WO2022033743A1 - Procédé pour disperser de la nanocellulose dans des polymères et produits correspondants - Google Patents
Procédé pour disperser de la nanocellulose dans des polymères et produits correspondants Download PDFInfo
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- WO2022033743A1 WO2022033743A1 PCT/EP2021/065227 EP2021065227W WO2022033743A1 WO 2022033743 A1 WO2022033743 A1 WO 2022033743A1 EP 2021065227 W EP2021065227 W EP 2021065227W WO 2022033743 A1 WO2022033743 A1 WO 2022033743A1
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- Prior art keywords
- nano
- cellulose
- dispersion
- thermoplastic
- composite
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 108
- 239000001913 cellulose Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims description 29
- 229920000642 polymer Polymers 0.000 title claims description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 56
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 54
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 238000013329 compounding Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000013022 venting Methods 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000008188 pellet Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002041 carbon nanotube Substances 0.000 claims description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 13
- 229920003023 plastic Polymers 0.000 claims description 13
- 239000004033 plastic Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004626 polylactic acid Substances 0.000 claims description 8
- 229920001046 Nanocellulose Polymers 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 108700005457 microfibrillar Proteins 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 235000013410 fast food Nutrition 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 229940063583 high-density polyethylene Drugs 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000013583 drug formulation Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
- B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
- B29B7/92—Wood chips or wood fibres
-
- 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
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
- C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/485—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with three or more shafts provided with screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates generally to a method for producing thermoplastic composites comprising nano-cellulose, specifically thermoplastic composites comprising 0.1-75% nano-cellulose by weight.
- the invention furthermore relates to products formed by the thermoplastic composite and articles produced from said thermoplastic composite products.
- Dispersion of nano-cellulose in polymers and products derived from these polymers are known.
- the dispersion is often difficult, for example due to the tendency of the nano-cellulose to agglomerate. It is therefore difficult to get nano-cellulose homogenously dispersed in a polymer, such as a thermoplastic.
- Dispersions of nano-cellulose can be concentrated by various means, including reverse osmosis and distillation of water. The viscosity increases significantly upon concentration.
- nano-cellulose has a tendency to re-agglomerate rather quickly, therefore incorporating as much nano-cellulose as possible in plastics is difficult. Avoiding re-agglomeration and achieving a homogenous distribution in the polymer will furthermore be a compromise between performance and costs.
- MALA Maleic anhydride
- MALA has traditionally been used as additive, e.g. at 1-6 %, typically 2-3 % wt., for increasing the adhesion between plastic and wooden material.
- MALA has a range of negative properties, including toxicity, smell, cost and corrosive stress for process equipment.
- thermoplastics and cellulose use surface-active ingredients, known as surfactants, to enable mixing of thermoplastics and cellulose in general: US 2008 0241 262 (nano-shells), US 2016 0303 102 (drug formulations), WO 2010 072 665 (Nano-fibers for textiles produced by electrospinning), US 2011 0250 256 (Genic Co, Seoul, Korea, Nano-web porous films, including gelling agent).
- surfactants surface-active ingredients
- CAB cellulose acetate butyrate
- a planetary extruder is a type of extruder generally comprising a central extruder spindle surrounded by a plurality of planetary spindles around its circumference.
- the planetary spindles are sometimes arranged with threads or inclined tracks, having an angle of approximately 45°.
- the barrel in which the spindles are commonly arranged, may be arranged with tracks on its inner surface to mesh with the planetary spindles.
- An example of a planetary extruder is disclosed in US Patent US4268176A.
- Another version of a planetary extruder is disclosed in US Patent US9061442B2, both of which are incorporated herein by reference.
- a plurality of screws also referred to as degassing screws, surround a central shaft. Both of these two extruders display how a plurality of screws may provide both a high level of kneading, as well as efficient degassing.
- Nano-cellulose shall be understood as cellulosic fibres, in particular cellulosic fibres obtained by defibring of lignocellulosic raw-material, optionally bleached, with typical fibre lengths of 10 nanometres up to 100 micrometres, wherein a size distribution of non-agglomerated fibres may peak at approximately 50-500 nanometres.
- the term may be understood as for example nanocrystalline cellulose (NCC) or microfibrillar cellulose (MFC).
- Thermoplastics shall be considered as the group of polymers which melt at a temperature in the range 60 - 200°C, comprising polyolefins, including polyethylene (PE), polypropylene (PP), polyesters including polyethylene terephthalate (PET), polylactic acid (PLA) and other plastics which can be processed in compounding devices such as twin-screw compounding machines or in extruders, specifically planetary extruders.
- polyolefins including polyethylene (PE), polypropylene (PP), polyesters including polyethylene terephthalate (PET), polylactic acid (PLA) and other plastics which can be processed in compounding devices such as twin-screw compounding machines or in extruders, specifically planetary extruders.
- aqueous dispersion is brought into contact with a hydrophobic polymer with the intention to transfer ingredients from the aqueous phase to the polymer.
- a compounding device shall denote any intensive mixer, such as kneaders, batch mixers, continuous mixers, extruders capable of mixing materials and standard twin-screw compounders which are able to mix polymer blends under pressure, and which allow venting and removal of gases such as water vapour in a controlled manner, e.g. by pressure relief valves.
- An object of the present invention is to overcome at least some of the difficulties outlined above. This is done by providing a method for producing a thermoplastic composite comprising 0.1-75 % by weight nano-cellulose, comprising the following steps: providing nano-cellulose as a waterborne dispersion wherein said dispersion comprises 0.2-30% by weight nano-cellulose; providing molten thermoplastic in a compounding device which allows for both mixing and controlled venting of gas through a venting system of the compounding device; adding said nano-cellulose dispersion to the compounding device and mixing said nano-cellulose dispersion and the thermoplastic in said compounding device to form the thermoplastic composite, wherein the mixing is performed at a temperature of 60-200° C and at a pressure of 1 bar or higher, preferably 10 bar or higher; removing water in the form of water vapour by controlled venting through the venting system of the compounding device; and forming the composite into a solidified composite product, such as, but not limited to, an extrusion product, a pellet or a film;
- nano-cellulose is highly prone to agglomeration into larger clusters of cellulose, it is provided in a water dispersion at low concentrations of 0.2-30% by weight nano-cellulose.
- the dispersion comprises a lot of water which must be removed.
- the water presents difficulties when striving for a homogenous dispersion of nano-cellulose in a thermoplastic due to the hydrophobic nature of the polymer. Therefore, controlling the temperature, pressure, mixing and venting is vital for achieving a homogenous dispersion.
- nano-cellulose may replace MALA in plastic / wood composites, i.e. adhesion between macroscopic, micrometre to millimetre size wooden material and plastic is improved by incorporation of nanocellulose.
- the nano-cellulose is cellulosic fibres, preferably cellulosic fibres obtained by defibring of lignocellulosic raw-material, and with fibre lengths of 10 nanometres to 100 micrometres.
- the nano-cellulose is one of nanocrystalline cellulose (NCC) or microfibrillar cellulose (MFC).
- the nano-cellulose dispersion further comprises an alcohol, preferably below 50% by weight.
- the nano-cellulose dispersion is added continuously to the compounding device.
- the nano-cellulose dispersion is added to the compounding device by use of a pressure pump.
- the thermoplastic is an organic polymer with a molecular weight above 10 000 g/mol.
- the thermoplastic is based on monomers comprising ethylene, and furthermore being selected from: polyester, polyolefins, high density polyethylene, propylene, butene, isoprene, butadiene, terephthalic acid, lactic acid (PLA), glycols, thermoplastic elastomers including SBS, SIS and SEBS or a mixture thereof.
- the method further comprises the step of, after forming of the composite, drying the composite to a residual water content of below 10% by weight, preferably below 5% and more preferably below 1 % by treatment in a drying device.
- the nano-cellulose dispersion further comprises carbon nano tubes (CNT) in an amount such that the content of CNT in a final composite composition ranges from 0.1 % by weight to 10% by weight, and wherein the CNT may be dispersed in the nano-cellulose dispersion by one of: dispersion by ultrasound separately in water and thereafter mixed with nano-cellulose water dispersion; or dispersed directly in the nano- cellulose dispersion.
- CNT carbon nano tubes
- the CNT gives the composite many advantageous properties e.g. electrical conductivity or microwave absorbency. Furthermore, mixing the CNT/cellulose dispersion with thermoplastics results in a faster phase transfer of CNT/cellulose into the thermoplastic compared with the phase transfer rate of only nano-cellulose. This is for example due to the increased hydrophobicity of the CNT/cellulose complex.
- the compounding device is a twin-screw compounder.
- the compounding device is an extruder comprising a screw assembly comprising more than two extruder screws.
- the more than two extruder screws are arranged surrounding a central axis of the extruder, wherein the central axis is one of a central screw or a central drive shaft.
- the compounding device is a planetary extruder.
- the planetary extruder is a compounding device which provides a large polymer surface available for the nano-cellulose dispersion and thereby improves the dispersion of nano-cellulose in the polymer.
- the planetary extruder is highly effective in shearing both molten plastics and agglomerated nano-cellulose. This is partly due to the threaded surfaces of the central and the planetary spindles. This way, the extruder constantly provides much more new, available surface than many other extruder types. New surface is important for the adsorption and incorporation of nano- cellulose in the polymer.
- the planetary extruder is furthermore equally efficient at lower (e.g. 0.5%) and higher (e.g. 25%) concentration of nano-cellulose in the dispersion.
- a composite product comprising 0.1-75 % by weight nano-cellulose and a thermoplastic, produced by the method according to the present disclosure.
- the thermoplastic is produced from recycled material, preferably with a content of a polymer from a single source of at least 90 %, such as high-density polyethylene from plastic bottles, low-density polyethylene films from agricultural use, or PLA from food packaging from fast food restaurants.
- thermoplastic composite comprising a thermoplastic polymer and 0.1-75% by weight nano-cellulose.
- the method results in thermoplastics comprising well dispersed nano-cellulose.
- the nano-cellulose may give the thermoplastic improved properties such as increased impact resistance, increased tensile strength, and improved barrier properties.
- Improved barrier properties may for example be provided by producing a film made of the thermoplastic composite, wherein the nano-cellulose may prevent or lessen diffusion of air through the film.
- the disclosed method is energy-efficient, economic and scalable.
- the method generally comprises mixing of a liquid or molten thermoplastic and nano-cellulose provided as water-borne dispersion in a compounding device.
- a liquid or molten thermoplastic and nano-cellulose provided as water-borne dispersion in a compounding device.
- nano-cellulose transfers to the organic polymer phase, and water is vaporized and removed through a venting system of the compounding device.
- the waterborne nano-cellulose dispersion comprises 0.2-30% by weight, preferably 0.2-10% by weight, more preferably 0.3-5% by weight nano-cellulose and the water removal from the nano-cellulose dispersion during mixing is at least 90% by weight, preferably at least 95%.
- the thermoplastic is an organic polymer with a molecular weight above 10 000 g/mol.
- the thermoplastic is based on monomers comprising ethylene.
- the thermoplastic may for example be selected from: polyester, polyolefins, high density polyethylene, propylene, butene, isoprene, butadiene, terephthalic acid, lactic acid (PLA), glycols, thermoplastic elastomers including SBS, SIS and SEBS or a mixture thereof.
- the thermoplastic may for example be, but is not limited to, polyethylene (PE) and polypropylene (PP) in the case of polyolefins, or polyethylene terephthalate (PET), polylactic acid (PLA) or similar in the case of polyesters.
- the thermoplastic is produced from recycled material, preferably with a content of a polymer from a single source of at least 90 %, wherein the single source may be for example high- density polyethylene from plastic bottles, low-density polyethylene films from agricultural use, or PLA from food packaging.
- simple one-screw extruders may be used as the compounding device.
- more advanced compounding devices may be used such as twin-screw extruders or planetary extruders.
- One technical problem to be solved by the invention is therefore to provide a large surface of hydrophobic plastic for the polar phase of nano-cellulose, in order to facilitate the efficient transfer of nano-cellulose to the organic polymer phase without the nano-cellulose re-agglomerating to micrometre or millimetre size particles during the removal of water.
- one-screw or twin-screw extruders provide a sufficiently large polymer surface for the nano-cellulose dispersion.
- an extruder having a screw assembly comprising more than two screws in order to provide an even larger contact surface between the polymer and the nano-cellulose dispersion.
- the screw assembly comprising more than two screws should be understood as more than two screws arranged in the same section of the extruder, being arranged essentially in parallel.
- the extruder may furthermore comprise a plurality of sections along its length, each comprising a screw assembly comprising one or a plurality of screws.
- the extruder comprising more than two screws enables both efficient mixing with little mechanical stress on the wooden or cellulosic fibres, as well as removal of water as steam through one or more venting zones.
- the extruder has a modular structure, with adjustable compounding and degassing sections, and can therefore be adapted to the compound at hand and is suitable for various combinations of thermoplastic and nano-cellulose. Low concentrations of cellulose in water require more intensive or longer agitation times. Various degassing stations are advisable. As the volume of material decreases significantly upon water removal, it is practical to produce master batches with different residual water levels, and the final dry product is produced from master batches.
- the extruder comprising more than two screws is a planetary extruder.
- the waterborne nano-cellulose dispersion comprises 0.2-30% by weight, preferably 0.2-10% by weight, more preferably 0.3-5% by weight nano-cellulose.
- the nano-cellulose dispersion is added to the compounding device containing the molten thermoplastic by means of a pressure pump.
- the nano-cellulose dispersion further comprises up to 50% of an alcohol, preferably ethanol.
- an alcohol preferably ethanol.
- other alcohols are possible such as isopropanol or methanol.
- the alcohol is also vaporized during mixing in the compounding device and let off through the venting system of the compounding device.
- the temperature during mixing of the composite in the compounding device is preferably 60-200°C, more preferably 100-200°C. Furthermore, a pressure inside the compounding device is kept at above 1 bar, preferably above 10 bar. To achieve this, the venting system of the compounding device allows for controlled venting in order to both release water vapor, and possibly alcohol, as well as keeping the desired pressure in the compounding device. The venting system furthermore provides that the water/alcohol is not removed too quickly, in order to make sure that the nano-cellulose is sufficiently dispersed in the thermoplastic before vaporizing.
- additives are added to the compounding device to be mixed with the composite.
- Additives may for example be, but are not limited to, functional additives such as carbon nano tubes (CNT) for imparting e.g. electrical conductivity or microwave absorbency, antioxidants, colorants, or fillers including wood fibres and mineral fillers such as silica, titanium dioxide, or other fillers, preferably with small particle sizes.
- functional additives such as carbon nano tubes (CNT) for imparting e.g. electrical conductivity or microwave absorbency, antioxidants, colorants, or fillers including wood fibres and mineral fillers such as silica, titanium dioxide, or other fillers, preferably with small particle sizes.
- polar particles such as fine silica or titanium dioxide can be added, e.g. at concentrations of 0.2-3% wt. of the final composite product. This is beneficial for the preservation of the nano-size distribution, i.e. for the prevention of agglomeration and subsequent presence of agglomerated cellulose particles in the final products.
- wooden materials including medium-density fibres (MDF) or wooden waste materials are added, in weight ratios of thermoplastic I wooden material between 5/1 to 1/5.
- materials for economically competitive composites can be obtained, alternatively pellets and sticks for use as combustible materials are prepared.
- These articles are useful for cooking food in outdoor activities or in developing countries where food is prepared over open fire.
- the a.m. products can replace firewood, and are even preferred to firewood due to higher energy density, clean combustion profile and due to the fact that recycling of plastic waste, in particular low density polyethylene is enabled.
- one of the main advantages of the nano-cellulose is to increase adhesion between the plastic and the wooden material, thereby significantly reducing, or even eliminating the need to add adhesion increasing agents such as MALA.
- the content of nano-cellulose is typically below 1 % by weight.
- residual water from the nano-cellulose dispersion may be used as blowing agent to afford porous products with higher surface, e.g. for easier use as combustible fuel.
- CNT carbon nano tubes
- the CNT are dispersed in water using ultrasound through known procedures.
- the CNT water dispersion is added to the nano-cellulose water dispersion, and the mixture is further dispersed in order to afford complexes of CNT and nano-cellulose.
- CNT may also be directly dispersed with ultrasound in the nano-cellulose water dispersion; however, increased temperatures are required in that case.
- Mixing said CNT/cellulose dispersion with thermoplastics results in a faster phase transfer of CNT/cellulose into thermoplastics compared with the phase transfer rate of pure nano-cellulose. This is for example due to the increased hydrophobicity of the CNT/cellulose complex.
- Products resulting from the CNT enhanced composite are characterized by increased electrical conductivity and microwave absorbance.
- the weight ratio CNT I nano-cellulose vary depending on intended use, e.g. between 5:95 to 95:5, but a 30:70 to 70:30 weight ratio is preferred.
- the desired homogeneity is reached and/or the desired amount of nano-cellulose is dispersed in the polymer.
- Homogeneity may for example be measured by visual measuring, using a suitable visual aid, of an average distance between the individual dispersed nano-cellulose fibres.
- the desired amount of nano-cellulose is achieved by performing the method of the present disclosure one time. In another embodiment the method of the present disclosure is repeated a plurality of times to achieve the desired amount of nano-cellulose in the polymer.
- thermoplastic composite product having improved mechanical and other properties, including barrier properties.
- such products may be typical extrusion products, or pellets for example for use in injection moulding machines, or films.
- the product may be used on its own, or further processed into a composite article. Forming into an article may be performed for example by extrusion, pressure-moulding, injection-moulding, blow-moulding, rotation-moulding or other suitable method.
- the article may for example be articles for cooking or heating, extruded articles such as tubes or profiles for fencing and terraces and construction, injection- moulded or pressure-moulded articles for furniture and car interior purposes, films for packaging coatings, adhesives, sealants, or other end-uses.
- the mixed raw materials or products can be further dried to a residual water content of below 10% by weight, preferably below 5% and more preferably below 1 % by treatment in a drying device for example by vacuum.
- thermoplastic composites comprising nano-cellulose and its derived products
Abstract
L'invention concerne un procédé pour la production d'un composite thermoplastique comprenant 0,1 à 75 % en poids de nanocellulose, comprenant les étapes suivantes : l'utilisation de nanocellulose sous forme d'une dispersion à base aqueuse, ladite dispersion comprenant 0,2 à 30 % en poids de nanocellulose ; l'introduction de thermoplastique fondu dans un dispositif de mélange qui permet à la fois le mélange et l'évacuation contrôlée de gaz par un système d'évent du dispositif de mélange ; l'addition de ladite dispersion de nanocellulose dans le dispositif de mélange et le mélange de ladite dispersion de nanocellulose et du thermoplastique dans ledit dispositif de mélange pour former le composite thermoplastique, le mélange étant effectué à une température de 60 à 200 °C et à une pression supérieure ou égale à 1 bar ; l'élimination d'eau sous la forme de vapeur d'eau par évacuation contrôlée par le système d'évent du dispositif de mélange ; et la transformation du composite en un produit composite solidifié, tel que, mais non exclusivement, un produit d'extrusion, une pastille ou un film, l'élimination d'eau provenant de la dispersion de nanocellulose pendant le mélange étant d'au moins 90 % en poids, de préférence d'au moins 95 %.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268176A (en) | 1979-01-12 | 1981-05-19 | Hermann Berstorff Maschinenbau Gmbh | Planetary extruder for thermoplastics material |
US20080241262A1 (en) | 2004-03-29 | 2008-10-02 | The University Of Houston System | Nanoshells and Discrete Polymer-Coated Nanoshells, Methods For Making and Using Same |
WO2010072665A1 (fr) | 2008-12-23 | 2010-07-01 | Basf Se | Modification de nanofibres ou de mésofibres ou de produits textiles plats produits par électrofilage à l'aide de protéines amphiphiles |
US20110250256A1 (en) | 2007-08-10 | 2011-10-13 | Genic Co, Ltd. | Dissolvable Nano Web Porous Film and Method of Preparing the Same |
US8105682B2 (en) | 2006-09-01 | 2012-01-31 | The Regents Of The University Of California | Thermoplastic polymer microfibers, nanofibers and composites |
US20120292578A1 (en) * | 2009-11-18 | 2012-11-22 | Alexander Bacher | METHOD FOR PRODUCING COMPOSITE MATERIALS BASED ON POLYMERS AND CARBON NANOTUBES (CNTs), COMPOSITE MATERIALS PRODUCED IN THIS WAY AND USE THEREOF |
US20130133848A1 (en) | 2008-06-17 | 2013-05-30 | Akzo Nobel N.V. | Cellulosic product |
US9061442B2 (en) | 2013-03-01 | 2015-06-23 | Gneuss Gmbh | Extruder |
US20160303102A1 (en) | 2013-12-05 | 2016-10-20 | Alrise Biosystems Gmbh | Process for the production of drug formulations for oral administration |
JP2019044164A (ja) * | 2018-08-23 | 2019-03-22 | 旭化成株式会社 | セルロース強化樹脂組成物の製造方法 |
-
2021
- 2021-06-08 WO PCT/EP2021/065227 patent/WO2022033743A1/fr active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268176A (en) | 1979-01-12 | 1981-05-19 | Hermann Berstorff Maschinenbau Gmbh | Planetary extruder for thermoplastics material |
US20080241262A1 (en) | 2004-03-29 | 2008-10-02 | The University Of Houston System | Nanoshells and Discrete Polymer-Coated Nanoshells, Methods For Making and Using Same |
US8105682B2 (en) | 2006-09-01 | 2012-01-31 | The Regents Of The University Of California | Thermoplastic polymer microfibers, nanofibers and composites |
US20110250256A1 (en) | 2007-08-10 | 2011-10-13 | Genic Co, Ltd. | Dissolvable Nano Web Porous Film and Method of Preparing the Same |
US20130133848A1 (en) | 2008-06-17 | 2013-05-30 | Akzo Nobel N.V. | Cellulosic product |
WO2010072665A1 (fr) | 2008-12-23 | 2010-07-01 | Basf Se | Modification de nanofibres ou de mésofibres ou de produits textiles plats produits par électrofilage à l'aide de protéines amphiphiles |
US20120292578A1 (en) * | 2009-11-18 | 2012-11-22 | Alexander Bacher | METHOD FOR PRODUCING COMPOSITE MATERIALS BASED ON POLYMERS AND CARBON NANOTUBES (CNTs), COMPOSITE MATERIALS PRODUCED IN THIS WAY AND USE THEREOF |
US9061442B2 (en) | 2013-03-01 | 2015-06-23 | Gneuss Gmbh | Extruder |
US20160303102A1 (en) | 2013-12-05 | 2016-10-20 | Alrise Biosystems Gmbh | Process for the production of drug formulations for oral administration |
JP2019044164A (ja) * | 2018-08-23 | 2019-03-22 | 旭化成株式会社 | セルロース強化樹脂組成物の製造方法 |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 202003, Derwent World Patents Index; AN 2020-32553A, XP002804074 * |
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