CELLULOSIC SUBSTRATE MADE HYDROPHOBIC AND OLEOPHOBIC BY GRAFTING FLUORINE-FREE COMPOUNDS, AS WELL AS METHODS FOR OBTAINING SAME

Abstract

The present invention relates to a cellulosic substrate made hydrophobic and oleophobic by grafting fluorine-free compounds (formula 1), such as a fabric, as well as methods for obtaining it by grafting isocyanate-type compounds. (abstract figure = formula (1))

Description

Title of the invention: CELLULOSIC SUBSTRATE MADE HYDROPHOBIC AND OLEOPHOBIC BY GRAFTING FLUORINE-FREE COMPOUNDS, AS WELL AS METHODS FOR OBTAINING SAME

[0001] The present invention relates to a cellulosic substrate made hydrophobic and oleophobic by grafting fluorine-free compounds, as well as its methods of obtaining.

[0002] The textile and clothing industry uses 25% of all chemicals manufactured worldwide and contributes significantly to environmental pollution, particularly through the ubiquitous water-repellent finishes in textiles, both for consumer products and technical applications.

[0003] The textile industry often refers to these chemicals as durable water repellents (DWRs), but the market's leading technology doesn't just repel water. Since their introduction in the 1950s, per- and polyfluoroalkyl polymer substances (PFAS) have achieved the highest level of oil and water resistance.

[0004] Water-repellent properties are essential for protection against harmful liquids, for example in medical textiles and protective clothing in the oil and gas industry; they are also vital for the health, safety and comfort of outdoor sports enthusiasts in adverse weather or extreme environmental conditions. End-user requirements differ depending on the specific risks encountered and the environment of use. Water repellency in outdoor clothing is most often associated with outdoor rainwear, providing protection against rain and the external environment, resisting rain penetration while allowing thermoregulation of the body; a garment with insufficient water-repellent properties increases the risk of hypothermia.When it comes to medical textiles, the exposure and transfer of blood and body fluids between patients and medical staff during first aid or in hospitals is of great concern, with the risk of transferring bacteria and viruses. Repellency of blood and body fluids is essential for occupational protection and a repellent finish is required to achieve sufficient barrier properties, a high level of repellency of which is currently provided by fluoropolymers.

[0005] PFAS used for repellent-type textile modifications most often comprise non-fluorinated polymer backbones with side chains polyfluoropolymers that branch from the main chain in comb-like structures. The length and degree of fluorination, the chemical nature of the carbon backbone, and the flexibility of the spacer units (non-fluorinated segments) that connect the side chains to the main chain influence the performance characteristics of these side-chain fluorinated polymers (SFPs). The most effective water repellents are based on SFPs with long perfluoroalkyl side chains (L-SFPs). The high level of hydrophobicity and oleophobicity provided by SFPs is due to the generation of low surface energy fiber surfaces by the orientation and stacking of the -CF3 end groups within the side chains.

[0006] The dispersal of PFAS by-products during the production of textiles containing them, their use and their end of life is of great concern. These PFAS derivatives can be production residues, substances released by tearing (e.g., abrasion) or compounds formed by degradation processes. The ultimate contaminants released from textiles containing L-SFP-based compounds are long-chain perfluoroalkyl-carboxylic acids (PFCAs). These perfluoroalkyl acids (PFAAs) are criticized for their toxicity and extreme persistence in the environment and have been widely identified in wildlife and humans worldwide. Within the European Union (EU), perfluorooctanesulfonic acid (PFOS) is regulated at detectable levels of 1pg.m2 in textile fabrics.While limits for perfluorooctanoic acid (PFOA) are currently under discussion within the EU, Norway has already set its limit at 1pg.m2 in textile applications. The bioaccumulation of PFOA in humans and in the food chain, combined with its toxicity, is a major concern.

[0007] The main challenge is to eliminate long-chain PFAS and maintain the required functionality in water-repellent textiles. Substitution with "short" side-chain fluoropolymers (S-SFPs) with shorter fully fluorinated chain lengths such as C6 or C4 analogues has taken place, but there are also increasing concerns about the persistence and toxicology of these short-chain analogues. The extreme persistence of short-chain PFAS means that the release of these compounds from textiles (and other sources) could become a global threat, as not all future effects are currently known and their release to groundwater, for example, is difficult to reverse.

[0008] In this context, various new non-fluorinated solutions have been developed to make textile surfaces water-repellent. Permanent non-fluorinated water repellents consist of or include different architectures, including linear polyurethanes, hyperbranched polymers, or nanoparticles. Functional motifs in terms of liquid repellency are generally either saturated alkyl chains or related to polydimethylsiloxane (PDMS) chemistry.

[0009] Thus, some manufacturers have developed and are currently producing non-fluorinated permanent water repellents that are more environmentally friendly alternatives to the persistent PFAS chemistry. However, these compounds generally have low oleophobicity. This lack of oleophobicity makes the ultimate application of these non-fluorinated compounds in textiles still uncertain.

[0010] The aim of the invention is to provide non-fluorinated materials and their methods of obtaining which avoid the aforementioned drawbacks.

[0011] Thus, one of the objectives of the invention is to provide hydrophobic non-fluorinated materials which also have sufficient oleophobicity for the desired applications.

[0012] Another objective of the invention is to enable robust treatment, by formation of covalent bonds, of cellulose substrates, using an easily implemented, simple, rapid and inexpensive method.

[0013] Yet another object of the invention is to provide materials as described above, which are also soft to the touch.

[0014] Thus, according to a first aspect, the invention relates to a cellulosic substrate carrying on at least part of its surface a plurality of groups of the following formula (I):

[0015] [Chem.l] OO YL JL 1Z ] ....... O 'NK-hT 'Y'^ Ht । t - m

[0016] in which:

[0017] Y is selected from O and NH, or is a single bond;

[0018] i is chosen from 0 and 1;

[0019] X represents a group of the following formula (II):

[0020] [Chem.2]

[0021] j and k are independently chosen from 0 and 1;

[0022] Xa and Xc are independently chosen from: - the Xai groups being linear, branched and / or cyclic C1-C12 alkane diyls, in particular the groups of formula -(CH2)n- with n from 1 to 12, or linear and branched C2-Ci2 alkene diyls, the Xai groups being in particular linear and branched C1-Ci2 alkane diyls; - groups of formula -Xai-NH-Xar, where Xai is at each occurrence independently as defined above, in particular groups of formula -(CH2)n-NH-(CH2)m- with n and m being independently from 1 to 12; - groups of formula -Xai-NHC(=O)-NH-Xar or -XarNHC(=O)-NH-X ai-NHC(=O)-NH-Xar, where Xai is at each occurrence independently as defined above, in particular groups of formula -(CH2)n-NHC(=O)-NH-(CH2)m- with n and m being independently from 1 to 12;

[0023] Xb is chosen from: - linear, branched and / or cyclic CrCi2 alkane diyls, in particular groups of formula -(CH2)n- with n from 1 to 12, branched CrCi2 alkane triyls, linear and branched C2-Ci2 alkene diyls, the Xb groups being in particular linear and branched CrCi2 alkane diyls or triyls; optionally carrying, in particular in terminal position(s), at least one group -(O-CH2-CH2)P- or -(O-CH2-C(CH3)H)P-, with p being an integer from 1 to 3; - arene diyls and heteroarene diyls;

[0024] Xb being optionally substituted by a group A of the following formula (III):

[0025] [Chem.3]

[0026] Xc, Y, i, Z and R being as defined above or below,

[0027] Z is chosen from linear, branched and / or cyclic C1-C12 alkane diyls and linear and branched C2-C12 alkene diyls, Z being in particular a linear C2 alkane or alkene diyl, said group Z being optionally substituted by a -COOH or -COO group;

[0028] R is chosen from: - the groups of formula -NRaRb, and the groups -N+RaRbRc, in which Ra, Rb and Rc are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), and - aliphatic polyols.

[0029] When the groups of formula (I) comprise an ionized group, such as for example a -COO group or an -N+RaRbRc group, said ionized groups may be in contact with a counterion, as is well known to those skilled in the art.

[0030] By ZR, we indicate that R substitutes Z, this substitution being able to be in the terminal position, or not, of Z.

[0031] Without wishing to be restricted to any theory, the chain carrying the R group makes it possible to confer hydrophobic properties on the cellulose substrate, while the R group itself, surprisingly, makes it possible to confer oleophobic properties on this cellulose substrate.

[0032] According to a preferred embodiment, the substrate of the invention does not comprise fluorinated compounds, nor does it carry fluorinated chains, for example polyfluorinated or even perfluorinated.

[0033] According to a particular embodiment, the substrate of the invention as described previously comprises a plurality of units of the following formula (1):

[0034] [Chem.4] (1).

[0035] Thus, the substrate of the invention is capable of comprising, in addition to the units of formula (1), units of the D-glucose type, substituted or not, in particular not substituted.

[0036] According to a particular embodiment, X is of one of the following formulas:

[0037] [Chem.5] O M " - NN HH (nbk or OO v U v A: - * , . At t,. Ah £. ...Ar ■ NNNN -n ri n (He).

[0038] According to a particular embodiment, R is chosen from the groups of formula -NRaRb, wherein Ra and Rb are independently selected from H and alkyl linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R being in particular chosen from the groups of formula -NH2, -NRaH, Ra being more particularly a methyl or an ethyl, or -NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in the terminal position(s), -NRaRb being for example of the following formula:

[0039] [Chem.6] ..OH 'N' HOX OH

[0040] According to a particular embodiment, R is chosen from the groups of formula -N+RaRbH, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in terminal position(s), R being in particular chosen from the groups of formula -N+H2, -N+RaH, Ra being more particularly a methyl or an ethyl, or -N+RaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N+RaRb being for example of the following formula:

[0041] [Chem.7] ..OH 'NH' OH

[0042] Aliphatic polyols are in particular polyols comprising at least two -OH groups, in particular polyols comprising at least three -OH groups, for example polyols comprising three -OH groups.

[0043] According to a particular embodiment, R is chosen from aliphatic polyols, in particular from linear and branched C1-C6 alkyls, substituted by at least two -OH groups, in particular in the terminal position(s), R being for example of the following formula:

[0044] [Chem. 8] HO^X^ GH OH

[0045] According to a particular embodiment, the group Y-(Z)rR is of one of the following formulas: • -NH-Z-NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s),

[0046] R being in particular chosen from the groups of formula -NH2, -NRaH, Ra being more particularly a methyl or an ethyl, or -NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s); • -OZ-NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls substituted by at least one -OH group, in particular in terminal position(s),

[0047] R being in particular -NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), -NRaRb being for example of the following formula:

[0048] [Chem.9] ^0H HO.^.À^OH OH - • -NH-Z-N+RaRbH, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R being in particular chosen from the groups of formula -N+H2, -N+RaH, Ra being more particularly a methyl or an ethyl, or -N+RaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in terminal position(s); • -OZ-N+RaRbH, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), R being in particular -N+RaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N+RaRb being for example of the following formula:

[0049] [Chem. 10] ..OH x ■ . ® ! "NH HOX XK, '"OH OH ; • -NH-R, in which R is chosen from aliphatic polyols, in particular from linear and branched C1-C6 alkyls, substituted by at least two -OH groups, in particular in terminal position(s), R being for example of the following formula:

[0050] [Chem. 11] OH

[0051] According to a particular embodiment, Xb is chosen from the following groups:

[0052] [Chem. 12]

[0053] A and p being as defined previously.

[0054] According to a particular embodiment, the groups of formula (I) are chosen from the groups of the following formula:

[0055] [Chem. 13] HHHH' ' R (M

[0056] According to a particular embodiment, the substrate of the invention as described previously is chosen from fabrics.

[0057] According to a particular embodiment, the substrate of the invention as described above is made of or comprises a material chosen from cottons, hemps, linens, Tencel, viscose.

[0058] Viscoses carrying free -OH groups can for example be obtained by partial acid hydrolysis of viscoses known to those skilled in the art, for example commercial viscose. Acid hydrolysis is also well known to those skilled in the art, particularly for the preparation of cellophane from viscose.

[0059] Said cellulosic substrate may further comprise, for example in addition to cotton, other materials such as polyurethanes, for example at a level of approximately 4% by mass, and / or optical brighteners (OBA).

[0060] According to a particular embodiment, the substrate of the invention as described above is made of or comprises a material chosen from woven cottons, woven hemps, woven linens, woven Tencel, woven viscose.

[0061] According to a particular embodiment, the substrate of the invention as described previously is such that: - the contact angle of a drop of water on the surface of said substrate is greater than or equal to 80°, in particular greater than or equal to 90, 100, 110 or 120°, in particular under a relative humidity (RH) of 20 and / or 80%, and / or - the contact angle of a drop of oil, for example dodecane, on the surface of said substrate is greater than or equal to 40°, in particular greater than or equal to 50, 60 or 70°, in particular under a relative humidity (RH) of 20 and / or 80%.

[0062] This contact angle can be measured by techniques well known to those skilled in the art, for example by goniometry. This is a technique which typically consists of depositing a small liquid drop, for example with a volume of 1 to 10 μl, on the surface and measuring the angle formed between the tangent to the drop at the point of contact and the surface of the cellulosic substrate.

[0063] This contact angle can in particular be measured on a sample of cellulosic substrate large enough to be stretched during measurement, for example on a wetting angle measuring plate. To do this, the samples typically weigh 0.8 to 1.2 g before drying.

[0064] The wetting angle measurements can for example be carried out on a KRÜSS DROP Shape Analyser (DSA100).

[0065] The cellulosic substrates of the present invention may be prepared by a number of methods well known to those skilled in the art, including, but not limited to, those described below, or by modifications of these methods by applying standard techniques known to those skilled in the art of organic synthesis. Suitable modifications and substitutions will be readily apparent and well known or may be readily obtained from the scientific literature by those skilled in the art. In particular, such methods may be found in RC Larock, Comprehensive Organic Transformations, Wiley-VCH Publishers, 1999.

[0066] All methods disclosed in association with the present invention can be carried out at any scale, including milligram, gram, from multigram, kilogram, multikilogram or on a commercial industrial scale.

[0067] It will be understood that the compounds of the present invention may contain one or more asymmetrically substituted carbon atoms, and may be isolated in optically active or racemic forms. Thus, all chiral, diastereomeric, racemic, isomeric forms of a structure are intended, unless the specific stereochemistry or isomeric form is specifically indicated. How to prepare and isolate such optically active forms is well known to those skilled in the art. For example, mixtures of stereoisomers may be separated by standard techniques including, but not limited to, resolution of racemic forms, conventional, reversed-phase, and chiral chromatography, preferential salt formation, recrystallization, and the like, or by chiral synthesis, either from chiral starting materials or by targeted synthesis of the corresponding chiral centers.

[0068] The compounds of the present invention can be prepared by a variety of synthetic routes. The reagents and starting materials are commercially available, or readily synthesized by techniques well known to those skilled in the art. All substituents, unless otherwise indicated, are as defined above.

[0069] More particularly, the cellulosic substrates of the invention, carrying a plurality of groups of formula (I), are capable of comprising groups -NH-C(=O)-NH- (urea), -NH-C(=O)-O- or -OC(=O)-NH- (urethane), and / or -NH-C(=O)- or -C(=O)-NH- (amide).

[0070] The -NH-C(=O)-NH- group may be formed by any method well known to those skilled in the art, in particular by contacting a compound bearing an -NH2 group (primary amine) with a compound bearing an -N=C=O group (isocyanate). This reaction may in particular be carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 1,4-dioxane, acetone, and / or in supercritical CO2. This reaction may be carried out at a temperature of from 35°C to 150°C, in particular at approximately 150°C, and / or for a period of from 30 minutes to 2 hours, in particular for approximately 1.5 hours.

[0071] The group -NH-C(=O)-O- or -OC(=O)-NH can be formed by any method well known to those skilled in the art, in particular by bringing a compound bearing an -OH group (primary alcohol) into contact with a compound bearing an -N=C=O group (isocyanate), in particular in the presence of a catalyst, in particular chosen from triethylamine, l,4-diazabicyclo[2,2,2]octane (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), dibutyltin dilaurate (DBTDL), l,8-diazabicylo[5,4,0]undec-7-ene (DBU), 3,4-dihydro-2H-pyrimido[2,1b]benzothiazole (DHPB), di-isopropylethylamine (DIPEA), 4-dimethylaminopyridine (DMAP), l,8-bis(dimethylamino)naphthalene (DMAN), for example triethylamine. This reaction can in particular be carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), and / or in supercritical CO2. This reaction can be carried out at a temperature of from 70°C to 150°C, in particular at about 150°C, and / or for a time of from 30 minutes to 2 hours, in particular for about 1.5 hours.

[0072] The NH-C(=O)- or -C(=O)-NH- group can be formed by any method well known to those skilled in the art, in particular by bringing a compound bearing a -COOH group (carboxylic acid) into contact with a compound bearing a -N=C=O group (isocyanate), in particular in the presence of a catalyst, in particular chosen from triethylamine, l,4-diazabicyclo[2,2,2]octane (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), dibutyltin dilaurate (DBTDL), l,8-diazabicylo[5,4,0]undec-7-ene (DBU), 3,4-dihydro-2H-pyrimido[2,1b]benzothiazole (DHPB), di-isopropylethylamine (DIPEA), 4-dimethylaminopyridine (DMAP), l,8-bis(dimethylamino)naphthalene (DMAN), for example triethylamine. This reaction can in particular be carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), and / or in supercritical CO2.This reaction can be carried out at a temperature of from 70°C to 160°C, in particular at about 150°C, and / or for a time of from 30 minutes to 2 hours, in particular for about 1.5 hours.

[0073] According to another aspect, the invention also relates to a process for preparing a cellulosic substrate as defined above, comprising the following step:

[0074] (i) Contacting at least a portion of the surface of a cellulosic substrate, with a compound (A) of the following formula:

[0075] [Chem. 14] O K (Z) O~C=NX< V ' (R 1 •; A l

[0076] in which X, Y, i, Z and R are as defined above;

[0077] or the following steps:

[0078] (i') bringing into contact at least a portion of the surface of a cellulosic substrate, with a compound (B) of the following formula:

[0079] [Chem. 15] O—CN—X—NC —O (B;

[0080] in which X is as defined above,

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] to obtain a cellulose substrate carrying on at least part of its surface a plurality of groups of the following formula (C): [Chem. 16] O -----O' H (O. in which W, i and X are as defined previously, (ii') bringing a substrate as obtained in the previous step (i') into contact with a compound of the following formula (D): [Chem. 17] in which Z and R are as defined above, and in which Y' is: - an -NH2 group when j = 1 and Y is -NH-; - an -OH group when j = 1 and Y is -O-; - a -COOH group when Y is a single bond; or, when Y is NH, and R is -NH2, the following steps: (i”) bringing at least part of the surface of a cellulosic substrate into contact with a compound (B) of the following formula: [Chem. 18] O~C—N—XN^QO (B), in which X is as defined previously, then contact with water, to obtain a cellulose substrate carrying on at least part of its surface a plurality of groups of the following formula (C): [Chem. 19] in which W, i and X are as defined previously, (ii”) bringing a substrate as obtained in the previous step (i') into contact with a compound of the following formula (D): [Chem. 20] OCN — Z—NQO in which Z is as defined previously,

[0099] then contact with water.

[0100] When water is used, residual water traces may be removed, for example by washing with a solvent as described below.

[0101] When R is of formula -N+RaRbRc, the compounds bearing this group R can be obtained from the corresponding compounds bearing a group -NRaRb, using techniques well known to those skilled in the art.

[0102] When group X comprises one or more urea groups, said group X may be constructed sequentially according to steps analogous to steps (i”) and (ii”) as described above.

[0103] The steps defined above are in particular carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), or acetone.

[0104] According to a particular embodiment, the steps defined previously are carried out in supercritical CO2 (sCO2).

[0105] According to another particular embodiment, the steps defined above are carried out in an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), or acetone, with supercritical CO2 (sCO2) as co-solvent.

[0106] The use of supercritical CO2 generally requires working in a pressurized autoclave, which protects operators from isocyanates.

[0107] The isocyanates described here can also be used via blocked isocyanate functions, such as for example defined in application FR 3 095 207.

[0108] Step (i) defined above may be preceded if necessary by a step in which the residual water is removed from the cellulosic substrate. This removal may be carried out by any technique well known to those skilled in the art.

[0109] The steps defined above are in particular carried out at a temperature of from 35°C to 160°C, in particular at approximately 150°C, and / or for a duration of from 30 minutes to 2 hours, in particular for approximately 1.5 hours.

[0110] When sCO2 is used, the reactions are notably carried out in an autoclave, for example under a pressure of approximately 250 bar. Definitions

[0111] As used herein, the value ranges in the form of "xy" or "from x to y" or "between x and y" include the bounds x and y, the integers between these bounds, as well as all other real numbers between these bounds. For example, "1-5", or "from 1 to 5" or "between 1 and 5" designates the integers 1, 2, 3, 4 and 5, as well as all other real numbers between 1 and 5. Preferred embodiments include each individual integer in the value range, as well as any subcombination of these integers and any set of real numbers between these integers. For example, preferred values ​​for "1-5" may include the integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2-4, 2-5, etc.

[0112] As used herein, the term "about" refers to a range of values ​​within ± 10% of a specific value. For example, the term "about 20" includes values ​​of 20 ± 10%, or values ​​from 18 to 22.

[0113] As used herein, the term "alkyl" means a straight or branched chain, especially straight, alkyl group having the number of carbon atoms indicated before said term, especially 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. Thus, a term such as "C1-C3 alkyl" means an alkyl radical containing from 1 to 3 carbon atoms.

[0114] The same applies to the term “alkane”.

[0115] By “diyl” is meant in particular a residue linked to two groups by a single bond between the residue and each of these two groups.

[0116] As used herein, the term "arene" means a mono- or bicyclic, substituted or unsubstituted, hydrocarbon aromatic ring system having 6 to 10 carbon atoms in the ring. Examples include benzene and naphthalene. Preferred arenes include unsubstituted or substituted benzene and naphthalene. Included within the definition of "arene" are fused ring systems, including, for example, ring systems in which an aromatic ring is fused to a cycloalkyl ring. Examples of such fused ring systems include, for example, indane, indene, and tetrahydronaphthalene.

[0117] As used herein, the term "heteroarene" means a cyclic aromatic system containing 5 to 10 carbon atoms in which one or more ring carbon atoms are replaced by at least one heteroatom such as -O-, -N- or -S-, particularly -N- and / or -O-. Examples of heteroarenes include pyrrole, furan, thiophene, pyrazole, imidazole, thiazole, isothiazole, isoxazole, oxazole, oxathiol, oxadiazole, triazole, oxatriazole, furazane, tetrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, indazole, benzofuran, isobenzofuran, purine, quinazoline, quinoline, isoquinoline, benzoimidazole, benzothiazole, benzothiophene, thianaphthene, benzoxazole, benzisoxazole, cinnoline, phthalazine, naphthyridine and quinoxaline. Included in the definition of "heteroarene" are fused ring systems, including, for example, ring systems in which an aromatic ring is fused to a heterocycloalkyl ring.Examples of such fused ring systems include, for example, phthalamide, phthalic anhydride, indoline, isoindoline, tetrahydroisoquinoline, chromane, isochromane, chromene, and isochromene. EXAMPLES

[0118] General operating protocols

[0119] The experiments were carried out on cotton containing 4 to 5% by mass of polyurethanes (elastane) and an optical brightener (OBA).

[0120] The samples weigh 0.8 to 1.2g before drying. This mass corresponds to a fabric surface area allowing the sample to be stretched on the wetting angle measuring plate.

[0121] The samples were pre-treated in a supercritical CO2 (sCO2) reactor using an aprotic solvent (e.g. acetone, THF, or DMSO) as co-solvent. The drying medium is, for example, 10 ml of aprotic solvent for 1 liter of sCO2. Typically, 20 cotton samples are treated. The treatment lasts 1 hour 30 minutes at 120°C and 250 bar. The treatment is finished by passing pure sCO2 (2 liters to 4 liters). The samples are stored in the reactor under a gaseous CO2 atmosphere.

[0122] This treatment can also be carried out by soaking the 5H samples in DMSO at 120-150°C. In this case, the substrates are dried in a ventilated oven and stored under argon.

[0123] These preliminary treatments allow the extraction of OBA and other finishing products. These treatments also allow the cotton to be dehydrated.

[0124] After treatment according to the invention, all the samples were extracted with a Soxhlet to remove the ungrafted compounds. This extraction was carried out in acetone for 4 hours (which corresponds to a passage of 5 liters of acetone) then the samples were placed in an oven at 110°C for 12 hours before being conditioned at the relative humidities (RH) chosen before the wettability measurement.

[0125] The contact angle (wetting) measurements were made using a DROP Shape Analyser KRÜSS (DSA100) device, on samples (5 samples for water and 5 for dodecane) previously stored in an oven at 100°C.

[0126] Example 1: Preparation of intermediate functionalized cellulose substrates

[0127] In a 1 liter sCO2 reactor of useful volume containing 10 to 15 cotton samples, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO containing 1 g of DABCO: (1,4-Diazabicyclo[2.2.2]octane anhydrous. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150°C at a pressure of 250 bar. The treatment lasts 1 hour 30 minutes. 10 ml of DI water are then introduced into the pressurized reactor via a high pressure pump. All the pendant isocyanate functions or HDMI which would not have reacted are immediately transformed into primary amine. Several volumes of supercritical sCO2 reactor are then passed (typically 5 volumes). DABCO, which is soluble in sCO2, and the primary amines corresponding to the unreacted HDMI are recovered from the reactor separators.

[0128] The cotton substrates are then covered with anhydrous primary amine.

[0129] In all of the above and the following, anhydrous DMSO may be used instead of sCO2. Example 2#:

[0130] Starting from the cotton substrates covered with anhydrous primary amine as obtained at the end of example 1, the initial treatment is repeated, i.e.:

[0131] In a sCO2 reactor with a useful volume of one liter containing 10 to 15 cotton samples carrying pendant grafted primary amines, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO. The formation of the urea function does not require the use of a catalyst. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30. 10 ml of DI water are then introduced into the pressurized reactor via a high pressure pump. All the pendant isocyanate functions or HD MI which have not reacted are immediately transformed into primary amine. Several reactor volumes of sCO2 are then passed (typically 5 volumes). The primary amines corresponding to the HDMI which has not reacted with the cotton and which is transformed into diamine are recovered in the reactor separators.

[0132] The reactor is opened, the samples are then soaked for 10 minutes in 100 ml of a solution (0.1 M HCl) then rinsed with DI water before being dried for 12 hours at 130°C in a ventilated oven.

[0133] These samples correspond to reference 1 in the table below. Example 3#:

[0134] Example 2 is repeated twice to form the species corresponding to reference 1b in the table below. Example 4#: Witness outside the invention

[0135] In a 1 liter sCO2 reactor of useful volume containing 10 to 15 samples of cotton carrying pendant grafted primary amines, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30. 5 g of octadecylamine are introduced by the high pressure pump into 5 g of DMSO. The reaction is left to react for 1 h 30 at 250 bar, 150 ° C. Several reactor volumes of sCO2 (typically 5 volumes) are then passed, still at 250 bar and 150 ° C to remove the ungrafted products.

[0136] These samples correspond to reference 2 in the table. Example 5#:

[0137] In a 1 liter sCO2 reactor of useful volume containing 10 to 15 cotton samples carrying pendant grafted primary amines, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30 min. 3 g of 1,3-Pentanediamine are then introduced into the pressurized reactor via a high pressure pump in 5 g of DMSO. The reaction is left to react for 1 h 30 min at 250 bar and 150 ° C. Several reactor volumes of sCO2 are then passed through (typically 5 volumes).

[0138] The reactor is opened, the samples are then soaked for 10 minutes in 100 ml of a solution (0.1 M HCl) then rinsed with DI water before being dried for 12 hours at 130°C in a ventilated oven.

[0139] These samples correspond to reference 3 in the table. Example 6#:

[0140] In a 1 liter sCO2 reactor of useful volume containing 10 to 15 samples of cotton carrying pendant grafted primary amines, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30 min. 5 g of 2-Amino-2-(hydroxymethyl)-1,3-propanediol are introduced by the high pressure pump into 5 g of DMSO. The reaction is left to react for 1 h 30 min at 250 bar, 150 ° C. Several reactor volumes of sCO2 (typically 5 volumes) are then passed, still at 250 bar and 150 ° C to remove the ungrafted products.

[0141] These samples correspond to reference 4 in the table. Example 7#:

[0142] In a 1 liter sCO2 reactor of useful volume containing 10 to 15 samples of cotton carrying pendant grafted primary amines, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO. Then 900 ml of liquid CO2 are introduced. The supercritical state is passed by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30. 5 g of 2,2-Bis(hydroxymethyl)-2,2'2'-nitrilotriethanol are introduced by the high pressure pump into 5 g of DMSO. The reaction is left to react for 1 h 30 at 250 bar, 150 ° C. Several reactor volumes of sCO2 (typically 5 volumes) are then passed, still at 250 bar and 150 ° C to remove the ungrafted products.

[0143] These samples correspond to reference 5 in the table. Example 8#: results

[0144]

[0145] The results recorded in the table below show that the treated substrates of the invention are hydrophobic while having a marked oleophobic character. Reference Structure Wetting angle 20% RH Wetting angle 80% RH 1 - ohPh o La OJ o A ACH2)6 N-(CH2)6-NN' \ H HH Nnj+Ci 0H2O 110 O ODode 70° 0H2O 60° ODode 30° 2 (reference outside the invention) ohPh ~rO 'A? L\ 0- | LOJOXAA / (CH2)17 0 N“(CH2)6“NNH HH CH3 0H2O 140 O 0Dode<30 O 0H2O 140 O 0Dode<30 O 1 bis - OF -OA-î- O ' Q o... A po 0 A-(CHA--N'Â HH HN "'NHACr 0H2O 110 O ODode 70° 0H2O 60° ODode 50° 3 - Q PO-A"2-OA 4 0H -Ao ■ p ''O''"' 9 O NHi+CF A.. . :CH k :l 1 N —(CH2)sN M '0 H ' 2Jb HH UN NH 0H2O 115 O 0Dode<60 O 0H2O 90° ODode 60- 80° 4 - C b" )H OH 'Ao- ■■ O- LA oh f- ,0H ? .A, ,(GHA i: ' r ■0- [pC-A KN 'OH 0H2O 80° ODode 70° 0H2O 80° ODode 70°

Claims

1. Claims Cellulosic substrate carrying on at least part of its surface a plurality of groups of the following formula (I): [Chem.22] OO To JL (zi O' N"X"NY :R HH 1 (IK in which: Y is chosen from O and NH, or is a single bond; i is chosen from 0 and 1; X represents a group of the following formula (II): [Chem.23] j and k are independently chosen from 0 and 1; Xa and Xc are independently chosen from: the Xai groups being linear, branched and / or cyclic CrCi2 alkane diyls, in particular the groups of formula -(CH2)n- with n from 1 to 12, or linear and branched C2-Ci2 alkene diyls, the Xai groups being in particular linear and branched CrCi2 alkane diyls groups of formula -Xai-NH-Xai-, where Xai is at each occurrence independently as defined above, in particular groups of formula -(CH2)n-NH-(CH2)m-with n and m being independently from 1 to 12; groups of formula -XarNHC(=O)-NH-Xai- or -Xar NHC(=O)-NH-Xal-NHC(=O)-NH-Xal-, where Xal is at each occurrence independently as defined above, in particular groups of formula -(CH2)n-NHC(=O)-NH-(CH2)m- with n and m being independently from 1 to 12; Xb is chosen from: - linear, branched and / or cyclic C1-C12 alkane diyls, in particular groups of formula -(CH2)n- with n from 1 to 12, branched CrCi2 alkane triyls, linear and branched C2-Ci2 alkene diyls, the Xb groups being in particular linear and branched CrCi2 alkane diyls or triyls; optionally carrying, in particular in terminal position(s), at least one group -(O-CH2-CH2)P- or -(O-CH2-C(CH3)H)P-, with p being an integer from 1 to 3; - arene diyls and heteroarene diyls; Xb being optionally substituted by a group A of the following formula (III): [Chem.24]

2. Xc, Y, i, Z and R being as defined above or below, Z is chosen from linear, branched and / or cyclic C1-C12 alkanes and linear and branched C2-C12 alkene diyls, Z being in particular a linear C2 alkane or alkene diyl, said group Z being optionally substituted by a -COOH or -COO group; R is chosen from: - the groups of formula -NRaRb, and the groups -N+RaRbRc, in which Ra, Rb and Rc are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), and - aliphatic polyols. Cellulosic substrate according to claim 1, comprising a plurality of units of the following formula (1):

3. [Chem.25] Cellulosic substrate according to claim 1, in which R is chosen from: - the groups of formula -NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R being in particular chosen from the groups of formula -NH2, -NRaH, Ra being more particularly a methyl or an ethyl, or -NRaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in the terminal position(s), -NRaRb being for example of the following formula: [Chem.26] "OH ''N"" HO^JOôH OH - groups of formula -N+RaRbH, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R being in particular chosen from the groups of formula -N+H2, -N+RaH, Ra being more particularly a methyl or an ethyl, or -N+RaRb, in which Ra and Rb are independently chosen from H and linear and branched C1-C6 alkyls, optionally substituted by at least one -OH group, in particular in terminal position(s), Ra and Rb being in particular independently chosen from linear and branched C1-C6 alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N+RaRb being for example of the following formula: [Chem.27] .OH -, OJ 'NH HO. .Àf'OH r OH

4. - aliphatic polyols, in particular among the linear and branched C1-C6 alkyls, substituted by at least two -OH groups, in particular in the terminal position(s), R being for example of the following formula: [Chem.28] H CK , X.-' OH Cellulosic substrate according to any one of the preceding claims, wherein Xb is selected from the following groups: [Chem.29] A and p being as defined in claim 1.

5. Cellulosic substrate according to any one of the preceding claims, in which the groups of formula (I) are chosen from the groups of the following formula: [Chem.30] (13)=

6.

7. Cellulosic substrate according to any one of the preceding claims, which is selected from fabrics. A cellulosic substrate according to any preceding claim, which is made of or comprises a material selected from cottons, hemps, Tencel, linens, viscose.

8. A cellulosic substrate according to any preceding claim, is made of or comprises a material selected from woven cottons, woven hemps, woven Tencel, woven linens, woven viscose.

9. Cellulosic substrate according to any one of the preceding claims, for which: - the contact angle of a drop of water on the surface of said substrate is greater than or equal to 80°, in particular greater than or equal to 90, 100, 110 or 120°, in particular under a relative humidity (RH) of 20 and / or 80%, and / or - the contact angle of a drop of oil, for example dodecane, on the surface of said substrate is greater than or equal to 40°, in particular greater than or equal to 50, 60 or 70°, in particular under a relative humidity (RH) of 20 and / or 80%.

10. A process for preparing a cellulosic substrate according to any one of the preceding claims, comprising the following step: (i) Contacting at least a portion of the surface of a cellulosic substrate with a compound (A) of the following formula: [Chem.31] OH ^z^ O-ON-XN' "Y ' H 1 (Al, in which X, Y, i, Z and R are as defined in claim 1. or the following steps: (i') contacting at least a portion of the surface of a cellulosic substrate with a compound (B) of the following formula: [Chem.32] O ~ G - N —X—N =C ~O (BK in which X is as defined in claim 1, to obtain a cellulosic substrate carrying on at least a portion of its surface a plurality of groups of the following formula (C): [Chem.33] in which W, i and X are as defined in claim 1, (ii') bringing a substrate as obtained in the preceding step (i') into contact with a compound of the following formula (D): [Chem.34] wherein Z and R are as defined in claim 1, and wherein Y' is: - an -NH2 group when j = 1 and Y is -NH-; - an -OH group when j = 1 and Y is -O-; - a -COOH group when Y is a single bond, or, when Y is NH, and R is -NH2, the following steps: (i”) bringing at least part of the surface of a cellulosic substrate into contact with a compound (B) of the following formula: [Chem.35] O“GN —X—NC~ O (B), in which X is as defined previously, then contact with water, to obtain a cellulosic substrate carrying on at least part of its surface a plurality of groups of the following formula (C): [Chem.36] O ----O' 'NX-"NH2 H (C), in which W, i and X are as defined previously, (ii”) bringing a substrate as obtained in the previous step (i') into contact with a compound of the following formula (D): [Chem.37] O~C=N—Z—NC—O (D), in which Z is as defined previously, then contact with water.