EP4579033A1 - Cellulosic substrate rendered hydrophobic and oleophobic by grafting discrete fluorine compounds, and methods for obtaining same - Google Patents

Abstract

The present invention relates to a cellulosic substrate made hydrophobic and oleophobic by grafting fluorine-free compounds, as well as methods for obtaining it.

Description

The present invention relates to a cellulosic substrate made hydrophobic and oleophobic by grafting fluorine-free compounds, as well as methods for obtaining it.

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 used in textiles, both for consumer products and technical applications.

The textile industry often refers to these chemicals as durable water repellents (DWRs), but cutting-edge technology on the market doesn't just repel water. Since their introduction in the 1950s, per- and polyfluoroalkyl polymers (PFAS) have achieved the highest levels of oil and water resistance.

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 commonly associated with outdoor rainwear, providing protection from rain and the external environment, resisting rain penetration while still allowing the body to regulate its temperature; a garment with insufficient water-repellent properties increases the risk of hypothermia. With regard to medical textiles, the exposure and transfer of blood and body fluids between patients and medical personnel during emergency care 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.

PFAS used for repellent-type textile modifications most commonly comprise non-fluorinated polymer backbones with polyfluorinated side chains that branch off 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 -CF ₃ end groups within the side chains.

The release of PFAS by-products during the production, use, and end-of-life of textiles containing them 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 1 µg.m ² in textile fabrics. While limits for perfluorooctanoic acid (PFOA) are currently under discussion within the EU, Norway has already set its limit at 1µg.m ² in textile applications. The bioaccumulation of PFAAs in humans and in the food chain, combined with their toxicity, is a major concern.

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 occurred, but there are also growing concerns about the persistence and toxicology of these short-chain analogues. The extreme persistence of short-chain PFAAs means that the release of these compounds from textiles (and other sources) could become a global threat, given that not all future effects are known. at present and that their release into groundwater, for example, is difficult to reverse.

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. The functional motifs in terms of liquid repellency are generally either saturated alkyl chains or related to polydimethylsiloxane (PDMS) chemistry.

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

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

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

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.

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

dans laquelle :

• Y est choisi parmi O et NH, ou est une liaison simple ;
• i est choisi parmi 0 et 1 ;
• X représente un groupe de formule (II) suivante :

• j et k sont indépendamment choisis parmi 0 et 1 ;
• X_a et X_c sont indépendamment choisis choisi parmi :
  • les groupes X_a1 étant des alcane diyles linéaires, branchés et/ou cycliques en C₁-C₁₂, en particulier les groupes de formule -(CH₂)_n- avec n de 1 à 12, ou des alcène diyles linéaires et branchés en C₂-C₁₂, les groupes X_a1 étant notamment des alcane diyles linéaires et branchés en C₁-C₁₂ ;
  • les groupes de formule -X_a1-NH-X_a1-, où X_a1 est à chaque occurrence indépendamment tel que défini ci-dessus, en particulier les groupes de formule -(CH₂)_n-NH-(CH₂)_m- avec n et m étant indépendamment de 1 à 12 ;
  • les groupes de formule -X_a1-NHC(=O)-NH-X_a1- ou -X_a1-NHC(=O)-NH-X_a1-NHC(=O)-NH-X_a1-, où X_a1 est à chaque occurrence indépendamment tel que défini ci-dessus, en particulier les groupes de formule -(CH₂)_n-NHC(=O)-NH-(CH₂)_m- avec n et m étant indépendamment de 1 à 12 ;
• X_b est choisi parmi :
  • les alcane diyles linéaires, branchés et/ou cycliques en C₁-C₁₂, en particulier les groupes de formule -(CH₂)_n- avec n de 1 à 12, les alcane triyles branchés en C₁-C₁₂, les alcène diyles linéaires et branchés en C₂-C₁₂, les groupes X_b étant notamment des alcane diyles ou triyles linéaires et branchés en C₁-C₁₂ ; portant optionnellement, notamment en position(s) terminale(s), au moins un groupe -(O-CH₂-CH₂)_p- ou -(O-CH₂-C(CH₃)H)_p-, avec p étant un entier de 1 à 3 ;
  • les arène diyles et les hétéroarène diyles ;
• X_b étant optionnellement substitué par un groupe A de formule (III) suivante :
  
  
• X_c, Y, i, Z et R étant tels que définis ci-dessus ou ci-dessous,
• Z est choisi parmi les alcane diyles linéaires, branchés et/ou cycliques en C₁-C₁₂ et les alcène diyles linéaires et branchés en C₂-C₁₂, Z étant en particulier un alcane ou un alcène diyle linéaire en C₂, ledit groupe Z étant optionnellement substitué par un groupe -COOH ou -COO^-;
• R est choisi parmi :
  • les groupes de formule -NR_aR_b, et les groupes -N⁺R_aR_bR_c, dans lesquels R_a, R_b et R_c sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, optionnellement substitués par au moins un groupe -OH, notamment en position(s) terminale(s), et
  • les polyols aliphatiques.

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):

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):

• j and k are independently chosen from 0 and 1;
• X _a and X _c are independently chosen from:
  • the groups X _a1 being linear, branched and/or cyclic C ₁ -C ₁₂ alkane diyls, in particular the groups of formula -(CH ₂ ) _n - with n from 1 to 12, or linear and branched C ₂ -C ₁₂ alkene diyls, the groups X _a1 being in particular linear and branched C ₁ -C ₁₂ alkane diyls;
  • groups of formula -X _a1 -NH-X _a1 -, where X _a1 is at each occurrence independently as defined above, in particular groups of formula -(CH ₂ ) _n -NH-(CH ₂ ) _m - with n and m being independently from 1 to 12;
  • groups of formula -X _a1 -NHC(=O)-NH-X _a1 - or -X _a1 -NHC(=O)-NH-X _a1 -NHC(=O)-NH-X _a1 -, where X _a1 is at each occurrence independently as defined above, in particular groups of formula -(CH ₂ ) _n -NHC(=O)-NH-(CH ₂ ) _m - with n and m being independently from 1 to 12;
• X _b is chosen from:
  • linear, branched and/or cyclic C ₁ -C ₁₂ alkane diyls, in particular groups of formula -(CH ₂ ) _n - with n from 1 to 12, branched C ₁ -C ₁₂ alkane triyls, linear and branched C ₂ -C ₁₂ alkene diyls, the X _b groups being in particular linear and branched C ₁ -C ₁₂ alkane diyls or triyls; optionally carrying, in particular in terminal position(s), at least one -(O-CH ₂ -CH ₂ ) _p - or -(O-CH ₂ -C(CH ₃ )H) _p - group, with p being an integer from 1 to 3;
  • arene diyls and heteroarene diyls;
• X _b being optionally substituted by a group A of the following formula (III):
  
  
• X _c , Y, i, Z and R being as defined above or below,
• Z is selected from linear, branched and/or cyclic C ₁ -C ₁₂ alkane diyls and linear and branched C ₂ -C ₁₂ alkene diyls, Z being in particular a linear C ₂ alkane or alkene diyl, said group Z being optionally substituted by a -COOH or ^-COO- group;
• R is chosen from:
  • the groups of formula -NR _a R _b , and the groups -N ⁺ R _a R _b R _c , in which R _a , R _b and R _c are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), and
  • aliphatic polyols.

When the groups of formula (I) comprise an ionized group, such as for example a ^-COO- group or an -N ⁺ R _a R _b R _c group, said ionized groups may be in contact with a counterion, as well known to those skilled in the art.

By Z-R, we indicate that R substitutes for Z, this substitution being able to be in the terminal position, or not, of Z.

Without wanting to be restricted to any theory, the chain carrying the R group allows the cellulose substrate to have hydrophobic properties, while the R group itself, surprisingly, allows this cellulose substrate to have oleophobic properties.

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.

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

Thus, the substrate of the invention is likely to comprise, in addition to the units of formula (1), units of the D-glucose type, substituted or not, in particular not substituted.

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

According to a particular embodiment, R is chosen from the groups of formula -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 -NH ₂ , -NR _a H, R _a being more particularly a methyl or an ethyl, or -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in the terminal position(s), -NR _a R _b being for example from the following formula:

According to a particular embodiment, R is chosen from the groups of formula - N ⁺ R _a R _b H, in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 ⁺ H ₂ , -N ⁺ R _a H, R _a being more particularly a methyl or an ethyl, or -N ⁺ R _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N ⁺ R _a R _b being for example of the following formula:

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.

According to a particular embodiment, R is chosen from aliphatic polyols, in particular from linear and branched C ₁ -C ₆ alkyls, substituted by at least two -OH groups, in particular in terminal position(s), R being for example of the following formula:

• -NH-Z-NR_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, optionnellement substitués par au moins un groupe -OH, notamment en position(s) terminale(s),
  R étant en particulier choisi parmi les groupes de formule -NH₂, -NR_aH, R_a étant plus particulièrement un méthyle ou un éthyle, ou -NR_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, optionnellement substitués par au moins un groupe -OH, notamment en position(s) terminale(s) ;
• -O-Z-NR_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆ substitués par au moins un groupe -OH, notamment en position(s) terminale(s),
  R étant en particulier -NR_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, substitués par au moins un groupe -OH, notamment en position(s) terminale(s), R_a et R_b étant notamment indépendamment choisis parmi les alkyles linéaires et branchés en C₁-C₆, substitués par au moins un groupe -OH, notamment en position(s) terminale(s), -NR_aR_b étant par exemple de la formule suivante :

• -NH-Z-N⁺R_aR_bH, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, optionnellement substitués par au moins un groupe -OH, notamment en position(s) terminale(s), R étant en particulier choisi parmi les groupes de formule -N⁺H₂, -N⁺R_aH, R_a étant plus particulièrement un méthyle ou un éthyle, ou - N⁺R_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, optionnellement substitués par au moins un groupe -OH, notamment en position(s) terminale(s) ;
• -O-Z-N⁺R_aR_bH, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, substitués par au moins un groupe -OH, notamment en position(s) terminale(s), R étant en particulier -N⁺R_aR_b, dans laquelle R_a et R_b sont indépendamment choisis parmi H et les alkyles linéaires et branchés en C₁-C₆, substitués par au moins un groupe -OH, notamment en position(s) terminale(s), R_a et R_b étant notamment indépendamment choisis parmi les alkyles linéaires et branchés en C₁-C₆, substitués par au moins un groupe -OH, notamment en position(s) terminale(s), -N⁺R_aR_b étant par exemple de la formule suivante :
  
• -NH-R, dans laquelle R est choisi parmi les polyols aliphatiques, en particulier parmi les alkyles linéaires et branchés en C₁-C₆, substitués par au moins deux groupes -OH, notamment en position(s) terminale(s), R étant par exemple de la formule suivante :
  

According to a particular embodiment, the group Y-(Z) _i -R is of one of the following formulas:

• -NH-Z-NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 -NH ₂ , -NR _a H, R _a being more particularly a methyl or an ethyl, or -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s);
• -OZ-NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls substituted by at least one -OH group, in particular in terminal position(s),
  R being in particular -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), -NR _a R _b being for example of the following formula:

• -NH-ZN ⁺ R _a R _b H, in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 ⁺ H ₂ , -N ⁺ R _a H, R _a being more particularly a methyl or an ethyl, or - N ⁺ R _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s);
• -OZN ⁺ R _a R _b H, in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), R being in particular -N ⁺ R _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N ⁺ R _a R _b being for example of the following formula:
  
• -NH-R, in which R is chosen from aliphatic polyols, in particular from linear and branched C ₁ -C ₆ alkyls, substituted by at least two -OH groups, in particular in terminal position(s), R being for example of the following formula:
  

According to a particular embodiment, X _b is chosen from the following groups:

A and p being as defined previously.

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

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

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

Viscoses bearing free -OH groups may, for example, be obtained by partial acid hydrolysis of viscoses known to those skilled in the art, for example commercial viscoses. Acid hydrolysis is also well known to those skilled in the art, in particular for the preparation of cellophane from viscose.

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).

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.

• l'angle de contact d'une goutte d'eau sur la surface dudit substrat est supérieur ou égal à 80°, notamment supérieur ou égal à 90, 100, 110 ou 120°, en particulier sous une humidité relative (RH) de 20 et/ou 80%, et/ou
• l'angle de contact d'une goutte d'huile, par exemple de dodécane, sur la surface dudit substrat est supérieur ou égal à 40°, notamment supérieur ou égal à 50, 60 ou 70°, en particulier sous une humidité relative (RH) de 20 et/ou 80%.

According to a particular embodiment, the substrate of the invention as described previously is such that:

• the contact angle of a water droplet 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%.

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.

This contact angle can be measured on a cellulosic substrate sample 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 1.2g before drying.

Wetting angle measurements can be carried out, for example, on a KRÜSS DROP Shape Analyser (DSA100).

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 .

All methods disclosed in association with the present invention may be carried out at any scale, including milligram, gram, multigram, kilogram, multikilogram, or commercial industrial scale.

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.

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.

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 -O-C(=O)-NH- (urethane), and/or -NH-C(=O)- or -C(=O)-NH- (amide).

The -NH-C(=O)-NH- group can be formed by any method well known to those skilled in the art, in particular by bringing into contact a compound bearing a -NH ₂ group (primary amine) with a compound bearing a -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 CO _2. This reaction may be carried out at a temperature of from 35°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.

The -NH-C(=O)-O- or -OC(=O)-NH group may 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, 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dibutyltin dilaurate (DBTDL), 1,8-diazabicylo[5,4,0]undec-7-ene (DBU), 3,4-dihydro-2H-pyrimido[2,1-b]benzothiazole (DHPB), di-isopropylethylamine (DIPEA), 4-dimethylaminopyridine (DMAP), 1,8-bis(dimethylamino)naphthalene (DMAN), for example triethylamine. This reaction may in particular be carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), and/or in supercritical CO ₂ . This reaction may 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.

The NH-C(=O)- or -C(=O)-NH- group may 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, 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dibutyltin dilaurate (DBTDL), 1,8-diazabicylo[5,4,0]undec-7-ene (DBU), 3,4-dihydro-2H-pyrimido[2,1-b]benzothiazole (DHPB), di-isopropylethylamine (DIPEA), 4-dimethylaminopyridine (DMAP), 1,8-bis(dimethylamino)naphthalene (DMAN), for example triethylamine. This reaction may in particular be carried out in an anhydrous solvent, in particular an anhydrous aprotic solvent, for example dimethyl sulfoxide (DMSO), and/or in supercritical CO _2. This reaction may 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.

• (i) La mise en contact d'au moins une partie de la surface d'un substrat cellulosique, avec un composé (A) de formule suivante :
  
  • dans laquelle X, Y, i, Z et R sont tels que définis précédemment ;
  • ou les étapes suivantes :
• (i') la mise en contact d'au moins une partie de la surface d'un substrat cellulosique, avec un composé (B) de formule suivante :
  [Chem. 15]
  
          O=C=N-X-N=C=O     (B),
  • dans laquelle X est tel que défini précédemment,
  • pour obtenir un substrat cellulosique portant sur au moins une partie de sa surface une pluralité de
  groupes de formule (C) suivante :
  
  dans laquelle W, i et X sont tels que définis précédemment,
• (ii') la mise en contact d'un substrat tel qu'obtenu à l'étape précédente (i') avec un composé de formule (D) suivante :
  
  • dans laquelle Z et R sont tels que définis précédemment,
  • et dans laquelle Y' est :
    • un groupe -NH₂ lorsque j = 1 et Y est -NH- ;
    • un groupe -OH lorsque j = 1 et Y est -O- ;
    • un groupe -COOH lorsque Y est une liaison simple ;
• ou, lorsque Y est NH, et R est -NH₂, les étapes suivantes : (i") la mise en contact d'au moins une partie de la surface d'un substrat cellulosique, avec un composé (B) de formule suivante :
  [Chem. 18]
  
          O=C=N-X-N=C=O     (B),
  
  
  • dans laquelle X est tel que défini précédemment,
  • puis une mise en contact avec de l'eau,
  • pour obtenir un substrat cellulosique portant sur au moins une partie de sa surface une pluralité de groupes de formule (C) suivante :
  
  dans laquelle W, i et X sont tels que définis précédemment,
• (ii") la mise en contact d'un substrat tel qu'obtenu à l'étape précédente (i') avec un composé de formule (D) suivante :
  [Chem. 20]
  
          O=C=N-Z-N=C=O     (D),
  
  
  • dans laquelle Z est tel que défini précédemment,
  • puis une mise en contact avec de l'eau.

According to another aspect, the invention also relates to a process for preparing a cellulosic substrate as defined above, 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:
  
  • in which X, Y, i, Z and R are as defined above;
  • or 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. 15]
  
  O=C=NXN=C=O (B),
  • in which X is as defined previously,
  • to obtain a cellulosic substrate carrying on at least part of its surface a plurality of
  groups of formula (C) following:
  
  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):
  
  • 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 -NH ₂ , 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. 18]
  
  O=C=NXN=C=O ( 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):
  
  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]
  
  O=C=NZN=C=O (D),
  
  
  • in which Z is as defined previously,
  • then contact with water.

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

When R is of formula -N ⁺ R _a R _b R _c , the compounds bearing this group R can be obtained from the corresponding compounds bearing a group -NR _a R _b , using techniques well known to those skilled in the art.

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.

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.

According to a particular embodiment, the steps defined previously are carried out in supercritical _CO2 ( _sCO2 ).

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 CO ₂ (sCO ₂ ) as co-solvent.

The use of supercritical _CO2 generally requires working in a pressurized autoclave, which protects operators from isocyanates.

The isocyanates described herein may also be used via blocked isocyanate functions, as for example defined in the application FR 3 095 207 .

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.

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.

When _sCO2 is used, the reactions are carried out in an autoclave, for example under a pressure of around 250 bar.

Definitions

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 limits. 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.

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.

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.

The same is true for the term "alkane".

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.

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. 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-, especially -N- and/or -O-. Examples of heteroarenes include pyrrole, furan, thiophene, pyrazole, imidazole, thiazole, isothiazole, isoxazole, oxazole, oxathiol, oxadiazole, triazole, oxatriazole, furazan, 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 General operating protocols

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

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.

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.

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.

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

After treatment according to the invention, all samples were extracted using a Soxhlet to remove 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. The contact angle (wetting) measurements were carried out using a DROP Shape Analyzer KRÜSS (DSA100) device, on samples (5 samples for water and 5 for dodecane) previously preserved in an oven at 100°C.

Example 1: Preparation of intermediate functionalized cellulose substrates

In a 1 liter sCO2 reactor with a useful volume containing 10 to 15 cotton samples, 5 g of hexamethyldiisocyanate are introduced into 10 g of DMSO containing 1 g of DABCO: (anhydrous 1,4-Diazabicyclo[2.2.2]octane). Then 900 ml of liquid CO ₂ are introduced. The reactor is brought to the supercritical state by heating 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 reactor volumes of supercritical sCO2 are then passed (typically 5 volumes). The DABCO which is soluble in sCO ₂ and the corresponding primary amines are recovered in the reactor separators. unreacted HDMI. The cotton substrates are then coated with anhydrous primary amine.

In all of the above and below, anhydrous DMSO may be used instead of _sCO2 .

Example 2:

• Dans un réacteur sCO2 d'un litre de volume utile contenant 10 à 15 échantillons de coton portant des amines primaires greffées pendantes, on introduit 5 g d'hexamethyldiisocyanate dans 10g de DMSO. La formation de la fonction urée ne nécessite pas l'utilisation d'un catalyseur. Puis on introduit 900ml de CO2 liquide. On passe à l'état supercritique en chauffant le réacteur à 150°C à une pression de 250 bar. Le traitement dure 1h30. On introduit alors dans le réacteur pressurisé via une pompe haute pression 10 ml d'eau DI. Toute les fonctions isocyanates pendantes ou de HDMI qui n'aurait pas réagi sont immédiatement transformées en amine primaire. On fait passer ensuite plusieurs volumes de réacteur de sCO2 (typiquement 5 volumes). On récupère dans les séparateurs du réacteur les amines primaires correspondantes à l'HDMI qui n'a pas réagi sur le coton est qui transformé en diamine.
• On ouvre le réacteur, les échantillons sont alors trempés 10 minutes dans 100ml d'une solution (0,1M d'HCl) puis rincés à l'eau DI avant d'être séchés 12H à 130°C dans une étuve ventilée. Ces échantillons correspondent à la référence 1 du tableau ci-dessous.

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

• In a 1-liter sCO2 reactor containing 10 to 15 cotton samples bearing 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 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 unreacted HDMI are immediately transformed into primary amine. Several reactor volumes of sCO2 are then passed (typically 5 volumes). The primary amines corresponding to the HDMI that has not reacted with the cotton are recovered in the reactor separators and transformed into diamine.
• The reactor is opened, the samples are then soaked for 10 minutes in 100ml of a solution (0.1M HCl) then rinsed with DI water before being dried for 12 hours at 130°C in a ventilated oven. These samples correspond to reference 1 in the table below.

Example 3:

Example 2 is repeated twice to form the species corresponding to reference 1b in the table below.

Example 4: Witness outside the invention

In a 1 liter sCO2 reactor with a useful volume containing 10 to 15 cotton samples bearing 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 achieved by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30 min. 5 g of octadecylamine are introduced into 5 g of DMSO using the high-pressure pump. 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.

These samples correspond to reference 2 in the table.

Example 5:

In a 1 liter sCO2 reactor containing 10 to 15 cotton samples bearing 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 achieved 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).

The reactor is opened, the samples are then soaked for 10 minutes in 100ml of a solution (0.1M HCl) then rinsed with DI water before being dried for 12 hours at 130°C in a ventilated oven. These samples correspond to reference 3 in the table.

Example 6:

In a 1 liter sCO2 reactor of useful volume containing 10 to 15 cotton samples bearing 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 at 150°C at a pressure of 250 bar. The treatment lasts 1h30. 5g of 2-Amino-2-(hydroxymethyl)-1,3-propanediol are introduced into 5g of DMSO using the high-pressure pump. The reaction is left to react for 1h30 at 250 bar, 150°C. Several reactor volumes of sCO2 (typically 5 volumes) are then passed through, still at 250 bar and 150°C, to remove the ungrafted products.

These samples correspond to reference 4 in the table.

Example 7:

In a 1 liter sCO2 reactor with a useful volume containing 10 to 15 cotton samples bearing 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 achieved by heating the reactor to 150 ° C at a pressure of 250 bar. The treatment lasts 1 h 30 min. 5 g of 2,2-Bis(hydroxymethyl)-2,2'2'-nitrilotriethanol are introduced into 5 g of DMSO using the high-pressure pump. 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. These samples correspond to reference 5 in the table.

Example 8: Results

The results recorded in the table below show that the treated substrates of the invention are hydrophobic while having a marked oleophobic character.

[Chem. 21]

Reference Structure Wetting angle 20% RH Wetting Angle 80%RH 1

θH2O 110° θH2O 60° θDode 70° θDode 30° 2 (reference outside invention)

θH2O 140° θH2O 140° θDode<30° θDode<30° 1 bis

θH2O 110° θH2O 60° θDode 70° θDode 50° 3

θH2O 115° θH2O 90° θDode<60° θDode 60-80° 4

θH2O 80° θH2O 80° θDode 40° θDode 40° 5

θH2O 80° θH2O 80° θDode 70° θDode 70°

Claims (10)

Cellulosic substrate carrying on at least part of its surface a plurality of groups of the following formula (I):

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):

j and k are independently chosen from 0 and 1; X _a and X _c are independently chosen from: - the X _a1 groups being linear, branched and/or cyclic C ₁ -C ₁₂ alkane diyls, in particular the groups of formula -(CH ₂ ) _n - with n from 1 to 12, or linear and branched C ₂ -C ₁₂ alkene diyls, the X _a1 groups being in particular linear and branched C ₁ -C ₁₂ alkane diyls; - groups of formula -X _a1 -NH-X _a1 -, where X _a1 is at each occurrence independently as defined above, in particular groups of formula -(CH ₂ ) _n -NH-(CH ₂ ) _m - with n and m being independently from 1 to 12; - groups of formula -X _a1 -NHC(=O)-NH-X _a1 - or -X _a1 -NHC(=O)-NH-X _a1 -NHC(=O)-NH-X _a1 -, where X _a1 is at each occurrence independently as defined above, in particular groups of formula -(CH ₂ ) _n -NHC(=O)-NH-(CH ₂ ) _m - with n and m being independently from 1 to 12; X _b is chosen from: - linear, branched and/or cyclic C ₁ -C ₁₂ alkane diyls, in particular groups of formula -(CH ₂ ) _n - with n from 1 to 12, branched C ₁ -C ₁₂ alkane triyls, linear and branched C ₂ -C ₁₂ alkene diyls, the X _b groups being in particular linear and branched C ₁ -C ₁₂ alkane diyls or triyls; optionally carrying, in particular in terminal position(s), at least one -(O-CH ₂ -CH ₂ ) _p - or -(O-CH ₂ -C(CH ₃ )H) _p - group, with p being an integer from 1 to 3; - arene diyls and heteroarene diyls; X _b being optionally substituted by a group A of the following formula (III):

X _c , Y, i, Z and R being as defined above or below, Z is chosen from linear, branched and/or cyclic C ₁ -C ₁₂ alkanes and linear and branched C ₂ -C ₁₂ alkene diyls, Z being in particular a linear C ₂ alkane or alkene diyl, said group Z being optionally substituted by a -COOH or ^-COO- group; R is chosen from: - the groups of formula -NR _a R _b , and the groups -N ⁺ R _a R _b R _c , in which R _a , R _b and R _c are independently chosen from H and linear and branched C ₁ -C ₆ 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):

Cellulosic substrate according to claim 1, in which R is chosen from: - the groups of formula -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 -NH ₂ , -NR _a H, R _a being more particularly a methyl or an ethyl, or -NR _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in the terminal position(s), -NR _a R _b being for example of the following formula:

- the groups of formula -N ⁺ R _a R _b H, in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ 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 ⁺ H ₂ , -N ⁺ R _a H, R _a being more particularly a methyl or an ethyl, or -N ⁺ R _a R _b , in which R _a and R _b are independently chosen from H and linear and branched C ₁ -C ₆ alkyls, optionally substituted by at least one -OH group, in particular in the terminal position(s), R _a and R _b being in particular independently chosen from linear and branched C ₁ -C ₆ alkyls, substituted by at least one -OH group, in particular in terminal position(s), -N ⁺ R _a R _b being for example of the following formula:

- aliphatic polyols, in particular among the linear and branched C ₁ -C ₆ alkyls, substituted by at least two -OH groups, in particular in the terminal position(s), R being for example of the following formula:

A cellulosic substrate according to any preceding claim, wherein X _b is selected from the following groups:

A and p being as defined in claim 1. 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:

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. Cellulosic substrate according to any one of the preceding claims, is made of or comprises a material selected from woven cottons, woven hemps, woven Tencel, woven linens, woven viscose. Cellulosic substrate according to any one of the preceding claims, wherein: - 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%. 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:

wherein X, Y, i, Z and R are as defined in claim 1. or 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. 32]

O=C=NXN=C=O (B),

wherein X is as defined in claim 1, to obtain a cellulose substrate carrying on at least part of its surface a plurality of groups of the following formula (C):

wherein W, i and X are as defined in claim 1, (ii') bringing a substrate as obtained in the previous step (i') into contact with a compound of the following formula (D):

wherein Z and R are as defined in claim 1, and in which Y' is: - a -NH ₂ 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 -NH ₂ , 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=C=NXN=C=O (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):

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=NZN=C=O (D),

in which Z is as defined previously, then contact with water.