EP4329932A1 - Funktionalisiertes cellulosedekontaminationsmittel - Google Patents

Funktionalisiertes cellulosedekontaminationsmittel

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Publication number
EP4329932A1
EP4329932A1 EP22726012.2A EP22726012A EP4329932A1 EP 4329932 A1 EP4329932 A1 EP 4329932A1 EP 22726012 A EP22726012 A EP 22726012A EP 4329932 A1 EP4329932 A1 EP 4329932A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
decontamination agent
dye
laundry
functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22726012.2A
Other languages
English (en)
French (fr)
Inventor
Vanja Kokol
Vera VIVOD
Branko NERAL
Ales Mihelic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Univerza v Mariboru
Original Assignee
Univerza v Mariboru
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Univerza v Mariboru filed Critical Univerza v Mariboru
Publication of EP4329932A1 publication Critical patent/EP4329932A1/de
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/002—Grey water, e.g. from clothes washers, showers or dishwashers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/12—Location of water treatment or water treatment device as part of household appliances such as dishwashers, laundry washing machines or vacuum cleaners
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention is based on the both the contaminant-capturing and anti-microbial effect of functionalized nanocellulose that was subjected to amination and quaternization reactions. These features are highly complementary and are the basis for a decontamination agent comprising functionalized cellulose as an active agent.
  • a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium is provided.
  • the invention pertains to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation comprising different phases, and in one of which the aforementioned decontamination agent is used in.
  • Cellulose is a polysaccharide that consists of b(i- 4) linked D-glucose units. Depending on their size and crystallinity, several distinct types cellulose are distinguished: Among nanocellulose variants, these are cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and microfibrillated cellulose (MFC). These cellulose types can be produced from bacteria or various plant-based sources such as wood, cotton, hemp, flax, sugar beet and potato tuber fibre. Cellulose is easily produced in large quantities and highly biocompatible. In form of nanocellulose, the material features great surface areas that can interact with their surrounding medium. Further, this large surface allows to fixate chemical functionalizations to a solid backbone. The combination of these properties make nanocellulose an interesting material for washing and water-decontamination applications.
  • CNC cellulose nanocrystals
  • CNF cellulose nanofibrils
  • MFC microfibrillated cellulose
  • cationic functional groups which can be realized by amination or quaternization.
  • individual glucose units of the cellulose polymer are first oxidized to display aldehyde groups. These are then functionalized in further reaction steps to exhibit amino group-bearing molecules.
  • the individual hydroxyl-groups at the glucose constituents of the cellulose polymer are replaced by quaternary ammonium derivatives.
  • both reactions result in a polymer, that exhibits cationic functionalities and thus is called cationized cellulose.
  • CN1054Q8733A A prominent example that is making use of the high-surface area of nanocellulose is given by heavy-metal capturing: In CN1054Q8733A. this is demonstrated on polyethyleneimine- functionalized and cross-linked nanocellulose. This functionalized cellulose can complex soluble metal-ions by their amino-containing Lewis-basic groups. CN107138135A uses the metal capturing properties of ethylenediamine- and thiocarbamide-functionalized crystalline nanocellulose to “imprint” the cellulose with metal-ions. The material can further be used to capture ions such as mercury, lead and copper.
  • CN 100608 4 A discloses anti-microbial nanofibrillated cellulose. They obtain their product by quaternizing cellulose bulk material (a cellulose slurry) with a mixture of different ammonium-chlorides and which is subsequently broken down into functionalized cellulose with a desired shape.
  • CN10Q678Q72A discloses the use of 2,3-dialdehyde-6-carboxy-nanocellulose in the field of antimicrobial textiles. This functionalized cellulose was obtained by conducting first an oxidation reaction on plant based cellulose that was performed in a 2,2,6,6,-tetramethylpiperidine oxide/NaBr/NaCIO oxidiation system.
  • Patent application WO 01/66600 discloses microfibrillar functionalized with amine or a quarternary amine for adsorption of detrimental substances in water, wherein the functionalized cellulose exhibits a degree of substitution of hydroxy groups in glucose units of 17%.
  • patent application WO 2016/181034 discloses a process for removing ions from waste water, wherein plant-derived cationic nanofibrillar cellulose having a degree of substation of maximally 27% was used.
  • Chaker Achraf et al (doi: 10.1016/J.CARBPOL.2015.06.003) disclose a quarternized nanofibrillar cellulose with degree of substitution of around 6%.
  • the problem of the current invention is to overcome the various drawbacks indicated above for the prior art and to provide an improved decontamination and laundry treatment agent.
  • the current invention solves the above problem by providing a cellulose-based decontamination agent that is characterized by a simultaneous anti-microbial effect and contaminant-removal function. It pertains to a decontaminant agent (cationized cellulose) that allows for the removal of chemical, particle-based and biological contaminants from a medium. Furthermore it can be used in laundry treatment, where it allows for the removal of dyes and colours present in the washing waters during the laundering of textiles, thus preventing "white” articles from being dyed from dye re-deposition. As a consequence, "coloured” and “white” garments may be washed at the same time in a washing machine in the presence of the product of the invention. At the same time, the invention eliminates microbiological species from the washing liquid and prevents their re-deposition among the washing articles as well as cross contamination.
  • a decontaminant agent cationized cellulose
  • the invention pertains to a decontamination agent, comprising functionalized cellulose as an active agent.
  • the invention pertains to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation, comprising (sequentially):
  • the invention pertains to a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium.
  • the invention pertains to a decontamination agent, comprising functionalized cellulose as an active agent.
  • cellulose refers to a biopolymer having one or multiple polysaccharide chains, that is composed of b(i- 4) linked D-glucose units.
  • functionalized cellulose refers to a polysaccharide that comprises cellulose with chemically modified b(i- 4) linked D-glucose units.
  • a “chemical modification” refers to the alteration of the chemical nature of the modified cellulose either by allowing reactive groups in the cellulose to react with a modifying agent, for example by binding of molecules or atoms via covalent and/ or coordinative covalent bonds or by non-covalent interactions such as to hydrogen bonding and/ or dipole-dipole, van der Waals and/or electrostatic interactions.
  • the term aboardagent“ in context of the invention shall be interpreted in its broadest sense and include both (i) a pure or essentially pure preparation of the functionalized cellulose of the invention, and (ii), which is particular preferred, a composition comprising the functional cellulose of the invention together with other compounds, such as a non-functionalized cellulose, or a differently functionalized cellulose, or other non-cellulose active agents useful for the intended purpose of the agent of the invention, as well as additives, carriers and/or excipients, and any combinations of the foregoing.
  • the decontamination agent is an aqueous suspension, dispersion and/or gel, or film, membrane or powder.
  • the decontamination agent can be provided as solid films and/or powders that are redispersible in water to provide a colloidal suspension. These forms are preferred for transportation and packaging of the invention.
  • Such powders and/or films maybe produced by drying at least one suspension of the components of the decontamination agent on a surface or in a mold, either at room temperature or at elevated temperatures. This drying can be done under air, nitrogen, vacuum or with a comparable method.
  • Such a powder and/ or film may also be produced by spray- drying or freeze-drying at least one suspension of the components of the decontamination agent on a surface or in a mold.
  • the decontamination agent can also be provided in form of a suspension and/or gel.
  • the decontamination agent comprises at least one solid phase, that is suspended in at least one liquid phase.
  • the at least one liquid phase comprise soluble components of the decontamination agent, water and/or any other suitable solvents such as ethanol and/or isopropanol.
  • Such a suspension can also be produced by sonicating at least one gel, dried powder and/ or film of components of the decontamination agent under exposure of the liquid phase and/or a solvent. In case of sufficient cross-linking of components of the suspension, the suspension can also be called a “gel”.
  • the decontamination agent is a coating, part of a composite material, membrane and/ or non-woven mat.
  • the decontamination agent is provided in form of a composite material, for example a composite textile. Such a composite material comprises the decontamination agent and at least one other material.
  • the other material preferably is a carrier material such as a man-made synthetic polymer that comprises at least one of high density polyethylene, low density polyethylen, polypropylene, polyvinylchloride, polyamides, ethylene vinyl acetate copolymer, polyimides, and/or organic polymers such as viscose, and/or any other organic-based materials such as cellulose, wool, silk, flax or hemp.
  • the decontamination agent is a carrier material for active agents with different function, for example zeolites.
  • the carrier material is a inorganic fiber such as glass fibers, microglass, carbon fibers, hydrated magnesium sulfat fibers, potassium titanate fibers, ceramic fibers, calcium silicate fibers and/or rockwool.
  • the decontamination agent may be provided in form of a membrane and/ or non-woven mat or as a component thereof.
  • a membrane and/ or non-woven mat is in form of a three dimensional shape. In preferred embodiments of the invention, this is realized by at least two membranes and/or mats that are connected to form 3-dimensional shapes.
  • a membrane in the context of the invention is a material that is woven from individual fibers. Such fibers can be generated with common techniques such as electrospinning, wet spinning, dry spinning, melt spinning such as extrusion spinning and direct spinning, gel spinning and/or drawing.
  • a mat in the context of the invention is a material that comprises fibers that are connected by chemical and/or physical interactions, or entangled mechanically.
  • the mat in addition to the aforementioned technqiues for fiber generation, can be generated with techniques such as melt-blowing or spinlaying.
  • the contamination agent may also be provided in form of a coating.
  • a coating can be situated on the internal and/or external surface of a carrier material.
  • External surface in the context of the invention is the interface of a material with its surrounding medium, for example the surface of a sphere or a cube.
  • Internal surface in the context of the invention is the interface of a material an its penetrating medium, for example the surface in pores.
  • the cellulose may assume any shape of the carrier material that it may be coated on.
  • a carrier material can for example be a sponge, a grid or a cylinder.
  • a coating in the context of the invention can be applied by any methods that are state of the art.
  • such methods comprise simple drying of emulsions containing the decontamination agent on a target surface under ambient air or vacuum, vacuum filtration, spin coating, dip coating, slot-die coating, spray painting, powder coating techniques, air knife coating, and/ or roll coating techniques such as roll- to-roll coating or roll-coating on a flat target surface.
  • the target surface bind the decontamination agent by chemical and physical means. These comprise binding of the decontamination agent via covalent and/ or coordinative covalent bonds or by non-covalent interactions such as to hydrogen bonding and/or dipole-dipole, van der Waals and/or electrostatic interactions and/or by steric interaction.
  • the decontamination agent is an anti microbial and dye-capturing agent.
  • the most preferred embodiment of the invention is that the decontamination agent is a laundry treatment additive.
  • the functionalized cellulose comprises at least one covalently modified glucose unit.
  • a “covalently modified glucose” unit maybe modified using any modification technique that is common to the field. These modification techniques include preferably but are not limited to hydrolysis, oxidation, esterification (acylation), amidation, imination, carbamation, etherification (carboxymethylation) and/or nuclephilic substitution. Functional groups that are introduced by these techniques can also act as precursors for subsequent modification steps.
  • the functionalized cellulose exhibits functional groups that replace at least a part of hydroxy groups in glucose units.
  • a “functional group” is a substituent or chemical moiety that is associated with the cellulose polysaccharide chain.
  • a functional group features distinct biological, chemical and/or physical properties and/or effects. These distinct biological, chemical and/or physical properties and/or effects include preferably, although not necessarily being limited to, chemical reactivity, capturing of colloids, molecules and/or atoms, anti-microbial effects, colour changes and/or the emission of light.
  • the functionalized cellulose can first be generated and then shaped or applied to another material. In preferred embodiments of the invention, the functionalized cellulose can be generated and shaped or applied to another material simultaneously. In preferred embodiments of the invention, the cellulose can be first shaped or applied to another material, and then functionalized.
  • the glucose unit is modified to exhibit at least one aldehyde group at its positions C2 and/or C3.
  • the aldehyde group can be introduced by exposing the cellulose or functionalized cellulose to oxidizing reaction conditions and agents. Any oxidation method or agent that is suitable and results in the desired functional group can be used.
  • suitable oxidation agents comprise preferably periodates chosen from sodium iodate, potassium iodate and/or periodic acid.
  • the glucose unit is further modified by substituting the at least one aldehyde group at its C2 and C3 positions.
  • the covalently modified glucose unit is modified by substituting at least one hydroxyl group at its ring positions C2, C3 or C6.
  • substitution in the context of the invention refers to the presence of a functional group that is, directly or via other bridging atoms, covalently bound to a carbon atom in a covalently modified glucose unit of a functionalized cellulose, wherein this functional group differs from the functional group that was bound to this carbon atom before the chemical modification was performed.
  • a substitution can be conducted to both modified or non-modified glucose units.
  • the entirety of the atoms that is substituting the at least one hydroxyl group at the ring positions C2, C3 or C6 respectively is referred to as a substituent.
  • the functionalized cellulose further is cationized, for example with quarternization.
  • these positively charged functional groups are in a majority compared to the negatively charged groups.
  • these positively charged functional groups are attached to the cellulose structure by techniques such as quaternization and amination. However, the methods to obtain such cationized cellulose are not limited to these two techniques.
  • the functionalized cellulose is quaternized cellulose.
  • quaternized cellulose is a type of functionalized cellulose that is obtained by a quaternization reaction.
  • a quaternization reaction comprises a covalent binding of a quaternary molecule to a carbon atom in a modified or non-modified glucose unit by a bridging oxygen atom and thus results in a substitution of the functional group that would normally be at this position.
  • cellulose is dispersed in aqueous basic conditions and stirred at elevated temperatures.
  • the exposure of cellulose to these basic conditions results in deprotonated cellulose, that allows for a binding of quaternary compounds such as glycidyltrimethylammonium chloride to the cellulose, and thereby, generates quaternized cellulose.
  • quaternization results in a “substitution” as in the context of the invention.
  • Quaternary molecules in the context of the invention comprise a positively charged central atom that is covalently linked to four aryl or alkyl substituents. In solid form, these cations can be associated with any possible anion to form a quaternary compound.
  • Such a quaternary molecules can be chosen from ammonium- (R 4 N + ), phosphonium- (i ⁇ P + l, arsonium- (R 4 As + ), stibonium- (R 4 Sb + ) or bismuthonium- (R 4 Bi + ) molecules.
  • the quaternized cellulose comprises at least one covalently bound quaternary ammonium molecule.
  • a quaternary ammonium-molecule constitutes the cation of a quaternary compound described with the formula [R 4 N + X ], wherein R, refers to ammonium molecules selected from up to four different aryl or alkyl residual chains, X- refers to a counter-ion that can be any suitable counter ion such as a halide or sulfate.
  • the quaternary ammonium molecule is a glycidyltrimethylammonium chloride.
  • the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose.
  • the functionalized cellulose is exhibiting a degree of substitution of at least 33%, preferably 40%, most preferably 50% of its hydroxyl groups.
  • the functionalized cellulose features different degrees of hydroxyl substitution.
  • the degree of hydroxyl substitution (%) in the functionalized cellulose is given by the following relationship:
  • Equation 1 100 wherein the n(hy dr oxy l groups be f 0re modi fi cation ) is the amount of hydroxyl groups in functionalized or non-functionalized cellulose, before the hydroxyl groups are substituted and n iydroxyl groups a f ter modi f ication ) is the residual amount of hydroxyl groups in the functionalized cellulose after modification.
  • This ratio can easily be determined with methods commonly found in many general laboratories such as nuclear magnetic resonance (NMR)-spectroscopy, X-ray photon spectroscopy (XPS) and Fourier-transform infrared (FTIR)- spectroscopy.
  • the functionalized cellulose is aminated cellulose.
  • Amination in the context of the invention refers to covalently binding molecules, that are bearing amino functional groups so that the resulting functionalized cellulose comprises amino-groups. Such a cellulose is referred to as “aminated cellulose”.
  • Amination in the context of the invention is conducted in “amination reactions”. Preferred methods for such an amination reaction are given in the examples.
  • Amination is conducted in a two-step process: First, (selected) hydroxyl groups of cellulose are oxidized with a suitable agent such as sodium periodate, potassium periodate or periodic acid. The resulting functionalized cellulose therefore comprises at least one aldehyde group. Second: The functionalized cellulose is then reacted in a Schiff-base reaction with an amine. The obtained material thus exhibits free amino groups and is referred to as “aminated cellulose”.
  • the functionalized cellulose is modified with a type of functional group chosen from a list comprising primary, secondary and tertiary amino groups and quaternary ammonium groups.
  • the at least one modified glucose unit of the functionalized cellulose comprises substitutions, in which hydroxyl or aldehyde groups may be substituted with amino groups. Depending on their degree of substitution, these amino groups are categorized as primary, secondary and tertiary amino groups or quaternary ammonium groups.
  • Primary amino groups can be described with the formula (G-NH 2 ), secondary amino groups can be described with the formula (G-NHR 1 ), tertiary amino groups can be described with the formula (G-NR’R 2 ) and quaternary ammonium groups can be described with the formula (G-NRT ⁇ R 3 *), wherein G is the (modified) glucose unit of the functionalized cellulose and R 1 , R 2 , and R 3 are residual organic groups and wherein between the (modified) glucose and the N of the amino and/ or ammonium group may be one or more bridging atoms.
  • aminated cellulose comprises at least one covalently bound amine molecule.
  • Aminated cellulose also refers to functionalized cellulose, whose modified glucose units are modified with molecules that comprise at least one amino functional group and at least one other functional group by which they are bound to the modified glucose chains.
  • amine molecule is bound via the at least one aldehyde group.
  • the amine molecule that comprises at least one amino group covalently binds to an aldehyde functional group that is part of a modified glucose unit in the functionalized cellulose.
  • the amine molecule is a diamine molecule.
  • a diamine molecule is any molecule, that exhibits two amino groups and refers to the formula H 2 N-R-NH 2 .
  • R in the context of such a diamine can be a linear or branched or cyclic aliphatic chain or a xylylenediamine or an aromatic ring system.
  • Linear aliphatic amines can be chosen from a list comprising diaminomethane, 1,2-diaminoethane, propane-i, 3-diamine, butane-i, 4-diamine, pentane-i, 5-diamine and hexane-i, 6-diamine.
  • Branched aliphatic amines can be chosen from a list comprising 1,2-diaminopropane, diphenylethylenediamine and 1,2- diaminocyclohexane.
  • Cyclic aliphatic amines can be chosen from a list comprising 1,4- diazacycloheptane, 1,5 diazacyclooctane, 1,4 diazacyclohexane.
  • Amines with aromatic ring can be chosen from a list comprising o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, dimethyl-4-phenylenediamine, A V-di-2-butyl-i,4-phenylenediamine, 4,4’-diaminobiphenyl and/or 1,8-diaminonaphthalene.
  • the amine molecule is bound by at least one of its amino groups.
  • the diamine can bind to the polysaccharide chain of functionalized cellulose by one of its amino groups and then still feature another free amino group.
  • This free amino functionality is capable of interacting with its environment. For example, it can excerpt dye-capturing or anti-microbial effects, or can bear charges that may stabilize the functionalized nanocellulose when in suspension.
  • the free amino group can bind to functional groups of the same or other cellulose chains and crosslink these chains.
  • the amine molecule is a linear primary diamine (H 2 N-R- NH 2 ) with R being a C to C 6 alkyl, preferably C 3 to C 6 alkyl, most preferably C 6 alkyl (hexane 1,6 diamine).
  • the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose.
  • the functionalized cellulose exhibits a degree of substitution of at least 50% of its aldehyde groups.
  • the functionalized cellulose is characterized by different degrees of aldehyde substitution.
  • the degree of aldehyde substitution (%) in the context of the present invention is defined by the following relationship:
  • Equation 2 wherein the n(aldehyde groups be f 0re amination) is the initial amount of aldehyde groups in aldehyde-functionalized cellulose before the completion of an amination reaction, and n(aldehyde groups a f ter amination ) is the residual amount of aldehyde groups in amine- functionalized cellulose after the completion of this amination-reaction.
  • This ratio can easily be stoichiometrically determined with methods commonly found in many general laboratories such as NMR-spectroscopy, XPS-spectroscopy, and FTIR-spectroscopy, and stoichiometrically using other relevant spectrophotometric methods.
  • the decontamination agent comprising aminated cellulose as an active agent, wherein individual glucose units of the cellulose exhibiting three hydroxy groups are first oxidized to display aldehyde groups, and then said aldehyde groups are substituted with amino groups, and wherein the aminated cellulose exhibits a degree of substitution of 50% of its aldehyde groups or at least 33% of its original hydroxy groups, and wherein said cellulose is selected from microfibrillated cellulose, cellulose nanocrystals, cellulose nanofibrils and combinations thereof, exhibits a surprising effect of improved pigment and dye removal as well as superior antimicrobial activity.
  • the decontamination agent significantly improves the shortcomings of existing products as it efficiently and quickly catches dyes and pigments extracted and/or released from textile fibers in the first minutes of washing after contact with water, even at very low temperatures, i.e. at 20 °C. Furthermore, the effect of such decontamination agent is inhibition of the transfer of potentially present microbial substances duirng laundry, or in some cases even acts bacteriocidly. In addition, the decontamination agent has been surprisingly found to catch or filter microplastic particles and bacteria, which is a significant improvement of currently known similar agents.
  • the functionalized cellulose comprises at least two different substituents each selected from an amino group-containing substituent or a quaternary ammonium group-containing substituent.
  • the amino group-containing substituent in the context of the invention may be any of the aforementioned covalently bound amine- molecules.
  • An ammonium group-containing substituent in the context of the invention may be any of the aforementioned ammonium-molecules.
  • the functionalized cellulose comprises at least two different types of functional groups, selected from amino group, aldehyde group, hydroxyl group, and quaternized ammonium group.
  • functionalized cellulose can be obtained with different modification methods. Generally, such methods are used to obtain functionalized cellulose, wherein the initial hydroxyl groups in the modified glucose units of the cellulose are substituted.
  • the functionalized cellulose comprises more than one functional group at the same time.
  • the modification according to one of the disclosed methods does not result in substitution of substantially all hydroxyl groups of the initial cellulose, and thus results in a functionalized cellulose with both the initial aldehyde/hydroxyl groups and newly introduced functional groups such as amino or ammonium groups.
  • the functional cellulose may be subjected to multiple successive or simultaneous functionalization reactions. Therefore, the resulting functionalized cellulose may comprise at least one type of amino group, at least one type of quaternary ammonium group, (residual) aldehyde groups, (residual) hydroxyl groups and/or any other functional group that is covalently bound or associated by other chemical modifications in the context of the present invention.
  • the decontamination agent may comprise the functionalized cellulose in any of the following combinations: aminated and native cellulose; aminated and quarternized cellulose; aminated and oxidized cellulose; native, aminated and oxidized cellulose; quarternized and oxidized cellulose; oxidized, aminated and quarternized cellulose; or oxidized, native, aminated and quarternized cellulose; or any other suitable combination.
  • the decontamination agent comprises at least two different types of functionalized cellulose.
  • the decontamination agent comprises at least three types of functionalized cellulose.
  • the decontamination agent according to the invention may comprise multiple types functionalized cellulose.
  • These functional cellulose types can be chosen from any type of functionalized cellulose that are disclosed in the present invention. This comprises functionalized cellulose types that were functionalized separately from each other and subsequently mixed in the decontamination agent. This also comprises different functionalized cellulose types such as at least one type of functionalized cellulose nanocrystals, functionalized cellulose nanofibers and/ or functionalized microfib rillated cellulose that were functionalized with the same or different types of functional groups.
  • this embodiment also comprises functional cellulose types that were functionalized simultaneously in the same reaction vessel.
  • This embodiment also comprises functional cellulose types that only differ by their respective amount of substituted hydroxyl or aldehyde groups.
  • the aqueous suspension, dispersion and/or gel and/or film and or powder comprises at least o.i-o.2wt% quaternized cellulose.
  • the decontamination agent further comprises at least one additional component selected from the group of surfactants, builders, anti redeposition agents, corrosion inhibitors, processing aids, colorants, fragrances, bleaching agents, enzymes, suds control agents, opacifiers and/or fabric softeners.
  • the decontamination agent comprises at least one type of functional cellulose as described in any other embodiment of the invention. Additionally, the decontamination agent may comprise other components that are commonly used in laundry treatment compositions.
  • surfactants for penetrating and wetting fabric, loosening soils, and emulsifying soils to keep them suspended in the wash solution
  • builders for enhancing the action of surfactants by, for example, softening the water, helping to disperse soils and prevent their redeposition out of solution, and assisting in dissolving oil-based soils
  • alkalis to raise the pH of wash water
  • anti-redeposition agents to prevent dislodged soils from being redeposited
  • enzymes to effect stain removal and provide color and fabric care
  • additional antimicrobial agents to hygienically clean fabrics
  • fabric softeners to impart softness, reduce static electricity and reduce crinkling
  • fragrances to neutralize odor in both the detergent chemicals and the soils in the laundry wash
  • optical brighteners to enhance the light reflected from washed fabric to make the fabric look whiter and
  • the functionalized cellulose is functionalized microfibrillated cellulose and/ or functionalized cellulose nanocrystals and/ or functionalized cellulose nanofibrils.
  • three types of functionalized nanocellulose are distinguished, based on the cellulose type that they are originating from.
  • “Functionalized cellulose nanofibrils” result from functionalizing cellulose nanofibrils, also known as CNF, cellulose nanofibers and nanofibrillated cellulose.
  • Cellulose nanofibrils are a cellulose type that features long and thin specimen. This type of nanocellulose features a diameter of below 150 nm, and a length of at least 8oo nm.
  • “Functionalized cellulose nanocrystals” result from functionalizing cellulose nanocrystals.
  • Cellulose nanocrystals are commonly also known as nanocrystalline cellulose, cellulose (nano) whiskers, CNC, or rod-like cellulose microcrystals. They exhibit a similar diameter than cellulose nanofibrils, however feature a much shorter length that is below 8oo nm.
  • “Functionalized microfibrillated cellulose” results from functionalizing microfibrillated cellulose.
  • Microfibrillated cellulose also known as MFC, is a material that is not composed of individual particles or fibers but is composed of an interconnected network for cellulose nanofibrils.
  • the nanofibrils in such a network exhibit a diameter of less than 200 nm, and a length of several micrometers.
  • Crystalline nanocellulose may be produced by different hydrolysis conditions and cellulose precursors by using strong acids or any other suitable method.
  • Microfibrillated cellulose may be generated by delamination from wood pulp cellulose by using mechanical pressure in combination with chemical/enzymatic treatment methods or any other suitable method.
  • the functionalized cellulose nanofibrils exhibit a diameter of 5 to 150 nm, preferably 10 to 150 nm, more preferably 20 to too nm, or most preferably 50 to 80 nm.
  • the functionalized cellulose nanofibrils exhibit a length of 0.8 to 6 pm, preferably 0.8 to 4 pm, or more preferably 0.8 to 2 pm.
  • the functionalized cellulose nanocrystals exhibit a diameter of 10 to 80 nm, preferably 20 to 60 nm or more preferably 30 to 50 nm.
  • the functionalized cellulose nanocrystals exhibit a length of too to 400 nm, preferably too to 300 nm, more preferably too to 200 nm.
  • the functionalized microfibrillated cellulose exhibits a diameter of 10 to 200 nm, preferably 20 to 200 nm, more preferably 20 to 150 nm, or most preferably 20 to too nm and length of 2 to 10 pm.
  • these sizes refer to the physical extensions of the cellulose particles or fibres as determined by scanning electron microscopy. They include both the average values and a standard deviation of ⁇ to. Due to the of the non-spherical morphology of the cellulose structures, the term “length” refers to the physical extension of the particles along their longer direction. The term “diameter” refers to the extension of the particles perpendicular to this direction.
  • the functionalized cellulose is semi crystalline.
  • crystallinity refers to the feature that the functionalized cellulose, when examined in an X-ray diffractometer or by electron microscopy, results in diffraction patterns that show significant reflections.
  • the atoms in a crystalline material are repeating in a periodic manner along the spatial dimensions of the particle.
  • the functionalized cellulose in this invention can feature different amounts of crystallinity, which is defined by the percentage of the volume of a particle that is crystalline, when compared to the volume of the particle that is both crystalline and not crystalline (“amorphous”).
  • particles of functionalized cellulose may have any degree of crystallinity.
  • some preferred embodiments of the invention refer to particles as “crystalline nanocellulose”, this does not imply the actual degree of crystallinity of these particles.
  • Semi-crystalline in the context of the invention refers to particles that feature a degree of crystalline in the range of 10-80%.
  • the degree of crystallinity of the functionalized cellulose referred to in the invention does not affect its usage as a decontamination agent.
  • the decontamination agent comprises functionalized cellulose as an active agent, wherein the functionalized cellulose is quaternized- and/or aminated cellulose selected from microfibrillated cellulose, cellulose nanocrystals, cellulose nanofibrils, and combinations thereof, and wherein the functionalized cellulose exhibits a degree of substitution of at least 33% of its hydroxyl groups.
  • the invention refers to a method for the treatment of laundry in a laundry treating appliance that is operating to an automated cycle of operation, comprising (sequentially): (i) A soaking phase,
  • a “soaking phase” refers to an incubation period during laundry washing, in which the laundry is first contacted with water.
  • the vessel, in which the soaking is conducted comprises the laundry and water in this vessel is referred to as “soaking water”.
  • the laundry appliance does not excerpt physical forces on the laundry.
  • the soaking water may be heated.
  • the decontamination agent is added to the incubation mixture, thus the vessel of the laundry treatment appliance, in which the soaking is conducted, comprises laundry, soaking water and the decontamination agent that is described in this invention.
  • other decontamination agents and laundry detergents can be added during this soaking phase.
  • This soaking phase can range between 1 to 35 min, preferably 1 to 25 min, most preferably 1 to 15 min.
  • the soaking water can be drained and replaced with new water in subsequent laundry treatment phases.
  • the wastewater of the soaking phase is filtrated or non-filtrated and reused or discarded.
  • the optional “prewashing phase” refers to a period of time, in which the laundry is submerged or partially submerged in water, and is subjected to treatment by the laundry treating appliance. This treatment may comprise heating periods and/or excerption of physical force on the laundry.
  • the laundry is subjected to the decontamination agent and, optionally, a laundry detergent.
  • washing phase refers to a phase, in which the laundry is submerged or partially submerged in water, and is subjected to treatment by the laundry treating appliance. During this washing phase, the laundry is subjected to a laundry detergent, and optionally the decontamination agent. The water during this washing phase is referred to as “washing water”. At the end of the washing phase, the washing water is drained. In preferred embodiments, depending on the laundry treating appliance, multiple washing phases can sequentially be conducted that are each started with first replacing or partially replacing the drained water previous washing phase.
  • a further aspect of the invention is also a method for decontamination or treatment of wastewater created during laundry washing.
  • the treatment of wastewaters of a laundry treating appliance is intended occurs at the outlet from the drum of the washing machine, wherein the functionalized cellulose according to the invention is provided in any suitable form, preferably as a filter or a cartridge comprising the invention, so as to clean the water prior to its release into the environment.
  • This treated cleaned water can be reused for cleaning, laundry washing or any other use.
  • the decontamination agent is contacted with the laundry water for 1 to 240 min, preferably 1 to 120 min, most preferably 1 to 35 min.
  • the phases of the automated cycle of operation of the laundry treating appliance do cumulatively not exceed treatment times of more than 4 hours. These treatment times depend on the type of laundry treating appliance and the amount and length of the individual phases. Shorter treatment times of any length are also preferred embodiments.
  • the laundry treating appliance comprises a rotatable treating chamber in which the laundry is received for treatment.
  • this ratable treatment chamber is also referred to as “drum” or “washing drum”.
  • the rotatable treating chamber is rotating or spinning at the speed of o to 2000 rpm.
  • the laundry is treated at water temperatures of 15 to 95°C, preferably 20 to 80 °C, more preferably 30 to 70 °C, most preferably at 20 to 40 °C.
  • the invention pertains to a use of functionalized cellulose for the removal of chemical, particle-based and biological contaminants from a medium.
  • Removal in the context of the invention refers to the ability of an agent to change the concentration of the contaminants in a medium.
  • the removal of biological contaminants is based on the anti-microbial effect of the functionalized cellulose of the invention, which refers to its ability of capturing or destroying microorganisms such as bacteria and viruses.
  • the removal of chemical and particle-based contaminants is referred to as dye and pigments, nano- and micro-plastics capturing. This does not indicate any mechanism by which the removal of chemical and particle-based contaminants occurs. Possible mechanisms comprise altering the color of a dye via chemical reaction, or by chemically and/or physical binding the dye molecules, pigments and/or particles to the surface of the dye binding agent.
  • this can be determined by the decrease in the optical absorption of the dye and pigment-solutions after incubation.
  • Such a decrease can easily be determined from aliquots of the incubation solution with any spectrometer measuring at UV/Vis wavelengths.
  • the chemical contaminants are atoms and/or molecules.
  • the chemical and particle-based contaminants are ionic, hydrophobic, organic and/or inorganic contaminants.
  • Ionic contaminants in the context of the invention comprise anionic and cationic contaminants in atomic, molecular and/or particle-based form.
  • the cationic contaminants comprise cationic molecules such as cationic dyes, surfactants such as benzalkonium chloride and pharmaceuticals such as tetracycline hydrochloride.
  • the cationic contaminants are heavy metal ions such as lead, copper, nickel, chromium, bismuth, mercury, cadmium, palladium, zinc, thallium, silver or non-heavy metal ions such as calcium and magnesium.
  • These metals comprise particles of single metals, alloys of metals, metal-containing compounds and/or metal ions that exist in the form of free cations or in form of metal-complexes.
  • the metal-containing compounds may be, for example, a metal-containing organic compound or a metal-containing inorganic compound.
  • the anionic molecules of the contaminants comprise charged molecules such as nitrates, phosphates, fluoride, sulfate ions and humic acids.
  • the contaminants are radioactive isotopes or compounds that comprise radioactive isotopes of iodine, radon, radium, cesium, sulfur, chromium, cobalt, technetium, uranium and/or phosphorous.
  • the hydrophobic contaminants comprise oil spills or dissolved drugs such as docetaxel.
  • the ionic or hydrophobic molecules of the contaminant are pesticides that are preferably selected from a group consisting of organophosphorus, carbamates, organochlorines, chlorophenols and pyrethroids.
  • the contaminants are dye-molecules.
  • the dye molecules comprise reactive dyes, disperse dyes, direct dyes, solvent dyes and pigment dyes.
  • the particle-based contaminants are nanoparticles and/or microparticles. In certain preferred embodiments of the invention, the particle-based contaminants are inorganic or organic particles.
  • the inorganic particle-based contaminants are metal oxides such as Ti0 2 , ZnO or iron oxides or pigment dyes. In other preferred embodiments of the invention, the inorganic particle-based contaminants are zero-valent metals such as iron or silver. In further preferred embodiments of the invention, the organic particle-based contaminants are plastic particles, carbon particles and/or disperse dyes. [61] In preferred embodiments of the invention, the biological contaminants are microorganisms.
  • the microorganisms comprise Burkholderia pseudomallei, Cryptosporidium parvum, Giardia lamblia, Salmonella, Norovirus, Enterococcus faecium (Ef) or Staphylococcus aureus (Sa).
  • Anti-microbial effect in the context of the present invention refers to the ability of capturing or destroying microorganisms such as bacteria upon exposure to the active agent (functionalized cellulose).
  • the strength of the anti-microbial effect was determined by a reduction factor R that is defined by the following definition:
  • Equation 3 wherein N 0 is the mass of the microorganisms before exposure to the agent and N is the mass of the microorganisms after exposure to the agent.
  • a larger factor R is equivalent to a stronger anti-microbial effect of the agent.
  • “applied concentration” refers to the actual concentration, in which the agent is used. This is different from the concentration, in which the agent is sold.
  • the medium is a liquid phase, preferably washing water and/or waste water.
  • Liquid phase in the context of the invention comprises aqueous solutions and/or organic solvents.
  • Aqueous solutions in the context of the invention comprise industrial or domestic waste water, washing water, ground water, rain, rivers, the ocean and/or any kind of drinking water.
  • the medium is a gaseous phase such as air and exhaust fumes.
  • the medium is industrial or domestic wastewater such as in laundry treatment.
  • the decontamination agent is used in laundry treatment.
  • removal of chemical, particles and biological contaminants from a medium is laundry treatment.
  • the decontamination agent can be added to the drum via the container or directly in the drum, or at the outlet from the drum, i.e. before water would be reused (returns back to the drum) or be discharged from the washing machine.
  • the functionalized cellulose is the functionalized cellulose recited in any one of the previous embodiments and aspects of the invention.
  • the decontamination agent according to the invention can be transported and sold in form of an aqueous suspension, gel, film and/or powder. Any of the previously disclosed methods or other common methods for generating such a decontamination agent can be used.
  • This also comprises mixing different types of functionalized cellulose of the invention and the mixing of other components to the functionalized cellulose that are chosen from a list of surfactants, builders, anti-redeposition agents, corrosion inhibitors, processing aids, colorants, fragrances, bleaching agents, enzymes, suds control agents, opacifiers and/or fabric softeners.
  • the decontamination agent is recycled.
  • recycling comprises the removal of contaminations that are bound to the functionalized cellulose. This can be conducted, for example, by exposing the decontamination agent to a solution and subsequently changing the pH of the solution to a level at which electrostatically and/or coordinatively bound contamimants are detached.
  • recycling comprises the repeated use of the decontaminating agent. For example this can be realized by recovering a sheet of functionalized cellulose after laundry treatment and using it again in a later laundry treatment process.
  • the functionalized cellulose is used in a concentration from 0.01 g/L to 0.5 g/L, preferably from 0.01 g/L to 0.2 g/L, most preferably from 0.01 g/L to 0.1 g/L in soaking water or washing water.
  • the functionalized cellulose is used in a concentration from 0.1 g/L to 1 g/L, preferably from 0.1 g/L to 0.5 g/L, most preferably from 0.1 g/L to 0.2 g/L in soaking water or washing water.
  • the term “comprising” is to be construed as encompassing both “including” and “consisting of’, both meanings being specifically intended, and hence individually disclosed embodiments in accordance with the present invention.
  • “and/or” is to be taken as specific disclosure of each of the two specified features or components with or without the other.
  • a and/or B is to be taken as specific disclosure of each of (i) A, (ii) B and (iii) A and B, just as if each is set out individually herein.
  • the terms “about” and “approximately” denote an interval of accuracy that the person skilled in the art will understand to still ensure the technical effect of the feature in question.
  • the term typically indicates deviation from the indicated numerical value by ⁇ 20%, ⁇ 15%, ⁇ 10%, and for example ⁇ 5%.
  • the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect.
  • a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect.
  • the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect.
  • a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect.
  • FIG. 1 The degree of aldehyde functionalization for various functionalized CNF samples.
  • the functionalized CNF samples are obtained by using different concentrations (1.3- 1.9 g) of sodium periodate per weight (in g) of CNF.
  • concentrations 1.3- 1.9 g
  • the degree of aldehyde functionalization mmol/g CNF
  • the reaction time in h is given.
  • the corresponding weight-loss %) is shown on the right axis vs. reaction time in h.
  • B Particle size data on the various of various CNF samples is provided in form of the Z-size (nm) as determined by dynamic light scattering and corresponding zeta potential values (mV) are shown.
  • HMDA hexamethylenediamine
  • FIG. 3 Depicted are the washing programs that are used the experiments using a domestic washing machine. For both the respective washing baths A and B, a SensoCare W8665K GORENJE d.d was used.
  • FIG. 4 (A) Potentiometric titration of HMDA-functionalized cellulose (aCNF, CNF- ox-HMDA) with total charge values vs. the corresponding pH values, and discoloration kinetics of bath A containing a dye concentration of 0.1 g/L. These room temperature experiments were performed with a cellulose concentration of 1 g/L. Dye concentrations are monitored at the wavelengths of 598 nm (B) and 474 nm (C).
  • aCNF HMDA-functionalized cellulose
  • Figure 5 (A) Reduction of dye concentration in bath A after 30 min and 24 h of incubation at room temperature without shaking. Bath images after 90 min and 24 h of incubation: aCNF-dispersion (left), aCNF-powder (middle), DP-sheet (right). (B) Reduction of dye concentration in bath A after 30 min and 24 h of incubation at room temperature without shaking. Bath images after 90 min and 24 h of incubation: aCNF-dispersion (left), aCNF-powder (middle), DP-sheet (right).
  • FIG. 6 Dye removal kinetics in baths A (without detergent) or B (addition of IEC 60456 standard detergent) using water-dispersed aCNF (0.1 g/L) and a reference DP sheet (10 g/L, called “1:100”) and different dye concentrations (0.05, 0.1 and 0.5 g/L).
  • Figure 8 Cells of S. Aureus (at 1000 x magnification) in the presence of aCNC (A). The log reduction factor of selected bacteria in dependence on the concentration of aCNC are shown for a suspension (B) without and (C) in the presence of o.i g/L of a Bezept Black V-CMR reactive dye.
  • Figure 9 (A) Normalized dye removal (according to Equation 5) in washing water of a domenstic washing machine according to bath A conditions in depencence of time (from left to right: o, 5, 10, 15, 20, 25, 30, 35 min). Each measurement point is determined from aliquots taken in accordance with Figure 3A. (B) Corresponding dye concentrations (g/L) in washing bath A in dependence of washing time. Data is shown for a reference, a DP sheet reference in the drum, aCNF positioned at the outlet of the drum and aCNF, which was added to the washing-drum. (C) Fotographs of the corresponding aliquots.
  • Figure 10 (A) Normalized dye removal (according to Equation 5) in washing water of a domenstic washing machine in dependence of time (from left to right: o, 5, 10, 15, 20, 25, 30, 35 min). The experiment caught out without detergent, after 15 min however, laundry detergent according to bath B conditions was added. Data is shown for a reference, a DP sheet-containing drum, and aCNF, which was added to the drum. (A) Fotographs of the corresponding aliquots.
  • Figure 12 Zeta-size analysis of (0.01 wt%) native (CNF/CNC), oxidized (CNF/CNC-ox), and HMDA-functionalized CNF/CNCs (CNF/CNC-ox-HMDA) in milli-Q water before and after 24h/48h of storage.
  • Figure 13 SEM images of (0.01 wt%) native (CNF/CNC), oxidized (CNF/CNC-ox) and HMDA-functionalized (CNF/CNF-ox-HMDA) samples dispersed in miliQ.
  • Figure 14 Multiple filtration of S. aureus with aCNF and qCNF decontamination agents, wherein the qCNF shows significantly inferior bacterial filtration properties.
  • Figure 15 Reduction of Bacteriophage phi6 after being placed upon the visous (VIS) membrane surface containing aCNF and qCNF decontamination agents.
  • Figure 16 Biodegradation properties in soil by analysing weight loss, wherein CNF-ox and CNC-ox are fully biodegradable, while CNF-ox-HMDA and CNC-ox-HMDA are not.
  • FIG. 17 Influence of CNF-ox-HMDA on the aggregation of synthetic microfibers in laundry wastewater and b) aggregates removal by sequential filtration of such a water using membranes of different porosity (180, too and 10 pm), compared to the control (without CNF) or that containing qCNF.
  • Cationized-nanocellulose Dispersions of differently cationized (aminated and quaternized) cellulose nanofibrils (CNF), cellulose nanocrystals (CNC) and microfibrillated cellulose (MFC) are used in the experiments disclosed.
  • the CNF with chain-like structures feature diameters in the range of 10-70 nm and a length of a few micrometers (1-3 pm). They were supplied by the University of Maine (USA).
  • the MFC was a commercial product of Exilva from Borregard, Norway and features a greater branching and interweaving of multi-micrometer long fibrils.
  • the CNC with up to 50 nm in diameter and up to a few 100 nm in length was a product of the University of Maine (USA).
  • Quatemization-Reaction A quaternization modification was performed on CNFs according to the patent WO/2017/075370 using glycidyltrimethylammonium chloride.
  • Standardized ISO 2267/DIN 53919, WFK liA, Testgewebe GmbH
  • 100% plain weaved cotton fabric 170 g/cm 2 weight, 270/270 pick/dm, 295/295 dtex.
  • Standardized ISO 2267/DIN 53919, WFK 60A, Testgewebe GmbH 100% plain weaved wool fabric of 125 g/cm 2 weight, 210/180 pick/dm, and 300/300 dtex.
  • Dyes and colours selected The different reactive dyes that are shown in the experiments below represent colourants with a high “bleeding” effect (up to 70%). These dyes include three mono-chromatic Bezept Yellow V-5GL, Bezept Red V-GG, and Bezept Blue V-R, and tri-chromatic Bezept Black V-CMR. In addition, direct dyes ( Tubantin Yellow 4GL, Tubantin Purple 4B, Tubantin Blue FF2GL 200 and Tubantin Black VSF 600 ) and disperse dyes ( Bemacron Red SE-RDL), as well as pigment dyes ( Bezaprint Colormatch 210 Red) were used.
  • direct dyes Tubantin Yellow 4GL, Tubantin Purple 4B, Tubantin Blue FF2GL 200 and Tubantin Black VSF 600
  • disperse dyes Bemacron Red SE-RDL
  • pigment dyes Bezaprint Colormatch 210 Red
  • Laundry washing baths used Two washing baths, “bath A” and “bath B”, were used to simulate different washing conditions. Both laundering baths met the characteristics of the following standard: SIST EN 60456:2010 (Clothes washing machines for household use - Methods for measuring the performance). These parameters include: Conductivity of ⁇ 10 pS/cm, total water hardness of 14 ⁇ 1.12 °dH, and a pH of 7.3-7.7.
  • Washing bath B was prepared from bath A by adding the IEC 60456 standard detergent A * ( WFK , Germany), composed of 77% of basic washing powder (containing: 8.8% of anionic surfactant sodium alkyl benzene sulfonate, 4.7% of the non-ionic surfactant ethoxylated fatty alcohol C12/14 / 7 EO, 3.2% of anionic surfactant sodium soap (tallow soap), 3.9% of foam inhibitor concentrate, 12% silicon on a inorganic carrier, 28.3% of zeolite 4 A, 11.6% of sodium carbonate, 2.4% of sodium salt of a copolymer from acrylic and maleic acid, 3.0% of sodium silicate (Si0 2 Na 2 0), 1.2% of carboxymethylcelluse, 2.8% of phosphonate (DEQUEST 2066 with 25% active acid), 0.2% of optical stilbene type whitener, 6.5% of sodium sulfate (Glauber's salt), 0.4% of protease (Savinase 8.0), 20% of
  • the liveliness of bacteria was tested in test tubes using different concentrations of aCNC without or with addition of 0.1 g/L Bezept Black V-CMR.
  • Washing bath dye removal measurements The dye concentration in both washing solutions A and B, before and after the washing experiments, was determined by optical absorption evaluated at the wavelengths of maximal adsorptions for each dye (i.e. Bezept Yellow V-5GL at 406 nm; Bezept Red V-GG at 504 nm; Bezept Blue V-R at 594 nm; Bezept Black V-CMR at 398 nm, 474 nm and 598 nm; Tubantin Yellow 4GL cone at 384 nm; Tubantin Purple 4B cone at 498 nm; Tubantin Blue FF2GL 200 at 576 nm; Tubantin Black VSF 600 at 482 nm; Bemacron Red SE-RDL at 464 nm; Bezaprint Colormatch 210 Red at 558 nm;). The data was generated using a plate-reader equipped with a Tecan UV-Vis spectrophotometer (USA). Dye removal (%) was calculated using the following equation:
  • Abs 0 and Abs n are absorbance values at the beginning and for aliquots taken at different washing times.
  • the CIE whiteness index ( W) of the samples was quantified in accordance with the AATCC test method 153 (1985).
  • the whiteness index (W) is given by:
  • Y shows the lightness value
  • x, y, and xicide, y modifier are the chromaticity coordinates of the samples and the illuminant, respectively.
  • aCNC and aCNF feature similar pK A values (5.6-7 and 5.99 respectively, both titration curves have a fairly similar course: the inverse titration curve from low to high pH values results in a lower overall charge titration from high to low pH values. This means that no presence of additional reactive groups could be detected.
  • the return curve is higher than the original curve (and more charge is detected), indicating that, after the first titration, some HMDA may be released from the functionalized cellulose surface. Alternatively, its detectability might have increased, due to an opening of a more networked fibrillar structure).
  • the colorized bath solutions were stirred for up to 140 min at a speed of too rpm at room temperature using a horizontal shaker ( Heidolph Promax 1020, Germany ).
  • the dye-concentrations, before and after exposure to the decontamination agent, were determined by measuring the samples’ optical absorption at two or three wavelengths corresponding to the three absorption maximums of the dye (398 nm, 474 nm and 598 nm).
  • UV-Vis ultraviolet-visible
  • aCNF (0.1 wt%) /qCNF (0.0067 wt%) mixtures feature the same dye removal kinetics and efficacy as a corresponding pure dispersion of aCNF, but do not aggregate and/or sediment (Figure 7B).
  • Example 2 Dye capturing studies performed in a Labomat apparatus
  • parameters that influence the dye-capturing performance comprise aCNF concentration, the type of dye and the washing conditions (bath A or bath B conditions).
  • Dye capturing generally performed better for aCNF than for corresponding DP sheets, and is more effective in bath A than in bath B.
  • the following data shows the dye-capturing performance of aCNF used in the conditions of bath A (therefore without washing powder) when incubated along with a WFK 11A cotton fabric and different dyes.
  • aCNF performed considerably better than an equal amount of DP sheet in removing various dyes from the washing solutions.
  • the dE* values of cotton, when it is exposed to various dye- solutions are generally lower in case of the aCNF containing samples when compared to the DP sheet containing samples.
  • aCNF performed consistently better in dye capturing than a corresponding amount of DP sheet.
  • Table 4 The table depicts the removal (%) of different dyes (0.1 g/L) from solution according to the condition “bath A”. In these solutions, a WFK 11A cotton fabric was incubated with the dyes, either with/without the addition of different concentrations of DP sheet and aCNF.
  • Table 5 The table shows the averages of whiteness (W) and colour differences (dE*) of a WFK 11A cotton fabric, when washed with various dyes (0.1 g/L) in the condition “bath A” with/without the addition of DP sheet and aCNF in different concentrations.
  • Table 6 Removal (%) of Bezept Black V-CMR (0.1 g/L) when washing WFK 11A cotton fabric with/without the addition of DP sheet and aCNF in different concentrations.
  • Table 7 The averages of whiteness ( W) and colour differences ( dE *) for WFK 11A cotton fabric, washed with o.i g/L of Bezept Black V-CMR with/without the addition of DP sheet or aCNF.
  • Table 8 and Table 9 show analogue dye-capturing performance of aCNF in bath A-conditions, wherein WFK 60A 100% plain weaved wool was incubated in a dye-solution along with the different decontamination agents without additional washing powder.
  • Table 8 Removal (%) of different dyes (0.1 g/L) from bath A in which WFK 60A wool fabric was incubated with/without the addition of DP sheet or aCNF in different concentrations.
  • Table 9 The averages of whiteness (W) and colour differences ( dE *) for WFK 60A wool fabric that was washed in a dye-solution (0.1 g/L) with/without the addition of DP sheet or aCNF in different concentrations.
  • aCNF shows improved dye-capturing performance compared to DP sheet for all but one case ( Blue-VR , 95.51% for DP, 94.86% for aCNF, 95.82% without addition of a decontamination agent).
  • Blue-VR 95.51% for DP, 94.86% for aCNF, 95.82% without addition of a decontamination agent.
  • Table 9 the colour increase of wool when incubated with the respective dye solutions and with/without DP, and aCNF (see dE* values) is shown.
  • Example 4 Anti-microbial effect of aCNC in laboratory conditions:
  • the anti-microbial effect is visualized in Figure 8A, in which free bacteria are visible along with bacteria that are glued to the surface of the aCNC particles.
  • the minimum inhibitory concentration (MIC) of aCNC, at which no growth was observed with the naked eye after overnight incubation and at which a reduction factor 6 or more was achieved (mortality 99.9999%), was 0.2 wt%. This was independent of the presence of a dye. This is also the concentration that is required to reach the microbiological standard for an effective antibacterial, bacteriostatic and even bactericidal washing.
  • Example 5 Anti-microbial effect of functionalized cellulose in a domestic washing machine.
  • Table 10 Microorganism removal using aCNC: Results of microorganism removal with aCNC fabric in bath A conditions, and the presence of Enterococcus faecium (Ef) or Staphylococcus aureus (Sa) bacteria.
  • Table 11 Results of microorganism removal with aCNF during the washing of cotton fabric in different washing conditions, and the presence of Enterococcus faecium (Ef) or Staphylococcus aureus (Sa) bacteria.
  • Example 6 Dye capturing and impurity removal effect of aCNF using a domestic washing machine
  • Table 12 11A cotton fabric was washed with 1.5 g/L of tri-chromatic Bezept Black V- CMR reactive dye with/without the addition of DP sheet or aCNF in the drum or at the outlet. Average colour differences dE* as well as the amount of adsorbed dye on the fabric or the dye- removal agent are shown.
  • the dye-capturing effect occurs within the first 15 minutes of the washing, when aCNF is present in the washing drum, or when the washing bath with the dye is passing a filter bag with an equal amount of dryed aCNF that is placed at the outlet of the washing bath.
  • This washing effect is the ratio of the sum of reflectance values for each soil type when washed according to the conditions of Table 13 and the corresponding values of a reference washing machine.
  • the Impurities Removed ( IR dE * ) were also calculated from the examined CIE L*a* b* colour characteristics ' values, according to Equation 7, and based on the following Equation 8:
  • Equation 8 100 (%) where dE* wash-unso u is a colour difference dE* D65 / o between washed soil sample and unwashed unsoiled fabric, and dE* soii-mso ais a colour difference dE D65 / o between the unwashed soil sample and the unwashed unsoiled fabric.
  • Table 13 11A cotton fabric is contaminated with various respective impurities and washed with the addition (i.e. in the presence) 1.5 g/L tri-chromatic Bezept Black V-CMR dye with or without a reference DP sheet or aCNF in the drum.
  • aCNF shows the least increase in the initial absorption difference, as it adsorbs most of the dye initially.
  • the absorption differences increase, presumably due to different optical properties of the laundry containing solutions.
  • the normalized absorption differences decrease again, due to the ongoing dye-adsorption by the dye-catcher materials and laundry in the drum.
  • Figure 10B demonstrates the decreasing dye-concentration and the changes of the optical properties of the washing solutions visually embracegraphs of the corresponding aliquots.
  • Example 7 Properties of CNF, CNF-ox, CNF-ox-HMDA and CNC, CNC-ox and CN C-ox-HMD A
  • the titration curve (not shown) of native CNF shows one small bend at pH 4.4, given the small quantity (0.12 mmol/g) of negative charge that may be related to the presence of rare anionic (preferably sulfonate) surface groups, formed during the preparation of CNF or resulting from the presence of lignin residues. These groups were reduced to 0.096 mmol/g after the oxidation (CNF-ox, figure 4), also giving another peak at pH -9.1, which might be related to the aforementioned phenomenon, while they could not be detected anymore after attachment of HMDA (CNF-ox-HMDA, figure 4), yielding a positive charge of around 5.64 mmol/g at pH ⁇ 8.i.
  • the titration curve of pure HMDA shows high positive charge at a wide pH range until -10.7 (being related to its complete deprotonation, pK) with a small band between pH 6.0-7.0 (representing the partial deprotonation stage of diamines, H2N-(CH2)6-NH2), thus confirming the high contribution of amino (CNF-NH2) groups.
  • a gradual reduction of the titration curve for the CNF-ox-HMDA sample and shifting of HMDA’s pK value towards lower pH may, thus, be because of its binding to CNF-ox.
  • Table 15 Minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) of different CNF/CNC suspensions for E. coli (EXB- V127) and S. aureus (EXB-V54) determined by the dilution antibiogram method. Results are given as the average of two independent replicates. Legend: N/A - could not be determined because no concentration-dependent inhibitory and bactericidal response was observed.
  • MIC minimum inhibitory concentrations
  • MMC minimum bactericidal concentrations
  • FIG. 14 shows results for multiple filtration of S. aureus with aCNF and qCNF decontamination agents, wherein the qCNF shows significantly inferior bacterial filtration properties as the number of bacterial cells remains approximately the same in all experiments.
  • aCNF CNF-ox-HMDA
  • Example 10 Reduction of virus
  • Figure 15 shows the results of the reduction of Bacteriophage phi6 after being placed upon the visous (VIS) membrane surface containing aCNF and qCNF decontamination agents, wherein the qCNF-decorated membrane shows significantly inferior virus reduction properties after 2 h of incubation, while membrane containing also aCNF (CNF-ox-HMDA) efficiently reduced the virus, thereby suggesting that aCNF is able to function also as a filter for viruses.
  • VIS visous
  • Figure 16 shows results of biodegradation properties in soil by analysing weight loss, wherein CNF-ox and CNC-ox are fully biodegradable (weight loss is increasing), while CNF-ox- HMDA and CNC-ox-HMDA are not (weigh loss is reduced) due capturing of soils microorganisms.
  • CNF-ox-HMDA suspension Prepared decontamination agents (CNF-ox-HMDA suspension) was mixed with 0.5 L of laundry wastewater containing an approximate 80 pm long synthetical microfibres. After 15 min of magnetic stirring the formed aggregates (A) were filtrated using commercial membranes of 180 pm pore size ( left column), followed by filtration using too pm pore size (middle column) and 10 pm pore size (right column) membranes, wherein filtration was performed sequentially (B). In parallel, qCNF was used showing much less efficiency. In case of control (using no CNF) the effect of microfibrils retention was insignificant.

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