WO2023126575A1 - Films hybrides à base de nanofibrilles de cellulose et de nanocristaux de cellulose - Google Patents

Films hybrides à base de nanofibrilles de cellulose et de nanocristaux de cellulose Download PDF

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WO2023126575A1
WO2023126575A1 PCT/FI2022/050873 FI2022050873W WO2023126575A1 WO 2023126575 A1 WO2023126575 A1 WO 2023126575A1 FI 2022050873 W FI2022050873 W FI 2022050873W WO 2023126575 A1 WO2023126575 A1 WO 2023126575A1
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cnc
cnf
cellulose
films
sorbitol
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PCT/FI2022/050873
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English (en)
Inventor
Ilona LEPPÄNEN
Ali Harlin
Hannes Orelma
Mika Vähä-Nissi
Vesa Kunnari
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Teknologian Tutkimuskeskus Vtt Oy
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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • 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
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • 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
    • 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
    • D21H11/20—Chemically or biochemically modified fibres
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to combination of cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) in preparing hybrid CNF-CNC films to complement each other in film forming ability and in mechanical and barrier performance.
  • CNF cellulose nanofibrils
  • CNC cellulose nanocrystals
  • This linear polymer consisting of P(1 ->4) linked D-glucopyranose units functions as the structural element in wood.[3] Due to its outstanding properties, such as high availability, renewability, low cost, biodegradability and broad chemical modifying capacity, it has currently obtained industrial and scientific interest in reducing the use of non-renewable synthetic plastic materials [2, 3], Owing to the hierarchical structure of cellulose, nanosized components can be extracted from this biopolymer. Recently, nanocellulose, extracted from plant-based cellulose-fibers, has emerged as a “green” nanomaterial and is commonly classified as cellulose nanofibers (CNFs) and cellulose nanocrystals (CNCs).
  • CNFs cellulose nanofibers
  • CNCs cellulose nanocrystals
  • CNFs are prepared from natural fibers by a top-down approach, where the destruction of the fibers is done mechanically by applying high shear forces on the cellulose fibers.
  • CNCs on the contrary are short and rod-like nano materials. They are prepared by acid hydrolysis, where the disordered regions are removed and the crystalline proportion remains. Depending on the acid used, different functionalities are introduced on the CNC surface.
  • CNC suspensions are known to form liquid crystal chiral nematic ordered structures above a critical concentration [5] and birefringent gels at even higher concentrations [6-9], which make their rheological behavior very different from CNFs and also induce interesting optical properties.
  • DE 2020/18103076 describes multi-layered articles, wherein three or more material layers are prepared from cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and cellulose micro fibrils (CMF).
  • CNC cellulose nanocrystals
  • CNF cellulose nanofibrils
  • CMF cellulose micro fibrils
  • a CNF/CNC hybrid film having both elevated oxygen barrier level and good mechanical properties.
  • the method of the present invention is mainly characterized by what is stated in the characterizing part of claim 1.
  • the hybrid film of the present invention is mainly characterized by what is stated in the characterizing part of claim 7.
  • CNC-films have excellent oxygen and grease barrier properties, but their mechanical performance is limited.
  • CNF and CNC materials have good compatibility that makes it possible to manufacture mechanically resistant films and coatings.
  • Mechanical performance of the CNC-films can be improved with CNF, where added cellulose fibrils bind cellulose crystals together from longer distances and increase ductility of the films.
  • CNC improves CNF films casting process by enhancing the spreading of the nanocellulose solution and preventing drying based shrinking of the films.
  • CNF/CNF hybrid films combine both nano materials’ good properties.
  • Polymer composites with nanocellulose as the reinforcing agent often lack good compatibility between the two components.
  • the present technology provides combined cellulose nanofibrils and cellulose nanocrystals to create hybrid films, which consist entirely of discrete nanocellulose objects that complement each other.
  • the similarity in surface chemistry both holding a negative charge and cellulosic materials) ease the fabrication of the films.
  • the inventors have found out that CNC has a positive effect on the film forming ability during film preparation as the films prepared from CNF/CNC mixtures spread more easily on the substrate and showed better adherence.
  • the prepared hybrid films were characterized chemically by FTIR, used AFM and SEM to visualize their nanostructure and characterized their mechanical and barrier properties.
  • FIGURE 1 shows viscosity of CNF/CNC suspensions without sorbitol (a) and with sorbitol (b) as the function of shear rate, (c) image of films: upper row without sorbitol and lower row with sorbitol starting from CNF100CNC0 to CNC100CNF0 from left to right, and (d) porosity of CNF/CNC hybrid films.
  • FIGURE 2 shows ATR-FTIR spectra of all CNF/CNC hybrid films without sorbitol (a) and with sorbitol (b).
  • FIGURE 3 shows AFM height (1 st column) and phase (2 nd column) images (5 pm x 5 pm) and their profiles (third column): (a) CNF100 + s (height bar ⁇ 110 nm), (b) CNF50CNC50 + s (height bar ⁇ 175 nm) and (c) CNC 100 ⁇ s (height bar ⁇ 30 nm).
  • FIGURE 4 shows stress-strain curves of CNF/CNC hybrid films without sorbitol (a) and with sorbitol (b).
  • the present method for producing hybrid films from cellulose nanofibrils and cellulose nanocrystals comprises at least the steps of:
  • CNC cellulose nanocrystal
  • the CNC-suspension is prepared from spray-dried CNC-powder by sulphuric acid hydrolysis.
  • the CNF-material used herein is preferably obtained from bleached hardwood pulp, such as bleached birch pulp.
  • the CNF to CNC dry weight ratio (%) is selected from 75 to 25, 50 to 50, 25 to 75 and 10 to 90, respectively. Most promising, but not limited to, results are obtained by using 50/50 dry weight ratio.
  • one suitable external plasticizer is sorbitol.
  • the amounts of sorbitol can vary from 20 to 40 %, such as 30 % of the amount of dry weight CNF+CNC.
  • other external plasticizers than sorbitol may also be used.
  • a polypropylene substrate which is plasma-treated, since it enhances the adhesion of CNF/CNC mixtures on the substrate.
  • One advantage of the present method is that films can be made at higher concentration by adding CNC without losing the benefits of CNF in mechanical and oxygen barrier properties.
  • CNF 100 the dry matter content is 1.68 wt-% vs.
  • the hybrid film has 10 to 75 %, preferably 25 to 75 % of CNF, and 25 to 90 %, preferably 25 to 75 % of CNC dry weight ratio, so that the CNF and CNC together form 100 % of the total cellulose material of the film.
  • the dry weight ratio (%) can thus be for example 50/50 (CNF/CNC).
  • the CNF/CNC hybrid film is characterized in having tensile strength of at least 85 MPa, Young’s modulus of at least 6.1 GPa and strain at break at least 1.5 %, without the external plasticizer, such as sorbitol.
  • tensile strength of at least 42 MPa, Young’s modulus of at least 3.7 GPa and strain at break at least 5.9 % was measure when sorbitol was included.
  • the CNF/CNF hybrid films should preferably have thickness between 20 and 50 pm.
  • the films have good oxygen and grease barrier properties. It was observed that the oxygen transmission rate of below 20 cc/m 2 *day, preferably below 5 cc/m 2 *day and most suitably below 2.5 cc/m 2 *day, with sorbitol, was reached. In addition, the CNF/CNC hybrid film according to the invention showed zero grease permeation during measuring period of 7 days. These barrier properties justify the applicability of the produced hybrid films in for example food packaging materials.
  • CNC Cellulose nanocrystals
  • the CNCs were prepared by sulfuric acid hydrolysis with a sulfate content of 246-261 mmol/kg.
  • Cellulose nano fibrils (CNF) were obtained by processing bleached Finnish hardwood (birch) pulp through a Masuko grinder with two passes with subsequent fluidization with six passes by a high pressure microfluidizer (Microfluidics Corp. Newton, MA, USA). The microfluidizer was equipped with two Z-type chambers that had diameters of 400 pm and 100 pm and it operated at 2000 bar pressure. The final consistency of the CNF was 1.68 %. All other chemicals used in this study were of analytical grade. Film preparation
  • a 6 wt-% cellulose nanocrystals suspension was prepared from the spray-dried CNC powder by adding the CNC to water through a sieve and simultaneously mixing strongly.
  • Different CNF to CNC dry weight ratio suspensions (CNF100CNC0, CNF75CNC25, CNF50CNC50, CNF25CNC75, CNF10CNC90 and CNF0CNC100) were prepared by mixing targeted amounts of CNC (6 wt-%) and CNF (1.68 wt-%) suspensions in a speed mixer (DAC 1100.1 VAC-P, Synergy Devices Limited, High Wycombe, UK).
  • CNF75CNC25 film has 75 wt% of CNF and 25 wt% of CNC.
  • sorbitol acts as an external plasticizer for the hybrid films.
  • Suspensions to which sorbitol was added contained 30 % of sorbitol of the amount of dry CNF+CNC. All hybrid mixtureswere solvent casted on a polypropylene substrate which was plasma-treated to enhance the adhesion of CNF/CNC mixtures on the substrate.
  • the CNF/CNC films were dried in room temperature and stored in 23 °C and 50 % relative humidity (RH).
  • the steady- state shear viscosity of the different samples were measured using a rotational rheometer (Anton Paar Rheometer MCR301) with a four-bladed vane geometry (ST22-4V- 40), which was brought down into a cylindrical measuring cup holding the sample. A 1 mm gap was used. Measurements were performed in RT. The viscosity was measured between shear rate 0.1 s’ 1 and 1000 s’ 1 . Viscosity of CNF/CNC suspension with and without sorbitol are presented in Figure 1 as the function of shear rate.
  • FT-IR Fourier transform infrared spectroscopy measurements
  • the surface topography and morphology of the prepared films was investigated using Atomic Force Microscopy (AFM) to reveal distribution of the two materials on the film.
  • AFM imaging of the films surfaces was performed using a NanoTA AFM+ instrument (Anasys Instruments, Bruker, MA, USA). The images were recorded in tapping mode in air with scan rate of 0.5 Hz with silicon cantilevers (Applied Nanostructures Inc., Santa Clara, CA, USA). The damping ratio was around 0.7-0.85 Hz.
  • the films were attached onto steel supports with double-sided tape and for each sample, three different areas were imaged and the images were not processed by any other means except flattening.
  • the AFM images of three of the CNF/CNC films are presented in Figure 3.
  • EDS Energy-dispersive X-ray spectroscopy
  • EDS Energy-dispersive X-ray spectroscopy
  • FE-SEM scanning electron microscopy
  • Tensile strength, Young’s modulus and strain at break of the films were measured by a Lloyd LS5 materials testing machine (AMETEK measurement and calibration technologies, USA) at 23 °C and 50 % RH with a load cell of 100 N.
  • the initial grip distance was 30 mm and the rate of the grip separation 10 mm min 1 .
  • the specimens were cut into 15 mm (original samples) or 5 mm (NMMO-treated and reference samples) wide strips with a lab film cutter.
  • the 5 mm width was the width of one square formed in the patterning. Thus, the partially dissolved and non-dissolved areas alternated within the sample. Seven replicates of each sample were measured. Thicknesses of each specimen was measured separately with a digital caliber from three different points. The average thickness was used for the calculations.
  • Air permeabilities of the samples were tested using an L&W Air Permeance Tester. Measurements were repeated three times.
  • Oxygen transmission rates (OTR) through the films were determined according to standard ASTM D3985 by using an Oxygen Permeation Analyzer Model 8001 (Systech Instruments Ltd., UK). The test was carried out at 23 °C and 50 % RH using 100 % oxygen as a test gas. Two parallel measurements were done. When the CNC content in the hybrid film reaches 50 %, the OTR value drops significantly (table 2). It seems that 50 % of CNCs in the hybrid film is able to fill most of the voids in the nanofibrillar network, thus having a significant effect on the oxygen permeability.
  • Oxygen transmission rates through the films were also determined by using Mocon OX- TRAN equipment with the following set-up:
  • Results (table 3) indicate that replacing CNF with CNC has no essential impact on the oxygen transmission rates, whereby it is possible in this context to partly replace CNF with CNC without essentially affecting to the oxygen barrier properties of the films.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Selon un aspect donné à titre d'exemple de la présente invention, l'invention concerne un procédé de production de films hybrides à partir de nanofibrilles de cellulose et de nanocristaux de cellulose complémentaires les uns des autres en ce qui concerne la capacité de formation de film et les performances des films hybrides produits.
PCT/FI2022/050873 2021-12-29 2022-12-28 Films hybrides à base de nanofibrilles de cellulose et de nanocristaux de cellulose WO2023126575A1 (fr)

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US20170027168A1 (en) 2015-07-27 2017-02-02 Stephan HEATH Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials
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WO2021123499A1 (fr) * 2019-12-16 2021-06-24 Åbo Akademi Procédé de production de films de nanocellulose
CN113152150A (zh) * 2021-04-09 2021-07-23 阿尔诺维根斯(衢州)特种纸有限公司 一种高透明高阻隔纤维素纸的制备方法

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