Novel (per) fluoropolyether polymers and uses thereof

Abstract

The present invention relates to novel (per) fluoropolyether (PFPE) polymers, to a process for the production thereof and to the use thereof as an additive in coating compositions. Specifically, the present invention relates to a (per) fluoropolyether polymer [polymer (PP)] comprising a (per) fluoropolyoxyalkylene chain having two chain ends [chain (Rpf)] bonded to opposite sides of said chain (Rpf), wherein: * one of the chain ends comprises at least one, preferably from 1 to 3 groups (groups [I]) selected from the group consisting of alkoxysilanes [groups (Si)] or crosslinkable groups, preferably selected from the group consisting of unsaturated moieties [groups (U)] and epoxides [groups (E)]; and * the other chain end comprises at least one, preferably from 1 to 3, group (group [II]) selected from the group consisting of optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole.

Description

[0001] Citation of Related Applications

[0002] This application claims priority from European patent application EP 22176290.9 filed on May 31, 2022, the entire contents of which are incorporated by reference into this application for all purposes. Technical Field

[0003] The present invention relates to novel (per)fluoropolyether (PFPE) polymers endowed with enhanced UV stability, a process for their manufacture and their use as additives in coating compositions. Background Art

[0004] It is known in the art to use (per) fluoropolyether (PFPE) polymers as ingredients for making antifouling coating compositions to coat different types of substrates. For example, EP 3312242 (3M Innovative Properties Company) discloses protective coating compositions with hybrid functionality, wherein PFPE is mentioned in, for example, the backbone; WO 2016 / 079195 (Solvay Specialty Polymers Italy S.pA) discloses zwitterionic derivatives of PFPE, which are disclosed as being suitable for coating applications; WO 2019 / 106366 (Sphere Fluidic Co., Ltd.) discloses surfactants comprising a perfluoropolyether structure.

[0005] Coatings based on (per)fluoropolyether (PFPE) polymers have been disclosed in the art, such as for example in US 5,623,037 and US 6,071,564 (both in the name of Ausimont SpA).

[0006] When a substrate is treated with a silane compound containing perfluoropolyether, a film layer having hydrophobicity, oleophobicity, antifouling, low friction coefficient and durability can be formed on its surface. For example, refer to US2020 / 407378 (Guangzhou UR Materials Technology Co., Ltd.).

[0007] PFPE polymers containing alkoxy-silane groups and aliphatic cyclic moieties comprising at least one nitrogen atom have been disclosed, for example, in US 2018 / 0244844 (in the name of Daikin Industries, Ltd.).

[0008] CN 109642000 (in the name of Nissan Chemical Industries, Ltd.) discloses a composition comprising a PFPE polymer having unsaturated moieties at both chain ends thereof. Summary of the invention

[0009] Many different substrates used today, for example in the automotive sector, require antifouling coatings which should meet certain requirements, especially with regard to clarity (transparency), durability and oil and water repellency as well as UV resistance.

[0010] Applicants have recognized that despite efforts in the art, there remains a need for additives that can improve the UV resistance of coating compositions without negatively affecting the anti-smudge properties as well as the clarity, durability and oil and water repellency of coatings for a variety of substrates.

[0011] Faced with the above technical problem, the applicant has found that (per)fluoropolyether polymers carrying two different functional groups at their chain ends can be advantageously used as additives to enhance the UV stability of coatings.

[0012] Therefore, in a first aspect, the present invention relates to a (per)fluoropolyether polymer [polymer (P P )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ),

[0013] in

[0014] * one of the chain ends comprises at least one, preferably from 1 to 3, groups (group [I]) selected from: alkoxysilanes [group (Si)] or crosslinkable groups, preferably selected from unsaturated moieties [group (U)] and epoxides [group (E)];

[0015] and

[0016] * The other chain end comprises at least one, preferably from 1 to 3, groups (group [II]) selected from one of the following: optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole.

[0017] Advantageously, in the (per)fluoropolyoxyalkylene chain (R pf ) provides an "asymmetric PFPE polymer" that can be used as an additive that can provide excellent UV resistance and good durability over time.

[0018] Advantageously, the polymers according to the invention (P P) is produced via a method that allows fine-tuning of the amounts of groups [I] and [II], which allows the use of polymers (P P ) to appropriately select the desired amount of functional group [I] or [II] according to the final composition.

[0019] Although the polymer (P P ) is particularly preferred, but the present invention also encompasses a polymer (P P ) and at least one other polymer having two groups [I] or two groups [II] at its chain ends.

[0020] When added as an additive to a coating composition, such compositions can also be used to provide good UV resistance over time without negatively affecting the water and oil repellency, easy cleaning, and stain release properties of the initial composition. DETAILED DESCRIPTION

[0021] For purposes of this specification and the following claims:

[0022] - The use of parentheses around symbols or numbers in an identifying format, such as in expressions such as "polymer (P P )" etc., have the sole purpose of making the symbol or number better distinguishable from the rest of the text, and therefore the parentheses may also be omitted;

[0023] - the acronym "PFPE" stands for "(per)fluoropolyether" and, when used as a noun, is intended to refer to the singular or plural form, depending on the context;

[0024] - the term "(per)fluoropolyether" is intended to indicate a fully or partially fluorinated polyether;

[0025] -The terms "clear" and "transparent" are used as synonyms.

[0026] The polymer (P P ) comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ),

[0027] in

[0028] * one of the chain ends comprises at least one group (group [I]) selected from alkoxysilanes [group (Si)] or crosslinkable groups, which are preferably selected from unsaturated moieties [group (U)] or epoxides [group (E)];

[0029] and

[0030] * The other chain end comprises at least one group (group [II]) selected from optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole.

[0031] For the avoidance of doubt, the expression "selected from one of the following: optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole" is used to indicate that group (II) is derived from any one of the optionally substituted compounds in the list. Group (II) is bonded to [chain (R pf )].

[0032] Polymer (P P ) may comprise one, two or three groups (I) at one chain end and one, two or three groups (II) at the other chain end.

[0033] In the polymer (P P ), chain (R pf ) is preferably a chain having the formula

[0034] -D'-(CFX') z1 O(R f )(CFX) z2 -D-

[0035] in

[0036] z1 and z2, identical or different from each other, are equal to or greater than 1, preferably from 1 to 10, more preferably from 1 to 3;

[0037] X and X', identical or different from each other, are -F or -CF3,

[0038] Provided that when z1 and / or z2 is greater than 1, X and X' are -F;

[0039] D and D', identical or different from each other, are a sigma bond or a hydrogenated alkylene chain containing from 1 to 6 carbon atoms and even more preferably from 1 to 3 carbon atoms, said alkyl chain optionally substituted with at least one perfluoroalkyl group containing from 1 to 3 carbon atoms;

[0040] (R f ) comprises, preferably consists of, repeating units R° independently selected from the group consisting of:

[0041] (i) -CFXO-, where X is F or CF3;

[0042] (ii) -CFXCFXO-, where X, being the same or different at each occurrence, is F or CF3, provided that at least one of X is -F;

[0043] (iii) -CF2CF2CW2O-, wherein each W, being the same as or different from each other, is F, Cl, or H;

[0044] (iv) -CF2CF2CF2CF2O-;

[0045] (v)-(CF2) j -CFZ-O-, wherein j is an integer from 0 to 3 and Z is a molecule having the general formula -OR (f-a) -T group, where R (f-a) is a fluoropolyoxyalkylene chain containing from 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and T is a C1-C3 perfluoroalkyl group.

[0046] More preferably, D' and D are each a sigma bond or -CH2-.

[0047] Preferably, the chain (R f ) conforms to the following formula:

[0048] (R f -I)

[0049] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]-in

[0050] -X 1 independently selected from -F and -CF3,

[0051] -X 2 , X 3 are the same as or different from each other and are independently -F, -CF3 at each occurrence, provided that at least one of X is -F;

[0052] - g1, g2, g3 and g4, identical or different from each other, are independently integers ≥ 0, such that g1+g2+g3+g4 is in the range of from 2 to 300, preferably from 2 to 100; if at least two of g1, g2, g3 and g4 are not zero, the different repeating units are usually statistically distributed along the chain.

[0053] More preferably, the chain (R f ) is selected from chains having the formula:

[0054] (Rf -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]-

[0055] in:

[0056] a1 and a2 are independently integers ≥ 0, such that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000; both a1 and a2 are preferably not zero, wherein the ratio a1 / a2 is preferably comprised between 0.1 and 10;

[0057] (R f -IIB)-[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]-

[0058] in:

[0059] b1, b2, b3, b4 are independently integers ≥ 0, such that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000; preferably, b1 is 0, b2, b3, b4> 0, wherein the ratio b4 / (b2+b3) ≥ 1;

[0060] (R f -IIC)-[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]-

[0061] in:

[0062] cw=1 or 2;

[0063] c1, c2 and c3 are independently integers ≥ 0, which are selected so that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000; preferably, c1, c2 and c3 are all > 0, wherein the ratio c3 / (c1+c2) is generally lower than 0.2;

[0064] (R f -IID)-[(CF2CF(CF3)O) d ]-

[0065] in:

[0066] d is an integer > 0 such that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000;

[0067] (R f -IIE)

[0068] -[(CF2CF2C(Hal*)2O) e1 -(CF2CF2CH2O) e2 -(CF2CF2CH(Hal*)O) e3 ]-

[0069] in:

[0070] -Hal*, being the same or different at each occurrence, is a halogen selected from a fluorine atom and a chlorine atom, preferably a fluorine atom;

[0071] e1, e2 and e3, identical or different from each other, are independently integers ≥ 0, such that the sum of (e1+e2+e3) is comprised between 2 and 300.

[0072] Still more preferably, the chain (R f ) conforms to the following formula (R f -III):

[0073] (R f -III)-[(CF2CF2O) a1 (CF2O) a2 ]-

[0074] in:

[0075] a1 and a2 are integers > 0, such that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000, wherein the ratio a1 / a2 is generally between 0.1 and 10, more preferably between 0.2 and 5.

[0076] As mentioned above, the polymer (P P ) is advantageously an asymmetric polymer, in other words, the polymer (P P ) comprises at least one group [I] at one chain end and at least one group [II] at the other chain end, wherein the group [I] and the group [II] are different from each other.

[0077] Preferably, the group [I] is linked to the chain (R pf ).

[0078] More preferably, the linking group conforms to the following formula:

[0079] *-(R a )t -(R b ) v -(R c ) u -§

[0080] in:

[0081] *Indicates to chain (R pf )

[0082] § indicates a bond to group [I];

[0083] R a is a poly(oxy)alkylene chain;

[0084] t is 0 or an integer from 1 to 15, preferably from 1 to 10;

[0085] v is 0 or 1;

[0086] R b is a group having the formula:

[0087] (R b -I) -OC(=O)-NH-(CH h ) e -

[0088] (R b -II) -C(=O)-NR'-(CH h ) f -

[0089] (R b -III) -O-(CH2) g -C(=O)-

[0090] in

[0091] e is an integer from 1 to 6,

[0092] R' is H or a straight or branched chain alkyl group having from 1 to 6 carbon atoms,

[0093] f is an integer from 1 to 4,

[0094] g is an integer from 1 to 4, and

[0095] Each h is independently 0 or an integer equal to 1 or 2, provided that when h is 0, e and f are each independently 1;

[0096] R c is a straight or branched alkyl chain having from 1 to 12 carbon atoms, optionally containing one or more oxygen atoms, or an optionally substituted aliphatic cycloalkyl containing 5 or 6 members; and

[0097] u is either 0 or 1.

[0098] As mentioned above, from 1 to 3 groups [I] may be present in the chain (R pf ) at one chain end. It will be appreciated that the presence of 1, 2 or 3 groups [I] depends on the group R b or R c valence.

[0099] For example, when (R b ) conforms to the above formula (R b -I) or (R b -II):

[0100] When h is equal to 2, the carbon atom carries two hydrogen atoms and a group [I]

[0101] When h is equal to 1, the carbon atom carries one hydrogen atom and two groups [I], and

[0102] When h is equal to 0, the carbon atom carries three groups [I].

[0103] Preferably, (R a ) is a poly(oxy)alkylene chain comprising from 1 to 50 fluorine-free oxyalkylene units. More preferably, the units, identical or different from each other, conform to the following formula:

[0104] -OCH(J)CH(J*)-

[0105] wherein J and J* are each independently selected from a hydrogen atom, a straight-chain or branched alkyl group or an aryl group, preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group.

[0106] More preferably, -(R a ) t - meets the following formula (R a -I) to (R a -III) one of:

[0107] (R a -I)-(OCH2CH2) t1 -

[0108] (R a -II)-[OCH(CH3)CH2] t2 -

[0109] (R a -III)-[(OCH2CH2) t3 -(OCH(CH3)CH2) t4 ] tx -

[0110] in

[0111] t1 and t2 are each independently an integer from 1 to 15, preferably from 1 to 10; and

[0112] t3, t4 and tx are integers greater than 1, such that the sum of t3 and t4 is from 2 to 15, more preferably from 2 to 10.

[0113] Preferably, group [I] is group (U).

[0114] More preferably, group (U) is selected from the group consisting of:

[0115] (UI)-OC(=O)-CR H =CH2

[0116] (U-II)-OC(=O)-NH-CO-CR H =CH2

[0117] (U-III)-OC(=O)-R A -CR H =CH2

[0118] in

[0119] R H is H or C1-C6 alkyl;

[0120] R A Is the choice free (R A -I) and (R A -II) Groups composed of:

[0121] (R A -I)

[0122]

[0123] in

[0124] Each j5 is independently 0 or 1, and

[0125] R B is a divalent, trivalent or tetravalent group selected from the group consisting of: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 an aromatic or alkylaromatic group, optionally containing at least one heteroatom selected from N, O and S;

[0126] (R A -II)

[0127]

[0128] in

[0129] j6 is 0 or 1;

[0130] Each j7 is independently 0 or 1;

[0131] R B ' is a divalent, trivalent or tetravalent group selected from the group consisting of: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 an aromatic or alkylaromatic group, optionally containing at least one heteroatom selected from N, O and S; and

[0132] R B* With the above for R B ' defined as having the same meaning or having the formula (R B -I) group:

[0133]

[0134] in

[0135] The substituent U is selected from the groups (UI) to (U-III) as defined above, and

[0136] * and # indicate the difference between the above formula (R A -II) is the bonding site of the nitrogen atom in the

[0137] Alternatively, group [I] is group (Si).

[0138] Preferably, the group (Si) conforms to the following formula:

[0139] -Si-(OR 30 )3

[0140] Where R 30 is a straight or branched alkyl chain having from 1 to 12 carbon atoms.

[0141] Preferably, according to this embodiment, the chain end comprises one to three groups (Si) as defined above.

[0142] Alternatively, the group [I] is group (E).

[0143] Preferably, according to this embodiment, the chain end comprises a group (E).

[0144] Preferably, the group (E) is bonded to the chain (R) via a linking group conforming to the formula pf ):

[0145] *-(R a ) t -(R c) u -§

[0146] Where *, §, R a ,t,R c and u are as defined above.

[0147] Preferably, the group [II] is bonded to the chain (R pf ) of a group D or D':

[0148] *-(R a ) t -NH-§ or

[0149] *-(R a ) t -O-§

[0150] in:

[0151] *Indicates to chain (R pf ), and § indicates a bond to group [II], and

[0152] R a and t each have the meanings given above for group [I].

[0153] According to this embodiment, the chain (R pf The radicals D and D' in ) are each a hydrogenated alkylene chain containing 1 to 6 carbon atoms.

[0154] Alternatively, the group [II] is bonded to the chain (R pf ):

[0155] -(R a ) t -(R*) p C(=O)NH-(R**) q ,or

[0156] -(R a ) t -(R***) r C(=O)O-(R****) s -

[0157] in

[0158] p, q, r and s are each independently 0 or an integer from 1 to 6,

[0159] R a and t have the meanings defined above and

[0160] R*, R**, R*** and R**** are each independently a straight or branched alkyl chain containing from 1 to 6 carbon atoms.

[0161] According to this embodiment, the chain (R pf ) each group D and D' is a sigma bond.

[0162] Preferably, group [II] is selected from (ie derived from) substituted piperidine, substituted pyridine and substituted pyrrole.

[0163] Good results have been obtained when group [II] is a derivative of 4-amino-2,2,6,6-tetramethyl-piperidine.

[0164] In a second aspect, the present invention relates to a composition [composition (C POL )], which contains:

[0165] - a polymer as defined above (P P );

[0166] -(Per)fluoropolyether polymers [polymers (P U )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ),

[0167] wherein both chain ends comprise groups of formula [I] as defined above; and

[0168] -(Per)fluoropolyether polymers [polymers (P N )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ),

[0169] wherein both chain ends comprise groups of formula [II] as defined above.

[0170] Advantageously, the composition (C POL ) comprises at least 25 wt.% of said polymer as defined above (P P ).

[0171] Preferably, the composition (C POL )Include:

[0172] - from 2.0 wt.% to 50.0 wt.% of polymer (P P ),

[0173] - from 0.1 wt.% to 25.0 wt.% of polymer (P N ),as well as

[0174] - from 25.0 wt.% to 95.0 wt.% of polymer (PU ).

[0175] Composition (C POL ) may further comprise a (per)fluoropolyether polymer [polymer (P x )], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein one chain end comprises a perfluoroalkyl group and the other chain end comprises at least one group having formula [I] or a group having formula [II] as defined above.

[0176] When present, based on the composition (C POL ) of the total weight of the polymer (P X ) is preferably in an amount of up to 15.00 wt.%, more preferably in an amount of from 0.01 wt.% to 12.00 wt.% and even more preferably from 0.05 wt.% to 10.00 wt.%.

[0177] Preferably, in the polymer (P U ), polymer (P N ) and polymer (P X ) in any of the chain (R pf ), group [I] and group [II] are each as described above for the polymer (P P ) as defined in the Regulations.

[0178] Preferably, the polymer (P x ) comprises at one chain end a perfluoroalkyl group selected from the group comprising, more preferably consisting of:

[0179] -CF3, -C2F5, -C3F7, -CF2Cl, -CF2CF2Cl and -C3F6Cl.

[0180] The polymer (P x ) is also called "monofunctional polymer (P x )”.

[0181] As known in the art, the functionality (F) of the polymer P according to the invention, i.e. the average number of functional groups per molecule of polymer, is from 1.00 to 2.00. The difunctional polymer P typically has a functionality (F) of from 1.50 to 1.99, more preferably from 1.70 to 1.98 and even more preferably from 1.85 to 1.95. The functionality (F) can be calculated, for example, as disclosed in EP 1810987 A (SOLVAY SOLEXIS SPA).

[0182] For the preparation of polymers (P P ) provides a mixture of polymers, which is referred to herein as composition (C POL If necessary, the composition (C POL ) may undergo one or more purification steps in order to obtain the polymer (P P ).

[0183] The composition as defined above (C POL ) can advantageously be prepared starting from (per)fluoropolyether (PFPE) polymers, these polymers comprising a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein the chain end comprises a chain having the formula -OH or -C(=O)OR 10 A group in which R 10 is H or a straight or branched alkyl chain containing from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms.

[0184] In another aspect, the present invention relates to a method for synthesizing a composition as defined above (C POL ) method.

[0185] Preferably, for the synthesis of the composition (C POL ) is carried out by synthesizing an intermediate composition [composition (INT)], which comprises:

[0186] -(Per)fluoropolyether polymers [polymers (P INT )], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein one of the chain ends comprises a residue having the formula -OH or -C(=O)OR 10 A group in which R 10 as defined above and the other chain end comprises a group [II] as defined above;

[0187] - (per)fluoropolyether polymers [polymer PFPE] comprising (per)fluoropolyether chains having two chain ends [chains (R pf )], the two chain ends are bonded to the chain (R pf ) on opposite sides, wherein the two chain ends contain -OH or -C(=O)OR 10 A group in which R 10 As defined above; and

[0188] -(Per)fluoropolyether polymers [polymers (P II)], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein the two chain ends comprise groups [II] as defined above.

[0189] The composition (INT) as defined above is a further aspect of the invention.

[0190] Therefore, in another aspect, the present invention relates to a method for synthesizing a composition as defined above (INT), comprising:

[0191] (i) providing a method comprising: providing a (per)fluoropolyether chain [chain (R pf )], the (per)fluoropolyether polymer [polymer PFPE] having a (per)fluoropolyether chain bonded to the chain (R pf ) at two chain ends on opposite sides, the two chain ends comprising a group selected from the following: -C(=O)OR° or -OH;

[0192] (ii) if present, converting at least a portion of the -OH group into a leaving group for a nucleophilic substitution reaction or into a group having the formula -O(R***) r C(=O)O-(R V ), wherein R*** and r are as defined above, R V is an alkyl chain containing from 1 to 3 carbon atoms;

[0193] (iii) contacting the PFPE polymer of step (i) or the composition obtained in step (ii) with at least one compound comprising a group having the formula -OH or -NH2 and a group derived from one of the following: optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole, thereby obtaining a composition as defined above [composition (INT)].

[0194] The composition according to the present invention (C POL ) can advantageously be prepared, starting from a composition (INT) as defined above, according to a process comprising the following steps:

[0195] (iv) providing a composition (INT) as defined above and contacting said composition (INT) with at least one compound selected from the group consisting of:

[0196] - a compound [A] carrying at least one group (U) as defined above and at least one of the following: a halogen atom, an isocyanate group or an amino group; or

[0197] - a compound [B] carrying at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or

[0198] - a compound [C] carrying at least one group (Si) as defined above and at least one of the following: an isocyanate group or an amino group,

[0199] Thus, the composition (C POL ).

[0200] Furthermore and advantageously, the composition (INT) as defined above may be purified according to methods known in the art in order to purify at least the polymer (P INT ).

[0201] According to this embodiment, the polymer (P INT ) is contacted with at least one of the compounds [A], [B] or [C] as defined in step (iv) above, thereby obtaining the polymer (P) as a pure compound P ).

[0202] According to one embodiment, the composition (C POL ) can be prepared via a one-pot synthesis, i.e. without recovering the composition (INT) from the reaction mixture.

[0203] According to this embodiment, the composition (C POL ) is prepared by a method comprising the following steps:

[0204] (i*) providing a (per)fluoropolyether chain [chain (R pf )], the (per)fluoropolyether polymer [polymer PFPE] having a (per)fluoropolyether chain bonded to the chain (R pf ) at two chain ends on opposite sides, the two chain ends comprising a group selected from the following: -C(=O)OR 10 or -OH, where R 10 As defined above;

[0205] (ii*) if present, converting at least a portion of the -OH groups into leaving groups for nucleophilic substitution reactions or into groups having the formula -O(R***) r C(=O)O-(R V ), wherein R*** and r are as defined above, R V is an alkyl chain containing from 1 to 3 carbon atoms;

[0206] (iii*) contacting the PFPE polymer of step (i) or the composition obtained in step (ii) with at least one compound comprising a group having the formula -OH or -NH2 and a group derived from one of the following: an optionally substituted piperidine, an optionally substituted pyridine or an optionally substituted pyrrole, thereby obtaining a composition (INT) as defined above; and

[0207] (iv*) contacting the composition (INT) obtained in step (iii) with at least one compound selected from the group consisting of:

[0208] - a compound [A] carrying at least one group (U) as defined above and at least one of the following: a halogen atom, an isocyanate group or an amino group; or

[0209] - a compound [B] carrying at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or

[0210] - a compound [C] carrying at least one group (Si) as defined above and at least one of the following: an isocyanate group or an amino group,

[0211] Thus, the composition (C POL ).

[0212] The polymer PFPE used as the starting material in steps (i) and (i*) above is preferably a PFPE polymer conforming to one of the following formulae:

[0213] (PFPE-i)HO-(R pf )-OH

[0214] (PFPE-ii)HO-[CH(J*)CH(J)O] t1 -(R pf )-[OCH(J)CH(J*)] t2 -OH

[0215] (PFPE-iii)HO-(O=)C-(R pf )-C(=O)OH

[0216] in

[0217] (R pf ) as defined above,

[0218] t1 and t2 are each independently an integer from 1 to 50, and

[0219] J and J* are each independently as described above for (R a ) as defined in the Regulations.

[0220] In the present invention, when the polymer is obtained from Solvay Specialty Polymers Italy S.p.A. under the trade name PFPE and PFPE Good results have been obtained starting with the commercially available polymer PFPE.

[0221] Advantageously, in step (ii) or step (ii*) above, at least a portion of the -OH groups in the PFPE polymer of formula (PFPE-i) or (PFPE-ii) are converted into a leaving group for nucleophilic substitution reaction selected from the group comprising, preferably consisting of, methanesulfonyl, toluenesulfonyl, perfluorobutanesulfonyl or trifluoromethanesulfonyl.

[0222] Alternatively, in the above step (ii) or step (ii*), at least a portion of the -OH groups in the PFPE polymer of formula (PFPE-i) or (PFPE-ii) is converted into a PFPE polymer of formula -O(R***) as defined above by reacting with methyl chloroacetate, methyl 3-bromopropionate, methyl 4-iodobutyrate. r C(=O)O-(R V ) group.

[0223] This reaction in step (ii) or step (ii*) can be appropriately controlled to convert a predetermined amount of such -OH groups. To this end, those skilled in the art can select the amount of reactants to provide a predetermined amount of the leaving group for the above defined compound having the formula -O(R***) r C(=O)O-(R V ) t - is a nucleophilic substitution of the group of -OH. The amount of -OH groups that can be converted is not limited and can be appropriately determined by a person skilled in the art according to the desired final product. For example, within the present invention, good results are obtained by converting about 30% of the -OH groups in the starting PFPE polymer. However, about 1% to 100% of the -OH groups in the starting PFPE polymer can be converted to groups as described in step (ii) or step (ii*) above.

[0224] Preferably, step (ii) or step (ii*) is carried out in the presence of a fluorinated solvent. The fluorinated solvent is preferably selected from the group consisting of fluorinated hydrocarbons, α,α,α,α',α',α'-hexafluoro-m-xylene, α,α,α,α',α',α'-hexafluoro-p-xylene, chlorotrifluorotoluene isomers (including 4-chlorotrifluorotoluene, 2-chlorotrifluorotoluene), α,α,α-trifluorotoluene, hexafluorobenzene and mixtures thereof.

[0225] Preferably, in step (iii) or (iii*), the compound comprising a group having the formula -OH or -NH2 and a group derived from one of the following: an optionally substituted piperidine, an optionally substituted pyridine or an optionally substituted pyrrole is selected from 4-amino-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 2-(2,2,6,6-tetramethyl-piperidin-4-yl)-ethanol.

[0226] Preferably, in step (iv) or step (iv*), the reaction is preferably with the compound [A] which carries at least one group (U) and at least one isocyanate group.

[0227] Preferably, in step (iv) or step (iv*), the compound [A] conforms to the following formula:

[0228] O=C=NR 20 -R 21 -CR H =CH2

[0229] in

[0230] R H has the same meaning as defined above for group (U);

[0231] R 20 is a straight or branched alkyl chain having from 1 to 6 carbon atoms, optionally substituted by a trialkoxy-silyl-containing group;

[0232] R 21 It has the formula -OC(=O)-, -OC(=O)-NH-CO-, -OC(=O)-R A - a divalent group, wherein R A As defined above for group (U-III).

[0233] More preferably, compound [A] is selected from the group consisting of isocyanatoethyl methacrylate (IEM), allyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, vinyl isocyanate, acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanatoethyl acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0234] The polymer (P P ) or the composition (C POL ) are advantageously used as additives in the composition of the antifouling coating.

[0235] Alternatively, the polymer (P P ) or the composition (C POL ) can be provided in a mixture with a suitable solvent and then used as an additive in the composition of the antifouling coating. The solvent is preferably a solvent that can react with the polymer (P P ) or a combination (C POL ) solvent for the reaction.

[0236] In another aspect, the present invention relates to a composition [composition (DIL)] comprising at least one polymer as defined above (P P ) or a combination (C POL ) and at least one solvent (S), which is preferably selected from (per)fluoropolyether polymers having at least one functional group at its chain end, which functional group is preferably selected from: unsaturated groups, alkoxysilane groups or epoxy groups.

[0237] Preferably, the composition (DIL) comprises from 0.01 wt.% to 50.00 wt.%, preferably from 1.00 wt.% to 25.00 wt.% of the composition (C POL ) or polymer (P P ) and from 50.00 wt.% to 99.99 wt.%, preferably 75.00 wt.% to 99.00 wt.% of at least one solvent (S) as defined above, these amounts being based on the total weight of the composition (DIL).

[0238] According to an embodiment, when the polymer (P P ) comprises a group (Si), the solvent (S) is selected from at least one hydrofluoroether or one or more (per)fluoropolyether polymers containing one silane group.

[0239] According to a preferred embodiment, when the polymer (P P ) comprises a group (U), the solvent (S) is selected from (per)fluoropolyether polymers having at least one, more preferably at least two, unsaturated groups at their chain ends.

[0240] According to a preferred embodiment, when the polymer (P P ) comprises a group (U), the composition (DIL) is advantageously added to a composition comprising at least one UV curable component to provide a composition comprising at least one polymer (P P ), at least one solvent (S) as defined above and at least one UV curable component [composition (C F )], so that the polymer (P P ) in the composition (C F ) is based on the composition (C F )'s total weight is from 0.01 wt.% to 8.00 wt.%, more preferably from 0.50 wt.% to 5.00 wt.%.

[0241] Preferably, the composition according to the present invention (C F ) can advantageously be prepared by contacting and optionally mixing a composition (DIL) as defined above with said composition comprising at least one UV curable component.

[0242] Depending on the final intended use, at least one additional ingredient may be added to the above composition.

[0243] Such at least one further ingredient is preferably selected from: crosslinkers, transparent fillers, photoinitiators, volatile or non-volatile additives, for example selected from binders, catalysts, leveling agents, wetting agents, anti-cratering agents, dyes, rheology control agents, antioxidants and / or light stabilizers.

[0244] Suitable crosslinking agents are selected from, for example, trans-esterified crosslinking agents, amino resin crosslinking agents, such as melamine-formaldehyde resins; trialkoxycarbonylaminotriazine crosslinking agents, and the like.

[0245] Suitable transparent fillers are selected from, for example, silicon dioxide, more preferably nano-silicon dioxide.

[0246] The additional ingredients and additives are each preferably used in conventional amounts, such as, for example, in amounts based on the composition (C F ) is used in an amount up to 8.00 wt.%, more preferably from 0.01 wt.% to 5.00 wt.%.

[0247] In another aspect, the present invention relates to said polymer (P P ), composition (C POL ), composition (DIL) or composition (C F ) for providing a transparent coating on at least one surface of at least one substrate.

[0248] The composition (DIL) or the composition (C F ) is applied to at least one surface of a suitable substrate to form a clear (ie, transparent) coating.

[0249] In yet another aspect, the present invention relates to a method for providing a transparent coating on at least one surface of a substrate, the method comprising:

[0250] (i) providing at least one glass substrate having at least one surface; and

[0251] (ii) contacting said at least one surface with a composition (DIL) or a composition (C F ) in at least one contact.

[0252] The suitable means and conditions for contacting the composition with the substrate can be selected by those skilled in the art according to the composition and substrate used.

[0253] For example, the contacting step (ii) can be carried out by mixing the composition (DIL) or the composition (C F) is sprayed onto at least one surface of a suitable substrate to provide a film.

[0254] More preferably, when the composition (DIL) or the composition (C F ) contains at least one polymer (P) containing a group (Si) at one chain end P ), the coating has a thickness below 1 μm, even more preferably from 10 nm to 50 nm.

[0255] More preferably, when the composition (DIL) or the composition (C F ) contains a polymer (P) containing a group (U) or a group (E) at least at one chain end P ), the coating has a thickness of from 20 μm to 500 μm, even more preferably from 30 μm to 250 μm.

[0256] Preferably, when the composition (DIL) or the composition (C F ) contains a polymer (P) containing a group (U) at least at one chain end P ), UV curing of the composition (DIL) or the composition (C F ) in step (iii).

[0257] The curing conditions can be determined by a person skilled in the art based on the composition (DIL) or composition (C F ) components and the environment in which the coating and curing processes are carried out.

[0258] Any radiation source may be used. The radiation dose may be determined by the skilled person based on the composition (DIL) or (C F ). Good results have been obtained by applying radiation from 200 W to 750 W. Preferably, when the curing step is performed using UV, the curing time is from 1 to 50 seconds, more preferably from 5 to 30 seconds.

[0259] The present invention will be explained in more detail hereinafter with the aid of the examples contained in the following experimental part; these examples are merely illustrative and are in no way to be construed as limiting the scope of the present invention.

[0260] Experimental Section

[0261] Materials and methods

[0262] E10H and Z DOL was obtained from Solvay Specialty Polymers Italy S.p.A.

[0263] Bis(trifluoromethyl)benzene, triethylamine, methanesulfonyl chloride, acid chloride (37% solution), potassium hydroxide, ethanol, methanol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-isocyanatoethyl methacrylate, 4-amino-2,2,6,6-tetramethylpiperidine, methyl chloroacetate and a solution of sodium methoxide in methanol (25 wt.%), dibutyltin dilaurate, ethyl methyl ketone, potassium tert-butoxide, tert-butyl epibromohydrin were obtained from Aldrich.

[0264] 3-(Trimethoxysilyl)propyl isocyanate was obtained from TCI Corporation.

[0265] SnapCure TM 1030 was obtained from Alfa Aesar GmbH & Co.

[0266] Recording on Agilent System 500 1 H-NMR and 19 F-NMR, for 1 H at 499.86MHz and for 19 F runs at 470.30MHz.

[0267] FT-IR spectra were measured on liquid samples (as thin films on KBr) using a ThermoScientific FTIR spectrophotometer. The FT-IR spectra were obtained by adding 256 scans at 2 cm -1 The spectrum was acquired with a resolution of .

[0268] Example 1 - Synthesis of Composition A

[0269] Step 1: A 4-necked round-bottom flask with a capacity of 0.5 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel was charged with 150 g (EW = 908 g / mol; 165.2 meq) E10H, 100 g 1,3-bis(trifluoromethyl)benzene and 6.0 g triethylamine (59.4 meq). Afterwards, the flask was cooled and 5.8 g methanesulfonyl chloride (50.1 meq) was added at such a rate that the temperature was maintained in the range of 15°C-30°C. When the addition of methanesulfonyl chloride was complete, the reaction mixture was stirred at 25°C-30°C for another 6 hours.

[0270] Then, 70 g of a 4 M aqueous HCl solution were added to the reaction mixture and the organic phase thus formed was separated.After distillation of the fluorinated solvent under reduced pressure (T=80° C., P=2 Pa), 151.9 g of a clear liquid were separated and characterized.

[0271] 1H-NMR analysis confirmed that the product obtained was E10H, in which 29% of the -OH groups were converted to mesylate.

[0272] Step 2: 30 g of 1,3-bis(trifluoromethyl)benzene, 15 g of ethanol, 100 g of the product obtained in step 1 and 11.5 g of 4-amino-2,2,6,6-tetramethylpiperidine (73.6 mmol) were charged into a 4-necked round-bottom flask having a capacity of 0.5 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel. The resulting mixture was heated to 70° C. and cooled to room temperature after vigorous stirring for 20 hours, and 100 g of a solution of potassium hydroxide in ethanol (10 wt.%) and 50 g of 1,3-bis(trifluoromethyl)benzene were added. After stirring for 3 hours, 100 g of water was added to the reaction mass, and the organic phase thus formed was separated and additionally washed 3 times by treating with 100 g of water and 50 g of ethanol. Finally, the lower organic phase was separated and distilled under reduced pressure (T=80° C., P=2 Pa) to remove the solvent, providing 103.5 g of the target PFPE-amine derivative, the structure of which is shown by 1 HNMR analysis confirmed.

[0273] Step 3: Into a 100 ml 4-necked round-bottom flask equipped with a condenser, a mechanical stirrer, a dropping funnel and a thermometer probe, 90 g of the product obtained in step 2, 3.5*10 -2 g 2,6-di-tert-butyl-4-methylphenol (BHT), 8.6*10 -2 g SnapCure TM 1030, and the obtained mixture was heated to 50°C.

[0274] Then, 10.8 g of 2-isocyanatoethyl methacrylate (69.4 mmol) was slowly added, the temperature was raised to 60° C., and the reaction mixture was kept under vigorous stirring for 3 hours. Thereafter, 1.0 g of methanol was added, the reaction mixture was stirred for another 2 hours and dried under reduced pressure (T=60° C., P=2 Pa), obtaining 98.1 g of composition A.

[0275] Example 2 - Synthesis of Composition B

[0276] Step 1: A 4-necked round-bottom flask with a capacity of 0.5 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel was charged with 250 g (EW = g / mol 871; 287.0 meq) ZDOL, 125 g 1,3-bis(trifluoromethyl)benzene and 18.7 g of a solution of sodium methoxide in methanol (25 wt.%). The flask was then heated to 60°C and kept under stirring for 1 hour under nitrogen and a gentle nitrogen flow. Thereafter, 9.7 g methyl chloroacetate (89.0 meq) was added and the reaction mixture was kept under stirring for another 4 hours.

[0277] Then, 100 g of 4M aqueous HCl and 10 g of methanol were added to the reaction mixture and the organic phase thus formed was separated.After distillation of the fluorinated solvent under reduced pressure (T=80°C, P=2 Pa), 253.9 g of a clear liquid were separated and characterized.

[0278] 1 H-NMR and 19 F-NMR analysis confirmed that the product obtained was ZDOL, in which 29% of the hydroxymethyl groups were converted to the corresponding methyleneoxymethyl acetate.

[0279] Step 2: A 4-necked round-bottom flask with a capacity of 0.25 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel was charged with 40 g of 1,3-bis(trifluoromethyl)benzene, 11.0 g (70.0 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine, and 150 g of the product obtained in step 1. The resulting mixture was heated to 70° C. and maintained under vigorous stirring for 36 hours. The solvent and excess 4-amino-2,2,6,6-tetramethylpiperidine were removed by distillation under reduced pressure (T=80° C., P=2 Pa), providing 154.8 g of a transparent liquid, which was characterized.

[0280] 1 H NMR and FT-IR analyses confirmed the quantitative conversion of the methyl ester to the target amide.

[0281] Step 3: Into a 100 ml 4-necked round-bottom flask equipped with a condenser, a mechanical stirrer, a dropping funnel and a thermometer probe, 100 g of the product obtained in step 2 was charged, 3.9*10 -2 g 2,6-di-tert-butyl-4-methylphenol (BHT), 9.7*10 -2 g SnapCure TM 1030, and the obtained mixture was heated to 50°C.

[0282] Then, 12.3 g of 2-isocyanatoethyl methacrylate (79.1 meq) was slowly added, the temperature was raised to 60° C., and the reaction mixture was kept under vigorous stirring for 3 hours. Thereafter, 1.2 g of methanol was added, the reaction mixture was stirred for another 2 hours and dried under reduced pressure (T=60° C., P=2 Pa), obtaining 110.7 g of composition B.

[0283] Example 3 - Synthesis of Composition C

[0284] Into a 3-necked round-bottom flask having a capacity of 50 ml, equipped with a condenser, a thermometer probe, a rubber septum and a magnetic stirrer, 40 g of the product obtained in step 2 of Example 2, 6.50 g of 3-(trimethoxysilyl)propyl isocyanate (31.6 mmol) were charged and the obtained mixture was heated to 50° C. Then, 187 μl of a solution of DBTDL in ethyl methyl ketone (20 wt.%) was added, the temperature was raised to 60° C. and the reactants were kept under vigorous stirring for 3 hours. Thereafter, 0.5 g of methanol was added, the reaction mixture was stirred for another 2 hours and dried under reduced pressure (T=60° C., P=2 Pa), obtaining 45.1 g of composition C.

[0285] Example 4 - Synthesis of Composition D

[0286] Step 1: A 4-necked round-bottom flask with a capacity of 0.5 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel was charged with 200 g (EW = g / mol 871; 229.6 meq) ZDOL, 150 g 1,3-bis(trifluoromethyl)benzene and 52.1 g of a solution of sodium methoxide in methanol (25 wt.%). The flask was then heated to 60°C and kept under stirring for 1 hour under nitrogen and a gentle nitrogen flow. Thereafter, 26.7 g methyl chloroacetate (245.7 meq) was added and the reaction mixture was kept under stirring for another 4 hours.

[0287] Then, 150 g of 4M aqueous HCl and 20 g of methanol were added to the reaction mixture and the organic phase thus formed was separated.After distillation of the fluorinated solvent under reduced pressure (T=80° C., P=2 Pa), 211.5 g of a clear liquid were separated and characterized.

[0288] 1 H-NMR and 19 N-NMR analysis confirmed 100% conversion of the hydroxymethyl group to the corresponding methyleneoxymethyl acetate.

[0289] Step 2: A 4-necked round-bottom flask with a capacity of 0.25 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, a thermometer probe and a dropping funnel was charged with 60 g of 1,3-bis(trifluoromethyl)benzene, 7.7 g (49.3 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine and 150 g of the product obtained in step 1. The resulting mixture was heated to 70° C. and maintained under vigorous stirring for 36 hours. The solvent was removed by distillation under reduced pressure (T=80° C., P=2 Pa), providing 152.1 g of a transparent liquid, which was characterized.

[0290] 1 H NMR confirmed 30% conversion of the methyl ester groups to the desired amide.

[0291] Step 3: A 4-necked round-bottom flask with a capacity of 0.25 L, maintained under a nitrogen atmosphere and equipped with a condenser, a mechanical stirrer, and a thermometer probe was charged with 100 g of 1,3-bis(trifluoromethyl)benzene, 50 g of the product obtained in Step 2 of Example 4, and 2.4 g (40.8 mmol) of oxirane-2-amine. The resulting mixture was heated to 65° C. and maintained under vigorous stirring for 35 hours. The solvent was removed by distillation under reduced pressure (T=80° C., P=2 Pa), providing 50.2 g of composition D.

[0292] Test A - UV resistance evaluation

[0293] Composition (A) was prepared by mixing 90 wt.% Fluorolink(R) MD700 and 10 wt.% of composition B according to the invention prepared as described in Example 2.

[0294] Will contain 100wt.% The composition (B) of MD700 was used for comparison.

[0295] The test specimens were coated with the composition according to the invention (A) and the comparative composition (B) and then exposed to UV rays for 300 hours (QUV test exposure). After this period of time, the coating was visually inspected after the QUV test exposure and the gloss was measured under the following settings (ASTM D2457-60°):

[0296] UVB: 310nm;

[0297] Irradiance 0.63W / m 2 ;

[0298] Watering time: 3 minutes / hour;

[0299] Dark plate temperature 63℃.

[0300] The coating obtained with the composition according to the invention (A) appears homogeneous, whereas the coating obtained with the comparative composition (B) exhibits some damaged areas with a gloss value below 100.

Claims

1. A (per)fluoropolyether polymer [polymer (P P )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), in * one of the chain ends comprises at least one, preferably from 1 to 3, groups (group [I]) selected from: alkoxysilanes [group (Si)] or crosslinkable groups, preferably selected from unsaturated moieties [group (U)] and epoxides [group (E)]; and * The other chain end comprises at least one, preferably from 1 to 3, groups selected from the group consisting of optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole (group [II]).

2. The polymer according to claim 1 (P P ),in, Chain (R pf ) is a chain with the following formula -D′-(CFX′) z1 O(R f )(CFX) z2 -D- in z1 and z2, identical or different from each other, are equal to or greater than 1, preferably from 1 to 10, more preferably from 1 to 3; X and X', identical or different from each other, are -F or -CF3, Provided that when z1 and / or z2 is greater than 1, X and X' are -F; D and D', identical or different from each other, are a sigma bond or a hydrogenated alkylene chain containing from 1 to 6 carbon atoms and even more preferably from 1 to 3 carbon atoms, said alkyl chain optionally substituted with at least one perfluoroalkyl group containing from 1 to 3 carbon atoms; (R f ) comprises, preferably consists of, a repeating unit R°, said The repeating units are independently selected from the group consisting of: (i) -CFXO-, where X is F or CF3; (ii) -CFXCFXO-, where X, being the same or different at each occurrence, is F or CF3, provided that at least one of X is -F; (iii) -CF2CF2CW2O-, wherein each W, being the same as or different from each other, is F, Cl, or H; (iv) -CF2CF2CF2CF2O-; (v)-(CF2) j -CFZ-O-, wherein j is an integer from 0 to 3 and Z is a molecule having the general formula -OR (f-a) -T group, where R (f-a) is a fluoropolyoxyalkylene chain containing from 0 to 10 repeating units selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and T is a C1-C3 perfluoroalkyl group.

3. The polymer according to claim 1 or 2 (P P ),in, The group [I] is linked to the chain (R pf ).

4. The polymer according to claim 3 (P P ),in, The linking group conforms to the following formula: *-(R a ) t -(R b ) v -(R c ) u -§ in: *Indicates to chain (R pf ) § indicates a bond to group [I]; R a is a poly(oxy)alkylene chain; t is 0 or an integer from 1 to 15, preferably from 1 to 10; v is 0 or 1; R b is a group having the formula: (R b -I)-O-C(=O)-NH-(CH h ) e - (R b -II)-C(=O)-NR'-(CH h ) f - (R b -III)-O-(CH2) g -C(=O)- in e is an integer from 1 to 6, R' is H or a straight or branched chain alkyl group having from 1 to 6 carbon atoms, f is an integer from 1 to 4, g is an integer from 1 to 4, and Each h is independently 0 or an integer equal to 1 or 2, provided that when h is 0, e and f are each independently 1; R c is a straight or branched alkyl chain having from 1 to 12 carbon atoms, optionally containing one or more oxygen atoms, or an optionally substituted aliphatic cycloalkyl containing 5 or 6 members; and u is either 0 or 1.

5. The polymer according to claim 4 (P P ),in, (R a ) is a poly(oxy)alkylene chain comprising from 1 to 50 fluorine-free oxyalkylene units.

6. A polymer according to any one of the preceding claims (P P ),in, Group [I] is group (U) and said group (U) is selected from the group consisting of: (U-I)-O-C(=O)-CR H =CH2 (U-II)-OC(=O)-NH-CO-CR H =CH2 (U-III)-O-C(=O)-R A -CR H =CH2 in R H is H or C1-C6 alkyl; R A Is the choice free (R A -I) and (R A -II) Groups composed of: (R A -I) in Each j5 is independently 0 or 1, and R B is a divalent, trivalent or tetravalent group selected from the group consisting of: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 an aromatic or alkylaromatic group, optionally containing at least one heteroatom selected from N, O and S; (R A −II) in j6 is 0 or 1; Each j7 is independently 0 or 1; R B ' is a divalent, trivalent or tetravalent group selected from the group consisting of: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 an aromatic or alkylaromatic group, optionally containing at least one heteroatom selected from N, O and S; and R B* With the above for R B ' defined as having the same meaning or it is a compound having the formula (R B -I) group: in The substituent U is selected from the groups (UI) to (U-III) as defined above, and * and # indicate the difference between the above formula (R A -II) is the bonding site of the nitrogen atom in the 7. The polymer according to any one of claims 1 to 5 (P P ),in, The group [I] is a group (Si) and the group (Si) conforms to the following formula: -Si-(OR 30 )3 Where R 30 is a straight or branched alkyl chain having from 1 to 12 carbon atoms.

8. The polymer according to any one of claims 1 to 5 (P P ),in, Group [I] is group (E) and group (E) is bonded to chain (R) via a linking group conforming to the formula pf ): *-(R a ) t -(R c ) u -§ Where *, §, R a ,t,R c and u have the meaning according to claim 4.

9. A polymer according to any one of the preceding claims (P P ),in, Group [II]: - is bonded to the chain via a group having the formula (R pf ) of each of the groups D or D': *-(R a ) t -NH-§ or *-(R a ) t -O-§ in: *Indicates to chain (R pf ), and § indicates a bond to group [II], and R a and t each have the meaning as claimed in claim 4 and Chain (R pf ) wherein the groups D and D' are each a hydrogenated alkylene chain containing 1 to 6 carbon atoms; or - is bonded to the chain via a group having the formula (R pf ) in each of the groups D or D': -(R a ) t -(R*) p C(=O)NH-(R**) q or -(R a ) t -(R***) r C(=O)O-(R****) s - in p, q, r and s are each independently 0 or an integer from 1 to 6, R a and t have the meanings defined above and R*, R**, R*** and R**** are each independently a straight or branched alkyl chain containing from 1 to 6 carbon atoms, and Chain (R pf ) each group D and D' is a sigma bond.

10. A polymer according to any one of the preceding claims (P P ),in, The group [II] is selected from substituted piperidine, substituted pyridine and substituted pyrrole.

11. A polymer according to any one of the preceding claims (P P ),in, Group [II] is a derivative of 4-amino-2,2,6,6-tetramethyl-piperidine.

12. A composition [composition (C POL )], which contains: - A polymer according to any one of claims 1 to 11 (P P ); -(Per)fluoropolyether polymers [polymers (P U )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein the two chain ends comprise groups having formula [I] as defined above; and -(Per)fluoropolyether polymers [polymers (P N )], which comprises a (per)fluoropolyoxyalkylene chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein the two chain ends comprise groups having formula [II] as defined above.

13. The composition according to claim 12 (C POL ), the composition (C POL ) further comprises a (per)fluoropolyether polymer [polymer (P x )], the (per)fluoropolyether polymer comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein one chain end comprises a perfluoroalkyl group and the other chain end comprises at least one group having formula [I] or a group having formula [II] as defined in any one of claims 1 or claims 6 to 11.

14. A composition [composition (INT)] comprising: -(Per)fluoropolyether polymers [polymers (P INT )], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein one of the chain ends comprises a residue having the formula -OH or -C(=O)OR 10 A group in which R 10 is H or a linear or branched alkyl chain containing from 1 to 6 carbon atoms and the other chain end containing the group [II]; - (per)fluoropolyether polymers [polymer PFPE] comprising (per)fluoropolyether chains having two chain ends [chains (R pf )], the two chain ends are bonded to the chain (R pf ) on opposite sides, wherein the two chain ends contain -OH or -C(=O)OR 10 A group in which R 10 As defined above; and -(Per)fluoropolyether polymers [polymers (P II )], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein the two chain ends comprise groups [II].

15. The composition according to claim 14 [composition (INT)], wherein Group [II] is as defined in any one of claims 9 to 11.

16. A (per)fluoropolyether polymer [polymer (P INT )], which comprises a (per)fluoropolyether chain having two chain ends [chain (R pf )], the two chain ends are bonded to the chain (R pf ), wherein one of the chain ends comprises a residue having the formula -OH or -C(=O)OR 10 A group in which R 10 is H or a straight or branched alkyl chain containing from 1 to 6 carbon atoms and the other chain end contains the group [II].

17. The (per)fluoropolyether polymer according to claim 16 [polymer (P INT )],in, Group [II] is as defined in any one of claims 9 and 10.

18. A method for synthesizing the composition (INT) according to claims 14 and 15, comprising: (i) providing a method comprising: providing a (per)fluoropolyether chain [chain (R pf )], the (per)fluoropolyether polymer [polymer PFPE] having a (per)fluoropolyether chain bonded to the chain (R pf ) on opposite sides, the two chain ends comprising a group selected from the following: -OH or -C(=O)OR 10 , where R 10 is H or a straight or branched alkyl chain containing from 1 to 6 carbon atoms; (ii) if present, converting at least a portion of the -OH group into a leaving group for a nucleophilic substitution reaction or into a group having the formula -O(R***) r C(=O)O-(R V ), wherein R*** and r are as defined above, R V is an alkyl chain containing from 1 to 3 carbon atoms; (iii) contacting the PFPE polymer of step (i) or the composition obtained in step (ii) with at least one compound comprising a group having the formula -OH or -NH2 and a group derived from one of the following: optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole, thereby obtaining a composition [composition (INT)].

19. A method for synthesizing a composition according to claim 12 or 13 (C POL ), the method comprising: (iv) providing a composition (INT) according to claim 13 or 14 and contacting the composition (INT) with at least one compound selected from the group consisting of: - a compound [A] carrying at least one group (U) as defined above and at least one of the following: a halogen atom, an isocyanate group or an amino group; or - a compound [B] carrying at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or - a compound [C] carrying at least one group (Si) as defined above and at least one of the following: an isocyanate group or an amino group, Thus, the composition (C POL ); or (i*) providing a (per)fluoropolyether chain [chain (R pf )], the (per)fluoropolyether polymer [polymer PFPE] having a (per)fluoropolyether chain bonded to the chain (R pf ) on opposite sides of the two chain ends, the two chain ends contain a group selected from the following: -OH or -C(=O)OR 10 , where R 10 is H or a straight or branched alkyl chain containing from 1 to 6 carbon atoms; (ii*) if present, converting at least a portion of the -OH groups into leaving groups for nucleophilic substitution reactions or into groups having the formula -O(R***) r C(=O)O-(R V ), wherein R*** and r are as defined above, R V is an alkyl chain containing from 1 to 3 carbon atoms; (iii*) contacting the PFPE polymer of step (i) or the composition obtained in step (ii) with at least one compound comprising a group having the formula -OH or -NH2 and a group derived from one of the following: an optionally substituted piperidine, an optionally substituted pyridine or an optionally substituted pyrrole, thereby obtaining composition (INT); and (iv*) contacting the composition (INT) obtained in step (iii) with at least one compound selected from the group consisting of: - a compound [A] carrying at least one group (U) according to claim 6 and at least one of the following: a halogen atom, an isocyanate group or an amino group; or - a compound [B] carrying at least one group (E) according to claim 8 and at least one halogen atom or at least one isocyanate group; or - a compound [C] carrying at least one group (Si) according to claim 7 and at least one of the following: an isocyanate group or an amino group, Thus, the composition (C POL ).

20. The method according to claim 19, wherein: In step (iv) or step (iv*), compound [A] conforms to the following formula: O=C=N-R 20 -R 21 -CR H =CH2 in R H has the same meaning as defined above for group (U); R 20 is a straight or branched alkyl chain having from 1 to 6 carbon atoms, optionally substituted by a trialkoxy-silyl-containing group; R 21 It has the formula -OC(=O)-, -OC(=O)-NH-CO-, -OC(=O)-R A - a divalent group, wherein R A As defined above for group (U-III).

21. The method according to any one of claims 18 to 20, wherein: The compound comprises a group having the formula -OH or -NH2 and a group derived from one of the following: an optionally substituted piperidine, an optionally substituted pyridine or an optionally substituted pyrrole, selected from 4-amino-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 2-(2,2,6,6-tetramethyl-piperidin-4-yl)-ethanol.

22. A composition [composition (DIL)] comprising: At least one polymer according to any one of claims 1 to 11 (P P ) or the composition according to any one of claims 12 and 13 (C POL );as well as At least one solvent (S) preferably selected from (per)fluoropolyether polymers having at least one functional group at the end of the chain selected from: an unsaturated group, an alkoxysilane group or an epoxy group.

23. A composition [composition (C F )], comprising at least one polymer (P P ) of the composition according to claim 22 (DIL), and at least one UV-curable component, The polymer (P P ) in the composition (C F ) is based on the composition (C F )'s total weight ranges from 0.01wt.% to 8.00wt.%.

24. A method for providing a clear coating on at least one surface of a substrate, the method comprising: (i) providing at least one substrate having at least one surface; as well as (ii) contacting the at least one surface with at least one selected from the group consisting of: a polymer (P) according to any one of claims 1 to 11 P ), according to any one of claims 12 and 13 (C POL ), the composition according to claim 22 (DIL) or the composition according to claim 23 (C F ).

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