Novel (all)fluoropolyether polymers and their applications

Abstract

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.

Description

[0001] Cross-referencing of related patent applications

[0002] This application claims priority to patent application No. 20201711.7 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 JP 2014237227 (Central Glass Corporation), TW 201512339 (Alpha Bright International Ltd.), US 2015 / 191608 (Seoul National University Industrial Academic Cooperation Group; Samsung Electronics Co., Ltd.; SnuR&DB Foundation); WO 2016 / 153230 (Ceko Ltd.); CN 105176342 (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, antifungal, and antiviral 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 composition [composition (C POL The composition comprises:

[0012] -(Fully)Fluoroether Polymer[(Polymer(P P )], which contains (per)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 )

[0013] in

[0014] One chain end contains at least one quaternary ammonium salt group [group (N + The group of )] and

[0015] The other end of the chain contains at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moieties [group (U)] and epoxides [group (E)];

[0016] -(Fully)Fluoroether Polymer[(Polymer(P U )], which contains (per)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 )

[0017] Two of the chain ends contain a group selected from the group consisting of: alkoxysilane [group (Si)] and a crosslinkable group, preferably selected from the unsaturated moiety [group (U)] and epoxide [group (E)]; and

[0018] - Contains (all)fluoropolyether chains with two ends [chain(R pf (Per)fluoropolyether polymers [polymer (P)] N The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, where the two chain ends contain at least one group (N + ).

[0019] Advantageously, based on the composition (C) P The total weight of the composition (C) POL The polymer (P) comprises from about 5 to about 50 wt.% of the polymer. P ).

[0020] The composition (C) POL It can be used as is to provide antimicrobial coatings, or it can be used as a component (also known as an "additive") in a solvent [solvent(S)].

[0021] Therefore, in a second aspect, the present invention relates to a composition [composition (DIL)] comprising the composition (C) as defined above. POL 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.

[0022] In a third aspect, the present invention relates to the composition (C) as described above. POL (or composition) used to impart antimicrobial properties to a substrate. Detailed Implementation

[0023] For the purposes of this specification and the following claims:

[0024] - 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;

[0025] - 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;

[0026] - The term "(per)fluorinated polyether" is intended to indicate a polyether polymer that is fully or partially fluorinated;

[0027] 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.

[0028] Preferably, the composition (C) POL )Include

[0029] - Polymer (P) from about 5.00 to about 50.00 wt%. P ),

[0030] - Polymer (P) from about 0.01 to about 15.00 wt%. N ),as well as

[0031] - Polymer content from approximately 35.00 to approximately 94.99 wt% (P U ),

[0032] These amounts are based on 100 wt.% of the composition (C POL ).

[0033] More preferably, the composition (C) POL )Include

[0034] - Polymer (P) from about 5.00 to about 48.00 wt%. P ),

[0035] - Polymer (P) from about 0.10 to about 12.00 wt%. N ),as well as

[0036] - Polymer from about 40.00 to about 85 wt% (P U ),

[0037] These amounts are based on 100 wt.% of the composition (C POL ).

[0038] The composition (C) POL It may further contain (per)fluoropolyether polymers [polymer (P x )], which contains (per)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 ), one end of the chain contains a perfluoroalkyl group and the other end contains at least one group as defined above (N + Or at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group, preferably selected from unsaturated moieties [group (U)] and epoxides [group (E)].

[0039] When present, based on the composition (C) POL The total weight of the polymer (P)X Preferably, it is in an amount of up to 15 wt.%, more preferably from 0.01 to 12 wt.%, and even more preferably from 0.05 to 10 wt.%.

[0040] Preferably, in polymer (P) P ), polymer (P) U ), polymer (P) N ) and polymers (P x In any of the following, the chain (R) pf ) is a chain with the following formula

[0041] -D-(CFX # ) z1 -O(R f (CFX) * ) z2 -D * -

[0042] in

[0043] z1 and z2 are the same or different from each other, and are equal to or greater than 1;

[0044] X # and X * Whether they are the same or different, it is either -F or -CF3.

[0045] The premise is that X is greater than 1 when z1 and / or z2. # and X * It is -F;

[0046] D and D*, which may be the same as or different from each other, are σ bonds or 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;

[0047] (R f ) contains repeating unit R o Preferably, the repeating units are selected independently from the group consisting of the following:

[0048] (i)-CFXO-, where X is F or CF3;

[0049] (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;

[0050] (iii)-CF2CF2CW2O-, where each W, which may be the same as or different from each other, is F, Cl, or H;

[0051] (iv)-CF2CF2CF2CF2O-;

[0052] (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.

[0053] 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.

[0054] 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)-.

[0055] Preferably, the chain (R) f It conforms to the following formula:

[0056] (R f -I)

[0057] -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]-

[0058] in

[0059] -X 1 Independently selected from -F and -CF3,

[0060] -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;

[0061] -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.

[0062] More preferably, chain (R) f Selected from chains having the following formula:

[0063] (R f -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]-

[0064] in:

[0065] - 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;

[0066] (R f -IIB)-[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]-

[0067] in:

[0068] 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;

[0069] (R f -IIC)-[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]-

[0070] in:

[0071] cw = 1 or 2;

[0072] 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.

[0073] (R f -IID)-[(CF2CF(CF3)O) d ]-

[0074] in:

[0075] 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;

[0076] (R f -IIE)-[(CF2CF2C(Hal*)2O) e1 -(CF2CF2CH2O) e2 -(CF2CF2CH(Hal*)O) e3 ]-

[0077] in:

[0078] -Hal*, which may be the same or different each time it appears, is a halogen selected from fluorine and chlorine atoms, preferably fluorine atoms;

[0079] -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.

[0080] Even more preferably, chain (R) f ) conforms to the following formula (R) f -III):

[0081] (R f -III)-[(CF2CF2O) a1 (CF2O) a2 ]-

[0082] in:

[0083] -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.

[0084] Preferably, in polymer (P) P ), polymer (P) N ) and polymers (P x In any of the following, the group (N) + The following are selected from the group consisting of, more preferably, the following items:

[0085] (N + -I)-N + (R h1 (R) h2 (R) h3 )

[0086] in

[0087] R h1 R h2 and Rh3 Each is independently selected from straight-chain or branched alkyl chains, benzyl groups, or R groups having 1 to 20 carbon atoms, more preferably 1 to 18, or even more preferably 3 to 18 carbon atoms. h1 R h2 and R h3 At least two of them together with nitrogen atoms form a 5- or 6-membered aliphatic ring, or R h1 R h2 and R h3 Together with nitrogen atoms, they form 5- or 6-membered aromatic rings.

[0088] 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.

[0089] 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.

[0090] Polymer (P) P ), polymer (P) N ) and polymers (P x Any one of them contains a group (N) + Counterions.

[0091] The counterions are preferably selected from halides, such as chlorides, iodides, bromides; methanesulfonates, toluenesulfonates, trifluoromethanesulfonates, and nonafluorobutanesulfonates. Methanesulfonates and toluenesulfonates are more preferred.

[0092] Preferably, in polymer (P) P ), polymer (P) N ) and polymers (P x In any of the following, the group (N) + ) via σ bonds or via poly(oxy)alkylene chains [chain(R a )] bonded to the chain (R) pf One end of a chain.

[0093] More preferably, the chain (Ra) 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.

[0094] Polymer (P) P ) and polymers (P UPreferably, each of them contains a group (U) at its chain end.

[0095] Preferably, in polymer (P) P ) and polymers (P U In any one of the following, the group (U) is selected from the group consisting of:

[0096] (UI)-OC(=O)-CR H =CH2

[0097] (U-II)-OC(=O)-NH-CO-CR H =CH2

[0098] (U-III)-OC(=O)-R A -CR H =CH2

[0099] in

[0100] R H It is an H or C1-C6 alkyl group;

[0101] R A It is a matter of choice (R) A -I) and (R) A Group -II) consists of:

[0102] (R A -I)

[0103]

[0104] Each j5 is independently 0 or 1, and

[0105] R B It is a divalent, trivalent, or tetravalent group, selected from the group consisting of the following: 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;

[0106] (R A -II)

[0107]

[0108] in

[0109] j6 is 0 or 1;

[0110] Each j7 is independently 0 or 1;

[0111] R B’It is a divalent, trivalent, or tetravalent group, selected from the group consisting of the following: 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

[0112] R B* Having the above for R B’ The same meaning as defined or that which has the formula (R) B -I) group:

[0113]

[0114] in

[0115] The substituent U is selected from groups (UI) to (U-III) as defined above, and

[0116] * and # indicate the above formula (R) A -II) The bonding site with nitrogen atoms.

[0117] Preferably, in polymer (P) P ) and polymers (P U In any of the following, the group (U) is bonded to the chain (R) by a group having the following formula. pf One end of the chain:

[0118] *-R 10 -NH-C(=O)-OR 11 -#

[0119] in

[0120] * indicates a bond to the U group.

[0121] # indicates a chain (R) pf ) key

[0122] 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;

[0123] R 11 It is a σ bond or a poly(oxy)alkylene chain [chain (R a ^)], wherein the chain (R) a ^) comprises from 1 to 50 fluorine-free oxoalkylene units, which may be the same as or different from each other and are selected from...

[0124] -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.

[0125] According to an alternative embodiment, the polymer (P) P ) and polymers (P U Each of them contains a group (Si) at its chain end.

[0126] Preferably, the group (Si) is a group having the following formula:

[0127] -Si-(OR 30 )3

[0128] Among them, R 30 It is a straight-chain or branched alkyl chain having 1 to 12 carbon atoms.

[0129] Preferably, the polymer (P) x One end of the chain contains a perfluoroalkyl group selected from the group consisting of, more preferably, the following:

[0130] -CF3, -C2F5, -C3F7, -CF2Cl, -CF2CF2Cl and -C3F6Cl.

[0131] The polymers (P) containing perfluoroalkyl groups as defined above x Also known as "monofunctional polymer (P)" x )".

[0132] As is known in the art, the polymer functionality (F), i.e., the average number of functional groups per polymer molecule, of the polymer P according to the invention is from 1.00 to 2.00. Bifunctional polymers P typically have a functionality (F) 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).

[0133] As defined above, the composition (C) POL It is advantageous to extract from (per)fluoropolyether chains [chain(R)] pf The preparation begins with a (per)fluoropolyether (PFPE) polymer, wherein the (per)fluoropolyether chains have bonds to the chain (R). pf The two chain ends on opposite sides of the chain, wherein the chain ends contain at least one -OH group.

[0134] For example, firstly, the composition [composition (INT)] can be prepared by a method including the steps (i) to (iii):

[0135] (i) Provides a (per)fluoropolyether chain [chain(R] comprising two chain ends. pf The (per)fluoropolyether (PFPE) polymer, wherein the two chain ends are bonded to the chain (R) pf On opposite sides of the chain, the two chain ends contain at least one -OH group;

[0136] (ii) Converting at least a portion of the -OH group into a leaving group for nucleophilic substitution reaction;

[0137] (iii) Contacting the composition obtained in step (ii) with at least one tertiary amine to obtain a composition [Composition (INT)] comprising:

[0138] -(Fully)Fluoroether Polymers[Polymer(P INT )], which contains (per)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 ), one of the chain ends contains at least one quaternary ammonium salt group [group (N + The chain contains a group and another chain end contains at least one -OH group;

[0139] - Contains (all)fluoropolyether chains with two ends [chain(R pf (Per)fluoropolyether polymers [polymer (P)] N The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, where the two chain ends contain at least one group (N + ),as well as

[0140] - The (per)fluoropolyether (PFPE) polymer provided in step (i).

[0141] The composition (INT) as defined above is another aspect of the present invention.

[0142] The composition according to the invention (C) POL It can advantageously be prepared from the composition (INT) as defined above, according to a method comprising:

[0143] (iv) Contacting the composition (INT) as defined above with at least one compound selected from the group consisting of:

[0144] - 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

[0145] - 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

[0146] - A compound having at least one group (Si) as defined above and at least one halogen atom or at least one isocyanate group [C],

[0147] Thus, the claimed composition (C) is obtained. POL ).

[0148] Furthermore, and advantageously, the composition (INT) as defined above can be purified according to methods known in the art to purify at least the polymer (P). INT ).

[0149] According to this embodiment, the polymer (P) INT Then it is contacted with at least one of the compounds [A], [B] or [C] as defined in step (iv) above to obtain a polymer (P) as a pure compound. P ).

[0150] Therefore, those skilled in the art will understand that polymers (P) P This is another objective of the present invention.

[0151] According to one embodiment, the composition (C) POL It can be prepared by one-pot synthesis, i.e., without the need to recover the composition from the reaction mixture (INT).

[0152] According to this embodiment, the composition (C) POL Prepared by a method including the following steps:

[0153] (i) Provides a (per)fluoropolyether chain [chain(R] comprising two chain ends. pf The (per)fluoropolyether (PFPE) polymer, wherein the two chain ends are bonded to the chain (R) pf On opposite sides of the chain, the two chain ends contain at least one -OH group;

[0154] (ii) Converting at least a portion of the -OH group into a leaving group for nucleophilic substitution reaction;

[0155] (iii) Contact the composition obtained in step (ii) with at least one tertiary amine to obtain the composition as defined above [composition (INT)];

[0156] (iv) Contact the composition (INT) obtained in step (iii) with at least one compound selected from the group consisting of:

[0157] - 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

[0158] - 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

[0159] - A compound having at least one group (Si) as defined above and at least one halogen atom or at least one isocyanate group [C],

[0160] Thus, the composition (C) is obtained. POL ).

[0161] The (per)fluoropolyether (PFPE) polymer used as the starting material in step (i) above is preferably a PFPE polymer that conforms to the following formula:

[0162] (PFPE-i)HO-(R pf )-OH

[0163] (PFPE-ii)HO-[CH(J*)CH(J)O] t1 -(R pf )-[OCH(J)CH(J*)] t2 -OH

[0164] in

[0165] (R pf As defined above,

[0166] t1 and t2 are each independent integers from 1 to 50, and

[0167] J and J* are each defined independently as above for the chain (Ra).

[0168] Advantageously, in step (ii) above, at least a portion of the -OH groups in the PFPE polymer having formula (PFPE-i) or (PFPE-ii) are converted into groups selected from the group consisting of, and preferably consisting of: methanesulfonyl, toluenesulfonyl, perfluorobutyryl, or trifluoromethanesulfonyl.

[0169] Preferably, in step (iii) above, the at least one tertiary amine conforms to the following formula:

[0170] N(R h1 (R) h2 (R) h3 )

[0171] in

[0172] R h1 Rh2 and R h3 Each is independently selected from straight-chain or branched alkyl chains having 1 to 20 carbon atoms, more preferably 3 to 18 carbon atoms, benzyl, or R h1 R h2 and R h3 At least two of them, together with the nitrogen atom, form an aliphatic ring containing 4 or 5 carbon atoms and a nitrogen atom, or R h1 R h2 and R h3 Together with nitrogen atoms, they form an aromatic ring containing 4 or 5 carbon atoms and nitrogen atoms.

[0173] 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.

[0174] 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.

[0175] More preferably, the at least one tertiary amine is selected from the group consisting of, or even more preferably, the following: N,N-dimethylbenzylamine; pyridine; 4-nonadecanylpyridine; 1-methylpyrrole; 1-butylpyrrolidine; tributylamine; triisooctylamine; trihexylamine; trioctylamine; N,N-dimethylhexadecylamine; N,N-dimethyloctylamine; triethylamine.

[0176] Preferably, in step (iv), the reaction is preferably with the compound [A] having at least one group (U) and at least one isocyanate group.

[0177] Preferably, in step (iv), the compound [A] conforms to the following formula:

[0178] O=C=NR 20 -R 21 -CR H =CH2

[0179] in

[0180] R H It has the same meaning as the above definition of the group (U);

[0181] R 20 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;

[0182] R21 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).

[0183] 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.

[0184] As disclosed above, the composition (C) POL It can be used as is, or it can be used as an additive in a suitable solvent.

[0185] Preferably, the composition (DIL) comprises from 0.01 to 50 wt.% of the composition (C POL (S) and at least one solvent as defined above, ranging from 50 to 99.99 wt.%.

[0186] 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.

[0187] According to another embodiment, the present invention relates to a method for imparting antimicrobial properties to an article, the method comprising:

[0188] (a) Provide the composition as defined above (C) POL ) or composition (DIL);

[0189] (b) Displaying an article having at least one surface;

[0190] (c) Making the composition (C) POL The composition (DIL) or the substance is in contact with at least a portion of the at least one surface;

[0191] (d) Using the composition (C) POL The at least portion of the at least one surface is coated with either a composition (DIL).

[0192] 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.

[0193] Preferably, when the composition (C)POL The composition (DIL) or the composition thereof contains a polymer (P) containing the group (U). P ) and (P U In step (d), the composition (C) is more preferably cured using ultraviolet light. POL It can be carried out using either a combination of ingredients (DIL).

[0194] 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.

[0195] 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.

[0196] Experimental Section

[0197] Materials and methods

[0198] E10H and MD700 was obtained from Solvay Specialty Polymers Italy S.p.A.

[0199] The following items are obtained from Aldrich: bis(trifluoromethyl)benzene, triethylamine, methanesulfonyl chloride, N,N-dimethylhexadecylamine, 2,6-di-tert-butyl-4-methylphenol (BHT) and ethyl 2-isocyanate of methacrylate.

[0200] SnapCure TM 1030 was obtained from Alfa Aesar GmbH & Co.

[0201] In regard 1 H at 499.86MHz and for 19 Recorded on an Agilent System 500 running at 470.30MHz 1 H-NMR and 19 F-NMR.

[0202] The FT-IR spectra of the liquid sample (as a thin film on KBr) were measured using a Thermo Scientific FTIR spectrophotometer. The spectra were obtained by combining 256 scans at 2 cm⁻¹. -1 The spectrum was obtained at a high resolution.

[0203] Example 1 - Composition C POL -A synthesis

[0204] Step 1: In a 0.5L four-necked round-bottom flask maintained under a nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe, and dropping funnel, add 150g (EW = g / mol 906; 165.6 meq). E10H, 100 g 1,3-bis(trifluoromethyl)benzene, and 5.9 g triethylamine (58.4 meq). The flask was then cooled, and 5.8 g methanesulfonyl chloride (50.6 meq) was added at a rate maintained within the range of 15°C–30°C. When the methanesulfonyl chloride addition was complete, the reaction mixture was stirred at 25°C–30°C for an additional 6 hours. The reaction mixture was then neutralized by adding 4 M HCl aqueous solution, and the resulting organic phase was separated. After distillation of the fluorinated solvent under reduced pressure (T = 80°C, P = 2 Pa), 152.1 g of a clear liquid was separated and characterized. 1 H-NMR analysis confirmed that the obtained product was the starting material. E10H, in which 29% of the -OH groups are converted to methanesulfonate.

[0205] Step 2: 100 g of 1,3-bis(trifluoromethyl)benzene and 9.0 g (33.4 meq) of N,N-dimethylhexadecylamine were added to a 0.25 L four-necked round-bottom flask maintained under a nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe, and dropping funnel. 100 g of the product obtained in Step 1 was added dropwise to the flask, and the resulting mixture was heated to 90 °C and stirred vigorously for 20 hours. The solvent was removed by distillation under reduced pressure (T = 80 °C, P = 2 Pa), yielding 107.1 g of a waxy product. 1 1H NMR analysis confirmed that the methanesulfonate underwent a quantitative transformation to generate the target quaternary ammonium salt.

[0206] Step 3: 100g of the product obtained in Step 2 was added to a 100ml 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), 8.5*10 -2 g SnapCure TM 1030, and heat the resulting mixture to 50°C.

[0207] Then, 11.8 g of ethyl 2-isocyanate methacrylate (76.1 meq) was slowly added, the temperature was raised to 60 °C, and the reaction mixture was vigorously stirred for 3 hours. Afterward, 1.6 g of methanol was added, the reaction mixture was stirred for another 2 hours, and then dried under reduced pressure (T = 60 °C, P = 2 Pa) to obtain 108.3 g of C. POL -A.

[0208] C POL-A was recovered as a viscous, pale yellow liquid, which statistically includes:

[0209] 41.2% polymer P P -A;

[0210] 50.4% polymer P U -A; and

[0211] 8.4% polymer P N -A.

[0212] Determination of antibacterial activity of glass substrate

[0213] According to ISO 22196, it contains 80 wt.% MD700 and 20 wt.% polymer C POL The antibacterial activity of the composition of -A (prepared according to Example 1 above).

[0214] The growth of two bacteria, Staphylococcus aureus and Escherichia coli, was evaluated on a glass substrate prepared as described in ISO 22196 test.

[0215] Glass substrates in contact with the compositions according to the invention passed the ISO 22196 test.

Claims

1. A composition [Composition (C)] POL ], which includes: - (Fully) fluoropolyether polymers [polymer (P P )], which contains (per)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 ), one of the chain ends contains at least one quaternary ammonium salt group [group (N + The chain contains a group and another chain end contains at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable group; - Contains (all)fluoropolyether chains with two chain ends [chain(R pf (Perfluoropolyether polymers) [polymer(P)] U 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 a group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable groups; and - Contains (all)fluoropolyether chains with two chain ends [chain(R pf (Perfluoropolyether polymers) [polymer(P)] N The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, where the two chain ends contain at least one group (N + ); The (fully) fluorinated polyethers mentioned therein refer to fully or partially fluorinated polyethers.

2. The composition according to claim 1 (C) POL ), wherein the (per)fluoropolyether polymer [polymer (P P In the (per)fluoropolyether chain [chain (R)], the (per)fluoropolyether chain [chain (R)] pf The other end of the chain contains at least one group selected from the group consisting of: unsaturated moiety [group (U)] and epoxide [group (E)].

3. The composition according to claim 1 (C) POL ), wherein the (per)fluoropolyether polymer [polymer (P U In the (per)fluoropolyether chain [chain (R)], the (per)fluoropolyether chain [chain (R)] pf The other end of the chain contains at least one group selected from the group consisting of: unsaturated moiety [group (U)] and epoxide [group (E)].

4. The composition according to claim 1 (C) POL The composition (C) POL ) Include: - From 5 to 50 wt.% of the polymer (P P ), - From 0.01 to 15 wt.% of the polymer (P N ),as well as - The polymer (P) from 35 to 94.99 wt.% U ) The amount is based on 100 wt.% of the composition (C POL ).

5. The composition according to claim 1 (C) POL The composition (C) POL Further includes: - (Fully) fluoropolyether polymers [polymer (P x )], which contains (per)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 ), one end of the chain contains a perfluoroalkyl group and the other end contains at least one group as defined above (N + Or at least one group selected from the group consisting of: alkoxysilane [group (Si)] and crosslinkable groups.

6. The composition according to claim 5 (C) POL ), wherein the (per)fluoropolyether polymer [polymer (P x In the (per)fluoropolyether chain [chain (R)], the (per)fluoropolyether chain [chain (R)] pf The other end of the chain contains at least one group (N) as defined above. + ) or at least one group selected from the group consisting of: unsaturated moieties [group (U)] and epoxides [group (E)].

7. The composition according to claim 5 (C) POL ),in, The polymer (P) X The amount of ) is up to 15 wt.%, based on the composition (C POL The total weight of ).

8. The composition according to claim 5 (C) POL ),in, In polymer (P) P ), polymer (P) U ), polymer (P) N ) and polymers (P x In any of the following, 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 bonds or 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 group consisting of: (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.

9. The composition according to claim 5 (C) POL ),in, In polymer (P) P ), polymer (P) N ) and polymers (P x In any of the following, the group (N) + Selected from the group below, which includes the following items: (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, benzyl groups, or R groups. h1 R h2 and R h3 At least two of them together with nitrogen atoms form a 5- or 6-membered aliphatic ring, or R h1 R h2 and R h3 Together with nitrogen atoms, they form 5- or 6-membered aromatic rings.

10. The composition according to claim 9 (C) POL ),in, The R h1 R h2 and R h3 Each is independently selected from straight-chain or branched alkyl chains having 1 to 18 carbon atoms.

11. The composition according to claim 9 (C) POL ),in, The R h1 R h2 and R h3 Each is independently selected from straight-chain or branched alkyl chains having 3 to 18 carbon atoms.

12. The composition according to claim 6 (C) POL ),in, In polymer (P) P ) and polymers (P U In any one of the following, the 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 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, and the group is selected from the group consisting of the following: 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, and the group is selected from the group consisting of the following: 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 that which has the formula (R) B -I) group: in The substituent U is selected from groups (UI) to (U-III) as defined above, and * and # indicate the above formula (R) A -II) The bonding site with nitrogen atoms.

13. The composition according to claim 6 (C) POL ),in, - In polymers (P P ), polymer (P) N ) and polymers (P x In any of the following, the group (N) + ) via σ bonds or via polyoxyalkylene chains [chain(R a )] bonded to the chain (R) pf One end of a chain; and / or - In polymers (P P ) and polymers (P U In any one of the following, the group (U) is bonded to the chain (R) by a group having the following formula. pf One end of the chain: * -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, J and J* are each independently selected from hydrogen atoms, straight-chain or branched alkyl or aryl groups.

14. A method for preparing a composition as defined in any one of claims 1 to 13 (C) POL The method includes: (iv) The composition (INT) comprises - Fully or partially fluorinated polyether polymers [polymer(P] INT )], which contains (per)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 ), one of the chain ends contains at least one quaternary ammonium salt group [group (N + The chain contains a group and another chain end contains at least one -OH group; - Contains (all)fluoropolyether chains with two chain ends [chain(R pf (Perfluoropolyether polymers) [polymer(P)] N The two ends of the chain are bonded to the chain (R). pf On opposite sides of the chain, where the two chain ends contain at least one group (N + ),as well as - Contains (all)fluoropolyether chains with two chain ends [chain(R pf The (per)fluoropolyether (PFPE) polymer, wherein the two chain ends are bonded to the chain (R) pf On opposite sides of the chain, the two chain ends contain at least one -OH group; The (fully)fluorinated polyethers mentioned above refer to fully or partially fluorinated polyethers. Contact with at least one compound selected from the group consisting of: - A compound having at least one group (U) as defined in claim 12 and at least one halogen atom or at least one isocyanate group [A]; or - A compound [B] having at least one epoxide [group (E)] and at least one halogen atom or at least one isocyanate group; 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, the composition (C) is obtained. POL ).

15. The method according to claim 14, wherein, In step (iv), the compound [A] conforms to the following formula: O=C=N-R 20 -R 21 -CR H =CH2 in R H It has the same meaning as the group (U) as defined in claim 12; 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 R 21 It has the formulas -OC(=O)-, -OC(=O)-NH-CO-, and -OC(=O)-R A - a divalent group, wherein R A As defined in claim 12.

16. A composition [composition (DIL)] comprising the composition (C) as defined in any one of claims 1 to 13. POL ) and at least one solvent selected from the group consisting of: A fully or partially fluorinated fluid, optionally containing at least one unsaturated portion; Hydrogenated fluid, optionally containing at least one unsaturated portion.

17. The composition (DIL) according to claim 16, wherein the composition (DIL) comprises from 0.01 to 50 wt.% of the composition (C) as defined in any one of claims 1 to 13. POL ) and at least one solvent (S) from 50 to 99.99 wt.%, wherein said solvent (S) is a (per)fluoropolyether polymer having at least one unsaturated group at its chain end.

18. A method for imparting antimicrobial properties to a substrate, the method comprising: (a) Providing a composition as defined in any one of claims 1 to 13 (C POL Or the composition (DIL) as defined in any one of claims 16 and 17; (b) Displaying an article having at least one surface; (c) Making the composition (C) POL 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) POL The at least portion of the at least one surface is coated with either a composition (DIL).

19. The method according to claim 18, wherein, The article is selected from articles made of plastic, metal, glass, paper or textiles.

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