WO2023118207A1 - Procédé de teinture d'une matière cellulosique - Google Patents

Procédé de teinture d'une matière cellulosique Download PDF

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WO2023118207A1
WO2023118207A1 PCT/EP2022/087086 EP2022087086W WO2023118207A1 WO 2023118207 A1 WO2023118207 A1 WO 2023118207A1 EP 2022087086 W EP2022087086 W EP 2022087086W WO 2023118207 A1 WO2023118207 A1 WO 2023118207A1
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Prior art keywords
cellulosic material
process according
group
laccase
borane
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PCT/EP2022/087086
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English (en)
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Awilda MACCOW
Guillaume BOISSONNAT
David GUIEYSSE
Magali Remaud-Siméon
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Pili
Institut National des Sciences Appliquées de Toulouse (INSA Toulouse)
Institut National De Recherche Pour L'agriculture, L'alimentation Et L'environnement
Centre National De La Recherche Scientifique
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Publication of WO2023118207A1 publication Critical patent/WO2023118207A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/41—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6016—Natural or regenerated cellulose using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/002—Locally enhancing dye affinity of a textile material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/0004—Oxidoreductases (1.)
    • C12N9/0055—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
    • C12N9/0057—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3)
    • C12N9/0061—Laccase (1.10.3.2)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/26—Preparation of nitrogen-containing carbohydrates
    • C12P19/28—N-glycosides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
    • C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
    • C12Y110/03002—Laccase (1.10.3.2)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre

Definitions

  • the present invention relates to the field of dyeing processes. More particularly, it relates to a process for dyeing a cellulosic material, comprising an enzymatic oxidation of a cellulosic material followed by a reductive amination in the presence of an aminated dye.
  • Reactive dyes have a wide color range and are commonly used for dyeing cellulosic fibers such as cotton and flax.
  • dye molecules are diffused into the fibers and establish chemical bonds with the fibers through a reactive functional group, such as a chlorotriazine, a vinyl sulfone, or a bromoacrylate, attached to the chromophore of the dye. Due to the formation of this permanent bond with the fiber, the reactive dye could not be easily removed by repeated treatment with boiling water under neutral conditions. Thus, the dyes become parts of the fiber, and allows outstanding colour fastness to wash.
  • the inventors have developed a two-step process for dyeing a cellulosic material.
  • This process comprises contacting a cellulosic material with an oxidoreductase and a redox mediator, and then contacting the resulting cellulosic material with a dye comprising at least one NH2 group, in the presence of a reducing agent.
  • This two-step process is cost-effective and environmentally-friendly.
  • the process uses inexpensive and non-toxic reagents, which are advantageously used in catalytic amounts.
  • the process can be implemented under mild conditions, in particular at low temperatures and from moderate acid to moderate basic pH’s. This process allows to create a strong covalent link between the amino dye and the cellulosic material, such that a high colour fastness is obtained.
  • the present invention relates to a process for dyeing a cellulosic material comprising the following steps:
  • step (b) contacting the oxidized cellulosic material of step (a) with a dye comprising at least one NH2 group, in the presence of a reducing agent, so as to obtain a dyed cellulosic material;
  • said dye in step (b) is a compound of formula (I):
  • - n is 0 or 1
  • - m is an integer from 1 to 4
  • - X is an arylene or heteroarylene group, said group being optionally substituted by at least one substituent selected from the group consisting of (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2- Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, heteroaryl, halogen, -CN, - NO2, -C(O)Ri, -C(O)OR2,-C(O)NR 3 R4, -S(O) 2 R 5 , -S(O) 2 OR 6 , -NHS(O) 2 R7, -NHS(O) 2 OR 8 , - OR9, -SR10, and -NR11R12,
  • Ri, R2, R3, R4, Rs, Re, R7, R 8 , R9, Rio, R11 and R12 being each independently chosen from hydrogen, (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2- Ci2)heterocycloalkyl, aryl, and heteroaryl,
  • - Y is a spacer chosen among the following groups: (Ci-Ci2)alkylene, (C2-Ci2)alkenylene, (C2- Ci2)alkynylene, (C3-Ci2)cycloalkylene, (C2-Ci2)heterocycloalkylene, arylene, and heteroarylene, said group being optionally interrupted by at least one group chosen from -O-, - S-, -NH-, -C(O)-, and -S(O) 2 , and
  • - Z is a chromophore moiety, or a salt thereof.
  • said compound of formula (I) is such that n is 0.
  • said compound of formula (I) is such that m is 1 or 2, preferably m is 1.
  • said compound of formula (I) is such that Z is a chromophore moiety selected from the group consisting of phenyls, rhodamines, anthraquinones, triarylmethanes, phthalocyanines, monoazo dyes, bisazo dyes, triazo dyes, polyazo dyes, biindolylidene diones, indanediones, quinolyl indanediones, acridines, thiazines, thiazoles, oxazines, phenoxazines, xanthenes, chlorines, diketopyrrolopyrroles, quinacridones, anthocyanidins, flavonoids, and derivatives thereof.
  • Z is a chromophore moiety selected from the group consisting of phenyls, rhodamines, anthraquinones, triarylmethanes, phthalocyanines, monoazo dyes, bis
  • said dye is represented by any one of the following formulae:
  • said dye is represented by any one of the following formulae:
  • said dye is represented by any one of the following formulae:
  • said redox mediator is TEMPO.
  • said oxidoreductase is a laccase.
  • the laccase may be a laccase from Bacillus velezensis, Bacillus stratosphericus, Anoxybacillus, Aspergillus, or Trametes versicolor, preferably Trametes versicolor.
  • the laccase comprises an amino acid sequence selected from the group consisting of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3, SEQ ID NO: 4, SEQ ID NO: 5, and variants thereof, wherein said variants exhibit laccase activity and have at least 60 % of amino acid sequence identity.
  • step (a) is carried out at a temperature comprised between 10 °C and 60 °C, preferably between 20 °C and 50 °C, and more preferably between 25°C and 35 °C.
  • step (a) is carried out at a pH comprised between 2.5 and 12, preferably between 4 and 10, more preferably between 4 and 8, even more preferably between 5 and 8.
  • step (b) is carried out at a temperature comprised between 10 °C and 60 °C, preferably between 30 °C and 50 °C, more preferably between 35°C and 45 °C.
  • step (b) is carried out in the presence of an acid, such as acetic acid.
  • step (a) is carried out in water.
  • step (b) is carried out in water.
  • said reducing agent is a borane compound, said borane compound being preferably selected from the group consisting of sodium or potassium borohydride, zinc borohydride, sodium cyanoborohydride, borane (BH3), diborane (B2H6), pyridine borane, picoline borane, 5-ethyl-2-methylpyridine borane, morpholine borane, 4- methylmorpholine borane, triethylamine borane, 9-borabicyclo[3.3.1]nonane (9-BBN), monoisopinocampheylborane, dicyclohexylborane, dimesitylborane, disiamylborane, catecholborane, pinacolborane, L-selectride, and a mixture thereof, more preferably picoline borane.
  • borane compound being preferably selected from the group consisting of sodium or potassium borohydride, zinc borohydride, sodium cyanoborohydr
  • said cellulosic material is chosen from cotton, flax, hemp, jute, viscose, lyocell, rayon, and modal, preferably cotton.
  • the process of the present invention comprises the following successive steps: (a) contacting a cellulosic material with a laccase and TEMPO or a derivative thereof, so as to obtain an oxidized cellulosic material;
  • step (b) contacting the oxidized cellulosic material of step (a) with a dye of formula (I) as defined herein, in the presence of a borane compound, so as to obtain a dyed cellulosic material;
  • Another object of the present invention is a dyed cellulosic material obtained by a process as defined herein.
  • FIG. 1 FTIR (Fourier-transform infrared spectroscopy) spectra of a cotton oxidized according to step (a) of the process of the invention, and an untreated cotton.
  • FIG. 1 LCUV (Liquid Chromatography-Ultra Violet) chromatograms of the hydrosylate of a cotton dyed according to the process of the invention and the hydrosylate of untreated cotton.
  • Figure 3. LC-MS/UV analysis of the supernatant after enzymatic hydrolysis with cellulases of cotton thread dyed with p-toluidine (A: UV286nm chromatograms - B: m/z detected for each product, Pl, P2 and P3, and corresponding to H + adducts in positive mode).
  • A UV286nm chromatograms - B: m/z detected for each product, Pl, P2 and P3, and corresponding to H + adducts in positive mode.
  • FIG. 4 LC-MS/UV analysis of the supernatant after enzymatic hydrolysis with cellulases of cotton threads dyed with RHO123 or AR33 (Fig. 4A, Fig. 4C: UV chromatograms obtained from cotton threads grafted with RHO123 or AR33, respectively; Fig. 4B, Fig. 4D: m/z detected for each product and corresponding to H + adducts in positive mode).
  • Figure 5 Images of cotton threads dyed according to the process of the invention with RHO123 (Al) or AR33 (Bl), and comparative samples of cotton threads dyes without oxidation (A2, B2) or without reducing agent (A3, B3).
  • Figure 7 Images of a cotton fabric dyed with AR33 according to the process of the invention, before washing and after three washing cycles.
  • Ci-Ce can also be used with lower numbers of carbon atoms such as C1-C2.
  • C1-C12 it means that the corresponding hydrocarbon chain may comprise from 1 to 12 carbon atoms, especially 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.
  • Ci-Ce it means that the corresponding hydrocarbon chain may comprise from 1 to 6 carbon atoms, especially 1, 2, 3, 4, 5, or 6 carbon atoms.
  • alkyl refers to a saturated, linear or branched aliphatic group.
  • (C1-C12) alkyl includes for instance methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.
  • alkenyl refers to an unsaturated, linear or branched aliphatic group, having at least one carbon-carbon double bond.
  • (C2-Ci2)alkenyl includes for instance ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl.
  • alkynyl refers to an unsaturated, linear or branched aliphatic group, having at least one carbon-carbon triple bond.
  • (C2-Ci2)alkynyl includes for instance ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl.
  • cycloalkyl corresponds to a saturated or unsaturated mono-, bi- or tri-cyclic alkyl group. It also includes fused, bridged, or spiro-connected cycloalkyl groups.
  • (C3- Ci2)cycloalkyl includes for instance cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • heterocycloalkyl corresponds to a saturated or unsaturated cycloalkyl group as above defined further comprising at least one heteroatom such as nitrogen, oxygen, or sulphur atom. It also includes fused, bridged, or spiro-connected heterocycloalkyl groups.
  • (C2-Ci2)heterocycloalkyl includes for instance dioxolanyl, benzo [1,3] dioxolyl, azetidinyl, oxetanyl, pyrazolinyl, pyranyl, thiomorpholinyl, pyrazolidinyl, piperidyl, piperazinyl, 1,4- dioxanyl, imidazolinyl, pyrrolinyl, pyrrolidinyl, piperidinyl, imidazolidinyl, morpholinyl, 1,4- dithianyl, pyrrolidinyl, oxozolinyl, oxazolidinyl, isoxazolinyl, isoxazolidinyl, thiazolinyl, thiazolidinyl, isothiazolinyl, isothiazolidinyl, dihydropyranyl, tetrahydropyranyl, t
  • Cycloalkyl and “heterocycloalkyl” also include cycloalkenyl and heterocycloalkenyl which correspond respectively to a cycloalkyl having at least one carbon-carbon double bond and a heterocycloalkyl having at least one carbon-carbon double bond such as cyclohexenyl, and dihydropyranyl.
  • aryl corresponds to a mono- or bi-cyclic aromatic hydrocarbon having from 6 to 12 carbon atoms.
  • the term “aryl” includes phenyl, naphtalenyl, or anthracenyl.
  • the aryl is a phenyl or a naphtalenyl, more preferably a phenyl.
  • heteroaryl refers to an aromatic, mono- or poly-cyclic group comprising between 5 and 14 atoms and comprising at least one heteroatom such as nitrogen, oxygen or sulphur atom.
  • heteroaryl further includes the “fused arylheterocycloalkyl” and “fused heteroarylcycloalkyl”.
  • fused arylheterocycloalkyl and “fused heteroarylcycloalkyl” correspond to a bicyclic group in which an aryl as above defined or a heteroaryl is respectively bounded to the heterocycloalkyl or the cycloalkyl as above defined by at least two carbons.
  • the aryl or the heteroaryl shares a carbon bond with the heterocycloalkyl or the cycloalkyl.
  • Examples of such mono- and poly-cyclic heteroaryl group, fused arylheterocycloalkyl and fused arylcycloalkyl may be: pyridinyl, thiophenyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, tetrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, tetrazolyl, benzofuranyl, thianaphthal enyl, indolyl, indolinyl, indanyl, quinolinyl, isoquinolinyl, benzimidazolyl, tetrahydroquinolinyl, tetrahydrois
  • a fused arylheterocycloalkyl is for instance an indolinyl (phenyl fused to a pyrrolidinyl) and a dihydrobenzofuranyl (phenyl fused to a dihydrofuranyl).
  • halogen corresponds to a fluorine, chlorine, bromine, or iodine atom, preferably a fluorine or a chlorine.
  • alkylene refers to a divalent alkyl group, wherein “alkyl” is as defined herein.
  • (Ci-Ci2)alkylene refers in particular to a group of formula -(CH2) q - where q is an integer from 1 to 12.
  • “(Ci-Ci2)alkylene” includes for instance methylene, ethylene, propylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, or dodecylene.
  • alkenylene refers to a divalent alkenyl group, wherein “alkenyl” is as defined herein.
  • alkynylene refers to a divalent alkynyl group, wherein “alkynyl” is as defined herein.
  • cycloalkylene refers to a divalent cycloalkyl group, wherein “cyclolalkyl” is as defined herein.
  • a (C3-Ci2)cycloalkylene includes cyclopropylene, cyclopentlyene, or cyclohexylene.
  • heteroalkylene refers to a divalent hetercycloalkyl group, wherein “hetercyclolalkyl” is as defined herein.
  • a (C3-Ci2)cycloalkylene includes thiomorpholinylene, pyrazolidinylene, piperidylene, or piperazinylene.
  • arylene refers to a divalent aryl group, wherein “aryl” is as defined above.
  • arylene includes phenylene.
  • heteroarylene refers to a divalent heteroaryl group, wherein “heteroaryl” is as defined herein.
  • a heteroarylene includes pyridinylene, thiophenylene, or furanyl ene.
  • substituted by at least one substituent means “substituted by one or several substituents” of a given list.
  • optionally substituted by means “not substituted or substituted by”.
  • the term “comprise(s)” or “comprising” is “open-ended” and can be generally interpreted such that all of the specifically mentioned features and any optional, additional and unspecified features are included. According to specific embodiments, it can also be interpreted as the phrase “consisting essentially of’ where the specified features and any optional, additional and unspecified features that do not materially affect the basic and novel character! stic(s) of the claimed invention are included or the phrase “consisting of’ where only the specified features are included, unless otherwise stated.
  • the “salts” include inorganic as well as organic acids salts.
  • suitable inorganic acids include hydrochloric, hydrobromic, hydroiodic, phosphoric, and the like.
  • suitable organic acids include formic, acetic, trichloroacetic, trifluoroacetic, propionic, benzoic, cinnamic, citric, fumaric, maleic, methanesulfonic and the like.
  • the “salts” also include inorganic as well as organic base salts.
  • suitable inorganic bases include sodium or potassium salt, an alkaline earth metal salt, such as a calcium or magnesium salt, or an ammonium salt.
  • sequence identity refers to the number (%) of matches (identical amino acid residues) in positions from an alignment of two polypeptide sequences.
  • sequence identity is determined by comparing the sequences when aligned so as to maximize overlap and identity while minimizing sequence gaps.
  • sequence identity may be determined using any of a number of mathematical global or local alignment algorithms, depending on the length of the two sequences. Sequences of similar lengths are preferably aligned using a global alignment algorithm (e.g. Needleman and Wunsch algorithm; Needleman and Wunsch, 1970) which aligns the sequences optimally over the entire length, while sequences of substantially different lengths are preferably aligned using a local alignment algorithm (e.g.
  • Alignment for purposes of determining percent amino acid sequence identity can be achieved in various ways that are within the skill in the art, for instance, using publicly available computer software available on internet web sites such as http://blast.ncbi.nlm.nih.gov/ or http://www.ebi.ac.uk/Tools/emboss/). Those skilled in the art can determine appropriate parameters for measuring alignment, including any algorithms needed to achieve maximal alignment over the full length of the sequences being compared.
  • BLAST Basic Local Alignment Search Tool
  • the present invention provides a simple and environmentally-friendly two-step process for dyeing a cellulosic material.
  • the process of the present invention comprises the following steps:
  • step (b) contacting the oxidized cellulosic material of step (a) with a dye comprising at least one NEL group, in the presence of a reducing agent, so as to obtain a dyed cellulosic material;
  • a “cellulosic material” refers to any material comprising or consisting of cellulose.
  • the cellulosic material may have any size and any form, and may be from any source.
  • the cellulose may be from a natural or synthetic source.
  • the cellulosic material comprises at least 20%, 30%, or 40%, preferably at least 50%, 60%, or 70%, more preferably at least 80%, 90%, 95%, 98%, 99%, or 100% by weight of cellulose.
  • the cellulosic material comprises or consists of fibers comprising or consisting of cellulose. More particularly, the cellulosic material may be a textile, for instance a non-woven or woven fabric.
  • the cellulosic material is chosen from cotton, flax, hemp, jute, viscose, lyocell, rayon, and modal. More preferably, the cellulosic material is cotton.
  • step (a) of the process of the invention the cellulosic material is contacted with an oxidoreductase and a redox mediator, such that an oxidized cellulosic material is obtained.
  • an “oxidoreductase” refers to an enzyme which is able to trigger or catalyze an oxidoreduction reaction.
  • the oxidoreductase may in particular be able to oxidize the redox mediator.
  • the oxidoreductase may be from any source, such as bacteria, fungi, lichen, insects, or plants.
  • the oxidoreductase may in particular be any known oxidoreductase, and variants thereof. More particularly, the oxidoreductase may be selected from known bacteria, fungi, lichen, insect, or plant oxidoreductases, and variants thereof.
  • said variants exhibit oxidoreductase activity and have at least 60 %, preferably at least 70% or 80%, more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to any of said oxidoreductase.
  • the oxidoreductase may be thermostable or not.
  • the oxidoreductase is selected from the group consisting of a laccase, a p-diphenol: oxygen oxidoreductase, a ferroxidase (such as EC 1.10.3.2), a laccaselike multicopper oxidase (such as EC 1.10.3.-), a cellobiose dehydrogenase (such as EC 1.1.99.18), a glucose 1-oxidase (such as EC 1.1.3.4), an aryl alcohol oxidase (such as EC 1.1.3.7) , an alcohol oxidase (such as EC 1.1.3.13), a pyranose oxidase (such as EC 1.1.3.10), an acceptor-oxygen oxidase (such as EC 1.1.3.-) , a galactose oxidase (such as EC 1.1.3.9), a glyoxal oxidase (such as EC 1.2.3.
  • the EC number refers to the Enzyme Commission number, which is a numerical classification scheme for enzymes based on chemical reactions such enzymes catalyze.
  • the oxidoreductase is a laccase.
  • the laccase may be from any source, such as bacteria, fungi, lichen, insects, or plants.
  • Said laccase may be any known laccase, in particular may be selected from known bacteria, fungi, lichen, insect, or plant laccases, and variants thereof.
  • said variants exhibit laccase activity and have at least 60 %, preferably at least 70 % or 80%, more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to any of said laccase.
  • the laccase activity can be determined by photometrical test using phenolic substrates and by monitoring the oxidized products.
  • phenolic substrates for the laccase assay include, but are not limited to, guaiacol, 2.6-dimethoxyphenol, syringaldazine, 2,2-azino-bis-(3-ethylbenzothiazoline-6- sulphonic acid, benzenediol, and 3,4-dimethoxybenzyl alcohol.
  • a method for the determination of laccase activity is in particular described in the following articles: Johannes & Maicherczyk, Journal of Biotechnology, 2000, 78, 193-199; Harkin & Obst, Ex-perientia 1973, 37, 381-387; Prillinger & Esser Molec. Gen. Genet. 1975, 156, 333-345.
  • the laccase is a laccase from a bacterium or a fungus.
  • bacteria producing an oxidoreductase include, but are not limited to:
  • Bacillus such as Bacillus velezensis (for instance Bacillus velezensis TCCC 111904), Bacillus stratosphericus (for instance Bacillus stratosphericus BCMC2), Bacillus subtilis, Bacillus pumilus, Bacillus clausii, Bacillus halodurans, or Bacillus tequilensis (for instance Bacillus tequilensis SN4),
  • Bacillus velezensis for instance Bacillus velezensis TCCC 111904
  • Bacillus stratosphericus for instance Bacillus stratosphericus BCMC2
  • Bacillus subtilis Bacillus pumilus
  • Bacillus clausii Bacillus halodurans
  • Bacillus tequilensis for instance Bacillus tequilensis SN4
  • Anoxybacillus for instance Anoxybacillus sp. UARK-01,
  • Pseudomonas such as Pseudomonas extremorientalis
  • Streptomyces such as Streptomyces viridochromogenes, Streptomyces ipomoea, or Streptomyces cyaneus
  • Marinomonas such as Marinomonas mediterranea
  • Escherichia such as Escherichia coli
  • Klebsiella such as Klebsiella pneumoniae
  • Yersinia such as Yersinia enter ocolitica.
  • laccase from Bacillus pumilus is Bacillus pumilus CotA.
  • laccase from Bacillus subtilis is Bacillus subtilis CotA.
  • laccase from Bacillus clausii is Bacillus clausii CotA.
  • oxidoreductase from Escherichia coli is Escherichia coli CueO.
  • fungi producing an oxidoreductase include, but are not limited to:
  • Trametes such as Trametes versicolor (for instance Trametes versicolor 52J or Trametes versicolor ATCC 32745), Trametes pubescens, Trametes villosa, Trametes hirsuta, o Trametes trogii,
  • Antrodiella such as Antrodiella faginea
  • Aspergillus such as Aspergillus oryzae or Aspergillus niger (for instance Aspergillus niger CBS 513.88),
  • Pycnoporus such as Pycnoporus cinnabarinus or Pycnoporus sanguineus
  • Lentinus such as Lentinus tigrinus, or Lentinus sp. WR2
  • Coriolopsis gallica for instance Coriolopsis gallica SAH-12
  • Coriolopsis cinerea for instance Coriolopsis cinerea A3387
  • Coriolopsis caperata for instance Coriolopsis caperata
  • Coriolus zonatus such as Coriolus zonatus
  • Phlebia such as Phlebia brevispora
  • Steccherinum such as Steccherinum ochraceum or Steccherinum murashkinski
  • Rigidoporus such as Rigidoporous microporus
  • Myceliophtora such as Myceliophtora thermophila
  • Laccaria such as Laccaria bicolor
  • Coprinopsis cinerea such as Coprinopsis cinerea
  • Abortiporus such as Abortiporus biennis
  • Thielavia such as Thielavia arenaria
  • Deconica such as Deconica castanella
  • Trichoderma such as Trichoderma asperellum (Tor instance Trichoderma asperellum BPI.MBT1).
  • the laccase is a laccase from Bacillus velezensis, Bacillus stratosphericus, Anoxybacillus, Aspergillus (such as Aspergillus niger), or Trametes versicolor, preferably from Trametes versicolor.
  • the laccase comprises, or consists of, an amino acid sequence selected from the group consisting of SEQ ID NO: 1 to 5, and variants thereof, said variants exhibiting laccase activity and having at least 60 %, preferably at least 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to any of SEQ ID NO: 1 to 5.
  • the laccase is a laccase from Bacillus velezensis, and more particularly from Bacillus velezensis TCCC 111904. More particularly, the laccase is preferably a laccase comprising, or consisting of, the following amino acid sequence: SEQ ID NO: 1, or a variant thereof exhibiting laccase activity and having at least 60 %, preferably at least 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to SEQ ID NO: 1.
  • a laccase having the amino acid sequence SEQ ID NO: 1 is described in Li et al. Sci. Total. Environ. 2020, 713, 136713.
  • the laccase is a laccase from Anoxybacillus and more particularly from Anoxybacillus sp. UARK-01. More particularly, the laccase is preferably a laccase comprising, or consisting of, the following amino acid sequence: SEQ ID NO: 2, or a variant thereof exhibiting laccase activity and having at least 60 %, preferably at least 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to SEQ ID NO: 2.
  • a laccase having the amino acid sequence SEQ ID NO: 2 is described in Al-Kahem Al-balawi et al. Curr Microbiol. 2017,74, 762-771.
  • the laccase is a laccase from Bacillus stratosphericus, and more particularly from Bacillus stratosphericus BCMC2. More particularly, the laccase is preferably a laccase comprising, or consisting of, the following amino acid sequence: SEQ ID NO: 3, or a variant thereof exhibiting laccase activity and having at least 60 %, preferably at least 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to SEQ ID NO: 3.
  • a laccase having the amino acid sequence SEQ ID NO: 3 is described in Xiao et al. Int J Biol Macromol. 2021, 179, 270-278.
  • the laccase is a laccase from Aspergillus, such as Aspergillus niger. More particularly, the laccase is preferably a laccase comprising, or consisting of, the following amino acid sequence: SEQ ID NO: 5, or a variant thereof exhibiting laccase activity and having at least 60 %, preferably at least 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to SEQ ID NO: 5.
  • the laccase is a laccase from Trametes versicolor. More particularly, the laccase is preferably a laccase comprising, or consisting of, the following amino acid sequence: SEQ ID NO: 4, or a variant thereof exhibiting laccase activity and having at least 60 %, preferably at least 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 75%, more preferably at least 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, and even more preferably at least 90%, 95%, 96%, 97%, 98% or 99%, amino acid sequence identity to SEQ ID NO: 4.
  • a “redox mediator” refers to a compound that is able to exchange (in particular, provide and then recover) at least one electron.
  • the redox mediator may be able to be oxidized by the oxidoreductase to form an oxidized redox mediator, and said oxidized redox mediator may be able to oxidize the cellulose.
  • the redox mediator is an oxyl radical, preferably a nitroxyl radical.
  • an “oxyl radical” denotes an organic compound having one free radical (i.e. one single unpaired electron) on an oxygen atom.
  • a “nitroxyl radical” denotes an oxyl radical as defined herein, wherein said oxygen atom having one free radical is bound to a nitrogen atom.
  • the redox mediator is an nitroxyl radical selected from the group consisting of 2,2,6,6-tetramethylpiperidin-l-yl)oxyl (TEMPO), 2,2,5,5-tetramethyl-l- pyrrolidinyloxyl (PROXYL), aminyloxyl, imino nitroxyl, nitronyl nitroxyl, iminoxyl, derivatives thereof, and a mixture thereof.
  • TEMPO 2,2,6,6-tetramethylpiperidin-l-yl)oxyl
  • PROXYL 2,2,5,5-tetramethyl-l- pyrrolidinyloxyl
  • aminyloxyl imino nitroxyl, nitronyl nitroxyl, iminoxyl, derivatives thereof, and a mixture thereof.
  • an aminyloxyl is a compound of formula (Il-a): wherein R13 and R14 are each independently chosen from (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2- Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, and heteroaryl.
  • an imino nitroxyl is a compound of formula (Il-b) : wherein R15, Ri6, and R17 are each independently chosen from (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, and heteroaryl, or R15 and Ri6 form together with the atoms to which they are attached a C5-C12 nitrogencontaining cycle.
  • a nitronyl nitroxyl is a compound of formula (II-c): wherein Ris, R19, and R20 are each independently chosen from (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Cn)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, and heteroaryl, or Ris and R19 form together with the atoms to which they are attached a C5-C12 nitrogencontaining cycle.
  • Ris, R19, and R20 are each independently chosen from (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Cn)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, and heteroaryl, or Ris and R19 form together with the atoms to which they are attached a C5-C12 nitrogen
  • an iminoxyl is a compound of formula (Il-d): wherein R21 and R22 are each independently chosen from (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2- Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, and heteroaryl.
  • the redox mediator is TEMPO or a derivative thereof.
  • TEMPO can be represented as follows:
  • a “derivative of TEMPO” refers to a molecule of TEMPO which is substituted by at least one (for instance, one, two or three, preferably one) substituent.
  • a derivative of TEMPO can be represented by the following formula (II- 1): wherein R23 is selected from the group consisting from OH, NH2, CN, C(O)OH, oxo, (Ci- C 6 )alkyl, -O-(Ci-C 6 )alkyl.
  • the redox mediator is TEMPO.
  • contacting may be carried out by mixing the cellulosic material, the oxidoreductase and the redox mediator in a suitable solvent, preferably water. More particularly, such contacting may be carried out by dipping the cellulosic material into a solvent (preferably water) comprising the oxidoreductase and the redox mediator.
  • Step (a) of the process of the invention can be carried out under mild conditions, in particular mild temperatures and pH’s.
  • step (a) is carried out at a temperature comprised between 10 °C and 60 °C, preferably between 20 °C and 50 °C, more preferably between 25°C and 35 °C.
  • step (a) is carried out at a pH comprised between 2.5 and 12, preferably between 4 and 10, more preferably between 4 and 8, even more preferably between 5 and 8.
  • Step (a) may be carried out in aqueous medium.
  • the pH of step (a) can in particular be controlled by using a pHstat system and/or a buffer. Examples of buffer include, but are not limited to, a sodium phosphate buffer, an acetate buffer, a citrate buffer or Tri-CuCh buffer.
  • step (a) is carried out for a duration comprised between 1 hour and 30 hours, for instance between 5 hours and 15 hours.
  • Step (a) may be carried out under air.
  • the oxidoreductase and the redox mediator may be used in catalytic amounts.
  • the concentration of the redox mediator in step (a) may for instance be comprised between 0.1 mM and 100 mM.
  • the concentration of the oxidoreductase in step (a) may for instance be comprised between 0.001 U/mL and 100 U/mL.
  • Step (a) of the process of the invention allows to obtain an oxidized cellulosic material.
  • An “oxidized cellulosic material” may in particular refer to a cellulosic material in which all or part of the alcohol functions of the cellulose are in oxidized forms, preferably in aldehyde and optionally ketone and/or carboxylic acid.
  • the solvent preferably water
  • the oxidoreductase and the redox mediator may be re-used after recovering of the oxidized cellulosic material.
  • Step (b) of the process of the invention comprises contacting the oxidized cellulosic material of step (a) with a dye comprising at least one NH2 group, in the presence of a reducing agent, so as to obtain a dyed cellulosic material.
  • the “dye comprising at least one NH2 group” refers to any inorganic or organic compound comprising a chromophore moiety and at least one NH2 group.
  • the term “chromophore moiety” denotes a chemical moiety comprising conjugated double bonds (for instance, aromatic bonds) and imparting a color to the dye, typically by absorbing a part of a visible light and by reflecting, transmitting, or diffusing a complementary part of said visible light.
  • the chromophore moiety and the at least one NH2 group may be covalently linked to each other directly or indirectly (i.e. through a spacer), preferably directly.
  • the chromophore moiety may in particular be chosen among chromophore moieties that are usually used in dyeing processes, and derivatives thereof. Such chromophore moieties are in particular described in the following articles: Klaus Hunger, Industrial dyes, chemistry, properties, applications, 2003, Wiley; Benkhaya et al. Inorganic Chemistry Communications, 2020, 115, 107891.
  • “Derivatives” of chromophore moieties include in particular derivatives substituted by one or more substituents (such as -CF3, -CN, -NO2, -OH, Ci-Ce alkyl, halogen, - S(O)2ONa, or -C(O)O(Ci-Ce alkyl)) and having their chromophore activity preserved.
  • substituents such as -CF3, -CN, -NO2, -OH, Ci-Ce alkyl, halogen, - S(O)2ONa, or -C(O)O(Ci-Ce alkyl
  • chromophore moieties include, but are not limited to, phenyls, rhodamines, anthraquinones, triarylmethanes, phthalocyanines, monoazo dyes, bisazo dyes, triazo dyes, polyazo dyes, biindolylidene diones, indanediones, quinolyl indanediones, acridines, thiazines, thiazoles, oxazines, phenoxazines, xanthenes, chlorines, diketopyrrolopyrroles, quinacridones, anthocyanidins, flavonoids, and derivatives thereof.
  • said dye is a dye comprising at least one NH2 group having a pKa equal to or less than 11, preferably equal to or less than 9, more preferably equal to or less than 7, even more preferably equal to or less than 5.
  • said pKa may be comprised between -5 and 11, between -5 and 9, between -5 and 7, between 0 and 7, between 3 and 7, between -5 and 5, between 0 and 5, or between 3 and 5.
  • the “pKa of said at least one NH2 group” refers to -log(Ka), where Ka is the acid dissociation constant between said at least one NH2 group and the corresponding acidic form NHC.
  • the pKa can be determined by any techniques known to the skilled artisan, for instance by potentiometric titration or conductometry.
  • said NH2 group is a NH2 group directly linked to an aromatic group such as an arylene or heteroarylene.
  • the dye is thus an aromatic amine.
  • said dye is a compound of formula (I): [H 2 N-(X-Y)n]m-Z (I), in which: - n is 0 or 1,
  • - m is an integer from 1 to 4,
  • - X is an arylene or heteroarylene group, said group being optionally substituted by at least one substituent selected from the group consisting of (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2- Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, heteroaryl, halogen, -CN, - NO2, -C(O)Ri, -C(O)OR2,-C(O)NR 3 R4, -S(O) 2 R 5 , -S(O) 2 OR 6 , -NHS(O) 2 R7, -NHS(O) 2 OR 8 , - OR9, -SR10, and -NR11R12,
  • Ri, R2, R3, R4, Rs, Re, R7, R 8 , R9, Rio, R11 and R12 being each independently chosen from hydrogen, (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2- Ci2)heterocycloalkyl, aryl, and heteroaryl,
  • - Y is a spacer chosen among the following groups: (Ci-Ci2)alkylene, (C2-Ci2)alkenylene, (C2- Ci2)alkynylene, (C3-Ci2)cycloalkylene, (C2-Ci2)heterocycloalkylene, arylene, and heteroarylene, said group being optionally interrupted by at least one group chosen from -O-, - S-, -NH-, -C(O)-, and -S(O) 2 , and
  • - Z is a chromophore moiety, or a salt thereof.
  • a compound of formula (I) according to the invention thus comprises a chromophore moiety Z linked to a number m of H2N-(X-Y) n - groups.
  • m represents the number of [H2N-(X-Y) n ]- groups covalently linked to the chromophore moiety Z.
  • m is an integer from 1 to 4, preferably m is 1 or 2, more preferably m is 1.
  • n represents the number of (X-Y) group in a [H2N-(X-Y) n ]- group, where the (X-Y) group is covalently linked to NH2 and to the chromophore moiety.
  • n is 0 or 1.
  • each NH2 of the compound of formula (I) may be linked to the chromophore, directly (when n is 0) or through a (X-Y) group (when n is 1).
  • n is independently 0 or 1.
  • said compound of formula (I) is such that n is 1. In such an embodiment, when m is higher than 1, it is understood that each n is 1.
  • X is an arylene group, preferably a phenylene, said group being optionally substituted by at least one substituent selected from the group consisting of (Ci- Cn)alkyl, (C2-Ci2)alkenyl, (C2-Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2-Ci2)heterocycloalkyl, aryl, heteroaryl, halogen, -CN, -NO2, -C(O)Ri, -C(O)OR2,-C(O)NR 3 R4, -S(O) 2 R 5 , -S(O) 2 OR 6 , - NHS(O) 2 R 7 , -NHS(O) 2 OR 8 , -OR9, -SR10, and -NR11R12
  • Ri, R2, R3, R4, Rs, Re, R7, R 8 , R9, Rio, R11 and R12 being each independently chosen from hydrogen, (Ci-Ci2)alkyl, (C2-Ci2)alkenyl, (C2-Ci2)alkynyl, (C3-Ci2)cycloalkyl, (C2- Ci2)heterocycloalkyl, aryl, and heteroaryl.
  • Y is a spacer chosen among the following groups: (Ci- Ci2)alkylene and arylene, said group being optionally interrupted by at least one group chosen from -O-, -S-, -NH-, -C(O)-, and -S(O) 2 .
  • said compound of formula (I) is such that n is 0.
  • n when m is higher than 1, it is understood that each n is 0.
  • a compound of formula (I) wherein n is 0 can be represented by the following formula (1-0):
  • said compound of formula (I) is such that Z is a chromophore moiety selected from the group consisting of phenyls, rhodamines, anthraquinones, triarylmethanes, phthalocyanines, monoazo dyes, bisazo dyes, triazo dyes, polyazo dyes, biindolylidene diones, indanediones, quinolyl indanediones, acridines, thiazines, thiazoles, oxazines, phenoxazines, xanthenes, chlorines, diketopyrrolopyrroles, quinacridones, anthocyanidins, and flavonoids.
  • Z is a chromophore moiety selected from the group consisting of phenyls, rhodamines, anthraquinones, triarylmethanes, phthalocyanines, monoazo dyes, bisazo dyes,
  • said dye (or the compound of formula (I)) is represented by any one of the following formulae:
  • said dye is represented by any one of the following formulae:
  • said dye (or the compound of formula (I)) is represented by any one of the following formulae:
  • said dye is represented by any one of the following formulae:
  • said dye or the compound of formula (I) is represented by any one of the following formulae:
  • said dye (or the compound of formula (I)) is represented by any one of the following formulae:
  • the compound of formula (I-a) as represented above is also called herein “/?ara-toluidine”.
  • the compound of formula (I-b) as represented above is also called herein “rhodamine 123”.
  • the compound of formula (I-f) as represented above is also called herein “acid red 266”.
  • the compound of formula (I-h) as represented above is also called herein “acid red 33”.
  • the compound of formula (I-p) as represented above is also called herein “acid violet 19”.
  • the compound of formula (I-r) as represented above is also called herein “acid blue 25”.
  • the compound of formula (I-s) as represented above is also called herein “acid black 41”.
  • the “reducing agent” relates to one or more compounds that are able to reduce an imine group into an amine group.
  • the reducing agent may in particular be any reducing agent usually used in a reductive amination reaction. More particularly, said reducing agent may be a hydride-type reducing agent.
  • a hydride-type reducing agent is a compound having one or more hydrides (formally: “H ”) that can be transferred to another compound, resulting in the reduction of said other compound.
  • said reducing agent is a borane compound.
  • a “borane compound” refers to any organic compound having at least one B-H bond.
  • the reducing agent is a borane compound selected from the group consisting of sodium or potassium borohydride, zinc borohydride, sodium cyanoborohydride, borane (BH3), diborane (B2H6), pyridine borane, picoline borane, 5-ethyl-2-methylpyridine borane, morpholine borane, 4-methylmorpholine borane, triethylamine borane, 9- borabicyclo[3.3.1]nonane (9-BBN), monoisopinocampheylborane, dicyclohexylborane, dimesitylborane, di si amylborane, catecholborane, pinacolborane, L-selectride, and a mixture thereof.
  • said reducing agent is picoline borane.
  • step (b) contacting may be carried out by mixing the oxidized cellulosic material obtained in step (a), said dye comprising at least one NH2 group, and said reducing agent in a suitable solvent, preferably water. More particularly, such contacting may be carried out by dipping said oxidized cellulosic material into a solvent (preferably water) comprising the dye and the reducing agent.
  • Step (b) of the process of the invention can be carried out under mild conditions, in particular mild temperatures.
  • step (b) is carried out at a temperature comprised between 10 °C and 60 °C, preferably between 30 °C and 50 °C, more preferably between 35°C and 45 °C.
  • step (b) is carried out for a duration comprised between 30 minutes and 30 hours, for instance between 2 hours and 5 hours.
  • Step (b) may be carried out under air.
  • step (b) is carried out in the presence of an acid.
  • acid include, but are not limited to, hydrochloric acid, sulfuric acid, a carboxylic acid such as formic acid, acetic acid, propionic acid, or benzoic acid.
  • said acid is acetic acid.
  • the concentration of said acid in step (b) may advantageously be comprised between 2 % and 30 % (v/v).
  • the dye and the reducing agent may be used in excess with respect to the oxidized cellulosic material.
  • the concentration of the dye (for instance a compound of formula (I)) in step (b) may for instance be comprised between 0.01 mM and 10 M.
  • the concentration of the reducing agent in step (b) may for instance be comprised between 0.1 mM and 1 M.
  • the molar ratio of the carbonyl groups of the oxidized cellulosic material to the dye is comprised between 1/20 and 1/1, preferably between 1/10 and 1/1. In a particular embodiment, the molar ratio of the carbonyl groups of the oxidized cellulosic material to the reducing agent is comprised between 1/2 and 1/1, preferably between 1/1.5 and 1/1.
  • the molar amount of carbonyl groups of the oxidized cellulosic material can be determined by spectrophotometry, in particular according to the method as described below in the examples.
  • a solvent preferably water
  • said solvent comprising the dye and the reducing agent may be re-used after recovering of the oxidized cellulosic material.
  • Step (b) of the process of the invention allows to obtain a dyed cellulosic material.
  • the dyed cellulosic material can be recovered by any suitable technique known to the skilled artisan, for instance by collecting the dyed cellulosic material from the solvent comprising the dye and the reducing agent.
  • steps (a), (b) and (c) of the process of the invention are carried out successively.
  • the process comprises the following successive steps:
  • step (b) contacting the oxidized cellulosic material of step (a) with a dye of formula (I) as defined herein (preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i), (I-j), (I- k), (1-1), (I-m), (I-n), (I-o), (I-p), (I-q), (I-r), or (I-s) as represented above, more preferably of formula (I-a), (I-b) or (I-h)), in the presence of a borane compound, so as to obtain a dyed cellulosic material; and
  • a dye of formula (I) as defined herein preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i
  • the process comprises the following successive steps:
  • a dye of formula (I) as defined herein preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i), (I-j), (I- k), (1-1), (I-m), (I-n), (I-o), (I-p), (I-q), (I-r), or (I-s) as represented above, more preferably of formula (I-a), (I-b) or (I-h)), in the presence of a borane compound, so as to obtain a dyed cellulosic material; and
  • a dye of formula (I) as defined herein preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i), (I-j), (I- k), (1-1), (I-m), (I
  • step (c) recovering a dyed cellulosic material, wherein step (a) is carried out at a temperature comprised between 10 °C and 60 °C (preferably between 20 and 50 °C), and step (b) is carried out at a temperature comprised between 10 °C and 60 °C (preferably between 30 and 50 °C).
  • the process comprises the following successive steps:
  • a cellulosic material chosen from cotton, flax, hemp, jute, viscose, lyocell, rayon or modal (preferably cotton) with a laccase from Bacillus velezensis, Bacillus stratosphericus, Anoxybacillus, Aspergillus, or Trametes versicolor, and TEMPO or a derivative thereof, so as to obtain an oxidized cellulosic material;
  • step (b) contacting the oxidized cellulosic material of step (a) with a dye of formula (I) as defined herein (preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i), (I-j), (I- k), (1-1), (I-m), (I-n), (I-o), (I-p), (I-q), (I-r), or (I-s) as represented above, more preferably of formula (I-a), (I-b) or (I-h)), in the presence of picoline borane, so as to obtain a dyed cellulosic material; and
  • a dye of formula (I) as defined herein preferably a dye of formula (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i
  • step (c) recovering a dyed cellulosic material, wherein step (a) is carried out at a temperature comprised between 10 °C and 60 °C (preferably between 20 and 50 °C), and step (b) is carried out at a temperature comprised between 10 °C and 60 °C (preferably between 30 and 50 °C).
  • Another object of the present invention is a dyed cellulosic material obtained by a process as defined herein.
  • the laccase from Trametes versicolor was purchased from Sigma Aldrich.
  • IC-HRMS of the oxidized Glc5 The mass of Glc5 oxidation products were determined using liquid anion exchange chromatography on a Dionex ICS-5000+ reagent-free HPIC (Thermo Fisher Scientific, Sunnyvale, CA, USA) system coupled with a Thermo Scientific linear trap quadrupole (LTQ) Orbitrap Velos hybrid Fourier-transform (FT) mass spectrometer (FTMS; Thermo Fisher Scientific, San Jose, CA, USA).
  • LTQ Thermo Scientific linear trap quadrupole
  • FTMS Orbitrap Velos hybrid Fourier-transform
  • Samples were separated within 50 min using a linear gradient elution of 7 mM to 100 mM of KOH applied to an IC DionexTM lonPacTM AS11- HC column (250 x 2 mm) equipped with an ASH Thermo ScientificTM DionexTM lonPacTM guard column (50 x 2 mm) at a flow rate of 0.38 mL/min.
  • the column and autosampler temperature were 25°C and 4°C, respectively.
  • the injected sample volume was 5 pL.
  • Conditions for the electrospray ionization (ESI) at negative mode was as follows: spray voltage was at 2.7 kV, capillary and desolvation temperatures were 350 and 350°C, respectively, and the maximum injection time was 50 ms. Nitrogen was used as the sheath gas (pressure, 50 units) and auxiliary gas (pressure, 5 units). The automatic gain control (AGC) was set at le6 for fullscan mode, with a mass resolution of 60.000 (at 400 m/z). For the full scan MS analysis, the spectra were recorded in the range of m/z 80.0-1000.0. Finally, data acquisition was performed using Thermo Scientific Xcalibur software.
  • LC-HRMS/UV analysis of the grafted Glc5 with ⁇ toluidine or Rhodamine Analyses were carried out on a vanquishTM system coupled to a Thermo Sceintific Q ExactiveTM Plus hydrid quadrupole-OrbitrapTM mass spectrometer (Thermo Fisher).
  • Samples were separated within 95 min using an isocratic elution with a mixture containing 10% ACN/ 40% H2O/ 50% 20 mM ammonium acetate applied to a ShodexTM AsahipakNH2P-504E (4,6mm x 250 mm) equipped with a ShodexTM Asahipak NH2P-50 4A guard column (4.6 x 10 mm) at a flow rate of 0.7 mL/min.
  • the column and autosampler temperature were 40°C and 4°C, respectively.
  • the injected sample volume was 10 pL.
  • the LC eluates was monitored at different wavelength according to the grafted compound: 286 nm for /?-toluidine and 540 nm for rhodamine 123.
  • Conditions for the electrospray ionization (ESI) at negative mode was as follows: Conditions for the electrospray ionization (ESI) at negative mode was as follows: spray voltage was at 2.75 kV, capillary and desolvation temperatures were 400 and 400°C, respectively, and the maximum injection time was 100 ms. Nitrogen was used as the sheath gas (pressure, 75 units) and auxiliary gas (pressure, 20 units).
  • the automatic gain control was set at le6 for fullscan mode, with a mass resolution of 70.000 (at 800 m/z).
  • AGC automatic gain control
  • the spectra were recorded in the range of m/z 80.0-1000.0.
  • data acquisition was performed using Thermo Scientific Xcalibur software.
  • Oligosaccharides grafted with p-toluidine (“pT”), Rhodamine 123 (“RHO123”) or Acid Red 33 (“AR33”) were respectively detected by UV at 286 nm, 500 nm and 532 nm depending on the maximum absorption wavelength of the dyes.
  • the gradient used for samples grafted with RHO123 was as following: 0-20 min from 10% B to 30% B for samples grafted with RHO123 or 0-50 min from 10% B to 30% B for sample grafted with AR33, then for all sample 30% B was increased to 40% B within 10 minutes, then 40% B was increased to 100% B within 5 min and kept with 100% B for 5 min finally return to the initial condition and 5 min equilibration of the column. In both cases, a flow rate of 0.5 mL per min was used.
  • the mass spectrometer was used in positive mode with a voltage cone at 75 V, the temperature of the electrospray ionization (ESI) ion source was 450 °C and the gas carrier was nitrogen. The spray voltage was set at 3.5 kV.
  • the mass spectrometer scanned from m/z 100 to 1500. The data acquisition and processing were performed using ChromeleonTM 7.2 data systems. of the freeze-dried oxidized cotton fibers were recorded using a Nicolet
  • Elemental analyses were performed on untreated and treated cotton fibers to determine their carbon, hydrogen, nitrogen content. Elemental analyses were performed in the facility available in Laboratoire de Chimie de Coordination du CNRS using PerkinElmer 2400 Series II Analyzer, Toulouse. The detection range for nitrogen was between 0.001 mg and 6.0 mg.
  • Color washing-fastness test the color resistance test of fabric colored samples consisted of three sequential washing cycles with laundry detergent. Each step was performed at 60 °C for 60 min. After the last step, the fabrics samples were dried overnight at room temperature for color strength evaluation.
  • the content of carbonyl groups in the cotton threads was determined using a spectrophotometric method published by Szabolcs (1961) and optimized by Strlic and Pihlar (1997).
  • the “TTC reagent” was prepared by mixing 20 mL of Triphenyltetrazolium chloride (TTC) at 0.5 M with 20 mL of KOH at 0.3 M. The solution was mixed well and left to stand for 10 min at room temperature before use. 10 mg of dry cotton thread was inserted in a glass tube with 2 mL of water and 2 mL of freshly prepared TTC reagent, and then incubated for 6 min at 80 °C in a water bath.
  • TTC Triphenyltetrazolium chloride
  • the suspension (4 mL) was mixed with MeOH (41 mL) to solubilize the reddish-crystals of TTF (triphenyltetrazolium formazan) produced.
  • the absorbance of the solution was measured at 482 nm.
  • the amount of carbonyl groups was calculated from the calibration curve determined with D-glucose. The mean values were calculated from at least three individual assays. A calibration curve was established using anhydrous D-glucose as standard.
  • a solution of D-glucose at 5.5 mM was prepared, left 30 min at room temperature and then dissolved in water to obtain Absorbances were measured at 482 nm using a UV-Vis Cary 3500 spectrophotometer (Agilent Technologies, Santa Clara, CA, United States) with the CaryWinUV Scan software (Vers.5.0.0.999).
  • Example 1 Process for dyeing a cellulosic material
  • Oxidation reaction was performed in the presence of 27 mM of Glc5, 6 mM of TEMPO and 5.4 U.mL' 1 of laccase from Trametes versicolor in 5 mL of acetate buffer (20 mM, pH 6.0) at 30 °C. The reaction was stirred at 500 rpm in open flask for 8h and monitoring by sampling 250 pL of the reaction mixture for subsequent analyses.
  • Rhodamine 123 (I-b)
  • the initial amount of carbonyl group (i.e., before oxidation with laccase/TEMPO) was 59 ⁇ 8 pmol per gram of cotton. After 7 hours of reaction, the amount is 178 ⁇ 9 pmol of carbonyl groups per gram of cotton threads, corresponding to 6173 pmoles of equivalent glucose.
  • Enzymatic hydrolysis of the dyed cotton using a cellulase cocktail from Trichoderma reesei was carried out and analyzed the hydrolysis products by LC-MS/UV: after washing, 50 mg of the dyed cotton were incubated with 500 pL of cellulase in sodium acetate buffer (50 mM, pH 4.5) at 40°C for 24h.
  • the untreated cotton fibers were also hydrolyzed in the same conditions to serve as control, and they were more rapidly degraded than the dyed threads. The reactions were stopped after 24 h.
  • Rhodamine 123 Reaction with the dye Rhodamine 123 (I-b).
  • Rhodamine 123 0.1 M
  • Figures 5 A and 5B show cotton threads dyed with Rhodamine 123 and Acid Red 33 dyes respectively for assays according to the invention (Al, Bl) and the controls (A2, A3, B2, B3), after reaction and washing steps (Table 1).
  • the oxidized cotton threads incubated with Rhodamine 123 (sample Al) or Acid Red 33 (sample Bl) and pic-BHs retain an intense coloration after washing in comparison to the controls, indicating an improved wet fastness.
  • the result obtained in absence of reducing agent shows that the coloration and wet fastness obtained with an amine bond (Al, Bl) are improved with respect to those obtained with an imine bond (A3, B3).
  • Table 2 shows the elemental composition obtained for each series of experiments (Series A and B). The amount of nitrogen found in oxidized threads treated with Rhodamine 123 and Acid Red 33, and pic-BEE was of 0.30% and 0.08%, respectively. No traces of nitrogen could be detected in the control showing that the persistent color remaining after washing of samples A2/B2 and A3/B3 is due to very low amounts of residual dyes.
  • Cotton fabric a) A 5.8 cm x 4 cm piece of cotton fabric was immersed in a solution containing 5.4 U/mL of laccase fiber and 0.6 mM of TEMPO. The solution was stirred at 140 rpm at 30°C during 7 h. After oxidation, the fabric was rinsed with 125 mL of water and then washed with 100 mL of EtOH/EEO 70/30 before a final rinse with 125 mL distilled water. The washed fabric was dried overnight at room temperature.
  • the reductive amination was carried out at 40°C in a solution containing 10% of acid acetic using the molar ratio of 1 : 1.5: 1.2 for carbonyl groups, amine groups and pic-BEE.
  • pic-BEE has a low solubility in water, it was previously prepared in 80% MeOH (v/v).
  • the dyed cotton material was rinsed three times with 150 mL of water, then washed twice with 50 mL of 50 mM NaOH solution before three successive final rinses with 150 mL of distilled water each. The washed fibers were dried overnight at room temperature.
  • Figure 6 shows that the cotton fabric dyed with AR33 according to the process of the invention retain an intense coloration after washing in comparison to the controls (sample 2: no oxidation, sample 3: no reducing agent) indicating an improved wet fastness.
  • the resulting fabric was then rinsed in 50 kg of water and in another tank containing 45 kg of water, 5 kg of acetic acid (10%), 0,1 mM of a dyestuff, 250 g of picoline borane (48mM, 5g/L) at 40
  • a cotton fabric dyed with AR33 was utilized for the study of the dye washing-fastness. For that propose, a piece of 23,2 cm 2 of colored cotton fabric with AR33 has been subjected to three washing cycles (in a washing machine) of one hour each at 60°C with a laundry detergent.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Coloring (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention se rapporte au domaine des procédés de teinture. Plus particulièrement, l'invention concerne un procédé de teinture d'une matière cellulosique, comprenant une oxydation enzymatique d'une matière cellulosique suivie d'une amination réductrice en présence d'un colorant aminé.
PCT/EP2022/087086 2021-12-21 2022-12-20 Procédé de teinture d'une matière cellulosique WO2023118207A1 (fr)

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