Antibacterial antiadhesive material

Abstract

The present invention relates to an antibacterial and antiadhesive material having good antibacterial efficacy and preventing proteins and / or cells from adhering to its surface, to its preparation method and to its use for preparing an article having antibacterial and antiadhesive properties, such as, in particular, medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional medium, etc.), textiles, such as, for example, dirt-trapping mats, shoes, clothing, components in the building field, such as, for example, a door handle, floor coverings, sports facilities, and personal protective equipment.

Description

[0001] DESCRIPTION

[0002] TITLE: ANTI-STICK AND ANTIBACTERIAL MATERIAL

[0003] FIELD OF INVENTION

[0004] The present invention relates to an antibacterial and non-stick material, having good antibacterial efficacy and allowing the prevention of the adhesion of proteins and / or cells to its surface, its preparation process and its use for the preparation of articles with non-stick and antibacterial properties such as in particular medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional media etc.), textiles, such as for example anti-soiling mats, shoes, clothing, building components, such as for example a door handle, floor coverings, sports facilities, personal protective equipment.

[0005] STATE OF THE ART

[0006] Antibiotic resistance to bacteria has become a public health issue. Some antibiotics have become ineffective against infections caused by bacteria such as methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Staphylococcus aureus (VRAS).Several methods exist today for developing antibacterial materials: i) the inclusion of biocidal molecules (antibiotics or silver-based molecules, for example) which are released outside the material, leading to a loss of activity of the material, in some cases side effects and / or an exacerbation of the phenomenon of antimicrobial resistance; ii) the modification of the surface of the material by grafting, coupling or coating, which is a long, expensive and multi-step method; iii) the use of anti-adhesive macrosurfactants (at a level of about 10% by weight) to create antimicrobial films by migration of the macrosurfactant to the surface of the material which prevents the adhesion of bacteria without killing them.Another approach involves the use of antibacterial materials for the manufacture of medical devices, such as those described in patent application FR3068704, the effectiveness of which is sometimes limited by the presence of bodily fluids.

[0007] However, the antibacterial efficacy of these materials can be reduced when bacterial access to the material is hindered by the presence of proteins, lipids, polysaccharides, and / or cells on its surface. US patents 6,127,507 and 9,731,049 propose using copolymers of the same chemical nature as the matrix but incorporating perfluorinated ends to give the material anti-adhesive properties. The presence of fluorine atoms at the chain ends allows the copolymer to migrate to the material's surface, rendering it hydrophobic.

[0008] The present invention aims to provide a material whose antibacterial efficacy is maintained during use thanks to its anti-adhesive properties through the application of proteins, lipids, polysaccharides, and / or cells on its surface. The material is manufactured industrially and is durable over time for its intended application. The presence in the material of a copolymer with antibacterial properties, combined with the use of a copolymer with anti-adhesive properties, prevents contamination of devices, such as catheters, made with this material. It also provides direct antibacterial protection to fluids circulating in or around these devices, without any loss of antibacterial activity.

[0009] DESCRIPTION OF THE INVENTION

[0010] A first object of the present invention relates to a material comprising a polymer matrix in which are dispersed:

[0011] • an amphiphilic block copolymer a) comprising:

[0012] - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl methacrylates, and

[0013] - a hydrophilic block comprising one or more repeating motifs selected from hydrophilic (meth)acrylates, hydrophilic acrylamides and their combinations, and

[0014] • an amphiphilic block copolymer b) comprising:

[0015] - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl methacrylates, and

[0016] - a hydrophilic block comprising one or more repeating motifs selected from alkyl methacrylates comprising at least one tertiary amine group and at least one quaternary ammonium ion group.

[0017] The present invention relates to the combined use of an amphiphilic block copolymer a) and a block copolymer b) as defined above for the preparation of a material with anti-stick and antibacterial properties.

[0018] The present invention relates to an article with anti-stick and antibacterial properties such as medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional media etc.), textiles, such as for example anti-soiling mats, shoes, clothing, building components, such as for example a door handle, floor coverings, sports facilities, personal protective equipment, comprising a material according to the present invention.

[0019] Finally, the present invention relates to the use of the material as defined above for the preparation of an article with anti-stick and antibacterial properties such as, in particular, medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as, for example, anti-soiling mats, shoes, clothing, building components, such as, for example, a door handle, floor coverings, sports facilities, personal protective equipment.

[0020] DESCRIPTION OF THE FIGURES

[0021] Figure 1 shows a block diagram of the process for preparing a material according to the invention.

[0022] Figure 2: Results of ISO22196 tests after pretreatment (human albumin, human serum, human plasma) of polyurethane-type materials containing a copolymer a) according to examples (2-4) of the invention and comparison

[0023] Figure 3: Results of ISO22196 tests after pretreatment (human albumin, human serum, human plasma) of polyurethane-type materials containing a copolymer a) according to example (5) of the invention and comparison

[0024] Figure 4: Results of ISO22196 tests after pretreatment (human albumin) of PETG-type materials containing a copolymer a) according to example 3 of the invention and comparison

[0025] Figure 5: Results of ISO22196 tests after pretreatment (gastric medium, intralipids) of polyurethane-type materials containing a copolymer a) according to examples (2-4) of the invention and comparison

[0026] DETAILED DESCRIPTION OF THE INVENTION In the context of the present invention, and unless otherwise indicated, the term "comprising" also includes the meaning of "consisting of".

[0027] The term "copolymer" refers to a polymer containing several (at least two) different repeating units. A "repeat unit" consists of a group of atoms repeated multiple times within the polymer to form the polymer chain. The group of atoms constituting the repeating unit is the group of atoms introduced into the polymer chain by the polymerization of a given monomer. A copolymer can be a random copolymer, an alternating copolymer, a block copolymer, or a gradient copolymer. In the context of this invention, it is a block copolymer.

[0028] The term "block copolymer" refers to a copolymer containing, in particular consisting of, a linear sequence of several different blocks, each block being made up of a homopolymer chain, that is to say, made up of a single repeating unit, two adjacent blocks therefore being made up of different repeating units

[0029] The term "statistical copolymer" refers to a copolymer comprising at least two different repeating motifs, in which these different repeating motifs are inserted randomly into the block.

[0030] In the context of the invention, a block of the copolymer can itself be a statistical copolymer.

[0031] In the context of the present invention, the expression "non-stick material" or "material having non-stick properties" indicates that said material has characteristics that prevent it from being passivated or coated by a certain substance. In the context of the present invention, the material is designed to prevent passivation by substances present in bodily fluids, such as blood and its derivatives, urine, saliva, juices, sweat, and in particular organic compounds from the protein, lipid, or polysaccharide families.

[0032] A first object of the present invention relates to a material comprising a polymer matrix in which are dispersed:

[0033] • an amphiphilic block copolymer a) comprising:

[0034] - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl methacrylates, and

[0035] - a hydrophilic block comprising one or more repeating motifs selected from hydrophilic (meth)acrylates, hydrophilic acrylamides and their combinations, and

[0036] • an amphiphilic block copolymer b) comprising: - a hydrophobic block comprising one or more repeating units selected from hydrophobic alkyl methacrylates, and

[0037] - a hydrophilic block comprising one or more repeating motifs selected from alkyl methacrylates comprising at least one tertiary amine group and at least one quaternary ammonium ion group.

[0038] In the context of the present invention, the term "hydrophilic block" refers to a block having favorable interactions with water, resulting in solubility and / or swelling capacity. In the context of the present invention, the term "hydrophobic block" refers to a block not having favorable interactions with water. In the context of the present invention, the term "amphiphilic" refers to a compound (for example, a block copolymer) possessing a hydrophilic portion and a hydrophobic portion. Advantageously, the material of the present invention exhibits the same characteristics on its surface and in its core. In particular, the contents of each of the ingredients throughout the material are identical; specifically, the contents of each ingredient are the same on the surface and in the core of the material.A material whose characteristics are the same on the surface and in its core makes it advantageous to prepare products of variable thickness and in particular of significant thickness.

[0039] Amphibious block copolymer a):

[0040] The amphiphilic block copolymer a) comprises, preferably is composed of:

[0041] - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl or aryl methacrylates, and

[0042] - a hydrophilic block comprising one or more repeating motifs selected from hydrophilic (meth)acrylates, hydrophilic acrylamides acrylates and their combinations.

[0043] By definition, the amphiphilic block copolymer is linear. Advantageously, no repeating motifs other than those constituting the blocks are grafted onto the amphiphilic block copolymer.

[0044] Hydrophobic block of the amphiphilic block copolymer a):

[0045] Preferably, the hydrophobic block consists of one or more repeating units selected from hydrophobic alkyl or aryl methacrylates. The hydrophobic block may consist of a single monomeric unit, thus forming a homopolymer block, or of several different monomeric units, for example, two, thus forming a copolymer block, typically an alternating copolymer. Preferably, the hydrophobic block consists of a single monomeric unit. An alkyl or aryl methacrylate is said to be "hydrophobic" when it lacks water-affinity groups such as carboxylates, sulfates, alcohols, polyoxyethylenated chains, quaternary ammonium compounds, etc.

[0046] Preferably, the hydrophobic block comprises one or more repeating units selected from the group consisting of linear, branched, cyclic, or cyclic and branched alkyl methacrylates, preferably having from 1 to 10 carbon atoms, or aryl methacrylates. Preferably, the hydrophobic block comprises one or more repeating units selected from methyl methacrylate (MMA) and butyl methacrylate (BMA), 2-ethylhexyl methacrylate, and benzyl methacrylate.

[0047] Preferably, the hydrophobic block comprises, in particular is made of, a polymer chosen from poly(butyl methacrylate) (PBMA), poly(methyl methacrylate) (PMMA), most preferably poly(butyl methacrylate).

[0048] In one or more embodiments, the hydrophobic methacrylic block has a number-average molar mass (Mn) between 4000 and 30000 g / mol. In one or more embodiments, the hydrophobic methacrylic block has a number-average molar mass (Mn) between 6000 and 20000 g / mol.

[0049] Hydrophilic block of the amphiphilic block copolymer a):

[0050] Preferably, the hydrophilic block consists of one or more repeating units selected from hydrophilic (meth)acrylates, hydrophilic acrylamides, and combinations thereof. The polymer of the hydrophilic block may consist of a single monomeric unit, thus forming a homopolymer block, or of several different monomeric units, for example, two, thus forming a copolymer block, typically an alternating copolymer.

[0051] In the context of the present invention, the hydrophilic block consists of one or more repeating motifs selected from poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and their combinations.

[0052] The hydrophilic block polymer can consist of a single monomeric motif, thus forming a homopolymer block, or of several different monomeric motifs, for example 2, thus forming a statistical block.

[0053] Preferably, the repeating unit of the hydrophilic block is uncharged. According to one embodiment of the present invention, the hydrophilic block may further comprise one or more repeating units of 4-tert-butylcyclohexyl acrylate (tBCHA). Preferably, the hydrophilic block consists of one or more repeating units selected from poly(ethylene oxide) methacrylates, the combination of 2-hydroxy-3-phenoxypropylacrylate and 4-tert-butylcyclohexyl acrylate, and the combination of N-hydroxyethylacrylamide and N,N-diethylacrylamide.

[0054] In the context of the present invention, the term poly(ethylene oxide) methacrylates (“MAPEG”) refers to poly(ethylene oxide) methacrylate of linear formula H2C=C(CH3)CO(OCH2CH2) n OH (“MAPEG-OH”) and methyl ether of poly(ethylene oxide) methacrylate with linear formula H2C=CCH3CO2(CH2CH2O) nCH3 (“MAPEG-CH3”). The number n is generally between 5 and 30.

[0055] According to one or more embodiments, the hydrophilic poly(methacrylic) block has an average number molar mass (Mn) between 5000 and 150000 g / mol.

[0056] The hydrophilic block polymer is not a zwitterionic species. The hydrophilic block polymer does not consist of, and preferably does not comprise, fluorinated monomeric units.

[0057] AMPHIPHILE BLOCK COPOLYMER a)

[0058] According to one or more embodiments, the amphiphilic block copolymer a) comprises at least one block selected from PBMA, PMMA, PDMAEMA, and PDEAEMA, preferably selected from PBMA and PMMA. According to one or more embodiments, the amphiphilic block copolymer comprises at least one of the following formulations: PBMA-b-PMAPEG, PBMA-bP(tBCHA-co-HPhOPA), PBMA-bP(HEAA-co-DEAA).

[0059] In general, the number-average molar mass of the amphiphilic block copolymer a) may be less than or equal to 500,000 g / mol, preferably between 10,000 and 300,000 g / mol.

[0060] According to one or more embodiments, the amphiphilic block copolymer a) comprises 20 to 80 mol% (mol%) of hydrophilic repeating motifs.

[0061] According to one or more embodiments, the amphiphilic block copolymer a) comprises 50 to 80 mol% (mol%) of hydrophilic repeating motifs.

[0062] According to one or more embodiments, the amphiphilic block copolymer a) comprises from 20 to 80 mol% of hydrophobic repeating units. According to one or more embodiments, the amphiphilic block copolymer a) comprises from 20 to 50 mol% of hydrophobic repeating units. In the context of the present invention, the amphiphilic block copolymer a) can be prepared by controlled polymerization, such as by controlled radical polymerization (reversible addition-fragmentation chain transfer polymerization (RAFT), controlled radical nitroxide polymerization (NMP), etc.).

[0063] Within the framework of the present invention, the polymeric matrix can be of any type provided that good dispersion of the amphiphilic block copolymer can be obtained.

[0064] Preferably, the polymer matrix comprises one or more polymers selected from the group consisting of polyurethane (PU), polyethylene (PE), polyester, glycolized polyester (PETG), alkyl poly(meth)acrylates, polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), ethylene vinyl acetate (EVA), acrylonitrile butadiene styrene (ABS), polysiloxanes, polycarbonates (PC), polyamides, polyacetals, polysulfones, polyaryletherketones (PAEK) and their combinations.

[0065] Preferably, the amphiphilic block copolymer a) is dispersed homogeneously in the matrix.

[0066] In the context of the present invention, the term "homogeneous dispersion" refers to a mixture of ingredients, such as the polymer matrix and the amphiphilic block copolymer, in which the proportions of each ingredient throughout the mixture are identical; in particular, the proportions of each ingredient are the same on the surface and in the core of the mixture. In other words, the amphiphilic block copolymer does not accumulate on the surface of the material. Advantageously, obtaining a homogeneous dispersion allows for good non-stick performance, even at a low concentration of amphiphilic block copolymer.

[0067] Within the framework of the present invention, the content of amphiphilic block copolymer a) in the material is generally greater than or equal to 0.5% by weight and less than or equal to 10% by weight relative to the total weight of the material, preferably less than or equal to 5% by weight, and very preferably less than or equal to 4% by weight.

[0068] According to one embodiment, the content of amphiphilic block copolymer a) is about 2% by weight relative to the total weight of the material, preferably between 1.8% by weight and 2.2% by weight relative to the total weight of the material.

[0069] Amphiphilic block copolymer b):

[0070] The amphiphilic block copolymer b) comprises, preferably consists of: - a hydrophobic block comprising one or more repeating units selected from hydrophobic alkyl methacrylates, and

[0071] - a hydrophilic block comprising one or more repeating motifs selected from alkyl methacrylates comprising at least one tertiary amine group and at least one quaternary ammonium ion group.

[0072] According to one embodiment, the block copolymer b) has a number-average molar mass (Mn) greater than or equal to 15,000 g / mol.

[0073] In one or more embodiments, the block copolymer has a number-average molar mass (Mn) less than or equal to 100,000 g / mol. In one or more embodiments, the block copolymer has a number-average molar mass (Mn) between 15,000 and 70,000 g / mol. In one or more embodiments, the block copolymer has a number-average molar mass (Mn) between 15,000 and 55,000 g / mol. In one or more embodiments, the block copolymer has a number-average molar mass (Mn) between 15,000 and 40,000 g / mol.

[0074] Hydrophobic block of the amphiphilic block copolymer b)

[0075] Preferably, the hydrophobic block consists of one or more repeating units selected from hydrophobic alkyl methacrylates. The hydrophobic block may consist of a single monomeric unit, thus forming a homopolymer block, or of several different monomeric units, for example, two, thus forming a copolymer block, typically a statistical copolymer. Preferably, the hydrophobic block consists of a single monomeric unit.

[0076] Preferably, the hydrophobic block comprises one or more repeating units selected from the group consisting of linear, branched, cyclic, or cyclic and branched alkyl methacrylates, preferably having from 1 to 20 carbon atoms. Preferably, the hydrophobic block comprises one or more repeating units selected from methyl methacrylate (MMA) and butyl methacrylate (BMA).

[0077] Preferably, the hydrophobic block comprises, in particular is made of, a polymer chosen from poly(butyl methacrylate) (PBM), poly(methyl methacrylate) (PMMA), most preferably poly(butyl methacrylate).

[0078] Hydrophilic block of the amphiphilic block copolymer b) According to one or more embodiments, the hydrophilic methacrylic block comprises at least one tertiary amine group and / or quaternary ammonium ion. According to one or more embodiments, the hydrophilic methacrylic monomer (i.e., hydrophilic repeating unit of the hydrophilic methacrylic block) is selected from the group consisting of an N,N-(dialkylamino)alkyl methacrylate, such as an N,N-(dialkylamino)ethyl methacrylate, and a quaternary ammonium ion thereof.

[0079] In one or more embodiments, at least one of the alkyl groups is a substituted or unsubstituted alkyl group and / or comprises between 1 and 8 carbon atoms, in particular between 2 and 6 carbon atoms. The term "substituted" means that the atom or group in question is substituted with at least one element other than a hydrogen atom, for example, substituted with at least one hydrocarbon substituent.

[0080] According to one or more embodiments, when at least one of the alkyl functions is substituted by an element, this element is chosen from the group consisting of an alkyl, an alkenyl, an alkynyl, an aryl, a heteroaryl, an alkylalkenyl, an alkenylalkyl, an alkylalkynyl, an alkynylalkyl, an alkylaryl, an arylalkyl, an alkylheteroaryl, a heteroarylalkenyl, an alkenyllaryl, an alkenylheteroaryl, an arylalkynyl, a heteroarylalkynyl, an alkynyllaryl and an alkynylheteroaryl, the element comprising from 1 to 20 carbon atoms, such as from 2 to 18, 3 to 16, 4 to 14 or 5 to 12 carbon atoms; which element optionally comprising one or more heteroatoms, such as for example N, O, S, P, Si, Sn, Ge, As, F, Cl, Br and I; and / or which element optionally comprising one or more functional groups selected from the list consisting of an alkyl, an alkene, an alkyne, an aryl, a heteroaryl, an alcohol, a ketone, a benzoyl, an aldehyde, a carbonate,a carboxylic acid, a carboxylate, an ester, an ether, a heterocycle, an amine, an amide, an azo, a diazo, a diazoamino, an azide, a secondary imine, a hydrazine, a hydrazone, an amidine, a carbamate, a guanidine, a carbodiimide, a nitrile, an isonitrile, an imide, an azide, a diimide, a thiol, a thioether, a thioketone, a cyanate, a nitrate, a nitrite, a nitro, a nitroso, an oxime, a pyridyl, a thioether, a disulfide, a sulfinyl, a sulfonyl, a thiocyanate, an isothiocyanate, a thione, a phosphorane, a phosphine, a boronate, a borinate, a silane and a halogen, functional groups comprising from 0 to 20 atoms of carbons, such as 1 to 20, 2 to 18, 3 to 5, 16, 4 to 14 or 5 to 12 carbon atoms.

[0081] In one or more embodiments, the hydrophilic methacrylic monomer is selected from the group consisting of N,N-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-(diethylamino)ethyl methacrylate (DEAEMA), and a quaternary ammonium ion thereof. In one or more embodiments, the hydrophilic methacrylic block and / or the hydrophobic methacrylic block further comprises at least one additional repeating unit, such as is selected from the group consisting of styrene (S) and acrylonitrile (ACN).

[0082] According to one or more embodiments, the amphiphilic block copolymer b) comprises at least one block selected from among the PBMA, PMMA, PDMAEMA and PDEAEMA. According to one or more embodiments, the amphiphilic block copolymer b) comprises at least one of the following formulations: PMMA-b-PDMAEMA, PMMA- b- PDEAEMA, PBMA- b- PDMAEMA, PBMA-b-PDEAEMA, P(MMA)-AMA,-co-PDAEMA P(MMA-co-S)-b-PDEAEMA, P(BMA-co-S)-b- PDMAEMA, P(BMA-co-S)-b-PDEAEMA, P(MMA-co-ACN)-b-PDMAEMA, P(MMA-co-ACN)-b- PDEAEMA, P(BMA)-b-co-ACPDAEMA P(BMA-co-ACN)-b-PDEAEMA, PMMA-bP(DMAEMA-co- S), PMMA-bP(DEAEMA-co-S), PBMA-bP(DMAEMA-co-S), PBMA-bP(DEAEMA-co-S), PMMA-b- P(EMAPA-co-ACPMA-co-co- PBMA-bP(DMAEMA-co-ACN), PBMA-b- P(DEAEMA-co-ACN), P(MMA-co-S)-bP(DMAEMA-co-S), P(MMA-co-S)-bP(DEAEMA-co-S), P(BMA-co-S)-bP(SAEMA), P(BMA-co-S)-bP(DEAEMA-co-S), P(MMA-co-ACN)-b- P(DMAEMA-co-ACN), P(MMA-co-ACN)-bP(DEAEMA-co-ACN), P(BMA-co-ACN)-bP(DMAEMA-co- ACN),P(BMA-co-ACN)-bP(DEAEMA-co-ACN), P(MMA-co-S)-bP(DMAEMA-co-ACN), P(MMA-co- S)-bP(DEAEMA-co-ACN), P(BMA-co-S)-bP(DMAEMA-co-ACN), P(BMA-co-S)-bP(DEAEMA-co-ACN), P(MMA-co-ACN)-bP(DMAEMA-co-S), P(MMA-co-ACN)-bP(DEAEMA-co-S), P(BMA-co-ACN)-bP(DMAEMA-co-S) and P(BMA-co-ACN)-bP(DEAEMA-co-S) and at least one quaternary ammonium ion thereof. According to one or more embodiments, the block copolymer comprises one of the following formulations: P(BMA-co-S)-bP(DMAEMA-co-S), and P(BMA-co-ACN)-bP(DMAEMA-co-ACN).

[0083] In one or more embodiments, the amphiphilic block copolymer b) comprises 20 to 80 mol% of cationic hydrophilic repeating units. In one or more embodiments, the amphiphilic block copolymer b) comprises 50 to 70 mol% of cationic hydrophilic repeating units. In one or more embodiments, the amphiphilic block copolymer b) comprises 20 to 80 mol% of hydrophobic repeating units. In one or more embodiments, the amphiphilic block copolymer b) comprises 20 to 50 mol% of hydrophobic repeating units. In one or more embodiments, the amphiphilic block copolymer b) comprises 3 to 20 wt% of additional repeating units. According to one or more embodiments, the amphiphilic block copolymer b) comprises 3 to 10 wt% of additional repeating motifs.In one or more embodiments, the hydrophobic methacrylic block has a number-average molar mass (Mn) between 4000 and 30000 g / mol. In one or more embodiments, the hydrophobic methacrylic block has a number-average molar mass (Mn) between 6000 and 20000 g / mol.

[0084] Within the framework of the present invention, the amphiphilic block copolymer b) can be prepared by controlled polymerization.

[0085] According to one or more embodiments, the process includes the preparation of the amphiphilic block copolymer b) by controlled polymerization. According to one or more embodiments, the radical polymerization is carried out by controlled radical polymerization with nitroxides (NMP) in the presence of the nitroxide N-(2-methylpropy1)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl, known as SG1. According to one or more embodiments, the radical polymerization is carried out in the presence of the alkoxyamine (N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropy1)-O-(2-carboxylprop-2-y1), marketed by Arkema under the name BlocBuilder MA.In one or more embodiments, the preparation of the methacrylic-type amphiphilic block copolymer comprises: the polymerization of one of the hydrophilic or hydrophobic monomers (optionally with an additional repeating unit) to form a first hydrophilic or hydrophobic block, respectively; then the extension of this first block by polymerization of the other hydrophobic or hydrophilic monomer (optionally with an additional repeating unit) to form the hydrophilic-hydrophobic-block or hydrophobic-hydrophilic-block copolymer. In one or more embodiments, the polymerization is carried out by heating the monomers, preferably under an inert atmosphere (e.g., nitrogen or argon), in the presence of a polymerization initiator (BlocBuilder MA or macroalkoxyamine forming the first block of the copolymer) and SG1 free nitroxide.According to one or more embodiments, polymerization is carried out at a temperature between 80°C and 130°C. According to one or more embodiments, polymerization is carried out at a temperature of 90°C. According to one or more embodiments, polymerization is carried out for a duration of between 4 and 15 hours. According to one or more embodiments, polymerization is carried out for a duration of between 4 and 10 hours, such as 5.5 hours. According to one or more embodiments, polymerization is carried out until a conversion of between 30% and 80% is achieved for each block (hydrophilic and hydrophobic). According to one or more embodiments, polymerization is carried out until a conversion of between 30% and 60% is achieved, such as between 30% and 50% for each block (hydrophilic and hydrophobic).Depending on one or more embodiments, the quaternization of tertiary amines can be carried out either directly on the monomer or on the copolymer. Quaternization can be achieved by alkylation using various agents such as alkyl halides or alkyl tosylates.

[0086] Within the framework of the present invention, the polymer matrix can be of any type provided that good dispersion of the amphiphilic block copolymers a) and b) can be obtained.

[0087] Preferably, the polymer matrix comprises one or more polymers selected from the group consisting of polyurethane (PU), polyethylene (PE), polyester, glycolized polyester (PETG), alkyl poly(meth)acrylates, polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), ethylene vinyl acetate (EVA), acrylonitrile butadiene styrene (ABS), polysiloxanes, polycarbonates (PC), polyamides, polyacetals, polysulfones, polyaryletherketones (PAEK) and their combinations.

[0088] Preferably, the amphiphilic block copolymers a) and b) are dispersed homogeneously in the matrix. In one particular embodiment, the dispersion of the amphiphilic block copolymers a) and b) is carried out simultaneously in the polymer matrix. In another particular embodiment, the dispersion of the amphiphilic block copolymers a) and b) is carried out successively in the polymer matrix. By way of illustration, the amphiphilic block copolymer a) may be dispersed in the polymer matrix followed by the dispersion of the amphiphilic block copolymer b) in the intermediate dispersion comprising the amphiphilic block copolymer a) and the polymer matrix.In the context of the present invention, the term "homogeneous dispersion" refers to a mixture of ingredients, such as the polymer matrix and amphiphilic block copolymers, in which the proportions of each ingredient throughout the mixture are identical; in particular, the proportions of each ingredient are the same on the surface and in the core of the mixture. In other words, the amphiphilic block copolymers do not accumulate on the surface of the material. Advantageously, obtaining a homogeneous dispersion allows for good non-stick performance, even at low concentrations of the amphiphilic block copolymer.

[0089] Advantageously, obtaining a homogeneous dispersion allows for good antibacterial efficacy, even at low concentrations of the amphiphilic block copolymer b).

[0090] Advantageously, obtaining a homogeneous dispersion allows for good antibacterial and anti-adhesive efficacy, even at low concentrations of amphiphilic block copolymers a) and b). In the context of the present invention, the content of amphiphilic block copolymer a) in the material is generally greater than or equal to 0.5% by weight and less than or equal to 10% by weight relative to the total weight of the material, preferably less than or equal to 6% by weight, and very preferably less than or equal to 4% by weight.

[0091] According to one embodiment, the content of amphiphilic block copolymer a) is about 2% by weight relative to the total weight of the material, preferably between 1.8% by weight and 2.2% by weight relative to the total weight of the material.

[0092] Within the framework of the present invention, the content of amphiphilic block copolymer b) in the material is generally greater than or equal to 0.5% by weight and less than or equal to 10% by weight relative to the total weight of the material, preferably less than or equal to 6% by weight, and very preferably less than or equal to 4% by weight.

[0093] According to one embodiment, the content of amphiphilic block copolymer b) is about 2% by weight relative to the total weight of the material, preferably between 1.8% by weight and 2.2% by weight relative to the total weight of the material.

[0094] Within the framework of the present invention, the total content of amphiphilic block copolymers a) and b) in the material is generally greater than or equal to 1% by weight relative to the total weight of the material, less than or equal to 20% by weight relative to the total weight of the material, preferably less than or equal to 10% by weight, and very preferably less than or equal to 6% by weight.

[0095] The present invention also relates to a method for preparing a material according to the present invention.

[0096] Preferably, the process includes a step in which the polymer matrix and the amphiphilic block copolymers a) and b) are mixed, simultaneously or successively, in at least one extruder to obtain a rod of material. In one embodiment, the amphiphilic block copolymers a) and b) are premixed. In another embodiment, the polymer matrix is ​​mixed with one of the amphiphilic block copolymers in at least one extruder, and then the second amphiphilic block copolymer is added in at least one extruder. The extrusion step can be carried out using one or more extruders. This rod of material is then shaped by extrusion or injection molding.

[0097] Advantageously, the preparation of the material according to the present invention by extrusion makes it possible to obtain a material in which the copolymers do not migrate to the surface. This process allows the preparation of a material with a stabilized composition. Optionally, the extrusion step can be preceded by a compounding step of the polymer matrix and one or more amphiphilic block copolymers.

[0098] The present invention relates to the combined use of an amphiphilic block copolymer a) and an amphiphilic block copolymer b) as defined above for the preparation of a material with anti-stick and antibacterial properties.

[0099] Advantageously, the material according to the present invention exhibits non-stick properties. This means that the material possesses characteristics that prevent the adhesion and / or accumulation of a substance on its surface. In particular, the material prevents the adhesion and / or accumulation of substances or dirt, especially substances derived from bodily fluids, such as blood and its derivatives, urine, saliva, juices, or sweat, and especially organic compounds from the protein, lipid, or polysaccharide families.

[0100] Advantageously, the materials according to the present invention have mechanical properties suitable for use in the preparation of an article with anti-stick and antibacterial properties such as, in particular, medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, filtration membranes, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as, for example, anti-soiling mats, shoes, clothing, building components, such as, for example, a door handle, floor coverings, sports facilities, personal protective equipment.

[0101] Preferably, the materials according to the present invention have mechanical properties suitable for their use in the preparation of an article with anti-stick and antibacterial properties such as, in particular, medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as, for example, anti-soiling mats, shoes, clothing, building components, such as, for example, a door handle, floor coverings, sports facilities, personal protective equipment.

[0102] Advantageously, the materials according to the present invention prevent the formation of a bacterial biofilm on their surface. In one or more embodiments, the materials are particularly active against Gram-positive and Gram-negative bacteria, as well as pathogenic bacteria. In one or more embodiments, the materials do not lose their activity over time and do not require replacement in the event of prolonged use or deterioration. In one or more embodiments, the materials do not release biocidal compounds into the environment. In one or more embodiments, the material and / or its manufacturing process is adapted to prevent the release of molecules and thus the loss of activity over time, as well as the problems of side effects and contamination of the patient and / or the environment.

[0103] The material according to the present invention may also be of interest as antifungal, antiviral or anti-inflammatory materials.

[0104] Advantageously, the combined use of an amphiphilic block copolymer a) and an amphiphilic block copolymer b) gives the resulting material anti-stick and antibacterial properties on its surface, but also provides antibacterial protection for fluids in contact with the material.

[0105] Examples:

[0106] [Table 1]

[0107] Example 1: Synthesis and Characterization of PMBA. In a suitable reactor, solubilize 1 eq. of AIBN (azobisisobutyronitrile), 5 eq. of RAFT agent 4-cyanopentanoic acid dithiobenzoate (CPADB), and 386 eq. of BMA in toluene (1 volume of monomer / 1 volume of solvent) and stir until the mixture is completely homogenized. Degas the mixture by bubbling with argon for 30 min. Then heat the mixture to 70°C with stirring (700 rpm) for 8 h. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in a MeOH / H2O mixture (4:1) twice to remove all residual monomers. Allow the mixture to settle and remove the supernatant before drying under vacuum.

[0108] Characterizations:

[0109] NMR 1 H: ô (CDCU) 3.93 (2H, m, -O-CH2-); 1.81 (2H, s, -C-CH2-C-); 1.61 (2H, m, -O-CH2-CH2-); 1.40 (2H, m, -CH2-CH3); 0.94 (6H, m, -CH3).

[0110] BMA conversion = 83%

[0111] SEC: (THF)

[0112] Mn = 8000 g / mol

[0113] D = 1.43

[0114] Example 2: Synthesis and characterization of an amphiphilic block copolymer PBMA-b-PMAPEG360 (AA360)

[0115] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of PBMA RAFT, and 930 eq. of PEGMA360 in methyltetrahydrofuran (MeTHF) (1 volume of monomer / 8 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture under argon for 30 minutes, then heat the mixture to 70°C with stirring (700 rpm) for 6 hours. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane to recover a gel.

[0116] Characterizations:

[0117] MAPEG conversion = 62%

[0118] (NMR Estimation) 1H) Mn = 50,000 g / mol

[0119] Example 3: Synthesis and characterization of an amphiphilic block copolymer PBMA-b-PMAPEG500 (AA500)

[0120] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of PBMA RAFT, and 930 eq. of PEGMA500 in methyltetrahydrofuran (MeTHF) (1 volume of monomer / 6 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture under argon for 30 minutes, then heat the mixture to 70°C with stirring (700 rpm) for 6 hours. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane.

[0121] Example 4: Synthesis and characterization of an amphiphilic block copolymer PBMA-b-PMAPEG950 (AA950)

[0122] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of PBMA RAFT, and 930 eq. of PEGMA950 in methyltetrahydrofuran (MeTHF) (1 volume of monomer / 4 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture under argon for 30 minutes, then heat the mixture to 70°C with stirring (700 rpm) for 6 hours. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane. The resulting solid is dried under vacuum.

[0123] Characterization of amphiphilic block copolymers a):

[0124] [Table 2]

[0125] Example 5: Synthesis and characterization of an amphiphilic block copolymer PBMA-bP(HEAA-co-DEAA). In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of RAFT PBMA macroinitiator, 258 eq. of DEAA, and 258 eq. of HEAA in a toluene / DMSO (1:1) mixture (1 volume of monomer to 3 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture by bubbling with argon for 30 min. Then heat the mixture to 70°C with stirring (700 rpm) for 3 h. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane twice to remove all residual monomers. Allow to settle and remove the supernatant before drying under vacuum.

[0126] Characterizations:

[0127] HEAA conversion = 99%

[0128] DEAA conversion = 99%

[0129] SEC: (DMF)

[0130] Mn = 23200 g / mol

[0131] D = 1.2

[0132] Example 6: Synthesis and characterization of an amphiphilic block copolymer b)

[0133] An amphiphilic block copolymer b) PBMA-b-PDMAEMA was prepared according to a previously described three-step procedure. (Benkhaled, BT; Hadiouch, S.; Olleik, H.; Perrier, J.; Ysacco, C.; Guillaneuf, Y.; Gigmes, D.; Maresca, M.; Lefay, C. Elaboration of antimicrobial polymeric materials by dispersion of well-defined amphiphilic methacrylic SG1-based copolymers. Polymer Chemistry 2018, 9 (22), 3127-3141. DOI: 10.1039 / c8py00523k). The amphiphilic block copolymer b)a was first prepared in two steps by nitroxide-mediated polymerization (NMP) with the alkoxyamine BlocBuilder as the initiator / controlling agent and in the presence of SG1 nitroxide. Acrylonitrile was used as a comonomer to ensure good control of the polymerization. At the end of polymerization, the copolymer was recovered by precipitation over cold pentane. The DMAEMA composition of the copolymer (FDMAEMA) was determined by NMR. 1H in CDCL (FDMAEMA = 0.64) and the number-average molecular weight (Mn) measured by SEC / DMF (Mn = 18,400 g mol-1). In a third step, the copolymer was quaternized with methyl iodide (Mel) to obtain the amphiphilic block copolymer b).

[0134] Example 7: Preparation of materials according to the invention

[0135] [Table 3]

[0136]

[0137] The amphiphilic block copolymers a) of examples 2, 3, 4 and 5 and the amphiphilic block copolymer b) of example 6 are used to form materials according to the invention.

[0138] Example 8 (Comparative) A comparative commercial polyurethane material comprising a silver zeolite-based antibacterial agent was used.

[0139] PHYSICO-CHEMICAL CHARACTERIZATION

[0140] Measurement of Young's modulus and breaking stress

[0141] Mechanical tests were performed according to ASTM D412, which describes a tensile testing protocol suitable for rubbers and elastomers. This method consists of performing tensile tests at a stretch rate of 500 mm / min at ambient temperature and humidity. For each formulation, the Young's modulus and maximum stress values ​​were extracted by taking the statistical average of 5 tensile bars.

[0142] [Table 4]

[0143] Epifluorescence Microscopy

[0144] A solution of bovine serum albumin labeled with fluorescein isocyanate (BSA-FITC) at 2 mg / mL is prepared and brought into contact with the analyte surfaces for 2 hours before being rinsed and left to dry.

[0145] After treatment, the surfaces are observed under an epifluorescence microscope to acquire images on which the proteins appear in green.

[0146] The surface area covered by proteins is calculated using ImageJ software. The results are presented in Table 5.

[0147] [Table 5]

[0148] ANTIBACTERIAL TESTS AGAINST S. AUREUS AND E. COLI AFTER DIFFERENT PRE-TREATMENTS (serum, plasma, albumin, gastric medium, intralipids)

[0149] The antibacterial activity of antibacterial and anti-adhesive materials was tested. To replicate the environment of use in blood, gastric fluid, or intralipids, the films were in contact with a pretreatment solution, and their antibacterial activity was then tested. To simulate the blood environment, the films were in contact with serum, plasma, and albumin, the main constituents of blood.

[0150] Reference surfaces and analytes in the form of discs with a diameter of D = 3 or squares with sides of 2 cm are sterilized (Et₂O, UV, etc.). These samples are placed in a 6-well plate. 2 mL of the desired biological medium (plasma, serum, protein solution) is added to each well to ensure complete immersion of the sample before incubation for 1 h at 37°C with orbital shaking. The biological fluid is then removed before two washes are performed with 2 mL of PBS followed by one wash with 2 mL of water, each with orbital shaking at 450 rpm for 5 min. Finally, the analytes are allowed to dry for 1 h at 37°C and are sterilized with UV as a precaution before running the ISO22196 test.

[0151] ISO22196 Test:

[0152] Reference surfaces and analytes in the form of discs with a diameter D = 3 or squares with sides of 2 cm are sterilized (Et₂O, UV, etc.). From this point onward, they will always be handled aseptically. These samples are placed in a 6-well plate before being covered with a 112 L drop of a 2 x 10⁻¹⁰ bacterial suspension. 6 bacteria. mL' 1 This droplet is then flattened by a piece of Stomacher™ homogenization bag cut into a 2 cm square and previously sterilized under UV light, to increase contact between the bacteria and the test surface. The analytes are then incubated at 37°C for 24 hours, before the addition of 5 mL of TSB to stop bacterial growth. This new mixture is then added to an additional 5 mL of TSB (1 / 10 dilution). ème ) then continue the dilutions to 1 / 100 ème , at 1 / 1000 ème and at 1 / 10000 èmeIn sterile water, 10 µL of each dilution are placed in a quarter of a Petri dish on an agar gel and then gently spread over the entire designated area. After overnight incubation at 37°C, the number of colonies formed can be counted, and by returning to the initial concentration, the number of bacteria that survived the antibacterial properties of the surfaces can be determined. The test is performed 5 times for each sample.

[0153] Antibacterial activity was tested on different pretreatments and in the presence of different bacteria. The results correspond to means ± SD. (n = 5). Statistical significance was obtained by ANOVA test (*p<0.05; **p<0.01 and ****p<0.001).

[0154] The results of the antibacterial tests carried out on polyurethane (Pellethan) type materials of examples 7.1, 7.2, 7.3, 7.5, 7.6, 7.7 and 7.8 are presented in Figure 2 for pretreatments of human albumin, human serum and human plasma and in Figure 5 for pretreatments of simulated gastric medium and intralipids.

[0155] The results of the antibacterial tests carried out on polyurethane (Pellethane) type materials from Examples 7.9 to 7.11 are shown in Figure 3 for pretreatments of human albumin, human serum and human plasma type.

[0156] The results of antibacterial tests carried out on glycolized poly(ethylene terephthalate) (PETG) type materials of example 7.12 are shown in Figure 4 for a human albumin type pretreatment.

[0157] The logarithm of reduction must be greater than 3 for the material to be considered antibacterial. It can be seen that, compared to materials without copolymers (b), materials containing both copolymers have better antibacterial activity in the presence of pretreatment (Figure 2, examples 7.2 and 7.7, to be compared with reference 7.5).

Claims

DEMANDS 1. Material comprising a polymeric matrix in which are dispersed: • an amphiphilic block copolymer a) comprising: - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl methacrylates, and - a hydrophilic block comprising one or more repeating motifs selected from hydrophilic (meth)acrylates, hydrophilic acrylamides and their combinations, and • an amphiphilic block copolymer b) comprising: - a hydrophobic block comprising one or more repeating motifs selected from hydrophobic alkyl methacrylates, and - a hydrophilic block comprising one or more repeating motifs selected from alkyl methacrylates comprising at least one tertiary amine group and at least one quaternary ammonium ion group.

2. Material according to claim 1 comprising from 0.5 to 10%, preferably from 0.5 to 6%, more preferably from 0.5 to 4%, by weight of the amphiphilic block copolymer a) relative to the total weight of the material, and / or from 0.5 to 10% by weight, preferably from 0.5 to 6% by weight, more preferably from 0.5 to 4%, of the amphiphilic block copolymer b) relative to the total weight of the material.

3. Material according to claim 1 or 2, wherein the repeating pattern of the hydrophobic block of the amphiphilic block copolymer a) and of the amphiphilic block copolymer b) is independently selected from the following hydrophobic alkyl methacrylates: methyl methacrylate, butyl methacrylate, and their combinations.

4. Material according to any one of claims 1 to 3, wherein the repeating pattern of the hydrophilic block of the amphiphilic block copolymer a) is selected from poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and combinations thereof.

5. Material according to any one of claims 1 to 4, wherein the repeating pattern of the hydrophilic block of the amphiphilic block copolymer b) is selected from N,N-(dialkylamino)alkyl methacrylates and quaternary ammonium ions thereof.

6. Material according to any one of claims 1 to 5, wherein the amphiphilic block copolymer a) is selected from the following copolymers: PBMA-b-PMAPEG, PBMA-bP(tBCHA-co-HPhOPA), PBMA-bP(HEAA-co-DEAA).

7. Matériau selon l’une quelconque des revendications 1 à 6 dans lequel le copolymère à blocs amphiphile b) est choisi parmi PMMA-b-PDMAEMA, PMMA-b-PDEAEMA, PBMA- b-PDMAEMA, PBMA-b-PDEAEMA, P(MMA-co-S)-b-PDMAEMA, P(MMA-co-S)-b-PDEAEMA, P(BMA-co-S)-b-PDMAEMA, P(BMA-co-S)-b-PDEAEMA, P(MMA-co-ACN)-b-PDMAEMA, P(MMA-co-ACN)-b-PDEAEMA, P(BMA-co-ACN)-b-PDMAEMA, P(BMA-co-ACN)-b- PDEAEMA, PMMA-b-P(DMAEMA-co-S), PMMA-b-P(DEAEMA-co-S), PBMA-b-P(DMAEMA- co-S), PBMA-b-P(DEAEMA-co-S), PMMA-b-P(DMAEMA-co-ACN), PMMA-b-P(DEAEMA-co- ACN), PBMA-b-P(DMAEMA-co-ACN), PBMA-b-P(DEAEMA-co-ACN), P(MMA-co-S)-b- P(DMAEMA-co-S), P(MMA-co-S)-b-P(DEAEMA-co-S), P(BMA-co-S)-b-P(DMAEMA-co-S), P(BMA-co-S)-b-P(DEAEMA-co-S), P(MMA-co-ACN)-b-P(DMAEMA-co-ACN), P(MMA-co- ACN)-b-P(DEAEMA-co-ACN), P(BMA-co-ACN)-b-P(DMAEMA-co-ACN), P(BMA-co-ACN)-b- P(DEAEMA-co-ACN), P(MMA-co-S)-b-P(DMAEMA-co-ACN), P(MMA-co-S)-b-P(DEAEMA- co-ACN), P(BMA-co-S)-b-P(DMAEMA-co-ACN), P(BMA-co-S)-b-P(DEAEMA-co-ACN), P(MMA-co-ACN)-b-P(DMAEMA-co-S),P(MMA-co-ACN)-bP(DEAEMA-co-S), P(BMA-co-ACN)-bP(DMAEMA-co-S) and P(BMA-co-ACN)-bP(DEAEMA-co-S) and a quaternary ammonium ion thereof.

8. Material according to any one of claims 1 to 7, wherein the amphiphilic block copolymer a) has a number-average molar mass (Mn) less than or equal to 500,000 g / mol, preferably between 10,000 and 300,000 g / mol.

9. Material according to any one of claims 1 to 8 in which the amphiphilic block copolymer b) has a number-average molar mass (Mn) greater than or equal to 15,000 g / mol and less than or equal to 100,000 g / mol, preferably between 15,000 and 70,000 g / mol.

10. Material according to any one of claims 1 to 9, wherein the polymer matrix comprises one or more polymers selected from polyurethane (PU), polyethylene (PE), polyester, glycol-modified polyester (PETG), alkyl poly(meth)acrylates, polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), ethylene vinyl acetate (EVA), acrylonitrile butadiene styrene (ABS), polysiloxanes, polycarbonates (PC), polyamides, polyacetals, polysulfones, polyaryletherketones (PAEK) and their combinations.

11. Combined use of an amphiphilic block copolymer a) and a block copolymer b) as defined in any one of claims 1 to 10 for the preparation of a material with anti-stick and antibacterial properties.

12. Article with anti-stick and antibacterial properties such as, in particular, medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as, for example, anti-soiling mats, shoes, clothing, building components, such as, for example, a door handle, floor coverings, sports facilities, personal protective equipment, comprising a material as defined in any one of claims 1 to 10.

13. Use of the material as defined in any one of claims 1 to 10 for the preparation of an article with non-stick and antibacterial properties.

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