WO2020044210A1 - Solvant eutectique profond pour la modification d'un film de nanocellulose - Google Patents

Solvant eutectique profond pour la modification d'un film de nanocellulose Download PDF

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WO2020044210A1
WO2020044210A1 PCT/IB2019/057175 IB2019057175W WO2020044210A1 WO 2020044210 A1 WO2020044210 A1 WO 2020044210A1 IB 2019057175 W IB2019057175 W IB 2019057175W WO 2020044210 A1 WO2020044210 A1 WO 2020044210A1
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film
nanocellulose
hydrophobic
mfc
modified
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PCT/IB2019/057175
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Matias LAKOVAARA
Susanne HANSSON
Adrianna SVENSSON
Juho SIRVIÖ
Henrikki LIIMATAINEN
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Stora Enso Oyj
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to methods for hydrophobic modification of nanocellulose films, as well as the hydrophobic modified nanocellulose films themselves so as to improve the barrier properties of said films.
  • Microfibrillated cellulose which is a kind of nanocellulose comprises partly or totally fibrillated cellulose or lignocellulose fibers.
  • the liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
  • the smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g . Chinga- Carrasco, G., Nanoscale research letters 2011, 6 :417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril, is the main product that is obtained when making MFC e.g.
  • the length of the fibrils can vary from around 1 to more than 10 micrometers.
  • a coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber) .
  • microfibrils in MFC provide a great number of surface OH-groups, making MFC hydrophilic.
  • Films of MFC have excellent barrier properties, in particular oxygen and fat barrier properties, but are affected by water because of the hydrophilic nature. Above ambient temperatures and moisture conditions the dense fibrillar structure loses its integrity and the properties can deteriorate. Enhanced hydrophobicity will introduce water repellency to the material. Hydrophobicity can also help to maintain the integrity of the film at high humidity and thereby the low oxygen permeability can be maintained .
  • a layer of a thermoplastic polymer like PE onto a MFC film water-vapor properties can be achieved .
  • the strong network can render the MFC films more brittle than plastic films, and this can limit their production as well as post-handling in different applications.
  • Plasticizers can be utilized but such components normally reduce the oxygen barrier properties.
  • DESs Deep Eutectic Solvents
  • a DES is a fluid generated by mixing two or three components that are capable of self-association through hydrogen bond interactions, to form a eutectic mixture having a melting point lower than each of its constituents, and can thereby be a solvent at ambient temperature. These solvents also have low vapour pressure, and hence low volatility.
  • DESs have been applied as a pretreatment to produce MFC.
  • J. Sirvio et al. Green Chem 2015, 17, 3401-3406 and P. Li et al., ACS Appl mater. Interfaces 2017, 9, 2846-2855. They can also be utilized as solvents for further chemical modification of fibrils.
  • T. Selkala et al. Chem. Sus. Chem. 2016, 9, 1-11; J. Sirvio et al., J. Mater. Chem A. 2017, 5, 21828-21835).
  • crosslinking between DES component and polysaccharides have been proven by FT-IR. (C. Zdanowicz, Carbohydrate Polymers 2016, 151, 103-112).
  • a method for increasing the hydrophobicity of a nanocellulose film comprising exposing the nanocellulose film to (i) a deep eutectic solvent (DES) and (ii) a hydrophobic surface-modifying agent, wherein exposure to (i) and (ii) can take place sequentially, or simultaneously (preferably simultaneously) .
  • DES deep eutectic solvent
  • a hydrophobic surface-modifying agent wherein exposure to (i) and (ii) can take place sequentially, or simultaneously (preferably simultaneously) .
  • a nanocellulose film which has a hydrophobic surface with a water contact angle of at least 90°, suitably at least 100°.
  • the hydrophobic surface is provided by hydrophobic chains, such as e.g. C 2 -C 28 hydrocarbon chains.
  • the present technology relates to using a deep eutectic solvent system combined with a hydrophobic surface-modifying agent (such as n-octylsuccinic anhydride or alkenyl succinic anhydride) to produce hydrophobic, moisture stable, and/or strainable MFC barrier films, where the modification takes place after the production of a nanocellulose film to not interfere with the hydrogen bonding between the fibrils.
  • a hydrophobic surface-modifying agent such as n-octylsuccinic anhydride or alkenyl succinic anhydride
  • DES for nanocellulose film modification
  • a DES system e.g . imidazole- triethylmethylammonium chloride
  • the pre-made nanocellulose film can also be subjected to a pre-treatment prior to exposure to a DES system to create an all-cellulose composite film.
  • the contact angle of the modified film was clearly improved .
  • the oxygen barrier properties are in the same range as for the reference nanocellulose film at high moisture conditions.
  • the enclosed experiments investigate whether it is possible to modify nanocellulose, especially MFC and all-cellulose composite films in deep eutectic solvents to improve their oxygen barrier properties in high relative humidity conditions.
  • the chemistry behind the modification is to add functional groups through ester bonds to the cellulose chain by replacing free hydroxyl groups.
  • the goal of the modification was that chemical reaction only occurs with the free hydroxyl groups on surface of the film, so that most of the inner hydrogen bond network will not be disturbed, keeping the required mechanical properties intact or further improving the flexibility of the film.
  • a method for increasing the hydrophobicity of a nanocellulose film comprises exposing the nanocellulose film to (i) a deep eutectic solvent and (ii) a hydrophobic surface-modifying agent, wherein exposure to (i) and (ii) can take place sequentially, or simultaneously.
  • exposure of the nanocellulose film to (i) and (ii) takes place simultaneously.
  • exposure of the nanocellulose film to (i) and (ii) takes place sequentially, with exposure to the deep eutectic solvent (i) taking place before exposure to the hydrophobic surface-modifying agent (ii).
  • the hydrophobic surface-modifying agent (ii) may also be mixed with said deep eutectic solvent (i), and the nanocellulose film will be exposed to said mixture of (i) and (ii).
  • the exposure of the film to the deep eutectic solventand the hydrophobic surface modifying agent is preferably done for a period of 30 seconds to 1500 minutes, preferably for a period of 1 minute to 60 minutes, even more preferably for a period of 1 minute to 15 minutes.
  • the treatment is preferably done at a temperature of 20-100 °C, preferably between 60-100 °C and even more preferred at a temperature of 60-80 °C. However, the optimal temperature may differ depending on the DES system used.
  • the dry content of the film being exposed is high, preferably above 85 % by weight, even more preferably above 95% by weight. If the film comprises too much water the reagents in the DES system will not react with the film but with the water instead.
  • the dry content of the film needs to high in order for the treatments to be successful.
  • the deep eutectic solvent, the hydrophobic surface-modifying agent and the optionally aqueous solvent used in the pre-treatment may be added to the nanocellulose film by spraying, coating, spreading, vapour deposition and/or printing the solution onto the surface/s of the film.
  • the film may also be submerged into the solutions.
  • the nanocellulose film may be subjected to a pre-treatment, prior to exposure to (i) and (ii).
  • Pre-treatment may be carried out using any solvent that can interact with the hydroxyl groups on cellulose and partly dissolve the sample.
  • pre-treatment of the nanocellulose film may take place using an aqueous solution of tetraalkylammonium hydroxide, such as tetraethylammonium hydroxide, tetraalkylammonium chloride, such as tetraethylammonium chloride or tetrabutylammonium chloride or mixtures of hydroxides of group I or II metals, such as sodium hydroxide and urea, thiourea or a zinc salt, preferably zinc oxide.
  • tetraalkylammonium hydroxide such as tetraethylammonium hydroxide, tetraalkylammonium chloride, such as tetraethylammonium chloride or
  • the nanocellulose film can be treated with a solvent to remove the aqueous solution and terminate the dissolution reaction and to precipitate the dissolved parts.
  • the solvent is preferably a water miscible solvent, preferably an alcohol, such as ethanol, methanol, isopropanol and/or water.
  • the nanocellulose film is treated with the solvent prior to the following surface-modification.
  • Pre-treated nanocellulose films are referred to herein as "all-cellulose composite film".
  • the pre-treatment with the aqueous solution may occur for a period of 1 second to 60 minutes and at a temperature between 20- 50°C, preferably at a temperature between 20-30°C.
  • the deep eutectic solventand any excess hydrophobic surface-modifying agent should be removed from the modified nanocellulose film.
  • the deep eutectic solvent is removed by washing the modified nanocellulose film with a solvent, e.g. alcohols or water, or combinations thereof, suitably water. It has been discovered that washing with ethanol forms pores in the film which are not formed when water is utilized.
  • the treated film is preferably dried after being modified and the liquids have been removed.
  • the film may be dried using any drying equipment known to a person skilled in the art.
  • unmodified cellulose pulp is exposed to (i) a deep eutectic solvent and (ii) a hydrophobic surface modifying agent, wherein exposure to (i) and (ii) can take place sequentially, or
  • hydrophobically-modified cellulose pulp followed by the steps of: a. microfibrillation of said hydrophobic-modified cellulose pulp to provide hydrophobically modified microfibrillated cellulose (MFC), b. optionally, blending the hydrophobically modified nanocellulose with another grade of polysaccharide such as e.g. native nanocellulose, native microfibrillated cellulose or starch; and c. film formation of said hydrophobically modified microfibrillated cellulose (MFC) or said blend, to provide a hydrophobically modified nanocellulose film.
  • MFC hydrophobically modified microfibrillated cellulose
  • hydrophobically modified nanocellulose is blended with another grade of polysaccharide it is preferred that the mixture comprises 20-100% of hydrophobically modified MFC, preferably between 30-80%, even more preferred 40-60%.
  • nanocellulose any one of nanofibrillated cellulose (NFC), microfibrillated cellulose (MFC), bacterial cellulose and/or nanocrystalline cellulose.
  • film is meant a thin substrate with good gas, aroma or grease or oil barrier properties, preferably oxygen barrier properties.
  • the film preferably has a basis weight of less than 100 g/m 2 and a density in the range from 700-1400 kg/m 3 .
  • the film may be produced by applying a suspension comprising nanocellulose, for example microfibrillated cellulose onto a wire.
  • the wire may be porous felt wire or made from polymer of metal. It may also be possible to apply the suspension comprising nanocellulose by casting the suspension onto a substrate.
  • the substrate may be a polymer or metal substrate.
  • the casted fibrous web can then be dried and optionally peeled off from the substrate.
  • the applied nanocellulose suspension is thereafter dried to form a nanocellulose film.
  • the film preferably comprises 70-100% by weight of nanocellulose, for example
  • microfibrillated cellulose based on total dry weight of the film, preferably between 80-95% by weight of nanocellulose.
  • the film may further comprise other additives such as any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, wet strength additives, dry strength additives, plasticizers and polymers, such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl alcohol-acetate (PVOH/Ac), ethylene vinyl alcohol (EVOH), softeners or mixtures thereof.
  • additives such as any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, wet strength additives, dry strength additives, plasticizers and polymers, such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl alcohol-acetate (PVOH/Ac), ethylene vinyl alcohol (EVOH), softeners or mixtures thereof.
  • PVAc polyvinyl acetate
  • PVH
  • Microfibrillated cellulose or so called cellulose microfibrils (CMF) shall in the context of the present invention mean a micro-scale cellulose particle fiber or fibril with at least one dimension less than 100 nm.
  • MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers.
  • the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m 2 /g, such as from 1 to 200 m 2 /g or more preferably 50-200 m 2 /g when determined for a freeze-dried material with the BET method.
  • MFC multi-pass refining
  • pre-treatment followed by refining or high shear disintegration or liberation of fibrils.
  • One or several pre treatment steps are usually required in order to make MFC manufacturing both energy- efficient and sustainable.
  • the cellulose fibers of the pulp to be supplied may thus be pre treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin.
  • the cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose.
  • Such groups include, among others, carboxymethyl, aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxidation, for example "TEMPO”), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC.
  • TEMPO N-oxyl mediated oxidation
  • quaternary ammonium cationic cellulose
  • the microfibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source.
  • Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, single - or twin-screw extruder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, single - or twin-screw extruder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or other lignocellulosic fibers used in papermaking processes.
  • the product might also contain
  • MFC can be produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
  • MFC includes, but is not limited to, the proposed TAPPI standard W13021 on cellulose nano- or microfibril (CNF or CMF, respectively) defining a cellulose nanofiber material containing multiple elementary fibrils with both crystalline and amorphous regions, having a high aspect ratio with width of 5-30 nm and aspect ratio usually greater than 50.
  • CNF or CMF cellulose nano- or microfibril
  • the deep eutectic solvent (component i) activates the nanocellulose film, and provides a (non-aqueous) environment in which the hydrophobic surface-modifying agent (component ii) is stable and can react with the nanocellulose film.
  • DESs are a particular class of ionic liquids, but DESs can also be obtained from non-ionic species. They comprise a eutectic mixture of compounds having a melting point much lower than either of the individual components.
  • the DES may be selected from imidazole - triethylmethylammonium chloride, lithium chloride-urea, malic acid - choline chloride, malic acid - proline, AlCh - l-ethyl-3- methylimidazolium chloride, AlCh - urea as well as combinations of imidazole or choline chloride with one or more salts selected from AgCI, CuCI, LiCI, CuCh, SnCh, ZnCI 2 , LaCh,
  • DES deep eutectic solvent
  • the hydrophobic surface-modifying agent (component ii) reacts with the activated OH-groups on the nanocellulose or MFC surface.
  • the hydrophobic surface-modifying agents for use herein may therefore comprise at least one hydrophobic moiety and at least one OH-reactive moiety.
  • hydrophobic moiety of said hydrophobic surface-modifying agent(s) may be a
  • hydrophobic chain suitably a hydrocarbon chain, preferably a C 2 -C 28 hydrocarbon chain, more preferably a C 5 -C 22 hydrocarbon chain.
  • the OH-reactive moiety is selected from an epoxy, a silicon halide, a silazane, a silane, a chlorosilane, an organic acid, an organic acid ester, an organic acid anhydride, an organic acid halide, an organic amide, or a combination thereof.
  • the hydrophobic surface-modifying agent is selected from the group of C 2 -C 28 fatty acids, C 2 -C 28 fatty acid esters, C 2 -C 28 fatty acid anhydrides, C 2 -C 28 fatty acid amides and C 2 -C 28 fatty acid halides such as C 2 -C 28 fatty acid chlorides.
  • hydrophobic surface-modifying agent examples include acetic anhydride, alkenyl succinic anhydrides (ASA), n-octyl succinic anhydride, tetradecenyl succinic anhydride (TDSA), iso-octadenyl succinic anhydride (iso-ODSA), acetyl chloride, ethyl acetate, 1- acetylimidazole, isopropenyl acetate, palmitic acid, stearic acid, palmitoyl chloride, octadecanoyl chloride, hexadecyltrimethoxysilane (HMDS), (3-aminopropyl)triethoxysilane or bis(trimethylsilyl)acetamide (BSA), preferably acetic anhydride, alkenyl succinic anhydrides (ASA), n-octyl succinic anhydride, palmitic acid, stearic acid,
  • the method described herein provides a route to modify nanocellulose films and especially microfibrillated cellulose films to be more hydrophobic.
  • a hydrophobically-modified nanocellulose film is also provided, which has a water contact angle of at least 90°, suitably at least 100°.
  • the hydrophobic modification is suitably provided by hydrophobic chains, such as e.g. C 2 -C 28 hydrocarbon chains. Such hydrophobic chains are bonded to the cellulose fibrils of the nanocellulose, preferably at least partly at the surface of the nanocellulose film.
  • a hydrophobically modified nanocellulose film has a water contact angle (CA) of at least 90°, suitably at least 100°, measured by contact angle measurement.
  • CA water contact angle
  • the contact-angle measurement is based on the ISO standard TC 6/SC 2/WG 41 : Paper and board - Measurement of water contact angle by optical methods.
  • hydrophobic modification can be established by e.g. infrared spectroscopy. Indeed, infrared spectroscopy on the nanocellulose film modified in the mixture of DES and hydrophobic surface-modifying agent showed that the dissolved agent reacted with the nanocellulose film.
  • hydrophobically-modified nanocellulose film obtained or obtainable via the methods described herein.
  • the hydrophobically-modified nanocellulose films have uses as liquid barriers in e.g. liquid- or food- packaging material.
  • a liquid or food packaging material is provided which is a laminate of one or more layers of a hydrophobically-modified
  • nanocellulose film as described herein, with one or more base layers of paper or paperboard and/or one or more layers of a polymer.
  • the polymer may preferably be polyethylene (PE), polypropylene (PP) and/or polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the film may be coated or laminated with one or more layers of polymer/s on one or both sides of the film.
  • the polymer laminate can for example be used as a pouch in food packaging. All details of the methods described above are also relevant for the modified nanocellulose film, as described herein.
  • Pre-Masuko ground dissolving pulp in aqueous solution (consistency of 1.66 %-w) was used as a cellulose raw material for MFC production, and birch pulp for modified MFC production.
  • the pre-Masuko ground dissolving pulp was diluted to a consistency of 0.5%-w and then mixed at 10000 rpm with an Ultra-Turrax mixer (IKA T25, Germany) for 1 min to achieve a homogeneous suspension.
  • the suspension was microfibrillated through microfluidizer (Microfluidics M-110EH-30, USA) 5 times: one time through 400 pm and 200 pm chambers at a pressure of 1000 bar, and 4 times through 400 pm and 100 pm chambers at a pressure of 1500 bar. After microfibrillation, two samples were taken from the suspension and dried overnight at 100°C to determine the dry-matter content.
  • MFC films were prepared by measuring 0.265 g abs. (grammage of the film 60 g/m 2 ) of dry microfibril suspension into a decanting glass and then dilution with water to total weight of 100 g. After this, the sample was degassed by ultrasonic treatment for 10 min. Next the sample was vacuum filtered on top of the membrane (Durapore DVPP 0,65 pm, Merck Millipore Ltd., Ireland) using a negative pressure of approximately 800 mbar. When the film was formed and the excess water was removed, the film was dried by vacuum drier (Karl Schroder KG, Germany) for 10 min at temperature of 93°C and negative pressure of 930 mbar. Finally, the weight of the film was measured.
  • vacuum drier Karl Schroder KG, Germany
  • Imidazole-TEMACI DES (molar ratio of 7 :3) was prepared by weighing the components into a decanting glass (total of 120 g) and heating it in the oil bath at 80°C or 100°C, depending on the sample. When approximately half of the liquid was formed, the magnetic stirrer was enabled and kept constantly mixing to speed until formation of the DES.
  • the hydrophobic surface-modifying agent was added to the DES when a clear liquid was observed.
  • the film was washed with acetone to remove possible impurities that could disturb the chemical reaction.
  • the film was submerged in the DES/reagent system horizontally and a film protection device prevented the magnetic stirrer touching the film. The stirrer was kept on throughout the reaction.
  • the ratio between reagent and film was 10: 1 in weight and the amount of DES was selected so that there was enough liquid around the film.
  • the film was washed three times (approximately 5 min at a time) with ethanol or water (depending on the sample) to remove the DES and the reagent from the film.
  • the washing liquid was changed between washing steps.
  • the film was dried by vacuum drier for 10 min using the same apparatus and conditions as in the preparation of MFC film.
  • All-cellulose composite film was fabricated by submerging the MFC film in
  • the oxygen transmission rate (OTR) of the films was measured using a MOCON Ox-Tran 2/22 (Minneapolis, MN, USA). The film was exposed to 100% oxygen gas on one side and to 100% nitrogen gas on the other side.
  • the oxygen permeability (OP) was calculated by multiplying the OTR by the thickness of the film and dividing it by the difference in the oxygen gas partial pressure between the two sides of the film. Before the OTR measurement, the thickness of the film was determined as an average of three random measuring points using Precision Thickness Gauge (FT3, Hanatek Instruments, United Kingdom). The measurements were carried out at 23°C or at 38°C, normal atmospheric pressure, and relative humidity of 50%, 80% and 90% with a specimen are of 5 cm 2 . The OTR were measured according to ASTM F 1927-98.
  • FTIR Fourier-transform infrared spectroscopy
  • Diffuse reflectance infrared Fourier transform spectroscopy was used to determine the spectrum for which a little piece of the film was cut.
  • the spectra were obtained by Bruker Vertex 80v (USA) with a wavelength range of 400-4000 cm 1 and with the total of 40 scans at a resolution of 4 cm 1 for each sample.
  • CA contact angle
  • the tensile strength of the films was measured by a universal testing machine (Instron 5544, USA).
  • the films were kept in a constant temperature and humidity conditions (temperature 23 ⁇ 0.5°C, RH 50 ⁇ 2%) 18 h before the measurements, during the sample preparations and during the measurements.
  • the thickness of the films was measured by taking an average value of five random points on the film using the same device as used above.
  • the samples were prepared by cutting 3-4 strips from the film with a width of 5 mm and length of 70 mm.
  • the gauge length was set to 40mm and the strain was controlled at 5 mm/min with a pre-strain value of 1 MPa, until the sample broke.
  • OTR measurements were carried out on certain water-washed films, and the OTR and OP results are presented in Table 2.
  • the OTR results at 38°C and 90% RH are the average of two different samples, except for sample Q. Best oxygen barrier properties are seen at low OTR and OP values.
  • the OP value takes the thickness of the film into account.
  • OTR values are expressed in ml/(m 2 -day); OP values in ml ⁇ m/(m 2 day kPa).
  • sample B, E, and F have the same reagent - isopropenyl acetate - but the reaction temperature is lower for F compared to E, which seems to give a slight higher OTR at 23/80 for F.
  • the reason for the high value for sample B is due to washing in ethanol and not in water as for E and F.
  • sample L, M, N, P and Q have the same reagent - n-octyl succinic anhydride - and lower reaction times have been applied : 10-60 minutes.
  • a much shorter reaction time was employed : 10-15 vs 60 min, and it seems like a shorter reaction time gives a better barrier in this DES system.
  • P was run at a higher reaction temperature, 100 compared to 80 °C for the other samples, but this did not improve the barrier to any larger extent.
  • Sample M showed the best OP at the higher climate of 38 C and 90 % relative humidity and outperformed also the reference.
  • Sample Q which was pretreated, shows a similar OP as for the other, but a significant increase of almost 20° in CA can be seen compared to the other samples (Table 2).
  • Imidazole-TEMACI DES (molar ratio 7 :3) was prepared by weighing the components into a round bottom flask, mixing it with magnetic stirrer and heating it in the oil bath at 80°C until the clear liquid was formed. Next, pulp was torn by hand and added into the DES and hydrophobic surface-modifying agent was added into the mixture after the pulp was dissolved into the DES. The reaction continued for 24 hours while being continuously mixed by magnetic stirrer. Then the suspension was washed with water and filtered by Buhner funnel. The modified cellulose was dried over night at 100°C.
  • the weight ratio between DES and pulp was 25: 1, so the total amount of DES and pulp was 40 g and 1.6 g in the case of pulp modified with n-octylsuccinic anhydride (molar ratio 3: 1) and acetylated cellulose, and 25 g and 1 g in pulp modified with n-octylsuccinic anhydride (molar ratio 2: 1).
  • Microfibrillation of this modified cellulose was done from two samples.
  • the modified dry pulp was diluted to consistency of 0.5 %-w and the suspension was mixed at 10000 rpm with an Ultra-Turrax mixer for 3 min before microfibrillation, which was conducted by microfluidizer (Microfluidics M-110EH-30, USA).
  • the pulp modified with n-octylsuccinic anhydride (molar ratio 2: 1) was passed three times through microfluidizer: two times through 400 pm and 200 pm chambers and one time through 400 pm and 100 pm chambers.
  • the acetylated cellulose was passed six times through microfluidizer: three times through 400 pm and 200 pm chambers and three time through 400 pm and 100 pm chambers. After microfibrillation, two samples from each suspension were taken and dried over night at 100°C to determine the dry matter content.
  • MFC films Four different types were made from the modified MFC using different weight ratios.
  • the films were made from octylsuccinylated MFC, acetylated MFC, octylsuccinylated and unmodified MFC with weight ratio of 1 : 1, and acetylated and unmodified MFC with weight ratio of 1 : 1.
  • the suspensions were weighed into a decanting glass so that the dry cellulose content was 0.265 g and then the mixture was diluted with water to total weight of 100 g. After that the same procedure was used to make the films as in the preparation of MFC films.
  • the films made from modified pulp were brittle, felt and looked more like paper.
  • the films gave over-range values in the OTR measurements, but the samples with octylsuccinylated MFC (50 or 100 wt%) exhibited contact angles above 90, see Table 4, suggesting improved hydrophobicity Table 4.

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Abstract

La présente invention concerne des procédés de modification hydrophobe de films de nanocellulose par exposition du film à un solvant eutectique profond (DBS), ainsi que les films de nanocellulose modifiés hydrophobes eux-mêmes de sorte à améliorer les propriétés de barrière desdits films.
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CN112266502A (zh) * 2020-10-15 2021-01-26 江南大学 一种多重响应纳米纤维素复合膜及其制备方法
CN112411235A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种豆渣纳米纤维素的清洁高效尺寸可控制备方法
CN113136038A (zh) * 2021-03-31 2021-07-20 南京林业大学 微纳木质纤维素复合材料的制备方法、复合材料及应用
CN114133616A (zh) * 2021-11-10 2022-03-04 华南理工大学 一种可回收纤维素基导电自修复共晶凝胶及其制备方法与应用
CN114920969A (zh) * 2021-02-03 2022-08-19 天津科技大学 一种微纤维化纤维素基超疏水防护型复合材料的制备方法
US11421041B2 (en) 2020-10-15 2022-08-23 Jiangnan University Multi-response cellulose nanocrystals-composite film and preparation method thereof
CN115322445A (zh) * 2022-08-09 2022-11-11 河南师范大学 一种高韧性可生物降解淀粉基薄膜的制备方法
WO2022266796A1 (fr) * 2021-06-21 2022-12-29 深圳大学 Matériau biopolymère conducteur souple, procédé de préparation associé et son utilisation
WO2023129417A1 (fr) * 2021-12-29 2023-07-06 Schlumberger Technology Corporation Nanoparticules fonctionnalisées en tant que modificateur de mouillabilité
WO2023219587A1 (fr) * 2022-05-10 2023-11-16 Bursa Tekni̇k Üni̇versi̇tesi̇ Utilisation de solutions eutectiques profondes hydrophiles et hydrophobes en tant que plastifiants
JP7389660B2 (ja) 2020-01-24 2023-11-30 株式会社Kri セルロース微細繊維及びその製造方法
US11999843B2 (en) 2022-02-03 2024-06-04 The Procter & Gamble Company Polyvinyl alcohol compositions with eutectic solvents, articles thereof, and methods of making same

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JP7389660B2 (ja) 2020-01-24 2023-11-30 株式会社Kri セルロース微細繊維及びその製造方法
CN112266502B (zh) * 2020-10-15 2021-09-28 江南大学 一种多重响应纳米纤维素复合膜及其制备方法
WO2022078032A1 (fr) * 2020-10-15 2022-04-21 江南大学 Membrane composite de nanocellulose à réponses multiples et procédé de préparation associé
US11421041B2 (en) 2020-10-15 2022-08-23 Jiangnan University Multi-response cellulose nanocrystals-composite film and preparation method thereof
CN112266502A (zh) * 2020-10-15 2021-01-26 江南大学 一种多重响应纳米纤维素复合膜及其制备方法
CN112411235A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种豆渣纳米纤维素的清洁高效尺寸可控制备方法
CN114920969A (zh) * 2021-02-03 2022-08-19 天津科技大学 一种微纤维化纤维素基超疏水防护型复合材料的制备方法
CN113136038B (zh) * 2021-03-31 2022-11-15 南京林业大学 微纳木质纤维素复合材料的制备方法、复合材料及应用
CN113136038A (zh) * 2021-03-31 2021-07-20 南京林业大学 微纳木质纤维素复合材料的制备方法、复合材料及应用
WO2022266796A1 (fr) * 2021-06-21 2022-12-29 深圳大学 Matériau biopolymère conducteur souple, procédé de préparation associé et son utilisation
CN114133616B (zh) * 2021-11-10 2022-09-20 华南理工大学 一种可回收纤维素基导电自修复共晶凝胶及其制备方法与应用
CN114133616A (zh) * 2021-11-10 2022-03-04 华南理工大学 一种可回收纤维素基导电自修复共晶凝胶及其制备方法与应用
WO2023129417A1 (fr) * 2021-12-29 2023-07-06 Schlumberger Technology Corporation Nanoparticules fonctionnalisées en tant que modificateur de mouillabilité
US11999843B2 (en) 2022-02-03 2024-06-04 The Procter & Gamble Company Polyvinyl alcohol compositions with eutectic solvents, articles thereof, and methods of making same
WO2023219587A1 (fr) * 2022-05-10 2023-11-16 Bursa Tekni̇k Üni̇versi̇tesi̇ Utilisation de solutions eutectiques profondes hydrophiles et hydrophobes en tant que plastifiants
CN115322445A (zh) * 2022-08-09 2022-11-11 河南师范大学 一种高韧性可生物降解淀粉基薄膜的制备方法
CN115322445B (zh) * 2022-08-09 2023-04-14 河南师范大学 一种高韧性可生物降解淀粉基薄膜的制备方法

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