Polyacrylic PFPE derivatives

Abstract

The present invention relates to copolymers comprising repeat units derived from (per)fluoropolyether polymers and to their use in coatings, surface treatments and as additives in polymer composites and coating compositions.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority from European Patent Application No. 18202808.4, filed October 26, 2018, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to polyacrylic (per)fluoropolyether polymer derivatives obtained using controlled radical polymerization techniques and to their use as additives in coating compositions. [Background technology]

[0003] Providing a coating on a substrate is generally desirable for a variety of reasons, including protecting the substrate and providing desirable surface properties that the substrate material does not exhibit to the desired extent.

[0004] Materials that have been used to date for surface protection include fluoropolymers, which offer advantages over traditional hydrocarbon-based materials in terms of high chemical inertness (solvent, acid, and base resistance), dust and stain resistance (due to low surface energy), low moisture absorption, and resistance to weathering and sun conditions.

[0005] Fluoropolymer compositions are used as additives in the preparation of a wide variety of surface treatments to provide surface benefits to substrates. Many such compositions are fluorinated acrylate polymers or copolymers.

[0006] U.S. Patent Application Publication No. 2011 / 0293943 (DU PONT DE NEMOURS AND COMPANY) discloses compositions containing fluoropolymers and their use as additives to coating compositions, such as alkyd paints or polymer resins, to obtain durable surface effects. Specifically, the compositions disclosed in this patent application include solvent-based fluoroalkyl (meth)acrylate copolymers with short (per)fluoroalkyl groups of six or fewer carbon atoms, particularly two to six carbon atoms. When used as an additive to a coating base, such as a solvent-based paint, the fluoropolymer compositions of this invention are generally added in amounts of about 0.001% to about 1% by weight, more preferably about 0.01% to about 0.5% by weight, based on the dry weight of the fluoropolymer, of the weight of the as-applied paint.

[0007] Block copolymers containing a fluorinated block derived from Krytox®, a commercially available monofunctional perfluoropolyether (PFPE) polymer of the formula CF3(CF2)2O-[CF(CF3)CF2O]-CF(CF3)CH2OH from DuPont, are disclosed by ZHANG, Zhou et al., "Honeycomb Films from Perfluoropolyether-based Star and Micelle Architecture." Australian Journal of Chemistry. 2012, vol. 65, pp. 1186-1190, and WOODS, Helen et al., "Dispersion Polymerization of Methyl Methacrylate in Supercritical Carbon Dioxide: An Investigation into Stabilizer Anchor Group." Macromolecules. 2005, vol. 38, pp. 3271-3282.

[0008] However, one of the recognized limitations of the fluoroalkyl (meth)acrylate copolymers is their low compatibility with hydrogen-containing materials, which may hinder their use as reactive additives / building blocks in formulations for surface treatment.

[0009] WO 2017 / 014145 (DAINIPPON INK & CHEMICALS) January 26, 2017 discloses a PFPE of formula PFPE[CF2CH2CH2O-C(=O)-C(CH3)2-Br]2 for use as a radical initiator in the preparation of perfluoropolyether compound films characterized by excellent water- and liquid-repellent properties.

[0010] However, the perfluoropolyethers disclosed in this document and the films obtained therefrom have poor hydrolysis resistance properties which make them unsuitable for application as coatings.

[0011] The present invention addresses the above problems by introducing novel polyacrylic (per)fluoropolyether polymers.

[0012] They are utilized as coating additives to impart unexpectedly desirable surface effects such as uniform spreading, increased water and oil contact angles, enhanced cleanability to coating films and air-cured coating surfaces, increased solubility in hydrogen-containing solvents, and hydrolysis resistance.

[0013] WO 2017 / 108852 (Solvay Specialty Polymers Italy SpA) describes derivatives of (poly)alkoxylated (per)fluoropolyethers containing unsaturated end groups with acrylate, allyl or vinyl moieties. The unsaturated moieties are preferably: (UI)-C(=O)-CR H =CH2 (U-II) -C(=O)-NH-CO-CR H =CH2 (U-III)-C(=O)-R A -CR H =CH2 (U-IV) -R H1 -CH=CH2 is selected from.

[0014] EP 0622353 (Ausimont SpA) discloses coatings based on perfluoropolyethers terminated with acrylic groups and containing ethoxylic groups as linking bridges between the fluorinated moieties and the (meth)acrylic groups. The perfluoropolyether polymers have the following chemical structure: YCF2OR f CFXCH2(OCH2CH2) p OCOCR=CH2 (wherein R is H or —CH3) Follow. Summary of the Invention [Means for solving the problem]

[0015] The applicant has surprisingly found that novel (per)fluoropolyether polymers comprising acrylate monomers and oxyalkylene units are characterized by improved solubility in hydrogen-containing solvents, improved hydrolysis resistance, and improved compatibility with some materials.

[0016] Thus, in a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: - at least one (per)fluoropolyoxyalkylene chain [chain (R f )]and; - Said chain (R f at least one (poly)oxyalkylene chain [chain (R a )](the chain (R a ) contains at least one fluorine-free oxyalkylene unit); - Formula (I): TIFF0007794633000001.tif44170[In formula: - R1, R2 and R3, which are equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group; - X is an oxygen atom, a sulfur atom or a group NR8, where R8 is selected from a hydrogen atom and a C1-C3 hydrocarbon group; - R4 is a hydrogen atom or a C2-C 20 a hydrocarbon chain portion, wherein the C2 to C 20 The hydrocarbon chain portion optionally includes at least one functional group (FG). At least one (meth)acrylic monomer repeat unit [unit (MA)] of The at least one unit (MA) is of the formula *-(C=O)-R5-** wherein R5 is a C1-C8 alkylene or cycloalkylene group having at least one secondary or tertiary carbon atom; The symbol (*) indicates the chain (R a ) and The symbol (**) indicates the bond to the unit (MA) through the secondary or tertiary carbon atom. a unit (MA) linked to said at least one chain (Ra) via a linking group (LG) of (Per)fluoropolyether polymers containing [polymers (PFPE A )].

[0017] Advantageously, the novel polymers according to the invention are novel polymers as defined above (PFPE A The hydrophobic segment, i.e., the chain (R ), can have different functional groups so that the polymer can be used for several applications. f ), a hydrophilic hydrogen-containing spacer, i.e., a chain (R a ), and (meth)acrylic segments, i.e., units (MA), where the functional groups can be used to tailor the properties of the polymer or can be used as intermediates in the synthesis of further polymers.

[0018] In addition, the applicant has also found that these novel (per)fluoropolyether polymers can be advantageously obtained by atom transfer radical polymerization (ATRP) from certain novel PFPE macroinitiators.

[0019] In a second aspect, the present invention therefore provides a polymer as defined above (PFPE A ), a method for producing the compound, the method comprising: a) - at least one (per)fluoropolyoxyalkylene chain [chain (R f )]; - Said chain (R f At least one (poly)oxyalkylene chain [chain R a )](the chain (R a ) contains at least one fluorine-free oxyalkylene unit); and at least one group of the formula -(C=O)-R5-X', where R5 is a C1-C8 alkylene or cycloalkylene group containing at least one secondary or tertiary carbon atom, and X' is a halogen, wherein this halogen is bonded to R5 via said at least one secondary or tertiary carbon atom; PFPE macroinitiator [polymer (PFPE I )]; b) the polymer (PFPE) provided in step a) I ) by atom transfer radical polymerization (ATRP) to form a compound of formula (II): TIFF0007794633000002.tif43170[In formula: - R1, R2 and R3, which are equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group; - X is an oxygen atom, a sulfur atom or a group NR8, where R8 is selected from a hydrogen atom and a C1-C3 hydrocarbon group; - R4 is a hydrogen atom or a C2-C 20 a hydrocarbon chain portion, wherein the C2 to C20 The hydrocarbon chain portion optionally includes at least one functional group (FG). and at least one (meth)acrylic monomer [monomer (MM)] of the formula: reacting in the presence of at least one transition metal catalyst to form a polymer (PFPE A ) and obtaining; c) the polymer (PFPE) obtained in step b) A ) and purifying the This paper aims to provide a method including:

[0020] The Applicant has discovered that the polymer (PFPE) as provided in step (a) of the process according to the invention I I noticed that this is new.

[0021] Thus, in a third aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: - at least one (per)fluoropolyoxyalkylene chain [chain (R f )]and; - Said chain (R f At least one (poly)oxyalkylene chain [chain (R a )](the chain (R a ) contains at least one fluorine-free oxyalkylene unit); - at least one group of the formula -(C=O)-R5-X', wherein R5 is a C1-C8 alkylene or cycloalkylene group containing at least one secondary or tertiary carbon atom, and X' is a halogen, wherein this halogen is bonded to R5 via said at least one secondary or tertiary carbon atom; PFPE macroinitiator [polymer (PFPE I )].

[0022] The applicant has developed a polymer (PFPE I It has been found that the polymers (PFPE) according to the present invention are more resistant to hydrolysis than compounds known in the art that do not contain oxyalkylene units as defined above. I) polymer obtained by the reaction of A ) are also more resistant to hydrolysis than compounds known in the art that do not contain oxyalkylene units as defined above.

[0023] In a further aspect, the present invention relates to a composition [Composition S] comprising 1 to 90% by weight, based on the total weight of the composition, of at least one polymer (PFPE) as defined above. A ) and at least one solvent.

[0024] In a further aspect, the present invention relates to the use of said composition (S) for coating at least one surface of a substrate, said substrate being preferably selected from glass, plastic and metal.

[0025] In a still further aspect, the present invention relates to a method for coating at least one surface of a substrate, preferably selected from plastic, metal or glass, said method comprising: (i) contacting a substrate with said composition (S); (ii) drying the composition (S) onto the substrate; The present invention relates to a method comprising: DETAILED DESCRIPTION OF THE INVENTION

[0026] For purposes of this description and the following claims: - For example, "Chain (R f The use of parentheses around symbols or numbers identifying a formula, such as in expressions such as "(i)", "(ii)", "(iii)", "(iv)", "(v)", "(vi)", "(vii ... - 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 polyether.

[0027] Preferably, the chain (R f ) is a number average molecular weight M in the range of 100 to 8,000, preferably 300 to 6,000, more preferably 800 to 3,000. n and (i) -CFY'O- (wherein Y' is F or CF3), (ii) -CFY'CFY'O-, where Y', equal or different at each occurrence, is as defined above, with the proviso that at least one Y' is -F; (iii) —CFCFCWO—, where each W, equal to or different from each other, is F or H; (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 'T' is a group where R f Y′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, said repeating units being selected from the following: -CFY″O—, -CF2CFY″O—, -CF2CF2CF2O—, -CF2CF2CF2CF2O—, each occurrence of Y″ is independently F or CF3, and T is a C1 to C3 perfluoroalkyl group. The (per)fluoropolyoxyalkylene chain comprises, preferably consists of, repeating units which may be the same or different from one another and are selected from the following:

[0028] Preferably, the chain (R f ) is expressed as: (R f -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- (In the formula, - X1 is independently selected from -F and -CF3; - X, which are equal or different from each other and from occurrence to occurrence 2 , X 3 are independently -F, -CF3, provided that X 1 ~X 3 at least one of is -F; - g1, g2, g3 and g4, which are equal to or different from one another, are independently integers greater than or equal to 0, such that g1+g2+g3+g4 is in the range of 2 to 300, preferably 2 to 100; if at least two of g1, g2, g3 and g4 are different from zero, the different repeat units are generally distributed statistically along the chain. Follow.

[0029] More preferably, the chain (R f ) is the expression: (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 10,000, preferably between 400 and 5,000; a1 and a2 are both preferably different from zero, the ratio a1 / a2 being preferably 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 is 400 to 10,000, preferably 400 to 5,000; preferably, b1 is 0, b2, b3, and b4 are greater than 0, and the ratio b4 / (b2+b3) is 1 or greater; (R f -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 10,000, preferably 400 to 5,000; 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 10,000, preferably 400 to 5,000; (R f -IIE) -[(CF2CF2C(Hal*)2O) e1 -(CF2CF2CH2O) e2 -(CF2CF2CH(Hal*)O) e3 ]- (In the formula: - Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, 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 of (e1 + e2 + e3) is between 2 and 300. The chain is selected from:

[0030] Even more preferably, said 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 is between 400 and 10,000, preferably between 400 and 5,000; the ratio a1 / a2 is generally between 0.1 and 10, more preferably between 0.2 and 5. Follow.

[0031] Preferably, the chain (R a ) is a fluorine-free polyoxyalkylene chain, said chain containing 1 to 50 fluorine-free oxyalkylene units, said units being the same or different, and having the general formula: TIFF0007794633000003.tif23170 (in the formula, R n is independently at each occurrence hydrogen, a lower alkyl, or a lower alkoxy group, and m is an integer from 1 to 10. It has.

[0032] The term "lower alkyl" refers to an alkyl group having 1 to about 6 carbon atoms, including primary, secondary, and tertiary alkyl groups. Typical lower alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

[0033] The term "lower alkoxy" refers to the group -O-lower alkyl. Typical lower alkoxy groups include methoxy, ethoxy, and the like.

[0034] More preferably, said free oxyalkylene units are selected from -CH2CH2O- and -CH2CH(J)O-, where J is linear or branched alkyl or aryl, preferably methyl, ethyl or phenyl.

[0035] Typically, the (PFPE A ) in which chain R a is expressed by the following formula (R a -I): (R a -I) -(CH2CH2O) r (CH2CH(CH3)O) s (CH2CH(CH2CH3)O) t (CHCH(Ph)O) u - (wherein r, s, t, and u are independently selected from 0 and positive numbers, and r+s+t+u is in the range of 1 to 50, preferably 1 to 15, and more preferably 1 to 10). Follow.

[0036] In one preferred embodiment, the chain (R a In -I), r is a positive number ranging from 1 to 15, preferably from 1 to 10, and s, t and u are 0.

[0037] In another preferred embodiment, r, t, and u are 0, and s is a positive number ranging from 1 to 15, preferably from 1 to 10.

[0038] In another preferred embodiment, r and s are positive numbers, t and u are 0, and r+s is in the range of 1-15, preferably 1-10.

[0039] Two or more of -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(CH2CH3)O- and -CH2CH(Ph)O- units form a chain (R a -I), they can be arranged in blocks or they can be randomly arranged.

[0040] The term "(meth)acrylic" refers to moieties such as acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate, and thio-methacrylate.

[0041] Polymer (PFPE A The units (MA) in (MA) are derived from (meth)acrylic monomers (MM) of formula (II) as defined above according to the method of the present invention.

[0042] Depending on the nature of the group R4, the unit (MA) of formula (I) may be ionizable or non-ionizable.

[0043] According to the present invention, ionizable groups are groups capable of forming ionic groups, such as carboxylic acids, phosphates, sulfides, amines, and the like.

[0044] In particular, when R4 is a hydrogen atom, the group -X-R4 of the unit (MA) can be converted under suitable conditions into an ionic group -X - The polymer (PFPE) is dissolved in a solvent containing A ) can provide improved solubility.

[0045] R4 is a C2-C group containing at least one functional group (FG). 20 When it is a hydrocarbon chain moiety, the functional group (FG) can be ionizable or non-ionizable. The ionizable functional group (FG) is C2-C 20 When contained in the hydrocarbon chain portion, the functional group (FG) can take the form of an ionic group under suitable conditions to dissolve the polymer (PFPE) in certain solvents. A ) may provide improved solubility.

[0046] In the present invention, the "functional unit (f-MA)" is a C2-C4 alkylene group represented by the formula (I) [wherein R4 is a C2-C4 alkylene group containing at least one functional group (FG)] 20 In the present invention, a "non-functional unit (nf-MA)" is defined as a (meth)acrylic monomer repeating unit of formula (I) [wherein R4 is a hydrogen atom or a C2-C6 alkyl group that does not contain any functional group (FG)]. 20 The (meth)acrylic monomer repeating unit is defined as a repeating unit of the hydrocarbon chain moiety.

[0047] Non-limiting examples of suitable functional groups (FG) include those FGs that are polymers (PFPE A ), so long as they are compatible with the overall formation of the copolymer.

[0048] Non-limiting examples of non-functional units (nf-MA) include, among others, (meth)acrylic monomers (MM): - acrylic acid (AA), - methacrylic acid, - methyl methacrylate (MMA), ethyl methacrylate, - butyl methacrylate (BMA), - hexyl methacrylate, - benzyl methacrylate (BzMA), - lauryl methacrylate, - Stearyl methacrylate Examples include those derived from:

[0049] More preferably, the non-functional unit (nf-MA) is derived from acrylic acid (AA), methyl methacrylate (MMA), ethyl methacrylate (EMA), or the like.

[0050] Suitable functional units (f-MA) include, inter alia, (meth)acrylic monomers (MM): - those derived from hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), hydroxyethylhexyl(meth)acrylate, methacryloxypropyl-trimethoxysilane, methacryloxyethyl trimellitic anhydride, bis(2-methacryloxyethyl)phosphate, monoacryloxyethyl phosphate, 2-aminoethyl methacrylamide, n-(2-aminoethyl)methacrylamide, n-(3-aminopropyl)methacrylamide, 2-(t-butylamino)ethyl methacrylate, allyl methacrylate, 2-cyanoethyl methacrylate, n,n-diallylacrylamide, propargyl methacrylate, 2-carboxyethyl acrylate, 4-hydroxybutyl acrylate, and hydroxypropyl acrylate.

[0051] Two or more units (MA) are polymers (PFPE A ), they can be equal or different at each occurrence.

[0052] Different units (MA) are polymers (PFPE A ), they can be arranged in blocks or they can be randomly arranged.

[0053] The repeating unit (MA) has the formula: *-(C=O)-R5-** wherein R5 is a C1-C8 alkylene or cycloalkylene group having at least one secondary or tertiary carbon atom; The symbol (*) indicates the chain (R a ) and The symbol (**) indicates the bond to the unit (MA) through the secondary or tertiary carbon atom. It is connected to the chain (Ra) via a linking group (LG).

[0054] In one preferred embodiment of the present invention, the linking group (LG) is typically represented by the following formula (LG-I): (LG-I) *-(C=O)-C(R6R7)-** wherein R6 and R7 are independently hydrogen, methyl, or benzyl groups, provided that R6 and R7 cannot both be hydrogen; wherein the symbols (*) and (**) have the meanings defined above. Follow.

[0055] More preferably, the linking group (LG) is represented by the following formula (LG-II): (LG-II)*-(C=O)-C(CH3)2-** wherein the symbols (*) and (**) have the meanings defined above. Follow.

[0056] In one preferred embodiment of the present invention, the polymer (PFPE A ) is represented by the following formula (III): AOR f -(CF2) x -CFZ-CH2-OR a -C(=O)-C(R6R7)-Y w-Q (III) [In formula: -R f is a number average molecular weight M in the range of 100 to 8,000, preferably 300 to 6,000, more preferably 800 to 3,000. n and (i) -CFY'O- (wherein Y' is F or CF3), (ii) -CFY'CFY'O-, where Y', equal or different at each occurrence, is as defined above, with the proviso that at least one Y' is -F; (iii) —CFCFCWO—, where each W, equal to or different from each other, is F or H; (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 'T' is a group where R f Y′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being selected from the following: -CFY″O—, -CF2CFY″O—, -CF2CF2CF2O—, -CF2CF2CF2CF2O—, each occurrence of Y″ is independently F or CF3, and T is a C1 to C3 perfluoroalkyl group. a (per)fluoropolyoxyalkylene chain comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from: Z is fluorine or CF3; - x is 0 or 1, provided that when x is 1, Z is F; -R a is a fluorine-free polyoxyalkylene chain comprising 1 to 50 fluorine-free oxyalkylene units, said units being the same or different and selected from -CH2CHO- and -CH2CH(J)O-, where J is a linear or branched alkyl or aryl, preferably methyl, ethyl or phenyl; - R6 and R7 are independently hydrogen, methyl or benzyl groups, provided that R6 and R7 cannot both be hydrogen; - Y, which is equal or different at each occurrence, is a group of formula (I): TIFF0007794633000004.tif43170 (wherein R1, R2 are equal to or different from each other, 2、 R3 is independently selected from a hydrogen atom and a C1-C3 hydrocarbon group; X is an oxygen atom, a sulfur atom, or a group NR8, where R8 is selected from a hydrogen atom and a C1-C3 hydrocarbon group; R4 is a hydrogen atom or a C2-C optionally containing at least one functional group (FG). 20 hydrocarbon chain portion) is the unit of (MA); - w is an integer of 1 to 200, preferably 10 to 100, more preferably 50 to 100; Q is hydrogen or a halogen atom selected from chlorine, bromine and iodine; -A, -R a -C(=O)-C(R6R7)-Y w -Q(wherein, R a , R6, R7, Y, w and Q are as defined above), or a straight or branched C1-C4 (per)fluoroalkyl group, in which one fluorine atom can be replaced by one chlorine atom or one hydrogen atom. Follow.

[0057] According to a more preferred embodiment, the polymer (PFPE A ) is represented by the above formula (III) (wherein A is -R a -C(=O)-C(R6R7)-Y w -Q and R a , R6, R7, Y, w and Q are as defined above) A )

[0058] According to another preferred embodiment, the polymer (PFPE A) is a "monofunctional polymer (PFPE)" according to the above formula (III) (wherein A is a linear or branched C1-C4 (per)fluoroalkyl group, where one fluorine atom can be replaced by one chlorine atom or one hydrogen atom). A )".

[0059] Preferably, the polymer of formula (III) (PFPE A ) in R f is the formula (R f -I), (R f -IIA)~(R f -IIE) or (R f -III), more preferably of the formula (R f -III).

[0060] In a preferred embodiment, the polymer of formula (III) (PFPE A ) in R a is the formula (R a -I) (wherein r, s, t and u are independently selected from 0 and a positive number, and r+s+t+u is in the range of 1 to 50, preferably 1 to 15, and more preferably 1 to 10).

[0061] In another preferred embodiment, the polymer of formula (III) (PFPE A ) in R a is the formula (R a -I) (wherein r is a positive number ranging from 1 to 15, preferably from 1 to 10, and s, t, and u are 0).

[0062] In another preferred embodiment, the polymer of formula (III) (PFPE A ) in R a is the formula (R a -I) (wherein r, t, and u are 0, and s is a positive number ranging from 1 to 15, preferably from 1 to 10).

[0063] In yet another preferred embodiment, the polymer of formula (III) (PFPE A) in R a is the formula (R a -I) (wherein r and s are positive numbers, t and u are 0, and r+s is in the range of 1 to 15, preferably 1 to 10).

[0064] In one embodiment of the present invention, the polymer (PFPE) of the present invention A ) is a compound of formula (III) as defined above, f , Z, R a , R6, R7, x, w and Q are as defined above; Y is a unit (MA), preferably Y is a (MMA) unit, and w is an integer from 1 to 100.

[0065] In one embodiment of the present invention, the polymer (PFPE) of the present invention A ) is the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(Y A ) wa -(Y B ) wb -Q]2 [In the formula, R f and Q is as defined above; Y A is the first unit (MA): Y B is Y A is a second unit (MA) that is different from the above; Wa and wb are integers independently selected from 1 to 100, where Y A and Y B The units can be arranged in blocks or they can be randomly arranged. is a compound of

[0066] A preferred polymer according to this embodiment (PFPE A ) is the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(MMA) wa -(HEMA)wb -Q]2 [In the formula, R f and Q are as defined above, and wa and wb are integers independently selected from 1 to 100, wherein the (MMA) and (HEMA) units can be arranged in blocks or they can be randomly arranged. Polymer (PFPE) A ) Preferably, wa is an integer of 1 to 100, and wb is an integer of 1 to 10.

[0067] A preferred polymer according to this embodiment (PFPE A ) is also the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(MMA) wa -(BzMA) wb -Q]2 [In the formula, R f and Q are as defined above, and wa and wb are integers independently selected from 1 to 100, wherein the (MMA) and (BzMA) units can be arranged in blocks, or they can be randomly arranged. Polymer (PFPE) A Preferably, wa is an integer of 1 to 100, and wb is an integer of 1 to 100.

[0068] In another embodiment of the present invention, the polymer (PFPE A ) is the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(Y A ) wa -(Y B ) wb -(Y C ) wc -Q]2 [In the formula, R f and Q is as defined above, Y A is the first unit (MA); YB is the second unit (MA); Y C is the third unit (MA), where Y A , Y B and Y C are different from each other; wa, wb, and wc are integers independently selected from 1 to 100; where Y A, Y B and Y C The units can be arranged in blocks or they can be randomly arranged. is a compound of

[0069] A preferred polymer according to this embodiment (PFPE A ) is the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(MMA) wa -(BMA) wb -(HEMA) wc -Q]2[wherein, R f and Q are as defined above, and wa, wb, and wc are integers independently selected from 1 to 100, wherein the (MMA), (BMA), and (HEMA) units can be arranged in blocks, or they can be randomly arranged. Polymer (PFPE) A Preferably, wa and wb are independently selected from integers of 1 to 100, and wc is an integer of 1 to 10.

[0070] A preferred polymer according to this embodiment (PFPE A ) is also the expression: R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-(MMA) wa -(BzMA) wb -(HEMA) wc -Q]2 [In the formula, R fand Q are as defined above, and wa, wb, and wc are integers independently selected from 1 to 100, wherein the (MMA), (BzMA), and (HEMA) units can be arranged in blocks, or they can be randomly arranged. Polymer (PFPE) A Preferably, wa and wb are independently selected from 1 to 100, and wc is an integer of 1 to 10.

[0071] In more detail and in particular the polymer (PFPE) according to the invention A Regarding the method for producing the compound (I), the method comprises the steps of: a) - at least one (per)fluoropolyoxyalkylene chain [chain (R f )]; - Said chain (R f At least one (poly)oxyalkylene chain [chain (R a )](the chain (R a ) contains at least one fluorine-free oxyalkylene unit); - a group of formula *-(C=O)-R5-X', wherein R5 is a C1-C8 alkylene or cycloalkylene group containing at least one secondary or tertiary carbon atom, X' is a halogen, wherein the halogen is bonded to R5 via said secondary or tertiary carbon atom, and the symbol (*) indicates that the chain (R a ) showing a bond to the PFPE macroinitiator [polymer (PFPE I )]; b) reacting the initiator provided in step a) with a compound of formula (II): TIFF0007794633000005.tif43170c) where R1 and R2 are equal to or different from each other. 2、 R3 is independently selected from a hydrogen atom and a C1-C3 hydrocarbon group; X is an oxygen atom, a sulfur atom, or a group NR8, where R8 is selected from a hydrogen atom and a C1-C3 hydrocarbon group; R4 is a hydrogen atom or a C2-C optionally containing at least one functional group (FG) in the chain. 20 hydrocarbon chain moiety] and at least one (meth)acrylic monomer [monomer (MM)] of the formula: reacting in the presence of at least one transition metal catalyst and a ligand to form a polymer (PFPE A ) and obtaining; d) The polymer (PFPE) obtained in step b) A purifying the product to remove at least one transition metal catalyst; Includes.

[0072] In step a) of the method, the polymer (PFPE I ) (wherein at least one (per)fluoropolyoxyalkylene chain [chain (R f )] and at least one (poly)oxyalkylene chain [chain (R a )] is as defined above) is provided.

[0073] Preferably, at least one group of the formula *-(C=O)-R5-X', wherein the symbols (*) and R5 are as defined above, is a group of the formula *-(C=O)-C(R6R7)-X' wherein R6 and R7 are independently hydrogen, methyl, or benzyl groups, provided that R6 and R7 cannot both be hydrogen, and X' is a chlorine, bromine, or iodine atom. Follow.

[0074] More preferably, at least one group of formula *-(C=O)-R5-X' conforms to the formula *-(C=O)-C(CH3)2-Br, where the symbol (*) has the meaning defined above.

[0075] In one preferred embodiment of the present invention, the polymer (PFPE I ) is represented by the following formula (IV): AOR f -(CF2) x -CFZ-CH2-ORa -C(=O)-C(R6R7)-X' (IV) [In formula: -R f is a number average molecular weight M in the range of 100 to 8,000, preferably 300 to 6,000, more preferably 800 to 3,000. n and (i) -CFY'O- (wherein Y' is F or CF3); (ii) -CFY'CFY'O-, where Y', equal or different at each occurrence, is as defined above, with the proviso that at least one Y' is -F; (iii) —CFCFCWO—, where each W, equal to or different from each other, is F or H; (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 'T' is a group where R f Y′ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being selected from the following: -CFY″O—, -CF2CFY″O—, -CF2CF2CF2O—, -CF2CF2CF2CF2O—, each occurrence of Y″ is independently F or CF3, and T is a C1 to C3 perfluoroalkyl group. a (per)fluoropolyoxyalkylene chain comprising, preferably consisting of, repeating units, which may be equal to or different from one another, selected from: Z is fluorine or CF3; - x is 0 or 1, with the proviso that when x is 1, Z is F; -R ais a fluorine-free polyoxyalkylene chain, said chain comprising 4 to 50 fluorine-free oxyalkylene units, said units being identical or different and selected from -CH2CHO- and -CH2CH(J)O-, where J is a linear or branched alkyl or aryl, preferably methyl, ethyl or phenyl; - R6 and R7 are independently hydrogen, methyl or benzyl groups, provided that R6 and R7 cannot both be hydrogen; X' is a chlorine, bromine or iodine atom, preferably a bromine atom; -A, -R a -C(=O)-C(R6R7)-X' (where R a , R6, R7, and X' are as defined above), or a linear or branched C1-C4 (per)fluoroalkyl group, where one fluorine atom can be replaced by one chlorine atom or one hydrogen atom. Follow.

[0076] According to a more preferred embodiment, the polymer (PFPE I ) is represented by the above formula (IV) (wherein A is -R a -C(=O)-C(R6R7)-X', and R a , R6, R7, and X' are as defined above) I )

[0077] According to another preferred embodiment, the polymer (PFPE I ) is a "monofunctional polymer (PFPE)" according to the above formula (IV) (wherein A is a linear or branched C1-C4 (per)fluoroalkyl group, where one fluorine atom can be replaced by one chlorine atom or one hydrogen atom). I )".

[0078] Preferably, the polymer of formula (IV) (PFPE I ) in R f is the formula (R f-I), (R f -IIA)~(R f -IIE) or (R f -III), more preferably of the formula (R f -III).

[0079] In a preferred embodiment, the polymer of formula (IV) (PFPE I ) in R a is the formula (R a -I) (wherein r, s, t and u are independently selected from 0 and a positive number, and r+s+t+u is in the range of 1 to 50, preferably 1 to 15, and more preferably 1 to 10).

[0080] In another preferred embodiment, the polymer of formula (IV) (PFPE I ) in R a is the formula (R a -I) (wherein r is a positive number ranging from 1 to 15, preferably from 1 to 10, and s, t, and u are 0).

[0081] In another preferred embodiment, the polymer of formula (IV) (PFPE I ) in R a is the formula (R a -I) (wherein r, t, and u are 0, and s is a positive number in the range of 1 to 15, preferably 4 to 10).

[0082] In yet another preferred embodiment, the polymer of formula (IV) (PFPE I ) in R a is the formula (R a -I) (wherein r and s are positive numbers, t and u are 0, and r+s is in the range of 1 to 15, preferably 1 to 10).

[0083] Particularly preferred polymers of the present invention (PFPE I ) is the formula R f [CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-Br]2.

[0084] The polymer (PFPE) of the present invention I ) can be prepared by esterification of a (poly)alkoxylated (per)fluoropolyether polymer [polymer P*] with any suitable esterification reagent (ER), wherein polymer P* is - Two chain ends (R fe At least one (per)fluoropolyoxyalkylene chain [chain (R f )]; - Chain (R f ) at least one chain end (R fe at least one hydroxy-, alkoxy- or acyloxy-terminated (poly)oxyalkylene chain [chain (R a’ )], wherein the chain (R a’ ) comprises at least one fluorine-free oxyalkylene unit, said units being the same or different from one another, and has the general formula: TIFF0007794633000006.tif22170 (in the formula, R n is independently at each occurrence hydrogen, a lower alkyl, or a lower alkoxy group, and m is an integer from 1 to 10), and has another terminal (R fe ) is a chain (R a’ ) or a linear or branched C1-C4 (per)fluoroalkyl group, in which one fluorine atom can be replaced by one chlorine atom or one hydrogen atom) Chain (Ra') means a (per)fluoropolyether polymer comprising

[0085] Polymer P* is commercially available from Solvay Specialty Polymers (Italy) or can be obtained according to the methods disclosed in WO 2014 / 090649 (SOLVAY SPECIALTY POLYMERS ITALY SPA) or in WO 2016 / 020232 (SOLVAY SPECIALTY POLYMERS ITALY SPA).

[0086] The polymer (PFPE) of the present invention I Suitable esterification reactants (ER) for the preparation of ) are acid halides, acid anhydrides, carboxylic acids or acid alkyl esters, which have at least a terminal secondary or tertiary carbon atom to which the halide atom is directly bonded.

[0087] The chain end (R fe ) is a hydroxy-, alkoxy- or acyloxy-terminated (poly)oxyalkylene chain (R a’ ) and the other end (R fe ) carries a linear or branched C1-C4 (per)fluoroalkyl group as defined above, the polymer is also called a "monofunctional polymer P*".

[0088] The chain end (R fe ) are both hydroxyl-, alkoxy- or acyloxy-terminated (poly)oxyalkylene chains (R a’ ), the polymer is also referred to as a "difunctional polymer P*".

[0089] Examples of suitable acid halides are, inter alia, 2-bromoisobutyrate bromide, 2-bromo-2-methyl-butyric acid bromide, 2-chloro-2-methyl-butyric acid bromide, 2-bromoisobutyrate chloride, 2-bromo-2-methylbutyric acid chloride, 2-chloro-2-methylbutyric acid chloride, and the like.

[0090] Examples of suitable acid anhydrides are, inter alia, 2-bromoisobutyric anhydride, 2-bromo-2-methyl-butyric anhydride, 2-chloro-2-methyl-butyric anhydride, and the like.

[0091] Examples of suitable acid alkyl esters are, inter alia, ethyl 2-bromoisobutyrate, ethyl 2-bromo-2-methylbutyrate, ethyl 2-chloro-2-methylbutyrate, methyl 2-bromoisobutyrate, methyl 2-bromo-2-methyl-butyrate, methyl 2-chloro-2-methyl-butyrate, and the like.

[0092] Examples of suitable carboxylic acids are, among others, 2-bromoisobutyrate, 2-bromo-2-methylbutyric acid, 2-chloro-2-methylbutyrate, and the like.

[0093] The reaction of the polymer P* with the esterification reagent (ER) can be preferably carried out in an organic solvent. Examples of suitable organic solvents include ketones, esters, amides, sulfoxides, ethers, hydrocarbons, or fluorinated solvents. Examples of fluorinated solvents include hydrofluoroethers (HFEs) such as Galden® PFPE and Novec® HFE, hydrofluorocarbons (HFCs) such as Vertel® or Fluorinert®, and fluoroaromatic solvents such as hexafluorobenzene and 1,3-hexafluoroxylene.

[0094] Acid halides or acid anhydrides are polymerized with PFPE I When used in the preparation of ), it is preferred to add a basic compound such as triethylamine to neutralize by-products of the reaction such as hydrogen halides and carboxylic acids. The excess basic compound can then be treated with acid and the resulting reaction medium diluted with water.

[0095] The ratio between the polymer P* and the esterification reactant (ER) is typically in the range of 1:2 to 1:10 mol / mol.

[0096] The reaction temperature of the polymer P* and the esterification reagent (ER) is usually in the range of −40 to 60° C. The reaction time is usually 1 to 20 hours.

[0097] In step b) of the method, the polymer (PFPE) provided in step a) is I ) is reacted with at least one (meth)acrylic monomer in the presence of at least one transition metal catalyst by atom transfer radical polymerization (ARTP) according to methods known in the art. This method produces at least one chain (R ) having a well-defined structure, which in turn is linked to at least one unit derived from at least one (meth)acrylic monomer. a ) and at least one chain (R f )-containing polymer (PFPE A ) allows for controlled synthesis.

[0098] Two or more (meth)acrylic monomers are polymerized (PFPE I ), the repeating units (MA) derived from the at least two (meth)acrylic monomers form a polymer (PFPE A ) or they can be arranged randomly.

[0099] At least one chain (R a and at least a second block of units (MA) derived from another and different monomer (MM). A ) can be obtained by sequentially adding at least two different monomers (MM) batchwise to the reaction mixture.

[0100] Randomly arranged and connected to at least one chain (R a ) containing a unit (MA) bonded to A) can be obtained by adding a mixture of at least two different monomers (MM) batchwise to the reaction mixture.

[0101] Transition metal catalysts reported to be useful for ATRP are those that are capable of participating in the redox cycle of the initiator and the polymer chain.

[0102] Suitable transition metal catalysts for use in step b) of the process of the present invention include at least one transition metal from the group consisting of iron, copper, nickel, manganese, and chromium, and a ligand. Suitable transition metal catalysts can be in the form of a complex formed in a separate preliminary step by reaction of a salt of the transition metal with the ligand, or preferably are formed in situ from a transition metal salt which is then converted to the complex compound by addition of the ligand present in the complex catalyst.

[0103] Suitable ligands for use in step b) of the process of the present invention are those capable of forming complexes with transition metals. In particular, copper can be fed to the system starting from one of the salts of the group consisting of CuO, CuBr, CuCl, CuI, CuN, CuSCN, CuCN, CuNO, CuNO, CuBF, Cu(CHCOO) or Cu(CFCOO), and the transition metal catalyst can be formed in situ by adding a suitable ligand for copper, which can be selected from 2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethylenemethyltris(2-aminoethyl) complexes.

[0104] Suitable ligands for iron may be suitably selected from bistriphenylphosphine complexes, triazacyclononane complexes, and the like.

[0105] The transition metal is converted from its lower oxidation state in the redox system described above to its higher oxidation state during the ATRP reaction.

[0106] The reaction temperature in step b) of this method is usually in the range of 0 to 100° C. The reaction time is usually 1 to 20 hours.

[0107] In step c), the polymer (PFPE) obtained in step b) is A ) is purified to remove at least one transition metal compound from the reaction medium. Purification can be suitably carried out by any technique known in the art. By way of example, removal of the transition metal can be carried out by adding an ion exchange resin or by precipitation by adding a suitable precipitating agent, followed by removal by filtration.

[0108] The polymer (PFPE) obtained after purification step c) of the process of the present invention A ) is preferably a compound of formula (III) as defined above, wherein Q is a polymer (PFPE I ) is a halogen derived from ).

[0109] Polymers of formula (III) as defined above, where Q is a halogen obtained at the end of step b) or at the end of step c) (PFPE A ) is optionally subjected to an additional reduction step to reduce the halogen atoms to hydrogen atoms, thus producing a polymer (PFPE) of formula (III) as defined above, wherein Q is a hydrogen atom. A ) may be provided.

[0110] Polymers of formula (III) as defined above, wherein Q is a halogen (PFPE A ) can be a polymer (PFPE) having any suitable chain end functionality, which can be obtained by reacting the terminal halogen atoms with any suitable functionalizing reagent by transformations known in the art. A The polymers of formula (III) as defined above (wherein Q is a halogen) (PFPE) can also be used as starting materials for obtaining derivatives of the formula (III) as defined above (wherein Q is a halogen). A ) is in fact a halogen atom of formula (V): A'-OR f -(CF2) x-CFZ-CH2-OR a -C(=O)-C(R6R7)-Y w -F un (V) [In the formula, R f , R a , R6, R7, Y, x, and w are as defined above; - A' is -Ra-C(=O)-C(R6R7)-Y w -F (where R a , R6, R7, Y and w are as defined above), or a linear or branched C1-C4 (per)fluoroalkyl group, in which one fluorine atom can be replaced by one chlorine atom or one hydrogen atom; - Fun is hydroxyl, amino, carboxyl, C1-C 10 a moiety containing at least one functional group, such as an unsaturated carbon chain, epoxy, etc.] The corresponding polymer (PFPE F can be treated with a suitable reactant to provide

[0111] A polymer (PFPE) in which the repeating unit (MA) is a repeating unit derived from a (meth)acrylic monomer containing at least one functional group (FG). A ) can be any suitable functionalized polymer (PFPE) by the functional group (FG) of the unit (MA). A ) Polymer grafted to the main chain (PFPE A ) other derivatives [polymer (PFPE FA It can also be used as a starting material to obtain

[0112] Polymer (PFPE FA ) is preferably represented by the following formula (VI): A''-OR f -(CF2) x -CFZ-CH2-OR a -C(=O)-C(R6R7)-Y 2 w -Q (VI) [In the formula, R f , R a, R6, R7, x, w and Q are as defined above; A'' is -R a -C(=O)-C(R6R7)-Y 2 w -Q (where R a , R6, R7, w and Q are as defined above), or a linear or branched C1-C4 (per)fluoroalkyl group, where one fluorine atom can be replaced by one chlorine atom or one hydrogen atom; Y 2 is the expression: TIFF0007794633000007.tif36170 (wherein R1, R2 and R3, which are equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group; FA can be obtained by reacting the functional group of the functionalized (meth)acrylic monomer (MA) with any suitable functionalizing reagent, such as hydroxyl, amino, carboxyl, C1-C3 hydrocarbon group, by transformations known in the art. 10 (Any suitable moiety containing at least one functionality, such as an unsaturated carbon chain or epoxy) is the basis of The polymer may be:

[0113] The Applicant has surprisingly found that the process according to the invention allows the synthesis of repeating units (MA) derived from different (meth)acrylic monomers, functional groups FA grafted onto the polymer backbone and / or functional groups F at the chain ends. un It has been found that the ability to incorporate these groups makes it possible to adjust the structure of perfluoropolymers and therefore their physical and chemical properties, particularly their solubility in hydrogen-containing solvents, their resistance to hydrolysis, and their compatibility with certain materials.

[0114] In a still further aspect, the present invention therefore provides a polymer comprising at least one polymer (PFPE) as defined above. F ) or at least one polymer (PFPE FA at least one polymer (PFPE) as defined above as an intermediate compound in the synthesis of A) regarding the use of

[0115] The polymer according to the present invention (PFPE A ), polymer (PFPE F ) or polymer (PFPE FA ) can be used as such or as a composition [composition (S)] containing said polymer and at least one solvent.

[0116] Preferably, said composition (S) is in the form of a solution. Suitable solvents for use in composition (S) are selected from the group consisting of ketones, such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters, such as ethyl acetate, butyl acetate, and isobutyl acetate; organic solvents containing ester-ether groups in the molecule, such as polyoxyethylene monoethyl ether acetate, polyoxyethylene monobutyl ether acetate, polyoxybutylene monoethyl ether acetate, polyoxybutylene monobutyl ether acetate, polyoxyethylene diacetate, polyoxybutylene diacetate, 2-ethoxyethyl acetate, ethylene glycol diacetate, and butylene glycol diacetate; aromatic solvents, such as toluene, xylene, and ethylbenzene; halogenated hydrocarbons, such as chloroform; sulfur-containing compounds, such as dimethyl sulfoxide; and mixtures thereof. Esters are particularly preferred. Good results have been obtained using butyl acetate, ethyl acetate, and mixtures thereof. Preferably, the composition (S) contains a polymer (PFPE) in an amount of 1 to 90% by weight, preferably 10 to 75% by weight, based on the total weight of the composition (S). A ) or a derivative thereof.

[0117] The polymer (PFPE) of the present invention A ) derivative polymer (PFPE F ) or polymer (PFPE FA The main targeted uses of (S) and of composition (S) are for coatings, surface treatments and as additives in polymer and coating compositions.

[0118] In particular, derivative polymers (PFPE F ) or polymer (PFPE FA ) and of the composition (S), the polymer (PFPE) of the present invention A ) can be suitably used as an additive in coating compositions containing polyacrylic resins.

[0119] In another aspect of the present invention, the polymer (PFPE A ), derivative polymer (PFPE F ) or polymer (PFPE FA ) and composition (S) may be suitably used to prepare a curable coating composition further comprising a curing agent.

[0120] The presence of repeat units derived from (meth)acrylic monomers optionally bearing at least one functional group (FG) advantageously contributes to the formation of polymers (PFPE A ), derivative polymer (PFPE F ) or polymer (PFPE FA ) and compositions (S) containing them, to allow them to react with crosslinking agents to obtain cured coatings.

[0121] In particular, polymers (PFPE A ), derivative polymer (PFPE F ) or polymer (PFPE FA ) or (meth)acrylic monomers having at least one hydroxyl functionality (FG), and at least one polyisocyanate. A curable composition comprising the inventive composition (S) can be prepared and cured to obtain an improved coating composition.

[0122] If the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that it may render a term unclear, the statements of this application shall control.

[0123] The present invention is exemplified herein below in more detail by the examples contained in the experimental section below; however, the examples are illustrative only and should not be construed as limiting the scope of the invention in any way. [Example]

[0124] Materials and Methods Fluorolink® E10 and Fluorolink® D were obtained from Solvay Specialty Polymers Italy SpA. Trimethylamine, 2-bromoisobutyryl bromide, methyl-methacrylate, hydroxyethyl-methacrylate, CuBr and tributyltin hydride were purchased from Sigma-Aldrich® and used as such. Novec TM The HFE7100 was purchased from 3M. Polyisocyanate VESTANAT T1890 / 100, commercially available from Evonik. Commercially available from Brenntag: Setalux 1198 SS-70, Setalux 1907 BA-75, Setalux 1184 SS-51.

[0125] 1 H-NMR and 19 F-NMR 1 H is 499.86MHz and 19 F was recorded on an Agilent System 500 operating at 470.30 MHz.

[0126] Static contact angles were measured using a Drop Shape Analyzer "Kruess DSA10" manufactured by Kruess GmbH, Germany, by casting at least five drops of the liquid mixture (10% w / w solution of polymer in butyl acetate) onto an aluminum panel and drying at room temperature for 48 h. The contact angle was measured when a colorless, transparent, uniform film was obtained. Water and n-hexadecane solvents were used as reference solvents for measuring hydrophobicity and oleophobicity.

[0127] XRF (bromine measurement): A 1 g polymer sample was solubilized in MIBK (methyl isobutyl ketone); the clear, colorless solution was analyzed in liquid sample form using an XRF WD Panalalytical PW 2400 instrument. The instrument had the same matrix between the sample and the standard and was pre-calibrated using a solid standard of Br (2-bromobenzoic acid) solubilized in MIBK to eliminate interferences.

[0128] A quantitative determination of Br in a sample is obtained by comparison with a calibration solution. The method is applicable to samples with Br contents higher than 50 μg / g.

[0129] ICP (Cu measurement): 0.1 g of polymer samples were mineralized using a microwave acid digestion system with HNO3 and HCl 3:1; after specific dilution, the clear, colorless digestion solution was analyzed using an ICP-OES PerkinElmer Optima 4300 DV instrument, which had been previously calibrated using different solutions of Cu aqueous calibration standard.

[0130] Quantitative determination of Cu in a sample is provided by comparison with a calibration solution. The method has an analytical limit of 25 μg Cu / g sample.

[0131] Solubility in solvents One gram of polymer was placed in a glass container with a plastic screw cap and placed in a 10 cm 3of the desired solvent was added; the vessel was closed and placed in a mechanical shaker at room temperature for a minimum of 4 hours. The mixture was allowed to stand at room temperature for 24 hours. If there were no dispersed or settled solids in the mixture, the mixture was designated "soluble."

[0132] Synthesis of polymer P-1 Polymer P-1a (comparison) Fluorolink® D (30 g, EW=900, 33 meq), triethylamine (8.3 g, 82 mmol) were added to 35 ml of Novec in a 250 ml flask. TM The crude product was dissolved in HFE7100 and the solution was cooled to 0°C. 2-Bromoisobutyryl bromide (15.45 g, 65 mmol) was then added dropwise to the flask under a stream of N2. The reaction mixture was stirred at 0°C for 1 h and then at room temperature for 8 h. The crude product was first washed with HCl (5% aqueous solution, 12 ml), then washed several times with demineralized water until neutral pH, dried over MgSO4, filtered, and concentrated under vacuum at 35°C for 8 h to give 33 grams of (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-C(=O)-C(CH3)2-Br]2 (polymer P-1a) (where a1 / a2 = approximately 1) was obtained as a yellowish liquid.

[0133] Polymer P-1b Fluorolink® E10 (31.6 g, EW=950, 33 meq), triethylamine (8.3 g, 82 mmol) were added to 35 ml of Novec in a 250 ml flask. TM The crude product was dissolved in HFE7100 and the solution was cooled to 0°C. 2-Bromoisobutyryl bromide (15.45 g, 65 mmol) was then added dropwise to the flask under a stream of N2. The reaction mixture was stirred at 0°C for 1 h and then at room temperature for 8 h. The crude product was first washed with HCl (5% aqueous solution, 12 ml), then washed several times with demineralized water until neutral pH, dried over MgSO4, filtered, and concentrated under vacuum at 35°C for 8 h to give 34 grams of (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O)n C(=O)-C(CH3)2-Br]2 (polymer P-1b) (where a1 / a2=approximately 1 and n is 1.5 on average) was obtained as a yellowish liquid.

[0134] Hydrolytic stability of polymer P-1 Polymer P-1a (10 g) in 100 ml of pH 10 buffer (boric acid / potassium chloride / sodium hydroxide) was stirred at T=80°C for 15 days. After 15 days, the solution was placed in a separatory funnel, and the lower phase containing polymer a1 was separated and subjected to NMR analysis to determine the ratio (CFCFO). a1 (CF2O) a2 -[CF2CH2O - ]2 / (CF2CF2O) a1 (CF2O) a2 The degree of hydrolysis was measured as -[CF2CH2O-C(=O)-C(CH3)2-Br]2. After 15 days, the hydrolysis of polymer P-1a was greater than 10%.

[0135] Polymer P-1b (10 g) in 100 ml of pH 10 buffer (boric acid / potassium chloride / sodium hydroxide) was stirred at T=80° C. for 15 days. After 15 days, the solution was placed in a separatory funnel, and the lower phase containing polymer P-1b was separated and subjected to NMR analysis to determine the ratio (CFCFO). a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n ]2 / (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -C(=O)-C(CH3)2-Br] 2. After 15 days, no hydrolysis of polymer P-1b was detectable.

[0136] Synthesis of polymer P-2 Polymer P-2a (CF2CF2O) a1 (CF2O) a2- [CF2CH2O-(CH2CH2O) n[—C(═O)—C(CH)—Br] (polymer P-1b, 13.0 g, 12 meq), bipyridyl (4.3 g, 28 mmol), methyl methacrylate (MMA, 20.5 g, 205 mmol), and hydroxyethyl methacrylate (HEMA, 8.9 g, 68 mmol) were dissolved in freshly distilled acetone (50 ml) in a 250 ml flask filled with N. After 30 min of stirring at room temperature (RT), CuBr (3.9 g, 28 mmol) was added, and the mixture was placed in an oil bath at 60 °C. Polymerization was allowed to proceed for 16 h; tributyltin hydride (6.98 g, 24 meq) was added, and the mixture was allowed to proceed for an additional 8 h at 60 °C until complete replacement of the terminal —C—Br with CH. After cooling to RT, the reaction mixture was diluted with acetone and passed through a plug of acidic alumina or acidic exchange resin to remove the copper catalyst. The filtrate was purified by precipitation from water / ethanol; the copolymer thus precipitated was collected by filtration to remove the unreacted MMA and HEMA present as the supernatant.

[0137] Formula (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 16.8 -(HEMA) 5.2 The thus obtained polymer of [—H]2 (where a1 / a2=approximately 1 and 1, and n=1.5 on average) was dried under vacuum at 35° C. to give a white powder.

[0138] Polymer P-2b (CF2CF2O) a1 (CF2O) a2- [CF2CH2O-(CH2CH2O) n[—C(═O)—C(CH)—Br] (polymer P-1b, 13.0 g, 12 meq), bipyridyl (4.3 g, 28 mmol), methyl methacrylate (MMA, 20.5 g, 205 mmol), and benzyl methacrylate (BzMA, 12.0 g, 68 mmol) were dissolved in freshly distilled acetone (50 ml) in a 250 ml flask filled with N. After 30 min of stirring at room temperature (RT), CuBr (3.9 g, 28 mmol) was added, and the mixture was placed in an oil bath at 60 °C. Polymerization was allowed to proceed for 16 h; tributyltin hydride (6.98 g, 24 meq) was added, and the mixture was allowed to proceed for an additional 8 h at 60 °C until complete replacement of the terminal —C—Br with CH. After cooling to RT, the reaction mixture was diluted with acetone and passed through a plug of acidic alumina or acidic exchange resin to remove the copper catalyst. The filtrate was purified by precipitation from water / ethanol; the copolymer thus precipitated was collected by filtration to remove the unreacted MMA and HEMA present as the supernatant.

[0139] Formula (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 17 -(BzMA) 5.1 The thus obtained polymer of formula [—H]2 (where a1 / a2=approximately 1 and n=1.5 on average) was dried under vacuum at 35° C. to give a white powder.

[0140] Measurement of Cu content by ICP, Br by XRF, and solubility in different solvents for samples of polymers P-2a and P-2b were carried out as reported above, and the data are summarized in Table 1.

[0141] TIFF0007794633000008.tif113170

[0142] contact angle A 10% solution of each polymer P-2a and P-2b in butyl acetate was prepared, and each solution was applied by casting onto an aluminum panel and allowed to dry at room temperature for 48 hours.

[0143] Contact angles using water as the solvent were measured as described above, and the results are shown in Table 2.

[0144] TIFF0007794633000009.tif30170

[0145] Compatibility Test The following polymers were prepared essentially as described above: Polymer P-2c: (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 20 -(BMA) 4.5 -(HEMA) 1.5 -H]2 (where a1 / a2 = approximately 1 and n = 1.5 on average); Polymer P-2d: (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 20 -(BzMA) 4.5 -(HEMA) 1.5 -H]2 (where a1 / a2 = approximately 1 and n = 1.5 on average); Polymer P-2e: (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 15 -(BMA) 7.5 -(HEMA)3-H]2 (where a1 / a2 = approximately 1 and n = 1.5 on average); Polymer P-2f: (CF2CF2O) a1 (CF2O) a2 -[CF2CH2O-(CH2CH2O) n -(MMA) 15 -(BMA)6-(HEMA)3-H]2, where a1 / a2 = approximately 1 and n = 1.5 on average.

[0146] Prepare a 10% solution of each polymer in butyl acetate and mix each solution with three commercially available polyacrylic resins: Setalux 1198 SS-70 70% in butyl acetate Setalux 1907 BA-75 75% in butyl acetate Setalux 1184 SS-51 52% in butyl acetate (1 part commercial polyacrylic resin and 1 part 10% solution of polymer).

[0147] The mixture was applied by casting onto an aluminum panel and allowed to dry at room temperature for 48 h.

[0148] Contact angles were measured using water and n-hexadecane as solvents, and the results are shown in Table 3.

[0149] TIFF0007794633000010.tif105170

[0150] These results show that the polymer according to the present invention has good compatibility with polyacrylic resin.

[0151] Compatibility test of cured compositions Curable compositions were prepared by mixing 10% solutions of each polymer P-2c, P-2d, P-2e, and P-2f in butyl acetate, and each solution was mixed with three commercially available polyacrylic resins (1 part commercially available polyacrylic resin and 1 part 10% solution of the polymer), and with a polyisocyanate in a 1 / 1 ratio between the OH equivalents (derived from the hydroxyl groups of the HEMA units) and the NCO equivalents of the polyisocyanate.

[0152] Comparative blank compositions were prepared, each containing one of three commercially available polyacrylic resins and a polyisocyanate.

[0153] The mixture was applied by casting onto an aluminum panel, dried at room temperature for 24 h, and cured at 80° C. for 4 h.

[0154] Contact angles were measured using water and n-hexadecane as solvents, and the results are shown in Table 4.

[0155] TIFF0007794633000011.tif228170

Claims

1. (Per)fluoropolyether polymer [polymer (PFPE Ａ ) ], at least one (per)fluoropolyoxyalkylene chain with two chain ends [chain (R ｆ )]and; - the chain (R ｆ at least one (poly)oxyalkylene chain [chain (R ａ )] (the chain (R ａ ) comprises at least one fluorine-free oxyalkylene unit; Formula (I): [In the formula: - R equal to or different from each other １ , R ２ and R ３ represents a hydrogen atom and C １ ~C ３ independently selected from hydrocarbon groups; X is an oxygen atom, a sulfur atom or a group NR ８ where R ８ represents a hydrogen atom and C １ ~C ３ selected from hydrocarbon groups; -R ４ is a hydrogen atom or C ２ ~C ２０ a hydrocarbon chain moiety, wherein said C ２ ~C ２０ The hydrocarbon chain portion optionally comprises at least one functional group (FG). At least one (meth)acrylic monomer repeat unit [unit (MA)] of The at least one unit (MA) is of the formula *-(C=O)-R ５ -** [In the formula, R ５ C having at least one secondary or tertiary carbon atom １ ~C ８ is an alkylene or cycloalkylene group, The symbol (*) indicates the chain (R ａ ) and The symbol (**) indicates a bond to the unit (MA) through the secondary or tertiary carbon atom. a unit (MA) linked to said at least one chain (Ra) via a linking group (LG) of Polymer containing PFPE Ａ ).

2. Chain (R ｆ ) has a number average molecular weight M in the range of 100 to 8,000 ｎ and (i) -CFY'O- (wherein Y' is F or CF ３ (which is (ii) -CFY'CFY'O-, wherein Y', equal or different at each occurrence, is as defined above, with the proviso that at least one Y' is -F; (iii) -CF ２ CF ２ CW ２ O—, wherein each W, equal to or different from each other, is F or H; (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 a group represented by the general formula -OR ｆ 'T, where R ｆ ' is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being selected from the following: -CFY"O-, -CF ２ CFY"O-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O—, and each Y″ is independently selected from F or CF ３ and T is C １ ~C ３ perfluoroalkyl group) The polymer (PFPE) according to claim 1, wherein the (per)fluoropolyoxyalkylene chain comprises repeating units, which may be equal to or different from each other, selected from Ａ ).

3. Chain (R ｆ ) is expressed by the following formula (R ｆ -I), (R ｆ -IIA), (R ｆ -IIB), (R ｆ -IIC), (R ｆ -IID), (R ｆ -IIE) or (R ｆ -III): (R ｆ -I) -[(CFX １ O) ｇ１ (CFX ２ CFX ３ O) ｇ２ (CF ２ CF ２ CF ２ O) ｇ３ (CF ２ CF ２ CF ２ CF ２ O) ｇ４ ]- (In the formula, -X １ is -F and -CF ３ are independently selected from - X, which are equal or different from each other and from one occurrence to the other ２ , X ３ are independently -F, -CF ３ where X １ ~X ３ at least one of is -F; g1, g2, g3 and g4, which are equal to or different from one another, are independently integers greater than or equal to 0, such that g1+g2+g3+g4 is in the range of 2 to 300; if at least two of g1, g2, g3 and g4 are different from zero, the different repeat units are generally distributed statistically along the chain; (R ｆ -IIA) -[(CF ２ CF ２ O) ａ１ (CF ２ O) 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 10,000, the ratio a1 / a2 being comprised between 0.1 and 10; (R ｆ -IIB) -[(CF ２ CF ２ O) ｂ１ (CF ２ O) ｂ２ (CF(CF ３ )O) ｂ３ (CF ２ CF(CF ３ )O) ｂ４ ]- (In the formula: b1, b2, b3, and b4 are independently integers greater than or equal to 0 such that the number average molecular weight is 400 to 10,000, and the ratio b4 / (b2+b3) is greater than or equal to 1; (R ｆ -IIC) -[(CF ２ CF ２ O) ｃ１ (CF ２ O) ｃ２ (CF ２ (CF ２ ) ｃｗ CF ２ O) 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 from 400 to 10,000, and the ratio c3 / (c1+c2) is less than 0.2; (R ｆ -IID) -[(CF ２ CF(CF ３ )O) ｄ ]- (In the formula: d is an integer greater than 0 such that the number average molecular weight is from 400 to 10,000; (R ｆ -IIE) -[(CF ２ CF ２ C(Hal*) ２ O) ｅ１ -(CF ２ CF ２ CH ２ O) ｅ２ -(CF ２ CF ２ CH(Hal*)O) ｅ３ ]- (In the formula: Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms; e1, e2, and e3, which are equal to or different from one another, are independently integers greater than or equal to 0 such that the sum of (e1+e2+e3) is in the range from 2 to 300; (R ｆ -III) -[(CF ２ CF ２ O) ａ１ (CF ２ O) ａ２ ]- (In the formula: a1 and a2 are integers greater than 0 such that the number average molecular weight is between 400 and 10,000, the ratio a1 / a2 being comprised between 0.1 and 10. The polymer (PFPE) according to claim 2, Ａ ).

4. Chain (R ａ ) is a fluorine atom-free polyoxyalkylene chain, said chain containing 1 to 50 fluorine atom-free oxyalkylene units, said units being the same or different from one another, and having the general formula: (In the formula, R ｎ is independently at each occurrence hydrogen, a lower alkyl, or a lower alkoxy group, and m is an integer from 1 to 10. The polymer (PFPE) of claim 1 having Ａ ).

5. The fluorine-free oxyalkylene unit is —CH ２ CH ２ O- and -CH ２ The polymer (PFPE) according to claim 4, wherein the PFPE is selected from CH(J)O-, where J is linear or branched alkyl or aryl. Ａ ).

6. Chain R ａ is expressed by the following formula (R ａ -I): (R) ａ -I) -(CH ２ CH ２ O) ｒ (CH) ２ CH(CH ３ )O) ｓ (CH) ２ CH(CH ２ CH ３ )O) ｔ (CH) ２ CH(Ph)O ｕ - wherein r, s, t, and u are independently selected from 0 and positive numbers, and r+s+t+u ranges from 1 to 50. The polymer (PFPE) according to claim 4 or 5 Ａ ).

7. 2. The polymer (PFPE) of claim 1, wherein said at least one functional group (FG) is selected from the group consisting of hydroxyl groups, ether groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, amide groups, halogen-containing groups such as fluoro and perfluoro groups, halogen atoms, phosphate groups, ester groups, siloxane groups and polysiloxane groups. Ａ ).

8. The linking group (LG) is represented by formula (LG-I) or (LG-II): (LG-I) *-(C=O)-C(R ６ R ７ )-** (In the formula, R ６ and R ７ are independently hydrogen, methyl, or benzyl groups, provided that R ６ and R ７ cannot both be hydrogen) (LG-II) *-(C=O)-C(CH ３ ) ２ -*** The polymer according to claim 1 (PFPE) Ａ ).

9. The polymer (PFPE) according to any one of claims 1 to 8 Ａ ), the method comprising the steps of: a) at least one (per)fluoropolyoxyalkylene chain [chain (R ｆ ) ]; - the chain (R ｆ at least one (poly)oxyalkylene chain [chain (R ａ )] (the chain (R ａ ) contains at least one fluorine-free oxyalkylene unit; and - Formula *-(C=O)-R ５ -X' [wherein, R ５ is a C containing at least one secondary or tertiary carbon atom １ ~C ８ an alkylene or cycloalkylene group, and X′ is a halogen, wherein said halogen is bonded to R through said secondary or tertiary carbon atom; ５ and the symbol (*) indicates the chain (R ａ ) at least one group PFPE macroinitiators [polymer(PFPE Ｉ ) ]; b) converting the initiator provided in step a) by atom transfer radical polymerization (ATRP) to a compound of formula (II): [In the formula, - R equal to or different from each other １ , R ２ and R ３ represents a hydrogen atom and C １ ~C ３ independently selected from hydrocarbon groups; X is an oxygen atom, a sulfur atom or a group NR ８ where R ８ represents a hydrogen atom and C １ ~C ３ selected from hydrocarbon groups; -R ４ is a hydrogen atom or C ２ ~C ２０ a hydrocarbon chain moiety, wherein said C ２ ~C ２０ The hydrocarbon chain portion optionally comprises at least one functional group (FG). and at least one (meth)acrylic monomer [monomer (MM)] of the formula: reacting in the presence of at least one transition metal catalyst and a ligand to form a polymer (PFPE Ａ ) and c) the polymer (PFPE) obtained in step b) Ａ purifying the product to remove at least one transition metal catalyst; A method comprising:

10. Formula *-(C=O)-R ５ said at least one group of -X' is of the formula *-(C=O)-C(R ６ R ７ )-X’ (In the formula, R ６ and R ７ are independently hydrogen, methyl, or benzyl groups, provided that R ６ and R ７ cannot both be hydrogen, and X' is a chlorine, bromine, or iodine atom.

10. The method according to claim 9 .

11. at least one (per)fluoropolyoxyalkylene chain [chain (R ｆ )]and; - the chain (R ｆ at least one (poly)oxyalkylene chain [chain (R ａ )] (the chain (R ａ ) comprises at least one fluorine-free oxyalkylene unit; - Formula *-(C=O)-R ５ -X' [wherein, R ５ is a C containing at least one secondary or tertiary carbon atom １ ~C ８ an alkylene or cycloalkylene group, and X′ is a halogen, wherein said halogen is bonded to R through said secondary or tertiary carbon atom; ５ and the symbol (*) indicates the chain (R ａ ) showing a bond to the Polymer containing PFPE Ｉ ).

12. Formula (IV): A-O-R ｆ -(CF ２ ) ｘ -CFZ-CH ２ -O-R ａ -C(=O)-C(R ６ R ７ )-X’ (IV) [In the formula: -R ｆ is the number average molecular weight M in the range of 100 to 8,000 ｎ and (i) -CFY'O- (wherein Y' is F or CF ３ (which is (ii) -CFY'CFY'O-, wherein Y', equal or different at each occurrence, is as defined above, with the proviso that at least one Y' is -F; (iii) -CF ２ CF ２ CW ２ O—, wherein each W, equal to or different from each other, is F or H; (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 a group represented by the general formula -OR ｆ 'T, where R ｆ ' is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, the repeating units being selected from the following: -CFY"O-, -CF ２ CFY"O-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O—, and each Y″ is independently selected from F or CF ３ and T is C １ ~C ３ perfluoroalkyl group) is a (per)fluoropolyoxyalkylene chain containing repeating units, which may be equal to or different from one another, selected from: Z is fluorine or CF ３ and x is 0 or 1, with the proviso that when x is 1, Z is F; -R ａ is a fluorine-free polyoxyalkylene chain, said chain containing 4 to 50 fluorine-free oxyalkylene units, said units being the same or different from one another, -CH ２ CH ２ O- and -CH ２ CH(J)O—, where J is a linear or branched alkyl or aryl; -R ６ and R ７ are independently hydrogen, methyl, or benzyl groups, provided that R ６ and R ７ cannot both be hydrogen; X' is a chlorine, bromine or iodine atom; -A is -R ａ -C(=O)-C(R ６ R ７ )-X' (where R ａ , R ６ , R ７ and X' are as defined above), or a linear or branched C １ ~C ４ (per)fluoroalkyl groups, where one fluorine atom can be replaced by one chlorine atom or one hydrogen atom. The polymer according to claim 11 (PFPE Ｉ ).

13. Formula R ｆ [CF ２ CH ２ O-(CH ２ CH ２ O) ｎ -C(=O)-C(CH ３ ) ２ -Br] ２ The polymer (PFPE) of claim 12, Ｉ ).

14. A composition (S) comprising a polymer according to any one of claims 1 to 8 and at least one solvent.

15. 1. A method for coating at least one surface of a substrate selected from plastic, metal or glass, said method comprising: (i) contacting a substrate with the composition (S) of claim 14; (ii) drying the composition (S) onto the substrate; A method comprising:

Images