The functionality (F) is defined as the number of functional groups of interest per polymer molecule according to the following formula: 19It can be measured by F-NMR.

[0043] Advantageously, the polymer (PFPE) used as starting material in the process (P) of the invention comprises a perfluoropolyether backbone having two chain ends attached to opposite sides of said backbone, wherein the backbone has the following formula: -D-(CFX # ) z1 -O(R f )(CFX * ) z2 -D * - (In the formula, D, D * , X # , X * , z1, z2 and Rf are as defined above, and wherein the chain ends contain at least one hydroxy group or a group of formula -F and -CF3; The polymer (PFPE) is characterized by a functionality (F) of at least 1.90.

[0044] Advantageously, the functionality (F) of the polymer (PFPE) is at least 1.95, and even more preferably 1.99. The functionality (F) of the polymer (PFPE) is determined by the following equation: F OH =2×E f / (E f +E n ) (where: Ef is the number of -OH end groups, En is the number of -F and -CF3 end groups. It is calculated according to:

[0045] Preferably, the chain (R f ) is expressed by the following 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, which are equal or different from each other and for each occurrence 2 , X 3 are independently -F, -CF3, with the proviso that at least one X is -F; - g1, g2, g3 and g4, which are equal to or different from each other, are independently integers equal to or greater than 0, such that g1+g2+g3+g4 is in the range of 2 to 70, preferably 2 to 60; 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. Follow.

[0046] More preferably, the chain (R f ) is the formula: (R f -IIA) -[(CF2CF2O) a1 (CF2O) a2 ]- (In the formula: a1 and a2 are independently integers greater than or equal to 0 such that the number average molecular weight is between 400 and 5,000, preferably between 500 and 3,000; both a1 and a2 are preferably different from zero, the ratio a1 / a2 being 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 more such that the number average molecular weight is 400 to 5,000, preferably 400 to 3,000; preferably, b1 is 0, b2, b3, and b4 are greater than 0, and the ratio b4 / (b2+b3) is 1 or more; (Rf -IIC) -[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]- (In the formula: cw=1 or 2; c1, c2, and c3 are independently integers greater than or equal to 0 selected such that the number average molecular weight is 400 to 5,000, preferably 400 to 3,000; preferably, c1, c2, and c3 are all greater than 0 and the ratio c3 / (c1+c2) is generally less than 0.2; (R f -IID) -[(CF2CF(CF3)O) d ]- (In the formula: d is an integer greater than 0 such that the number average molecular weight is 400 to 5,000, preferably 400 to 3,000; (R f -IIE) -[(CF2CF2C(Hal * )2O) e1 -(CF2CF2CH2O) e2 -(CF2CF2CH(Hal * )O) e3 ]- (In the formula: - Hal, which is equal or different for each occurrence * is a halogen selected from a fluorine atom and a chlorine atom, preferably a fluorine atom; - e1, e2, and e3 are equal to or different from each other, and are independently integers greater than or equal to 0 such that the sum (e1+e2+e3) is in the range of 2 to 50. The chain is selected from:

[0047] Even more preferably, the chain (R f ) is herein defined as follows: 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 is 400 to 5,000, preferably 400 to 3,000, and the ratio a1 / a2 is generally comprised between 0.1 and 10, more preferably between 0.2 and 5. Follow.

[0048] Preferably, said compound (F) has the following formula: CF2=CF(CF2) z OR CF O(CF2) z* CF=CF2 (In the formula, z and z * each is independently 0 or 1; R CF has the same meaning as defined above for polymeric PFPE. Follow.

[0049] Preferred compounds (F) are represented by the following formulae (FI) to (F-VIII): (FI) CF2 = CFO(CF2)2OCF = CF2 (F-II) CF2=CFO(CF2)3OCF=CF2 (F-III) CF2=CFO(CF2)4OCF=CF2 (F-IV) CF2=CFCF2O(CF2)4OCF2CF=CF2 (FV) CF2=CFO-CF2O-(CF2)2O(CF2)2O-CF2O-CF=CF2 (F-VI) CF2=CFO-CF2O-(CF2)2O-CF2O-CF=CF2 (F-VII) CF2=CFO-CF2O-(CF2)3O-CF2O-CF=CF2 (F-VIII) CF2=CFO-CF2O-(CF2)4O-CF2O-CF=CF2 (F-IX) CF2=CFO-CF2CF2O-(CF2)2O-CF2O-CF=CF2 This is in accordance with the following.

[0050] The equivalent ratio between the polymer (PFPE) and the compound (F) is determined by the amount of the polymer (HFPE) and most importantly the amount of the final polymer (PFPE OHOH ) can be appropriately selected depending on the desired number average molecular weight.

[0051] Advantageously, the equivalent ratio between said polymer (PFPE) and said compound (F) is between 1.01 and 1.50, and more preferably between 1.05 and 1.25.

[0052] Advantageously, said step (I) is carried out so that the functionality of the polymer (HFPE) is greater than or equal to 90%, preferably greater than or equal to 92% and even more preferably greater than or equal to 95% of the functionality of the starting polymer (PFPE).

[0053] Preferably, said step (I) is carried out in the presence of a base, even more preferably in the presence of potassium carbonate.

[0054] Preferably, said step (I) is carried out in the presence of a polar aprotic solvent, preferably selected from the group comprising, and more preferably consisting of, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane (glyme), bis(2-methoxyethyl)ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), dimethylsulfoxide, dimethylformamide, ethylene peroxide dimethyl ether, with acetonitrile, tetrahydrofuran and dioxane being particularly preferred.

[0055] Step (I) can be carried out by adding said polymer (PFPE) to said compound (F), or vice versa by adding said compound (F) to said polymer (PFPE).

[0056] Preferably, said step (I) is carried out at a temperature ranging from room temperature (ie, about 25°C) to 90°C.

[0057] Preferably, said step (I) is carried out in the presence of a phase transfer catalyst, advantageously chosen from tetra-alkylammoniums.

[0058] Advantageously, said step (I) is carried out working in an anhydrous reaction environment.

[0059] Preferably, after step (I) a polymer (HFPE) is provided which essentially comprises the following groups at its chain ends: -OH, -F, -CF3 and -COOH.

[0060] The expression "essentially comprises" is intended to indicate that the chain ends of the polymer (HFPE) may contain, in addition to the groups detailed above, small amounts of end groups derived from side reactions or impurities in the starting materials, the amount of which will not be such as to substantially alter the properties of the polymer (HFPE). For example, end groups other than -OH, -F, -CF3 and -COOH (such as those of formula -CH2Cl) may be present in an amount of less than 1 mol%, more preferably less than 0.5 mol%, and even more preferably less than 0.1 mol%, based on the total amount of end groups in the polymer (HFPE).

[0061] It will be clear to the skilled artisan that, although the reaction conditions of the steps of the method (P) of the present invention are controlled, at the end of step (I) a mixture of polymers (HFPE) characterized by different groups at their chain ends is obtained. Nevertheless, the fact remains that the conditions of step (I) of the method (P) of the present invention are adjusted to provide a polymer (HFPE) characterized by a functionality as defined above.

[0062] The same principles apply and are true for each and every step (II)-(IV) of the method (P).

[0063] As will be apparent to those skilled in the art, step (II) of the method (P) of the present invention involves the preparation of a polymer having protected chain ends (HFPE P ) is aimed at providing

[0064] Preferably, the step (II) is carried out in the presence of trifluoroacetic anhydride or carbonyl fluoride.

[0065] Preferably, the fluorine source in step (III) is a gas containing fluorine atoms. More preferably, the fluorine source is fluorine gas (F2).

[0066] Advantageously, the fluorine source in step (III) is used in admixture with a diluent gas, preferably chosen from inert gases, such as helium and nitrogen.

[0067] Advantageously, said step (III) is carried out in the presence of a compound capable of generating fluorine radicals to assist in the fluorination step.

[0068] Suitable compounds are selected from carbon monoxide and halogenated olefins.

[0069] The halogenated olefin may be selected, for example, from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), octafluorobutene, perfluoropentene, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorocyclobutene, perfluorocyclopentene, perfluorocyclohexene, chlorotrifluoroethylene (CTFE), dichlorodifluoroethylene, chloropentafluoropropene, perfluorobutadiene, perfluoro-methyl vinyl ether, perfluoro-ethyl vinyl ether, perfluoro-propyl vinyl ether; CFOClC=CClF, trichloroethylene, tetrachloroethylene, dichloroethylene isomers; and fluorodioxole.

[0070] In said step (IV), said compound comprising at least one group capable of providing a nucleophilic substitution is advantageously chosen from water or an alcohol having from 1 to 6 carbon atoms, more preferably ethanol, methanol or propanol.

[0071] Polymer (PFPE OHOH ) is advantageously (V) The polymer according to any one of the preceding claims (PFPE EST ), (VI) hydrolyzing the ester groups at the chain ends to the groups -CHOH, thus forming the polymer (PFPE OHOH The polymer (PFPE) EST ) with a reducing agent. Methods including OHOH )].

[0072] Preferably, step (VI) is carried out in the presence of a base, such as sodium borohydride.

[0073] The applicant further discloses a method for producing said polymer (PFPE OHOH ) was noted to be useful as an intermediate for the synthesis of additional difunctional PFPE polymers.

[0074] On the other hand, the polymer (PFPE OHOH ) can be used as macromers in polycondensation reactions, such as to provide PFPE polymers that contain polyurethane groups at their chain ends.

[0075] On the other hand, the polymer (PFPE OHOH ) can be reacted to modify the groups at its chain ends.

[0076] In particular, the polymer (PFPE OHOH ) is a polymer with two chain ends (PFPE OHOH A polymer comprising a perfluoropolyether backbone [polymer (PFPE) OHOH-X ), in which at least one chain end is of the formula -CF2CH2O-R 1 {where, R 1is a linear or branched alkyl chain containing 1 to 16 carbon atoms and substituted with at least 2, more preferably 2 to 8, groups -OH; -(CH2CH2O) n H (n is an integer from 1 to 10); -(CH2CH2O)nP(O)(OH)2 (n is an integer of 0 or greater than 1); -CH2CH=CH2; -C(=O)-R 2 [In the formula, R 2 is a linear or branched alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 12 carbon atoms, or -NHR 4 (R 4 is a hydrogen atom, a linear or branched alkyl chain containing 1 to 20 carbon atoms; a phenyl group optionally substituted with at least one nitro group; and a pyridinyl group optionally substituted with at least one -CF3 group. The group includes:

[0077] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that a term may be unclear, this statement shall control.

[0078] The invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not limiting the scope of the invention.

[0079] Experimental section raw materials Reagents used in the following examples were obtained from Sigma-Aldrich and were used as such.

[0080] Perfluoro-bis-vinyl ether was obtained from Ftoran GmbH & Co. KG / ANLES, Ltd.

[0081] Novec TM 7100 Engineered Fluid (Methoxynonafluorobutane-HFE 7100) was obtained from 3M and used as such.

[0082] The formula provided below: HOCH2CF2O(R f )CF2CH2OH [(R f ) is -(CF2CF2O) a1 (CF2O) a2 - (wherein the a2 / a1 ratio is about 1). Perfluoropolyoxyalkylene diol Fomblin® Z PFPE polymer according to the present invention was obtained from Solvay Specialty Polymers Italy SpA. *For polymer PFPE1: Mn=1,034 Daltons and F=1.99; *For polymer PFPE2: Mn=3,045 Daltons and F=1.98.

[0083] method NMR analysis 19 F-NMR and 1 The H-NMR spectrum 1 For H, it is 499.86MHz. 19 F was recorded on an Agilent System 500 operating at 470.30 MHz.

[0084] Approximately 0.6 cc of each sample was introduced into the NMR tube and analyzed neat.

[0085] 19 F-NMR spectra were acquired to encompass all signals from approximately -10 to -170 ppm, with a pulse flip angle of 90° and a relaxation delay suitable for quantitative analysis (3-5 times the maximum d1 value, at least 6 s). The number of scans was selected to obtain a reasonable signal-to-noise ratio (at least 400).

[0086] 1H-NMR spectra were acquired with a spectral width of approximately 16 ppm, a pulse flip angle of 45°, and a relaxation delay suitable for quantitative analysis (3-5 times the maximum d1 value, at least 5 s). The number of scans was selected to obtain a reasonable signal-to-noise ratio (at least 100).

[0087] Both spectra were acquired at room temperature with a spin rate of 20 Hz.

[0088] 19 The number average molecular weight (Mn) of the polymers was measured using F-NMR spectroscopy. As is known in the art, this is because each structure 19 This is made possible by the fact that they resonate at different frequencies in the F-NMR spectrum and therefore can be integrated separately. Thus, the integrated signals of the internal units (such as -(CF2CF2O)- and -(CF2O)-) and the chain end groups, after normalization to the same number of fluorine atoms, are as follows: M n =2×[(Σ i U i * M i ) / Σ t T t ] (where: U i is the integrated signal of the internal units of the polymer, M i Formula weight of each unit, T i (integrated signal at chain end) Number average molecular weight M n was used to calculate

[0089] The relative amounts of the different chain ends (measured as defined above) can also be F=2×E f / (E f +E n ) (where: E f is the functional chain end of interest, E n is a different chain end than Ef) This allows the calculation of functionality, which is defined as:

[0090] Example 1 Process 1 Into a three-necked 250 ml flask equipped with a magnetic stirrer, 0.66 g of a 25% w / w solution of tetramethylammonium hydroxide in water (0.047 mmol) was introduced and 20 g (38.7 meq) of PFPE1 was added.

[0091] The mixture was heated under vacuum at 80° C. for 1 hour to completely remove water. After cooling at room temperature, it was added with 40 g of acetonitrile and 5.85 g (33.33 meq) of a compound of the formula: CF2=CF2CF2CF2OCF=CF2 of perfluoro-bis-vinyl ether was added.

[0092] Then, 2.7 g (19.5 moles) of anhydrous potassium carbonate was added in one portion under stirring and the reaction mixture was left under stirring at 50° C. for about 7 hours. 19 The completion was considered when F-NMR analysis showed disappearance of the vinyl ether double bond signal.

[0093] When the reaction was complete, the mixture was cooled to room temperature and washed with 50 g of water. Then, 37 g of HFE 7100 and 4 g of isobutyl alcohol were added to the reaction mixture to obtain the separation of two phases. The organic phase was separated and washed with 20 g of water and 3.6 g of hydrochloric acid 37%. After decanting, two phases were obtained. The fluorinated phase (the one at the bottom) was evaporated under vacuum to obtain 23.1 g of a viscous, colorless, transparent liquid.

[0094] 1 H-NMR and 19 The structure of the product, as determined by F-NMR, is as follows: X-CF2O-(R f )-OCF2CH2[OCF2CFHOC3F6OCFHCF2OCH2CF2O-(Rf)-OCF2CH 2]t OH (where: t=6.80 X=-CH2OH(95%), -F(2%), -COOH(3%), Mn = 10,300 Daltons (F OH )=1.90) It was.

[0095] Process 2 18.8 g of the polymer obtained in step 1 described above was charged into a 100 ml round bottom flask equipped with a magnetic stirrer and 1.5 g of trifluoroacetic anhydride was added.

[0096] The mixture is kept under stirring at room temperature for 1 hour, then the trifluoroacetic acid formed and the excess acid anhydride are distilled off under vacuum at 80°C.

[0097] The following structure: X-CF2O-(R f )-OCF2CH2[OCF2CFHOC3F6OCFHCF2OCH2CF2O-(Rf)-OCF2CH2] t OC(=O)CF3 (where: t=6.80 X = -CH2OC(=O)CF3, -F and -COOH; (F -OCOCF3 )=1.90) 18.3 g of product having the formula:

[0098] Process 3 18.3 g of the polymer obtained in step 2 described above was dissolved in 92.5 g of perfluoro-2-butyltetrahydrofuran (CF 16 The mixture was loaded into a 250 ml stainless steel reactor equipped with a mechanical stirrer, a thermocouple and two inlet pipes and kept at 0° C. by an external circulating bath.

[0099] While maintaining high speed stirring, 6.0 Nl / h of helium were fed into the reactor through the first inlet pipe for 1 hour, then 2.0 Nl / h of elemental fluorine were added in the same stream; after 2 hours, 0.3 Nl / h of carbon monoxide diluted in 1.5 Nl / h of helium was fed into the reactor through the second inlet pipe; after a further 4 hours the elemental fluorine and carbon monoxide streams were closed and the reactor was purged with the remaining helium stream.

[0100] The crude mixture 1 Analysis by H-NMR confirmed quantitative conversion of all hydrogen atoms. The mixture was then treated with excess ethanol at reflux to convert all terminal perfluoroester groups to the corresponding ethyl ester groups. The mixture was washed twice with water, then treated with sodium sulfate, and finally evaporated to remove the perfluorinated solvent to give the following formula: XCF2O-(R f )-OCF2[CF2OCF2CF2OC3F6OCF2CF2OCF2CF2O-(Rf)-OCF2]tC(=O)X1 [III] (where: t=6.38 X=-COOEt(90.5%), -F(7.8%), -CF3(1.6%) X1=-OEt (F -COOET )=1.81 Mn=10,600) The product was recovered according to:

[0101] Process 4 The polymer obtained in step 3 described above is reduced from the ethyl ester end groups to the corresponding alcohols according to the procedure reported in A. Russo, C. Tonelli; Journal of Fluorine Chemistry 125 (2004) 181-188 to give the following formula: X-CF2O-(Rf)-OCF2[CF2OCF2CF2OC3F6OCF2CF2OCF2CF2O-(Rf)-OCF2] t CH2OH[IV] (where: t=6.38 X = -CH2OH, -F, -CF3 (F OHOH )=1.81 Mn=10,500 Daltons) The final polymer conforming to the formula:

[0102] Example 2 Process 1 Into a three-necked 250 ml flask equipped with a magnetic stirrer was introduced 0.3 g of a 25 w / w% solution of tetramethylammonium hydroxide in water (0.823 mmol) and 25 g (16.3 meq) of PFPE2 was added.

[0103] The mixture was heated under vacuum at 80° C. for 1 hour. After cooling at room temperature, it was added with 35 g of acetonitrile and 2.45 g (14 meq.) of a compound of the formula: CF2=CF2CF2CF2OCF=CF2 of perfluoro-bis-vinyl ether was added.

[0104] Then, 1.18 g (8.55 moles) of anhydrous potassium carbonate was added in one portion under stirring and the reaction mixture was left under stirring at 50° C. for about 7 hours. 19 The completion was considered when F-NMR analysis showed disappearance of the vinyl ether double bond signal.

[0105] When the reaction was complete, the mixture was cooled to room temperature and washed with 50 g of water. Then, 37 g of HFE 7100 and 4 g of isobutyl alcohol were added to the reaction mixture to obtain the separation of two phases. The organic phase was separated and washed with 20 g of water and 3.6 g of hydrochloric acid 37%. After decanting, two phases were obtained. The fluorinated phase (the one at the bottom) was evaporated under vacuum to obtain 23 g of a viscous, colorless, transparent liquid.

[0106] 1 H-NMR and 19 The structure of the product, as determined by F-NMR, is as follows: X-CF2O-(R f)-OCF2CH2[OCF2CFHOC3F6OCFHCF2OCH2CF2O-(Rf)-OCF2CH2] t OH (where: t=6.04 X=-CH2OH, -F, -CF3, -COOH, Mn=23,560 Daltons, (F OH )=1.95) It was.

[0107] Example 3 Process 1 The same procedure as disclosed in Example 1-Step 1 was followed, but using the following reactants: 20g (38.7 meq) of PFPE2 0.66 g tetramethylammonium hydroxide 25% w / w (1.8 mmol) in water was used.

[0108] 22.6 g of a viscous, clear, colorless liquid was obtained.

[0109] 1 H-NMR and 19 The structure of the product, as determined by F-NMR, is as follows: X-CF2O-(R f )-OCF2CH2[OCF2CFHOC3F6OCFHCF2OCH2CF2O-(R f )-OCF2CH2] t OH (where: t=17.12, X=-CH2OH, -F, -CF3, -COOH, Mn=24,940 Daltons, (F OH )=1.90) It was.

Claims

1. Two chain ends [chain(E ＰＦＰＥ－ＥＳＴ A perfluoropolyether polymer having the main chain having the above-mentioned structure [polymer (PFPE)] ＥＳＴ ) ] The chain (E ＰＦＰＥ－ＥＳＴ ) is at least one of the formula -C(=O)X １ (X １ is —OH or an alkoxy chain containing 1 to 6 carbon atoms), and the other chain (E ＰＦＰＥ－ＥＳＴ ) is -F, -CF ３ and -C(=O)X １ (X １ is as defined above, and wherein the backbone has the following formula: -(CFX ＃ ) ｚ１ O(R ｆ )(CFX ＊ ) ｚ２ D Ｆ ＊ -[O-CF ２ CF ２ (CF ２ ) ｚ O-R ＣＦ -O(CF ２ ) ｚ＊ CF ２ CF ２ -R ｐｆ－Ｆ ] ｔ - {In the formula: t is an integer from 1 to 30, z and z ＊ each is independently 0 or 1; z1 is an integer of 1 or more; z2 is 0 or an integer of 1 or more; X is equal to or different from ＃ and X ＊ is -F or -CF ３ provided that when z1 and / or z2 are greater than 1, X ＃ and X ＊ is -F; D Ｆ ＊ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R ＣＦ is a perfluoroalkylene chain selected from -(CF 2 ) 2 -, -(CF 2 ) 3 -, -(CF 2 ) 4 -, -CF 2 O-(CF 2 ) 2 O(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 3 O-CF 2 O-, -CF 2 O-(CF 2 ) 4 O-CF 2 O, and -CF 2 CF 2 O-CF 2 CF 2 O-CF 2 O-; (R ｆ ) comprises a repeat unit R°, said repeat unit being independently (i) -CFXO- (wherein X is F or CF ３ ) (ii) -CFXCFXO-, where X is F or CF, which are equal or different at each occurrence. ３ with the proviso that at least one 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- [where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T (wherein, R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, the repeat units being as follows: -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O-(each X is independently F or CF ３ and T is selected from C １ ~C ３ perfluoroalkyl group). selected from the group consisting of: R ｐｆ－Ｆ is the formula: . Ｆ ︍F️ ＃ ) ｚ１ () ｆ )(|) ＊ ) ｚ２  (Here, z1, z2, X ＃ , X ＊ And (R ｆ ) is as defined above; D Ｆ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. A polymer conforming to the formula:

2. The polymer according to claim 1 (PFPE ＥＳＴ ) and the polymer has a molecular weight of 7,000 Daltons ( １９ Polymers having a number average molecular weight (Mn) of from 10,000 to 30,000 Daltons (as measured by F-NMR).

3. The polymer according to claim 1 (PFPE ＥＳＴ ), wherein the polymer has a functionality (F ＥＳＴ ).

4. Two chain ends [chain (E ＨＦＰＥ a partially fluorinated polyether polymer [polymer(HFPE)] comprising the backbone having a chain (E ＨＦＰＥ At least one of the chains (E ＨＦＰＥ ) is -OH, -F, -CF ３ or -COOH, wherein the backbone has the formula: -D(CFX ＃ ) ｚ１ O(R ｆ )(CFX ＊ ) ｚ２ D ＊ -[OCF ２ CFH(CF ２ ) ｚ O-R ＣＦ -O(CF ２ ) ｚ＊ CFHCF ２ -R ｐｆ ] ｔ - [In the formula, t is an integer from 1 to 30; z and z ＊ each is independently 0 or 1; R ＣＦ is a perfluoroalkylene chain containing 1 to 12 carbon atoms, optionally interrupted by one or more oxygen atoms; z1 and z2, which are equal to or different from each other, are integers equal to or greater than 1; X is equal to or different from ＃ and X ＊ is -F or -CF ３ provided that when z1 and / or z2 are greater than 1, X ＃ and X ＊ is -F; D and D are equal to or different from each other ＊ is a sigma bond or an alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R ｐｆ is the formula: ____________________________ ＃ ) ｚ１ () ｆ )(|) ＊ ) ｚ２ . ＊  (Here, z1, z2, X ＃ , X ＊ , D and D ＊ is as defined above, (R ｆ )teeth, (i) -CFXO- (wherein X is F or CF 3 ); (ii) -CFXCFXO-, where X, equal or different at each occurrence, is F or CF 3 , provided 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) -(CF2)j-CFZ-O-, where j is an integer from 0 to 3, Z is a group of the general formula -O-R(fa)-T, where R(fa) is a fluoropolyoxyalkene chain containing 0 to 10 repeat units selected from among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, each X is independently F or CF3, and T is a C1-C3 perfluoroalkyl group. The repeating unit R° is selected from the group consisting of: It is a chain of According to, polymer.

5. The polymer (HFPE) according to claim 4, wherein the polymer has a molecular weight of 7,000 Daltons ( １９ a number average molecular weight (Mn) of up to 30,000 Daltons as measured by F-NMR; and / or a functionality (F ＨＦＰＥ－ＯＨ ).

6. Two chain ends [chain(E ＨＦＰＥ－Ｐ A partially fluorinated polyether polymer [polymer(HFPE)] having the chain Ｐ ) )], wherein the chain (E ＨＦＰＥ－Ｐ At least one of the groups is R ３ A group OC(=O)R ３ (R ３ is -F, -CF ３ or a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms, optionally interrupted by oxygen atoms, with the other chain end being a group -OC(=O)R ３ (R ３ is as defined above) or the formula -F, -CF ３ or -COOH groups; -D(CFX ＃ ) ｚ１ O(R ｆ )(CFX ＊ ) ｚ２ D ＊ -[OCF ２ CFH(CF ２ ) ｚ O-R ＣＦ -O(CF ２ ) ｚ＊ CFHCF ２ -R ｐｆ ] ｔ - (In the formula, t, z, z ＊ , R ＣＦ , X ＃ , X ＊ , D, D ＊ and R ｐｆ is as defined in claim 4) According to, polymer.

7. The polymer according to claim 6 (HFPE Ｐ ) and the polymer has a molecular weight of 7,000 Daltons ( １９ a number average molecular weight (Mn) of up to 30,000 Daltons as measured by F-NMR; and / or a functionality (F ＨＦＰＥ－Ｐ ).

8. Two chain ends [chain(E ＰＦＰＥ－Ｐ A fully fluorinated polyether polymer having the above backbone having a polymer (PFPE Ｐ ) )], wherein the chain (E ＰＦＰＥ－Ｐ At least one of the groups is -OC(=O)R ３ (R ３ -F, -CF ３ or a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms, optionally interrupted by oxygen atoms), ＰＦＰＥ－Ｐ ) is represented by the formula -F, -CF ３ or the group -OC(=O)R ３ (R ３ is as defined above, The backbone has the following formula: -(CFX ＃ ) ｚ１ O(R ｆ )(CFX ＊ ) ｚ２ D Ｆ ＊ -[O-CF ２ CF ２ (CF ２ ) ｚ O-R ＣＦ -O(CF ２ ) ｚ＊ CF ２ CF ２ -R ｐｆ－Ｆ ] ｔ - {During the ceremony, t is an integer from 1 to 30, z and z ＊ each is independently 0 or 1; z1 is an integer of 1 or more; z2 is 0 or an integer of 1 or more; X is equal to or different from ＃ and X ＊ is -F or -CF ３ provided that when z1 and / or z2 are greater than 1, X ＃ and X ＊ is -F; D Ｆ ＊ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R ＣＦ is a perfluoroalkylene chain selected from -(CF 2 ) 2 -, -(CF 2 ) 3 -, -(CF 2 ) 4 -, -CF 2 O-(CF 2 ) 2 O(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 3 O-CF 2 O-, -CF 2 O-(CF 2 ) 4 O-CF 2 O, and -CF 2 CF 2 O-CF 2 CF 2 O-CF 2 O-; (R ｆ ) comprises a repeat unit R°, said repeat unit being (i) -CFXO- (wherein X is F or CF ３ ) (ii) -CFXCFXO-, where X is F or CF, which are equal or different at each occurrence. ３ with the proviso that at least one X is -F; (iii) -CF ２ CF ２ C.W. ２ O-, where W, equal to or different from each other, is F; (iv) -CF ２ CF ２ CF ２ CF ２ O-、 (v) -(CF ２ ) ｊ -CFZ-O- [where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T (wherein, R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, the repeat units being as follows: -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O-(each X is independently F or CF ３ and T is selected from C １ ~C ３ perfluoroalkyl group). are independently selected from the group consisting of: R ｐｆ－Ｆ is the formula: . Ｆ ︍F️ ＃ ) ｚ１ () ｆ )(|) ＊ ) ｚ２ . Ｆ ＊  (Here, z1, z2, X ＃ , X ＊ And (R ｆ ) are as defined above; are equal to or different from each other, D Ｆ and D. Ｆ ＊ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. is a chain of The polymer (PFPE Ｐ ).

9. The polymer according to claim 8 (PFPE Ｐ ) and the polymer has a molecular weight of 7,000 Daltons ( １９ a number average molecular weight (Mn) of up to 30,000 Daltons as measured by F-NMR; and / or a functionality (F ＨＦＰＥ－Ｐ ).

10. Polymer (PFPE ＥＳＴ A method for producing a compound (A) comprising the steps of: The method comprises the steps of: (I) At least one perfluoropolyether diol [polymer (PFPE)] having a functionality of at least 1.90 is reacted with at least one perfluoro-bis-vinyl ether [compound (F)] to form two chain ends [chain (E)] attached to opposite sides of a partially fluorinated polyether backbone. ＨＦＰＥ providing at least one partially fluorinated polyether polymer [polymer(HFPE)] comprising said backbone having a chain (E ＨＦＰＥ At least one of the chains (E ＨＦＰＥ ) is -OH, -F, -CF ３ or -COOH, wherein the equivalent ratio of said polymer (PFPE) to said compound (F) is greater than 1; (II) contacting the at least one polymer (HFPE) obtained in step (I) with at least one compound selected from perfluorinated acid anhydrides, perfluorinated carboxylic acids, carbonyl difluoride, perfluoroacyl fluorides or perfluoroacyl chlorides to convert the two chain ends [chain (E ＨＦＰＥ－Ｐ At least one partially fluorinated polyether polymer [polymer(HFPE)] having the backbone Ｐ providing a chain (E ＨＦＰＥ－Ｐ At least one of the chains (E) contains an ester group or a fluoroformate, and the other chain (E ＨＦＰＥ－Ｐ ) is an ester group, a fluoroformate or a group of the formula -F, -CF ３ or -COOH groups; (III) The at least one polymer (HFPE) obtained in step (II) Ｐ ) is contacted with at least one fluorine source to form two chain ends [chain(E ＰＦＰＥ－Ｐ At least one fully fluorinated polyether polymer [polymer(PFPE)] comprising said backbone Ｐ providing a chain (E ＰＦＰＥ－Ｐ At least one of the groups is -OC(=O)R ３ (R ３ -F, -CF ３ or a linear or branched perfluorinated alkyl chain containing 2 to 6 carbon atoms, optionally interrupted by oxygen atoms), ＰＦＰＥ－Ｐ ) is represented by the formula -F, -CF ３ or the group -OC(=O)R ３ (R ３ is as defined above; (IV) the at least one polymer (PFPE Ｐ ) with a compound containing at least one group capable of providing nucleophilic substitution to produce a perfluoropolyether polymer [polymer (PFPE ＥＳＴ and providing Including, a perfluoropolyether polymer [polymer(PFPE EST )] comprising a fully fluorinated backbone having two chain ends [chain(E PFPE-EST )] attached to opposite sides of said backbone; At least one of the chains (E PFPE-EST ) has the formula one group of -C(=O)X 1 (X 1 is -OH or an alkoxy chain containing 1 to 6 carbon atoms) and the other chain (E PFPE-EST ) contains a group selected from -F, -CF 3 and -C(=O)X 1 (X 1 is as defined above); and wherein the backbone has the following formula: -(CFX #) z1 O(R f )(CFX *) z2 D F * -[O-CF 2 CF 2 (CF 2 ) z O-R CF -O(CF 2 ) z* CF 2 CF 2 -R pf-F ] t - {In the formula: t is an integer from 1 to 30, Each of z and z* is independently 0 or 1; z1 is an integer of 1 or more; z2 is 0 or an integer of 1 or more; X # and X *, equal to or different from each other, are -F or -CF 3 , with the proviso that when z1 and / or z2 are greater than 1, then X # and X * are -F; D F * is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R CF is a perfluoroalkylene chain containing 2 to 12 carbon atoms optionally interrupted by one or more oxygen atoms; (R f ) comprises a repeat unit R°, said repeat unit being independently (i) -CFXO- (wherein X is F or CF 3 ); (ii) -CFXCFXO-, where X, equal or different at each occurrence, is F or CF 3 , provided 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) -(CF2)j-CFZ-O-, where j is an integer from 0 to 3, Z is a group of the general formula -O-R(fa)-T, where R(fa) is a fluoropolyoxyalkene chain containing 0 to 10 repeat units selected from among the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, each X is independently F or CF3, and T is a C1-C3 perfluoroalkyl group. selected from the group consisting of: R pf-F is represented by the formula: -O-D F -(CFX #) z1 -O(R f )(CFX *) z2 - where z1, z2, X # , X* and (R f ) are as defined above; D F is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. A method according to the present invention, which is a chain of

11. The compound (F) is represented by the following formula: CF ２ =CF(CF ２ ) ｚ OR ＣＦ O(CF ２ ) ｚ＊ CF=CF ２ (In the formula, z and z ＊ each is independently 0 or 1; R ＣＦ is a perfluoroalkylene chain containing 2 to 12 carbon atoms, optionally interrupted by one or more oxygen atoms.

11. The method (P) according to claim 10,

12. The method (P) according to claim 10, wherein the equivalent ratio of said polymer (PFPE) to said compound (F) is from 1.01 to 1.

50.

13. The step (I) in the presence of a base; and / or in the presence of a polar aprotic solvent; and / or at a temperature ranging from room temperature (i.e. about 25°C) to 90°C; and / or in the presence of a phase transfer catalyst; and / or - In an anhydrous reaction environment The method (P) according to any one of claims 10 to 12,

14. The method (P) according to any one of claims 10 to 13, wherein step (I) is carried out such that the functionality of the polymer (HFPE) is greater than or equal to 90% of the functionality of the polymer (PFPE).

15. Two chain ends [chain(E ＰＦＰＥ－ＯＨＯＨ A perfluoropolyether polymer having the main chain having the above-mentioned structure [polymer (PFPE)] ＯＨＯＨ ) )], wherein the chain (E ＰＦＰＥ－ＯＨＯＨ ) is of the formula -CH ２ The chain ends contain one group of -OH and the other group of -CH ２ OH, -F, and -CF ３ comprising a group selected from The backbone has the following formula: -(CFX ＃ ) ｚ１ O(R ｆ )(CFX ＊ ) ｚ２ D Ｆ ＊ -[O-CF ２ CF ２ (CF ２ ) ｚ O-R ＣＦ -O(CF ２ ) ｚ＊ CF ２ CF ２ -R ｐｆ－Ｆ ] ｔ - {During the ceremony, t is an integer from 1 to 30, z and z ＊ each is independently 0 or 1; z1 is an integer of 1 or more; z2 is 0 or an integer of 1 or more; X is equal to or different from ＃ and X ＊ is -F or -CF ３ With the proviso that when z1 and / or z2 are greater than 1, X ＃ and X ＊ is -F; D Ｆ ＊ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; R ＣＦ is a perfluoroalkylene chain selected from -(CF 2 ) 2 -, -(CF 2 ) 3 -, -(CF 2 ) 4 -, -CF 2 O-(CF 2 ) 2 O(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 2 O-CF 2 -, -CF 2 O-(CF 2 ) 3 O-CF 2 O-, -CF 2 O-(CF 2 ) 4 O-CF 2 O, and -CF 2 CF 2 O-CF 2 CF 2 O-CF 2 O-; (R ｆ ) comprises a repeat unit R°, said repeat unit being (i) -CFXO- (wherein X is F or CF ３ (which is (ii) -CFXCFXO-, where X is F or CF, which are equal or different at each occurrence. ３ with the proviso that at least one X is -F; (iii) -CF ２ CF ２ C.W. ２ O- (wherein, equal to or different from each other, each W is F); (iv) -CF ２ CF ２ CF ２ CF ２ O-、 (v) -(CF ２ ) ｊ -CFZ-O- [where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T (wherein, R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, the repeat units being as follows: -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O-(each X is independently F or CF ３ and T is selected from C １ ~C ３ perfluoroalkyl group). are independently selected from the group consisting of: R ｐｆ－Ｆ is the formula: . Ｆ ︍F️ ＃ ) ｚ１ () ｆ )(|) ＊ ) ｚ２ . Ｆ ＊  (Here, z1, z2, X ＃ , X ＊ And (R ｆ ) are as defined above; are equal to or different from each other, D Ｆ and D. Ｆ ＊ is a perfluorinated alkylene chain containing 1 to 6 carbon atoms, said alkylene chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms. is a chain of According to, polymer.

16. The polymer according to claim 15 (PFPE ＯＨＯＨ ) and the polymer has a molecular weight of 7,000 Daltons ( １９ a number average molecular weight (Mn) of up to 30,000 Daltons as measured by F-NMR; and / or a functionality (F ＨＦＰＥ－Ｐ ).

17. The polymer according to claim 15 (PFPE ＯＨＯＨ ) Synthesis method [Method (P ＯＨＯＨ ) )], wherein the method (P ＯＨＯＨ )but, (V) The polymer according to any one of claims 1 to 3 (PFPE ＥＳＴ providing a (VI) The polymer (PFPE ＥＳＴ ) to the ester group at the chain end of the ２ OH, thus forming the polymer (PFPE ＯＨＯＨ PFPE ＥＳＴ ) with at least one reducing agent; The method includes: