(Per)fluoropolyether polymers and uses thereof

Abstract

This invention relates to compositions comprising (all)fluoropolyether polymers having antimicrobial properties, methods for their preparation, and uses thereof in providing compositions having antimicrobial properties.

Description

[0001] Cross-referencing of related patent applications

[0002] This application claims priority to patent application No. 20201713.3 filed in Europe on October 14, 2020, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] This invention relates to compositions comprising novel (all)fluoropolyether polymers having antimicrobial properties, methods for their preparation, and uses thereof to provide compositions having antimicrobial properties. Background Technology

[0004] The use of (per)fluoropolyether (PFPE) polymers as components in the production of antifouling coating compositions for coating different types of substrates is known in the art. For example, EP 3312242 (3M Innovative Properties Company) discloses protective coating compositions with mixed functions, wherein PFPE is mentioned in, for example, the main chain; WO2016 / 079195 (Solvay Specialty Polymers Italy S.pA) discloses zwitterionic derivatives of PFPE disclosed as suitable for coating applications; WO 2019 / 106366 (Sphere Fluidic Ltd) discloses surfactants comprising a perfluoropolyether structure.

[0005] In addition, coatings for security documents (such as noteworthy banknotes) using such PFPE polymers are disclosed, for example, in WO2012 / 055885 (Oberthur Fiduciaire SAS) and WO 2013 / 045496 (Oberthur Fiduciaire, Solvay Specialty Polymers Italy).

[0006] Coatings with antibacterial and / or antiviral properties have also been disclosed in the art, for example in JP2014237227 (Central Glass Corporation), TW201512339 (Alpha Bright International Ltd.), US 2015 / 191608 (Seoul National University Industrial Academic Cooperation Group; Samsung Electronics Co., Ltd.; Snu R&DB Foundation); WO 2016 / 153230 (Ceko Ltd.); CN105176342 (Xiamen Borns Applied Materials Technology Co., Ltd.).

[0007] However, the recent spread of coronavirus disease (COVID-19) caused by SARS-CoV-2 has increased the importance of developing compositions with antimicrobial properties (including but not limited to antibacterial, antiviral and antifungal properties) suitable for coating a variety of substrates, notably including paper, banknotes, glass and plastics, and notably for use in electronic and smart devices. Summary of the Invention

[0008] Within this framework, the applicant faces the challenge of developing novel polymers with antimicrobial properties.

[0009] More specifically, the applicant has developed novel (per)fluoropolyether (PFPE) polymers with antimicrobial properties provided by specific functional groups bonded to the (per)fluoropolyether backbone.

[0010] Advantageously, the chemical structure of the novel PFPE polymer according to the invention endows the polymer with antimicrobial properties while providing coating properties such as significant transparency as well as water and oil repellency.

[0011] Therefore, in a first aspect, the present invention relates to a (per)fluoropolyether polymer [(polymer (P P )], which contains a (per)fluoropolyether chain [chain (R)] with two chain ends [chain (Re)]. pf The two chain ends [chain(Re)] are bonded to the chain(R). pf On the opposite side of ), where:

[0012] - The first chain end contains at least one quaternary ammonium salt group [group (N + The group and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable groups, preferably selected from unsaturated moieties [group (U)] and epoxy groups [group (E)]; and

[0013] - The second chain end contains a perfluoroalkyl or quaternary ammonium salt group [group (N + [ ] and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moiety [group (U)] and epoxy [group (E)].

[0014] In a preferred aspect, the present invention relates to bifunctional (per)fluoropolyether polymers [polymer (P P-bif )], which contains a (per)fluoropolyether chain [chain (R)] with two chain ends [chain (Re)]. pf The two ends of the chain are bonded to the chain (R). pfOn opposite sides of the chain, the two chain ends contain at least one quaternary ammonium salt group [group (N + The group and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moiety [group (U)] and epoxy [group (E)].

[0015] In another preferred aspect, the present invention relates to a monofunctional (per)fluoropolyether polymer [polymer (P P -monof )], which contains a (per)fluoropolyether chain [chain (R)] with two chain ends [chain (Re)]. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one chain end has a perfluoroalkyl group and the other chain end contains at least one quaternary ammonium salt group [group (N + [ ] and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moiety [group (U)] and epoxy [group (E)].

[0016] The above polymer (P) P-bif ) and polymers (P P-monof Each is advantageously provided either as the polymer itself or as a composition comprising a mixture of the two polymers.

[0017] Therefore, in another aspect, the present invention relates to a composition [composition (C)] P ], which includes:

[0018] -(Fully)Fluoroether Polymers[Polymer(P P-bif )], which contains a (per)fluoropolyether chain [chain (R)] with two chain ends [chain (Re)]. pf The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, the two chain ends contain at least one quaternary ammonium salt group [group (N + The group and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable groups, preferably selected from unsaturated moieties [group (U)] and epoxy groups [group (E)]; and

[0019] -(Fully)Fluoroether Polymers[Polymer(P P-monof )], which contains a (per)fluoropolyether chain [chain (R)] with two chain ends [chain (Re)]. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one chain end has a perfluoroalkyl group and the other chain end contains at least one quaternary ammonium salt group [group (N+ [ ] and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moiety [group (U)] and epoxy [group (E)].

[0020] According to another preferred embodiment, the composition (C) P The polymer (P) comprises up to 85 wt.%, preferably up to 95 wt.%, and even more preferably up to 99 wt.%. P-bif The composition (C) P Up to 100 wt.% of the remaining portion is composed of the polymer (P) P-monof It can be provided by the byproducts of chemical reactions.

[0021] The composition of the present invention (C) P It can be used to provide coatings with antimicrobial properties, or it can be used as an antimicrobial component (also known as an "additive") in a solvent [solvent(S)].

[0022] Therefore, in a second aspect, the present invention relates to a composition [composition (DIL)] comprising the composition (C) as defined above. P The solvent (S) is selected from the group consisting of: (per)fluorinated fluids, optionally containing at least one unsaturated portion; and hydrogenated fluids, optionally containing at least one unsaturated portion.

[0023] In a third aspect, the present invention relates to the composition (C) as described above. P (or composition) used to impart antimicrobial properties to a substrate. Detailed Implementation

[0024] For the purposes of this specification and the following claims:

[0025] - The use of parentheses around identifying symbols or numbers, such as in expressions like "polymer (P)," serves only to better distinguish the symbol or number from the rest of the text, and therefore the parentheses may be omitted;

[0026] - The acronym "PFPE" stands for "(per)fluoropolyether" and when used as a noun, it is intended to refer to either the singular or plural form depending on the context;

[0027] - The term "(per)fluorinated polyether" is intended to indicate a polyether polymer that is fully or partially fluorinated;

[0028] - Unless otherwise stated, the term "polymer (P)" is used to indicate that the polymer is a polymer (P) P ")" is intended to represent polymer (P P-bif) and polymers (P P -monof Both;

[0029] The statement "has antimicrobial properties" is intended to indicate that the polymer can kill or prevent the growth of microorganisms such as bacteria, viruses and fungi.

[0030] Preferably, in polymer (P) P In ), the chain (R) pf ) is a chain with the following formula

[0031] -D-(CFX # ) z1 -O(R f (CFX) * ) z2 -D * -

[0032] in

[0033] z1 and z2 are the same or different from each other, and are equal to or greater than 1;

[0034] X # and X * Whether they are the same or different, it is either -F or -CF3.

[0035] The premise is that X is greater than 1 when z1 and / or z2. # and X * It is -F;

[0036] D and D*, which may be the same as or different from each other, are σ-bonded alkylene chains containing 1 to 6 carbon atoms and even more preferably 1 to 3 carbon atoms, said alkyl chains being optionally substituted by at least one perfluoroalkyl group containing 1 to 3 carbon atoms;

[0037] (R f It includes repeating units R°, preferably composed of them, said repeating units being independently selected from the group consisting of the following items:

[0038] (i)-CFXO-, where X is F or CF3;

[0039] (ii) -CFXCFXO-, where X, which is the same or different each time it appears, is F or CF3, provided that at least one X is -F;

[0040] (iii)-CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H;

[0041] (iv)-CF2CF2CF2CF2O-;

[0042] (v)-(CF2) j-CFZ-O-, where j is an integer from 0 to 3 and Z is a set of integers with the general formula -OR (f-a) -T groups, where R (f-a) It is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units, wherein the repeating units are selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and T is a C1-C3 perfluoroalkyl group.

[0043] Preferably, z1 and z2 are the same as or different from each other, ranging from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3.

[0044] More preferably, D and D*, which may be the same as or different from each other, are σ bonds or chains having the formula -CH2-, -CH2CH2- or -CH(CF3)-.

[0045] Preferably, the chain (R) f It conforms to the following formula:

[0046] (R f -I)

[0047] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]-

[0048] in

[0049] -X 1 Independently selected from -F and -CF3,

[0050] -X 2 X 3 They may be the same as or different from each other and, each time they appear, are independently -F or -CF3, provided that at least one of X is -F;

[0051] -g1, g2, g3, and g4, which may be the same as or different from each other, are independent integers ≥0, such that g1+g2+g3+g4 is in the range of 2 to 300, preferably from 2 to 100; if at least two of g1, g2, g3, and g4 are not zero, then the different repeating units are statistically distributed along the chain in general.

[0052] More preferably, chain (R) f Selected from chains having the following formula:

[0053] (Rf -IIA)

[0054] -[(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 400 and 5,000; both a1 and a2 are preferably not zero, wherein the ratio a1 / a2 is preferably between 0.1 and 10;

[0057] (R f -IIB)

[0058] -[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]-

[0059] in:

[0060] b1, b2, b3, b4 are independently integers ≥ 0, such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably, b1 is 0, b2, b3, b4 > 0, wherein the ratio b4 / (b2+b3) ≥ 1;

[0061] (R f -IIC)

[0062] -[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]-

[0063] in:

[0064] cw = 1 or 2;

[0065] c1, c2, and c3 are independently integers ≥ 0, which are selected such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000; preferably, c1, c2, and c3 are all > 0, wherein the ratio c3 / (c1+c2) is generally less than 0.2.

[0066] (R f -IID)

[0067] -[(CF2CF(CF3)O) d ]-

[0068] in:

[0069] d is an integer greater than 0, such that the number-average molecular weight is between 400 and 10,000, preferably between 400 and 5,000;

[0070] (R f -IIE)

[0071] -[(CF2CF2C(Hal*)2O) e1 -(CF2CF2CH2O) e2 -(CF2CF2CH(Hal*)O) e3 ]-

[0072] in:

[0073] -Hal*, which may be the same or different each time it appears, is a halogen selected from fluorine and chlorine atoms, preferably fluorine atoms;

[0074] -e1, e2, and e3, which may be the same as or different from each other, are independent integers ≥ 0 such that the sum of (e1 + e2 + e3) is included between 2 and 300.

[0075] Even more preferably, chain (R) f ) conforms to the following formula (R) f -III):

[0076] (R f -III)

[0077] -[(CF2CF2O) a1 (CF2O) a2 ]-

[0078] in:

[0079] -a1 and a2 are integers >0, such that the number average molecular weight is between 400 and 10,000, preferably between 400 and 5,000, wherein the ratio a1 / a2 is generally between 0.1 and 10, more preferably between 0.2 and 5.

[0080] Preferably, the group (N) + Preferably selected from the group consisting of the following items, more preferably composed of the following items:

[0081] (N + -I)

[0082] -N + (R h1 (R) h2 (R) h3 )

[0083] in

[0084] R h1 、、R h2 and R h3 Each is independently selected from straight-chain or branched alkyl chains having 1 to 20, more preferably 1 to 18, and even more preferably 3 to 18 carbon atoms, said alkyl chain optionally substituted with one or more -OH groups; benzyl, or R h1 R h2 and R h3 At least two of them, together with nitrogen atoms, form an aliphatic ring containing 4 or 5 carbon atoms and nitrogen atoms.

[0085] Preferably, R h1 R h2 and R h3 At least one of them is a straight-chain or branched alkyl chain having 6 to 20, more preferably 6 to 18 carbon atoms.

[0086] Preferably, R h1 R h2 and R h3 At least two of them are independently straight-chain or branched alkyl chains having 1 to 6, more preferably 1 to 4 carbon atoms. Preferably, the polymer (P) P-bif ) and polymers (P P-monof Any one of them contains a group (N) + Counterions.

[0087] More preferably, the counterion is selected from halogen atoms, such as chlorine, iodine, bromine; methanesulfonate and toluenesulfonate. More preferably, halogen atoms.

[0088] Preferably, in polymer (P) P ), polymer (P) P-bif ) and polymers (P P-monof In any of the following, the chain (Re) is formed by a σ bond or by a poly(oxy)alkylene chain [chain (R) a )] bonded to the chain (R) pf ).

[0089] More preferably, the chain (R) a It comprises 1 to 50 fluorine-free oxyalkylene units, which may be the same as or different from each other and are selected from -OCH(J)CH(J*)-, wherein J and J* are each independently selected from hydrogen atoms, straight-chain or branched alkyl or aryl groups, preferably hydrogen atoms, methyl, ethyl or phenyl.

[0090] Preferably, the polymer (P) P ), polymer (P) P-bif ) and polymers (P P-monofAny of the following contains the group (U) at its chain end.

[0091] Preferably, the group (U) is selected from the group consisting of the following items:

[0092] (UI)-OC(=O)-CR H =CH2

[0093] (U-II)-OC(=O)-NH-CO-CR H =CH2

[0094] (U-III)-OC(=O)-R A -CR H =CH2

[0095] in

[0096] R H It is an H or C1-C6 alkyl group;

[0097] R A It is a matter of choice (R) A -I) and (R) A Group -II) consists of:

[0098] (R A -I)

[0099]

[0100] in

[0101] Each j5 is independently 0 or 1, and

[0102] R B It is a divalent, trivalent, or tetravalent group selected from the group consisting of the following items: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 An aromatic or alkyl aromatic group, optionally containing at least one heteroatom selected from N, O and S;

[0103] (R A -II)

[0104]

[0105] in

[0106] j6 is 0 or 1;

[0107] Each j7 is independently 0 or 1;

[0108] R B’It is a divalent, trivalent, or tetravalent group selected from the group consisting of the following items: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 An aromatic or alkyl aromatic group, optionally comprising at least one heteroatom selected from N, O, and S; and

[0109] R B* Having the above for R B’ The same meaning as defined or that which has the formula (R) B -I) group:

[0110]

[0111] in

[0112] The substituent U is selected from groups (UI) to (U-III) as defined above.

[0113] and

[0114] * and # indicate the above formula (R) A -II) The bonding site with nitrogen atoms.

[0115] Preferably, when the chain (Re) contains a group (U), the chain (Re) is bonded to the chain (R) by a group having the following formula. pf ):

[0116] *-R 10 -NH-C(=O)-OR 11 -#

[0117] in

[0118] * indicates a bond to the U group.

[0119] # indicates a chain (R) pf ) key

[0120] R 10 It is a straight-chain or branched alkyl chain having 1 to 6 carbon atoms, optionally substituted with a group containing a trialkoxy-silyl group;

[0121] R 11 It is a σ bond or a poly(oxy)alkylene chain [chain (R a ^)], wherein the chain (R) a ^) contains from 1 to 50 fluorine-free oxyalkylene units, which may be the same as or different from each other and are selected from -CH(J*)CH(J)-O, wherein J and J* are each independently selected from hydrogen atoms, straight-chain or branched alkyl or aryl groups, preferably hydrogen atoms, methyl, ethyl or phenyl.

[0122] According to an alternative embodiment, the polymer (P) P-bif ) and polymers (P P-monof Each of them contains a group (Si) at its chain end.

[0123] Preferably, the group (Si) is a group having the following formula:

[0124] -Si-(OR 30 )3

[0125] Among them, R 30 It is a straight-chain or branched alkyl chain having 1 to 12 carbon atoms.

[0126] As defined above, polymers (P) P-bif It is advantageous to begin preparation from a (per)fluoropolyether (PFPE) polymer ([PFPE polymer(bif)]), said (per)fluoropolyether polymer comprising (per)fluoropolyether chains [chain(R)] having two chain ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), both chain ends contain at least one -OH group.

[0127] As defined above, polymers (P) P-monof It is advantageous to begin preparation from a (per)fluoropolyether (PFPE) polymer ([PFPE polymer(monof)]), said (per)fluoropolyether polymer comprising (per)fluoropolyether chains [chain(R)] having two chain ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one of the chain ends contains at least one -OH group and the other chain end contains a perfluoroalkyl group.

[0128] The polymer of the present invention ( PP-bif ) and (P P-monof ), and compositions comprising them can be prepared from reactants and according to methods including reactions known in the art.

[0129] For example, the first intermediate composition [composition(INT)] 1 The [M1] can be prepared by method [method (M1)], which includes the following steps:

[0130] (i) Provide at least one PFPE polymer selected from the group consisting of: PFPE polymer (bif) or PFPE polymer (monof) as defined above;

[0131] (ii) Converting at least some of the -OH groups of the PFPE polymer to epoxy groups to obtain a composition (INT1) comprising:

[0132] - Contains chains with two ends (R) pf (Per)fluoropolyether polymers [polymer P] bif-INT1 The two ends of the chain are bonded to the chain (R). pf On the opposite side of the chain, two of the chain ends contain epoxy groups.

[0133] -Optionally with (fully) fluoropolyether polymers [polymer P] monof-INT1 The polymer comprises chains (R) having two ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one end of the chain contains an epoxy group and the other end contains a perfluoroalkyl group.

[0134] The composition (INT1) constitutes another aspect of the present invention.

[0135] The (per)fluoropolyether (PFPE) polymer used as a starting material in step (i) is preferably a PFPE polymer (bif) or a PFPE polymer (monof) conforming to the following formula:

[0136] (PFPE-i)T-(R pf )-[OCH(J)CH(J*)] t2 -OH

[0137] in

[0138] (R pf As defined above,

[0139] T is -OH, perfluoroalkyl, or a group having the following formula.

[0140] HO-[CH(J*)CH(J)O] t1 -,

[0141] t1 and t2 are each independently 0 or an integer from 1 to 50, and

[0142] J and J* are each defined independently as above for the chain (Ra).

[0143] Preferably, step (ii) is performed by contacting the PFPE polymer (bif) or PFPE polymer (monof) with at least one epoxy-containing compound [compound (E)].

[0144] Preferably, the compound (E) is selected from the group consisting of, and preferably composed of: epichlorohydrin, epibromopropane, and epiiodopropane.

[0145] Those skilled in the art will understand that, in step (ii), preferably, about 100% of the -OH groups of the starting PFPE polymer (monofunctional PFPE or bifunctional PFPE) are converted to epoxy groups.

[0146] However, partial conversion of the -OH group can also be achieved. In this embodiment, in subsequent steps of the above method, the resulting polymer will contain a statistical combination of different substituents at its chain ends.

[0147] Advantageously, the second intermediate composition [composition (INT2)] can be prepared by a method [method (M2)], which includes:

[0148] (iii) Contact the composition (INT1) obtained in step (ii) as defined above with at least one compound containing a secondary amine or a tertiary amine containing a -OH group to convert the -O-epoxy group into a group having the following formula:

[0149] -OR x1 -CH(OH)-R x2 -N(R h1 (R) h2 )

[0150] in

[0151] R x1 It is a straight-chain or branched alkyl chain containing 1 to 6 carbon atoms, a 5- or 6-membered alicyclic ring, or a 5- or 6-membered aromatic ring, wherein the alicyclic or aromatic ring is optionally substituted by at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur.

[0152] R X2 It is a straight-chain or branched alkyl or alkoxy chain containing 1 to 30 carbon atoms, optionally substituted with one or more -OH groups and optionally comprising a poly(oxy)alkylene chain, a 5- or 6-membered alicyclic ring, or a 5- or 6-membered aromatic ring, wherein the alicyclic or aromatic ring is optionally substituted with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; and

[0153] R h1 and R h2 As shown above in formula (N) + As defined in -I);

[0154] Thus, the composition (INT) is obtained. 2 ), which includes:

[0155] - Contains chains with two ends (R) pf (Per)fluoropolyether polymers [polymer P] bif-INT2 The two ends of the chain are bonded to the chain (R).pf On the opposite sides of the chain, the two chain ends contain groups having the following formula:

[0156] -OR x1 -CH(OH)-R x2 -N(R h1 (R) h2 )

[0157] Where R x1 R x2 R h1 and R h2 As defined above,

[0158] -Optionally with (fully) fluoropolyether polymers [polymer P] monof-INT2 The polymer comprises chains (R) having two ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of the chain, one end of the chain contains a perfluoroalkyl group and the other end of the chain contains a group having the following formula:

[0159] -OR x1 -CH(OH)-R x2 -N(R h1 (R) h2 )

[0160] Where R x1 R x2 R h1 and R h2 As defined above.

[0161] The composition (INT2) constitutes another aspect of the present invention.

[0162] Preferably, in step (iii), the compound containing the secondary amine conforms to the following formula:

[0163] HN(R h1 (R) h2 )

[0164] in

[0165] R h1 and R h2 Each is independently selected from straight-chain or branched alkyl chains having 1 to 20 carbon atoms, preferably 1 to 6, more preferably 1 to 4 carbon atoms (optionally substituted with one or more -OH groups), benzyl, or

[0166] R h1 and R h2 Together with nitrogen atoms, they form an aliphatic ring containing 4 or 5 carbon atoms and nitrogen atoms.

[0167] More preferably, the at least one secondary amine is selected from the group consisting of, or even more preferably, the following: dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, ditert-butylamine, dihexylamine, dioctylamine, didecylamine, and didodecylamine.

[0168] More preferably, dimethylamine, diethylamine, dipropylamine, and dibutylamine.

[0169] Preferably, the amine contains a tertiary amine (containing at least one tertiary amine).

[0170] Compounds with -OH groups conform to the following formula:

[0171] HO-(R X3 )-N(R h3 (R) h4 )

[0172] in

[0173] R X3 It is a straight-chain or branched alkyl or alkoxy chain containing 1 to 30 carbon atoms, which is optionally substituted with one or more -OH groups and optionally contains a poly(oxy)alkylene chain, a 5- or 6-membered alicyclic ring, or a 5- or 6-membered aromatic ring, wherein the alicyclic or aromatic ring is optionally substituted with at least one heteroatom selected from nitrogen, oxygen or sulfur.

[0174] R h3 and R h4 Each is independently selected from straight-chain or branched alkyl chains having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms (optionally substituted with one or more -OH groups), benzyl, or

[0175] R h3 and R h4 Together with nitrogen atoms, they form an aliphatic ring containing 4 or 5 carbon atoms and nitrogen atoms, or R h3 and R h4 With R X3 Together they form an aromatic ring containing 4 or 5 carbon atoms and nitrogen atoms.

[0176] Preferably, the compound containing a tertiary amine (with an -OH group) is selected from 2-(diethylamino)ethanol and 3-dimethylamino-1-propanol.

[0177] Furthermore, according to the polymer (P) of the present invention P-bif ) and (P P-monof It can be prepared by method [method (M3)], which includes the following steps:

[0178] (iv) Contact the composition (INT2) obtained in step (iii) as defined above with a compound selected from: alkyl halides, benzyl halides, alkyl sulfonates and alkyl aryl sulfonates, so as to react the compound having the formula -OR x1 -CH(OH)-R x2 -N(R h1 (R) h2 The group of ) is converted to

[0179] -OR x1 -CH(OH)-R x2 -N + (R h1 (R) h2 (R) h3 )

[0180] Where R x1 R x2 R h1 and R h2 As defined above, and

[0181] R h3 It is a straight-chain or branched alkyl or alkoxy chain containing 1 to 30 carbon atoms, which is optionally substituted with one or more -OH groups, and optionally contains a poly(oxy)alkylene chain, a 5- or 6-membered alicyclic ring, or a benzyl group;

[0182] (v) Contact the mixture obtained in step (iv) with compounds selected from the group consisting of:

[0183] - A compound [A] having at least one group (U) as defined above and at least one halogen atom or at least one isocyanate group; or

[0184] - A compound having at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group [B]; or

[0185] - A compound having at least one group (Si) as defined above and at least one halogen atom or at least one isocyanate group [C],

[0186] Thus, polymer (P) is obtained P-bif ) or polymer (P P-monof ).

[0187] Preferably, in step (iv), the reaction is preferably with an alkyl halide; more preferably, the alkyl halide is selected from iodooctane and bromooctane.

[0188] Preferably, in step (v), the reaction with compound [A] is preferred.

[0189] Preferably, in step (v), the compound [A] conforms to the following formula:

[0190] O=C=NR 20 -R 21 -CR H =CH2

[0191] in

[0192] R H It has the same meaning as the above definition of the group (U);

[0193] R 20 It is a straight-chain or branched alkyl chain having 1 to 6 carbon atoms, optionally substituted with a group comprising a trialkoxy-silyl group; and

[0194] R 21 It has the following formulas: -OC(=O)-, -OC(=O)-NH-CO-, -OC(=O)-R A - a divalent group, wherein R A As defined above for group (U-III).

[0195] More preferably, the compound [A] is selected from the group consisting of, or even more preferably, the following: ethyl isocyanate methacrylate (IEM), allyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, vinyl isocyanate, acryloyl isocyanate, methacryloyl isocyanate, ethyl 2-isocyanate acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0196] Those skilled in the art will understand that the steps from (i) to (iii) and from (i) to (v) described above can also be performed sequentially without separating each intermediate composition (INT1) and (INT2).

[0197] Therefore, another object of the present invention relates to a method for preparing polymers (P) as defined above. P-bif ) and (P P -monof The method comprises performing steps as defined above from (i) to (v) in a one-pot synthesis.

[0198] As disclosed above, the polymer (P) P ) or the composition (C) P It can be used as is, or it can be used as an additive in a suitable solvent.

[0199] Preferably, the composition (DIL) comprises from 0.01 to 50 wt.% of a polymer (PP ) or composition (C P Any of the solvents and at least one solvent (S) as defined above, ranging from 50 to 99.99 wt.%.

[0200] Advantageously, the solvent (S) is selected from (per)fluoropolyether polymers having at least one, more preferably at least two, unsaturated groups at their chain ends.

[0201] According to another embodiment, the present invention relates to a method for imparting antimicrobial properties to an article, the method comprising:

[0202] (a) Provide a polymer (P) as defined above. P ) or composition (C P ) or composition (DIL);

[0203] (b) Displaying an article having at least one surface;

[0204] (c) Make the polymer (P) P ) or the composition (C) P The composition (DIL) or the composition thereof is in contact with at least a portion of the at least one surface;

[0205] (d) Using the polymer (P) P ) or composition (C P The at least portion of the at least one surface is coated with either a composition (DIL).

[0206] Advantageously, the article is selected from articles made of plastic, metal, glass, paper, or textiles (e.g., notably cotton paper). More preferably, the article is a banknote.

[0207] Preferably, when at least one group (U) is present in the polymer (P) P ), composition (C P When either the composition (C) or the composition (DIL) is in use, step (d) is performed by curing the composition (C) P It can be carried out using a combination of light or a liquid (DIL), and more preferably using ultraviolet light.

[0208] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may lead to ambiguity in terminology, then this description shall take precedence.

[0209] The invention will be described in more detail below with the aid of examples included in the following experimental section; these examples are merely illustrative and are in no way intended to limit the scope of the invention.

[0210] Experimental Section

[0211] Materials and methods

[0212] Z DOL and MD700 was obtained from Solvay Specialty Polymers Italy S.p.A.

[0213] The following items are obtained from Aldrich: bis(trifluoromethyl)benzene, diethylamine, potassium hydroxide (≥85%), tetra-n-butylammonium bromide, epichlorohydrin, acetonitrile, methanol, 1-iodooctane, 2,6-di-tert-butyl-4-methylphenol (BHT) and ethyl 2-isocyanate of methacrylate.

[0214] The SnapCure™ 1030 is available from Alfa Aesar GmbH & Co.

[0215] Recorded on an Agilent System 500 operating at 499.86 MHz for the 1H and 470.30 MHz for the 19F. 1 H-NMR and 19 F-NMR.

[0216] FT-IR spectra were measured on a liquid sample (as a thin film on KBr) using a Thermo Scientific FTIR spectrophotometer. The spectra were obtained by combining 256 scans at a depth of 2 cm⁻¹. -1 The spectrum is obtained at a high resolution.

[0217] Example 1 - Synthesis of Polymer 1

[0218] Step 1: In a 1.0L four-necked round-bottom flask maintained under a nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe, and dropping funnel, add 200g (EW = g / mol 795; 251.6 meq). Z-DOL, 697 g 1,3-bis(trifluoromethyl)benzene, 2 g tetra-n-butylammonium bromide (6.2 meq), and 20 g potassium hydroxide (355.2 meq). The flask was stirred at room temperature for 1 h. Then, 86 g epichlorohydrin (628.9 meq) was added to the flask, and the reaction mixture was heated to 70 °C for 3 h. After that, the reaction was cooled, and the mixture was filtered. Distillation under reduced pressure (T = 70.0 °C, P = 2 Pa) gave 180.0 g of a clear, pale yellow liquid.

[0219] 1 H-NMR analysis confirmed that the obtained product was the starting Z-DOL, in which 90% of the hydroxyl end groups were quantitatively converted into 2,3-epoxypropane derivatives.

[0220] Step 2: In a 0.5 L four-necked round-bottom flask maintained under a nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe, and dropping funnel, 150 g of the product obtained in Step 1, 16 g of diethylamine (216.8 meq), and 75 g of 1,3-bis(trifluoromethyl)benzene were added. The resulting mixture was heated to 70 °C and subjected to vigorous stirring for 8 hours. Afterward, the reaction mixture was cooled to room temperature and washed with 80 g of distilled water. After phase separation, the bottom organic phase was recovered and distilled under reduced pressure (T = 70 °C, P = 2 Pa) to remove the solvent, yielding 153 g of a yellow product.

[0221] 1 1H NMR analysis confirmed the quantitative opening of the epoxide ring to produce an amino-ol derivative.

[0222] Step 3: In a 0.5 L four-necked round-bottom flask maintained under a nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe, and dropping funnel, add 100 g of the product obtained in Step 2, 26 g of 1-iodooctane (108.6 meq), 50 g of 1,3-bis(trifluoromethyl)benzene, and 50 g of acetonitrile. Heat the resulting mixture to 80 °C and allow it to remain under vigorous stirring for 40 hours. Afterward, distill off the solvent under reduced pressure (T = 70 °C, P = 2 Pa) to obtain 123 g of a yellow, viscous product.

[0223] 1 ¹H NMR analysis confirmed that the alkyl halide reacted quantitatively with the tertiary amine to generate the target quaternary ammonium salt.

[0224] Step 4: 100g of the product obtained in Step 3 is added to a 0.25L four-necked round-bottom flask equipped with a condenser, mechanical stirrer, dropping funnel, and thermometer probe. (3.9*10) -2 g 2,6-Di-tert-butyl-4-methylphenol (BHT), 6.1*10 -2 g SnapCure TM The mixture was heated to 50°C. Then, 11.7 g of ethyl 2-isocyanate methacrylate (76.1 meq) was slowly added to the flask. The temperature was raised to 60°C and the reaction was carried out under vigorous stirring for 3 hours. Afterward, 1.1 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) to obtain 111.9 g of polymer 1.

Claims

1. A fluoropolyether polymer [(polymer (P P )], which contains a fluoropolyether chain [chain(R)] with two chain ends [chain(Re)]. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), where: - The first chain end contains at least one quaternary ammonium salt group [group (N + The group and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable groups; and - The second chain end contains a perfluoroalkyl or quaternary ammonium salt group [group (N + [ ] and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group.

2. The polymer (P) according to claim 1 P The crosslinkable group is selected from the unsaturated portion (U) and the epoxy group (E).

3. The polymer (P) according to claim 1 P ), wherein the fluorinated polyether is a perfluoropolyether.

4. The polymer (P) according to claim 1 P ), wherein the polymer (P) P )yes: - Bifunctional fluoropolyether polymers [polymer (P P-bif )], which contains a fluoropolyether chain [chain(R)] with two chain ends [chain(Re)]. pf The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, the two chain ends contain at least one quaternary ammonium salt group [group (N + The group and at least one group selected from the group consisting of the following: alkoxysilanes [group (Si)] and crosslinkable groups; or - Monofunctional fluoropolyether polymers [polymer (P P-monof )], which contains a fluoropolyether chain [chain(R)] with two chain ends [chain(Re)]. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one chain end has a perfluoroalkyl group and the other chain end contains at least one quaternary ammonium salt group [group (N + [ ] and at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group.

5. The polymer (P) according to claim 4 P The crosslinkable group is selected from the unsaturated portion (U) and the epoxy group (E).

6. The polymer (P) according to claim 4 P ), wherein the fluorinated polyether is a perfluoropolyether.

7. The polymer (P) according to any one of claims 1 to 6 P ), wherein the chain (R) pf ) is a chain with the following formula -D-(CFX # ) z1 -O(R f )(CFX * ) z2 -D * - in z1 and z2 are the same or different from each other, and are equal to or greater than 1; X # and X * Whether they are the same or different, it is either -F or -CF3. The premise is that X is greater than 1 when z1 and / or z2. # and X * It is -F; D and D*, which may be the same as or different from each other, are σ-bonded alkylene chains containing 1 to 6 carbon atoms, said alkyl chains being optionally substituted by at least one perfluoroalkyl group containing 1 to 3 carbon atoms; (R f It includes a repeating unit R°, which is independently selected from the following group, which consists of the following items: (i) -CFXO-, where X is F or CF3; (ii) -CFXCFXO-, where X, which is the same or different each time it appears, is F or CF3, provided that at least one X is -F; (iii) -CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H; (iv) -CF2CF2CF2CF2O-; (v) -(CF2) j -CFZ-O-, where j is an integer from 0 to 3 and Z is a set of integers with the general formula -OR (f-a) -T groups, where R (f-a) It is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units, wherein the repeating units are selected from the following: -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, wherein each X is independently F or CF3 and T is a C1-C3 perfluoroalkyl group.

8. The polymer (P) according to claim 7 P ), where (R) f It is composed of the repeating unit R°.

9. The polymer (P) according to any one of claims 1 to 6 P ), wherein the group (N + Selected from the following group, which includes: (N + -I) -N + (R h1 )(R h2 )(R h3 ) in R h1 R h2 and R h3 Each is independently selected from straight-chain or branched alkyl chains having 1 to 20 carbon atoms, said alkyl chain optionally substituted with one or more -OH groups; benzyl, or R h1 R h2 and R h3 At least two of them, together with nitrogen atoms, form an aliphatic ring containing 4 or 5 carbon atoms and nitrogen atoms.

10. The polymer (P) according to any one of claims 1 to 6 P ), wherein the group (U) is selected from the group consisting of the following items: (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 It is an H or C1-C6 alkyl group; R A It is a matter of choice (R) A -I) and (R A -II) Groups composed of: (R A -I) in Each j5 is independently 0 or 1, and R B It is a divalent, trivalent, or tetravalent group selected from the group consisting of the following items: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 An aromatic or alkyl aromatic 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’ It is a divalent, trivalent, or tetravalent group selected from the group consisting of the following items: C1-C 10 Aliphatic group; C3-C 12 Alicyclic group; C5-C 14 An aromatic or alkyl aromatic group, optionally comprising at least one heteroatom selected from N, O, and S; and R B* Having the above for R B’ The same meaning as defined or is Having the formula (R) B -I) group: in The substituent U is selected from groups (UI) to (U-III) as defined above, and * and # indicate that in the above formula (R) A The bonding sites of nitrogen atoms in -II).

11. The polymer (P) according to any one of claims 1 to 6 P ),in: - When the chain end contains the group (N) + When ), the chain (Re) is formed by σ bonds or by polyoxyalkylene chains [chain (R)]. a )] bonded to the chain (R) pf ); - When the chain (Re) contains the group (U), the chain (Re) is bonded to the chain (R) by a group having the following formula. pf ): * -R 10 -NH-C(=O)-O-R 11 - # in * indicates a bond to the group (U). # indicates a chain (R) pf ) key R 10 It is a straight-chain or branched alkyl chain having 1 to 6 carbon atoms, optionally substituted with a group containing a trialkoxy-silyl group; R 11 It is a σ bond or a polyoxyalkylene chain [chain (R a ^)], wherein the chain (R) a ^) Contains from 1 to 50 fluorine-free oxoalkylene units, said units being identical or different from each other and selected from... -CH(J*)CH(J)-O, where J and J* are each independently selected from hydrogen atoms, straight-chain or branched alkyl or aryl groups.

12. A composition [Composition (C)] P ], which includes: - Fluoroether polymers as defined in any one of claims 4 to 11 [polymer(P] P-bif )];as well as - Fluoroether polymers as defined in any one of claims 4 to 11 [polymer(P] P-monof )).

13. The composition according to claim 12, wherein the fluorinated polyether is a perfluoropolyether.

14. A method for preparing a first composition [composition (INT1)] [method (M1)], said method (M1) comprising the following steps: (i) Providing at least one fluoropolyether (PFPE) polymer comprising: Fluoropolyether chains with two ends [chain(R pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), wherein the two chain ends contain at least one -OH group [PFPE polymer (bif)]; or contain a fluoropolyether chain having two chain ends [chain (R pf The fluoropolyether (PFPE) polymer, wherein the two chain ends are bonded to the chain (R) pf On the opposite side of ), wherein one of the chain ends contains at least one -OH group and the other chain end contains a perfluoroalkyl group [PFPE polymer (monof)]; (ii) Converting at least a portion of the -OH groups of the PFPE polymer (bif) or the PFPE polymer (monof) to epoxy groups to obtain a composition (INT1) comprising: - Includes chains with two ends (R) pf ) of fluoropolyether polymers [polymer P bif-INT1 The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, two of the chain ends contain epoxy groups. - Optionally with fluoropolyether polymers [polymer P] monof-INT1 The polymer comprises chains (R) having two ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one end of the chain contains an epoxy group and the other end contains a perfluoroalkyl group.

15. The method of claim 14, wherein the fluoropolyether is a perfluoropolyether.

16. A method for preparing a polymer (P) as defined in any one of claims 4 to 11. P-bif ) and (P P-monof The method [method (M3)] includes the following steps: (iv) Contact the composition (INT2) with a compound selected from: alkyl halides, benzyl halides, alkyl sulfonates, and alkyl aryl sulfonates. In order to have the formula -OR x1 -CH(OH)-R x2 -N(R h1 (R) h2 The group of ) is converted to -O-R x1 -CH(OH)-R x2 -N + (R h1 )(R h2 )(R h3 ) Where R x1 It is a straight-chain or branched alkyl chain containing 1 to 6 carbon atoms, a 5- or 6-membered alicyclic ring, or a 5- or 6-membered aromatic ring, wherein the alicyclic or aromatic ring is optionally substituted by at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. R x2 It is a straight-chain or branched alkyl or alkoxy chain containing 1 to 30 carbon atoms, which is optionally substituted with one or more -OH groups and optionally contains a polyoxyalkylene chain, a 5- or 6-membered alicyclic ring, or a 5- or 6-membered aromatic ring, wherein the alicyclic or aromatic ring is optionally substituted with at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. R h1 and R h2 As defined in claim 10, and R h3 It is a straight-chain or branched alkyl or alkoxy chain containing 1 to 30 carbon atoms, which is optionally substituted with one or more -OH groups, and optionally contains a polyoxyalkylene chain, a 5- or 6-membered alicyclic ring, or a benzyl group; The composition (INT) 2 )Include: - Includes chains with two ends (R) pf ) of fluoropolyether polymers [polymer P bif-INT2 The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, the two chain ends contain groups having the following formula: -O-R x1 -CH(OH)-R x2 -N(R h1 )(R h2 ) Where R x1 R x2 R h1 and R h2 As defined above, - Optionally with fluoropolyether polymers [polymer P] monof-INT2 The polymer comprises chains (R) having two ends. pf The two ends of the chain are bonded to the chain (R). pf On the opposite side of ), one end of the chain contains a perfluoroalkyl group and the other end contains a group having the following formula: -O-R x1 -CH(OH)-R x2 -N(R h1 )(R h2 ) Where R x1 R x2 R h1 and R h2 As defined above; (v) Contact the mixture obtained in step (iv) with compounds selected from the group consisting of: - A compound having at least one group (U) as defined above and at least one halogen atom or at least one isocyanate group [A]; or - A compound having at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group [B]; or - A compound having at least one group (Si) as defined above and at least one halogen atom or at least one isocyanate group [C], Thus, polymer (P) is obtained P-bif ) or polymer (P P-monof ).

17. The method of claim 16, wherein the fluoropolyether is a perfluoropolyether.

18. A composition [composition (DIL)] comprising the composition (C) as defined in claim 12 or 13. P ) and at least one solvent selected from the group consisting of: Fluorinated fluid, optionally containing at least one unsaturated portion; Hydrogenated fluid, optionally containing at least one unsaturated portion.

19. The composition of claim 18, wherein the fluorinated fluid is a perfluorinated fluid.

20. A method for imparting antimicrobial properties to an article, the method comprising: (a) Providing a polymer (P) as defined in any one of claims 1 to 11 P ) or the composition as defined in claim 12 or 13 (C P Or the composition (DIL) as defined in claim 18 or 19; (b) Displaying an article having at least one surface; (c) Making the composition (C) P The composition (DIL) or the substance is in contact with at least a portion of the at least one surface; (d) Using the composition (C) P The at least portion of the at least one surface is coated with either a composition (DIL).

21. The method of claim 20, wherein the article is selected from articles made of plastic, metal, glass, paper or textiles.

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