CA2549844C - Solid phase dispersion and processing of micro-and nano-cellulosic fibres in plastic phase to manufacture bio-nanocomposite products of commercial interest - Google Patents

Solid phase dispersion and processing of micro-and nano-cellulosic fibres in plastic phase to manufacture bio-nanocomposite products of commercial interest Download PDF

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CA2549844C
CA2549844C CA2549844A CA2549844A CA2549844C CA 2549844 C CA2549844 C CA 2549844C CA 2549844 A CA2549844 A CA 2549844A CA 2549844 A CA2549844 A CA 2549844A CA 2549844 C CA2549844 C CA 2549844C
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nano
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dispersed
plastic
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CA2549844A1 (en
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Mohini M. Sain
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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/162—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2311/00—Use of natural products or their composites, not provided for in groups B29K2201/00 - B29K2309/00, as reinforcement
    • B29K2311/10—Natural fibres, e.g. wool or cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2711/00—Use of natural products or their composites, not provided for in groups B29K2601/00 - B29K2709/00, for preformed parts, e.g. for inserts
    • B29K2711/14—Wood, e.g. woodboard or fibreboard
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with monomers containing atoms other than carbon, hydrogen or oxygen
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    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
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  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
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  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Plant stem are bundles of cellulose nanofibers with a diameter ranging between 10 to 70 nm and lengths of thousands of nanometers. The mechanical performance of the cellulose nanofibers is comparable to other engineering materials such as glass fibers, carbon fibers etc. In this invention a novel process has been developed to disperse cellulosic microfibres and nanofibres in solid phase into a molten plastic matrix or in a low viscosity water-based resin system in aqueous phase. Invention relates to manufacturing Bio-nanocomposites of high performance by dispersing micro-and nano-cellulosic fibres into plastic matrix using conventional plastic processing equipment. This invention also overcomes one unique challenge of bio-nanocomposite processing, which is to make them commercially viable by surface modifying cellulosic micro-and nano-fibres derived from renewable resources.

Description

DESCRIPTION
Background of the Invention Cellulose micro- and nano-fibres are entangled in solid phase and are hard to obtain in individualized form due to strong hydrogen bonding. In aqueous phase and in dilute solution they can be obtained in highly dispersed form. Therefore, one possible method could be dispersing cellulose micro-and nano-fibres in aqueous or in a phase containing right combination of hydrophilic-hydrophobic character, typically a water-alcohol mixture phase an then solubilizing a polymer that has film-forming property as well as are soluble, either in an aqueous phase or in a mixture of water and other solvent in which, those micro-and nano-fibres can be dispersed.
Summary of the Invention In this invention cellulose microfibres or nanofibres isolated from agro-residues1'2 such as wheat straw, soy straw, bagasse, wood pulp, recycled fibre, root fibres are dispersed in water or in a mixture of water and alcohol, in a concentration range 0.5 to 5% and a soluble polymer in the given mixture has been added. Mixture were stirred with or without temperature to dissolve the polymer completely and then casted into film by an efficient drying process. Films, thus produced are cut into small chips and added in a twin screw extruder to further disperse them in plastics in molten phase by introducing solid thermoplastic polymer in the extruder along with the dispersed film particles.
The uniqueness of the invention is as follows:
This process avoid handling of liquid or water during conventional nanocomposite processing by extrusion, compression, injection and other molding processes by introducing a masterbatch of pre-dispersed nanofibre in polymer of high or low molecular weight subsequently taking out excessive liquid by filtration, drying or casting.
The second unique aspect of the invention is to pre-disperse cellulosic micro-and nano-fibres into a polymer in solution phase that are having surface energies compatible =
to base polymers in which they are further dispersed during their solid-phase dispersion.
For example, acrylic and maleic derivatives of ethylene or vinyl backbone are good for their dispersion in polyethylene.
Extruded products are obtained in different shapes and sizes including profiles, sheets, rods, solid or hollow. Extrusion also includes pellet form of the mixed composition and then further using them for compression molding, blow molding, injection molding, thermoforming, rotomolding. This method of liquid phase casting followed by solid phase mixing provided a unique method to manufacture bio-nanocomposites.
This process of manufacturing bio-nanocomposite in solid phase is unique because it solves the micro-and/or nanofibre dispersion problem in solid or molten phase compounding of plastics with those fibres.
Typical examples of plastic phase could be any thermoplastic materials including those obtained from forest, petroleum and agro-derived sources. Typically, polyvinyl alcohol, polyolefins, vinyl polymers and copolymers, engineered plastics such as styrene-acrylonitrile copolymer (SAN), nylon, polyester, ABS/PC, bio-based plastics such as thermoplastic starch, polylactic acid (PLA), poly-hydroxy-alkonates (PHAs).
Typical examples are cited below:
Example 1:
Polyethylene glycol-maleic anhydride treatments increased cellulose content of soybean stock nanofibers from 40% to 60% when they are first filter deposited or casted into films and then these dispersed nanofibre films were introduced in molten PVA
during extrusion, injection or high shear mixing . Nanofibers reinforced PVA
films demonstrated at least a 4-5-fold increase in tensile strength, as compared to the untreated fiber/PVA film. In solid phase nanocomposites, improved mechanical properties were achieved with coated nanofibers. Typically, polylactic acid (PLA) having initial tensile strength 52 MPa was increased to about 65 MPa by introducing 3-4% of soybean stalk derived nanofibres.
2 Example 2:
In yet another example, hemp nanofibre dispersed in ethylene acrylate olegomer by casting process has been dried, chopped into flake and granules for easy introduction in high shear mixer, injection machine and extrusion, were melt-mixed with polyethylene and maleated polyethylene as an interface modifier improved tensile strength of the resulting nanocomposite by 50% and improved modulus by three folds.
Typical examples of plastic phase could be any thermoplastic materials including those obtained from forest, petroleum and agro derived. Typically, polyvinyl alcohol, polyolefins, vinyl polymers and copolymers, engineered plastics such as styrene-acrylonitrile copolymer (SAN), nylon, polyester, ABS/PC, bio-based plastics such as thermoplastic starch, polylactic acid (PLA), poly-hydroxy-alkonates (PHAs).
Example 3:
In yet another process these micro-and/or nanofibres from natural origin are dispersed in surface active oligomers or polymers ( styrene copolymers and their derivatives, polyethylene glycol ¨maleic anhydride, styrene-maleimide , ethylene-acrylic copolymers) in an aqueous or in a solvent phase in which these surface active agents polymers or oligomers are soluble. The liquid phase dispersed micro-and/or nano fibrils are then incorporated in a liquid thermoplastic or thermosetting resins including bio-resins ( such as polyesters, vinyl esters, epoxy or polyol-isocyante resins or in which one or all components of these resins are made from crop sources such as soy bean, canola, corn, sunflower, palm, peanut or any other oil or their derived chemical precursors), thereby partly or totally eliminating issues related to agglomeration of those micro-and/or nanofibres in the liquid resins during their solidification process.
3

Claims (7)

  1. Claim 1: A process to deposit films from a liquid phase of the cellulosic micro and nanofibre obtained from wood, root and nonwood sources, wherein said cellulosic micro and/or nanofiber is dispersed uniformly in a plastic which is soluble in the above liquid phase, drying the micro-and /or nanofibre film followed by cutting or shaping the micro-and/or nanofibre dispersed plastic film into small sized flakes, granules or pellets and then further incorporating this micro-and/or nanofibre dispersed plastic in a molten thermoplastic by using extrusion, high shear mixing or injection compression process, thereby giving a novel process to obtain a bio-nanocomposite product without any risk of agglomeration of micro-and /or nanofibers in the plastic matrix during their melt mixing process.
  2. Claim 2. A process as cited in claim 1, whereby the liquid phase is selected from materials obtained from forest, petroleum and agro-based resources representing group of thermoplastics of polyvinyl alcohol, polyolefins, vinyl polymers and copolymers, engineered plastics selected from styrene-acrylonitrile copolymer (SAN), nylon, polyester, ABS/PC, and bio-based plastics comprising thermoplastic starch, polylactic acid (PLA), and poly-hydroxy-alkonates (PHAs).
  3. Claim 3. A process as cited in claim 1, wherein the resulting PVA bio-nanocomposite reinforced with soybean stock nanofibers has demonstrated at least 4-5 fold increase in tensile strength compared to untreated fibres, whereas PLA nanocomposites experienced 25% enhancement in tensile strength.
  4. Claim 4. A process as cited in Claim 1 wherein the micro and nano-fibres are dispersed in surface active oligomers or polymers.
  5. Claim 5. A process according to Claim 4, characterized in that the surface active oligomers or polymers are from the group of styrene copolymers and their derivatives, polyethylene glycol ¨maleic anhydride, styrene-maleimide, and ethylene-acrylic copolymers in soluble liquid phase.
  6. Claim 6. A process as cited in Claim 1 wherein the liquid phase dispersed micro and/or nano fibrils are incorporated in liquid thermoplastic or thermosetting polymers.
  7. Claim 7. A process according to Claim 6, characterized in that thermoplastic or thermosetting polymers belong to unsaturated polyesters, vinyl esters, epoxy or polyol-isocyante resins and in which at least one of the components of these resins are obtained from renewable crop sources of soy bean, canola, corn, sunflower, palm, peanut or any other oil and their derived chemical precursors.
CA2549844A 2006-05-25 2006-05-25 Solid phase dispersion and processing of micro-and nano-cellulosic fibres in plastic phase to manufacture bio-nanocomposite products of commercial interest Expired - Lifetime CA2549844C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105415696A (en) * 2008-03-27 2016-03-23 伯利斯特兰德公司 Method for preparing improved base material and improved base material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103140542B (en) * 2010-09-29 2015-03-11 Dic株式会社 Method for pulverizing cellulose, cellulose noanofiber, materbatch and resin composition
CN103476802B (en) * 2011-03-11 2016-08-24 Dic株式会社 Modified cellulose nanofiber, its production method and use its resin combination
PL3580265T3 (en) 2017-02-13 2023-01-02 Norske Skog Saubrugs As A method to disperse nano-cellulose in organic polymer precursors
CN122080601A (en) * 2026-04-08 2026-05-26 深圳市聚亿新材料科技股份有限公司 A biodegradable polylactic acid fruit and vegetable preservation bag and its preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105415696A (en) * 2008-03-27 2016-03-23 伯利斯特兰德公司 Method for preparing improved base material and improved base material
CN105415696B (en) * 2008-03-27 2019-01-15 普立万公司 The method and improvement substrate of preparation improvement substrate

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