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WO2024124291A1 - Composite algal - Google Patents

Composite algal Download PDF

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Publication number
WO2024124291A1
WO2024124291A1 PCT/AU2023/051293 AU2023051293W WO2024124291A1 WO 2024124291 A1 WO2024124291 A1 WO 2024124291A1 AU 2023051293 W AU2023051293 W AU 2023051293W WO 2024124291 A1 WO2024124291 A1 WO 2024124291A1
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WO
WIPO (PCT)
Prior art keywords
composition
algal
algae
polymer
derived material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU2023/051293
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English (en)
Inventor
Lakshmi Krishnan
Unnikrishnan KUZHIUMPARAMBIL
Peter Ralph
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Technology Sydney
Original Assignee
University of Technology Sydney
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2022903824A external-priority patent/AU2022903824A0/en
Application filed by University of Technology Sydney filed Critical University of Technology Sydney
Publication of WO2024124291A1 publication Critical patent/WO2024124291A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • 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
    • 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—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • 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
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present disclosure broadly relates to plastic compositions comprising algae biomass or algae-derived materials.
  • Plastics are used extensively in all areas of modern society. However, the manufacture of conventional plastics is energy intensive, relies on non-renewable resources and has a large carbon footprint. Plastic waste also represents an environmental problem as conventional plastics are not biodegradable.
  • Bioplastics seek to address some of these problems by forming plastics incorporating renewable materials, such as plant-derived materials. Such plastics may have a lower carbon footprint, utilise renewable resources, and be biodegradable. However, the high cost and inferior performance of bioplastics remain obstacles to their widespread adoption.
  • composition comprising or consisting of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives, wherein the algal biomass or algae-derived material are obtained from an algae selected from Kappaphycus alvarezii and Euchema denticulatum.
  • the composition may consist of about 40-60% w/w of a non-algal polymer; and about 40-60% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 40% w/w of a non-algal polymer; and about 60% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 50% w/w of a non-algal polymer; and about 50% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 60% w/w of a non-algal polymer; and about 40% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 20-80% w/w of a non-algal polymer; about 20- 80% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • the composition may consist of about 30-70% w/w of a non-algal polymer; about 30- 70% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • the composition may consist of about 30-70% w/w of a non-algal polymer; about 30- 70% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the composition may consist of about 60-70% w/w of a non-algal polymer; about 30- 40% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the composition may consist of about 60% w/w of a non-algal polymer; about 35% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the algae-derived material may be a sulfated polysaccharide.
  • the sulfated polysaccharide may be selected from the group consisting of carrageenan, ulvan, and fucoidan.
  • the sulfated polysaccharide may be ulvan.
  • the sulfated polysaccharide may be carrageenan.
  • the non-algal polymer may be selected from the group consisting of polycaprolactone (PCL), poly(lactic acid) (PLA), low density polyethelene (LDPE), polypropylene (PP) and poly(hydroxybutyrate) (PHB).
  • PCL polycaprolactone
  • PLA poly(lactic acid)
  • LDPE low density polyethelene
  • PP polypropylene
  • PHB poly(hydroxybutyrate)
  • the non-algal polymer may be PCL.
  • the PCL may have a number average molecular weight of between about 50,000 and 100,000.
  • the PCL may have a number average molecular weight of about 80,000.
  • the one or more additives may be selected from the group consisting of polyethylene glycol, citric acid, polyethylene glycol dimethacrylate, urea, glycerol, choline chloride, a beeswax product, and palmitic acid.
  • the one or more additives may be a beeswax product.
  • the one or more additives may be palmitic acid.
  • the composition may not be in the form of a film, a microbead, a nanoparticle or a fiber.
  • the composition may be in the form of a block or a pellet.
  • the composition may have a tensile strength of at least 3 MPa measured according to ASTM D638.
  • composition may have an elongation at break of at least 2% measured according to ASTM D638.
  • a method of preparing a composition comprising:
  • Step (i) may be carried out in a twin screw extruder.
  • the elevated temperature may be between about 80 °C and about 150 °C.
  • the method may further comprise:
  • the method may further comprise (iv.a.) compression moulding, injection moulding, thermoforming, blow moulding, calendaring, or extruding the composition in a desired shape.
  • the method may further comprise (iv.b.) 3D printing the composition in a desired shape.
  • the composition may comprise or consist of about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives.
  • the composition may consist of about 40-60% w/w of a non-algal polymer; and about 40-60% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 40% w/w of a non-algal polymer; and about 60% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 50% w/w of a non-algal polymer; and about 50% w/w of algal biomass or algae-derived material.
  • the composition may consist of about 60% w/w of a non-algal polymer; and about 40% w/w of algal biomass or an algae-derived material.
  • the composition may consist of about 20-80% w/w of a non-algal polymer; about 20- 80% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • the composition may consist of about 30-70% w/w of a non-algal polymer; about 30- 70% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • the composition may consist of about 30-70% w/w of a non-algal polymer; about 30- 70% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the composition may consist of about 60-70% w/w of a non-algal polymer; about 30- 40% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the composition may consist of about 60% w/w of a non-algal polymer; about 35% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the algae-derived material may be a sulfated polysaccharide.
  • the sulfated polysaccharide may be selected from the group consisting of carrageenan, ulvan, and fucoidan.
  • the sulfated polysaccharide may be ulvan.
  • the sulfated polysaccharide may be carrageenan.
  • the non-algal polymer may be selected from the group consisting of polycaprolactone (PCL), poly(lactic acid) (PLA), low density polyethelene (LDPE), polypropylene (PP), and poly(hydroxybutyrate) (PHB).
  • PCL polycaprolactone
  • PLA poly(lactic acid)
  • LDPE low density polyethelene
  • PP polypropylene
  • PHB poly(hydroxybutyrate)
  • the non-algal polymer may be PCL.
  • the PCL may have a number average molecular weight of between about 50,000 and 100,000.
  • the PCL may have a number average molecular weight of about 80,000.
  • the one or more additives may be selected from the group consisting of polyethylene glycol, citric acid, polyethylene glycol dimethacrylate, urea, glycerol, choline chloride, a beeswax product, and palmitic acid.
  • the one or more additives may be a beeswax product.
  • the one or more additives may be palmitic acid.
  • composition prepared according to the method of the second aspect of the disclosure.
  • an element means one element or more than one element.
  • Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range.
  • a range of 1 .0 to 5.0 is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 5.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 5.0, such as 2.1 to 4.5.
  • Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited herein is intended to include all higher numerical limitations subsumed therein.
  • Figure 1 Compression moulded blocks formed from compositions according to the disclosure.
  • a blend of algal material, a non-algal polymer, and optionally an additive can provide a bioplastic composition having good strength and elongation properties.
  • Algae are an ideal source of material for bioplastics as they have a high growth yield per area, ability to be grown in non-arable or arid regions, and ability to grow in non-freshwater environments.
  • composition comprising or consisting of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives, wherein the algal biomass or algae-derived material are obtained from an algae selected from Kappaphycus alvarezii and Euchema denticulatum.
  • the composition may comprise about 20-80% w/w of a non- algal polymer, or about 20-30, 20-40, 20-50, 20-60, 20-70, 30-40, 30-50, 30-60, 30-70, 30- 80, 40-50, 40-60, 40-70, 40-80, 50-60, 50-70, 50-80, 60-70, 60-80, or about 70-80% w/w of a non-algal polymer.
  • the composition may comprise about 40-60% w/w of a non-algal polymer.
  • the composition may comprise about 30-70% w/w of a non-algal polymer.
  • the composition may comprise about 60-70% w/w of a non-algal polymer. In some embodiments, the composition may comprise about 20% w/w of a non-algal polymer, or about 30, 40, 50, 60, 70, or about 80% w/w of a non-algal polymer. The composition may comprise about 40% w/w of a non-algal polymer. The composition may comprise about 50% w/w of a non-algal polymer. The composition may comprise about 60% w/w of a non-algal polymer. The composition may comprise about 70% w/w of a non-algal polymer.
  • the composition may comprise about 20-80% w/w of algal biomass or an algae-derived material, or about 20-30, 20-40, 20-50, 20-60, 20-70, 30-40, 30- 50, 30-60, 30-70, 30-80, 40-50, 40-60, 40-70, 40-80, 50-60, 50-70, 50-80, 60-70, 60-80, or about 70-80% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 40-60% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 30-70% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 30-40% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 20% w/w of algal biomass or an algae-derived material, or about 30, 40, 50, 60, 70, or about 80% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 30% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 35% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 40% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 50% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 60% w/w of algal biomass or an algae-derived material.
  • the composition may comprise about 0-20% w/w of one or more additives. That is, the total amount of all of the additives included in the composition is between 0 and 20% w/w.
  • the composition may comprise about 0-2, 0-5, 0-10, 0-15, 2-5, 2-10, 2-15, 2- 20, 5-10, 5-15, 5-20, 10-15, 10-20 or about 15-20% w/w of one or more additives.
  • the composition may comprise about 2-10% w/w of one or more additives.
  • the composition may comprise about 0% of one or more additives, or about 2, 5, 10, 15, or about 20% w/w of one or more additives.
  • the composition may comprise about 5% w/w of one or more additives.
  • Algal biomass refers to material obtained from as-harvested algae with minimal processing, for example limited to only drying and grinding to powder. Algal biomass also refers to algal mass remaining after extraction of high value products such as polysaccharides, proteins, pigments and/or hormones. For example, algal biomass includes the algal mass remaining after the extraction of sulfated polysaccharides or alginate as described below.
  • An algae-derived material refers to a component of algae which has been isolated from as- harvested algae. For example, sulfated polysaccharides and alginate are algae-derived materials that can be isolated from as-harvested algae.
  • Sulfated polysaccharides found in algae which may be included in the composite of the first aspect of the disclosure include carrageenan, ulvan, and fucoidan.
  • the non-algal polymer may be any conventional polymer known to the skilled person which is suitable for forming plastics.
  • the non-algal polymer may be a hydrocarbon-based polymer.
  • the non-algal polymer may be a polyester.
  • the non-algal polymer may be selected from the group consisting of polycaprolactone (PCL), low density polyethylene (LDPE), poly(lactic acid) (PLA), polypropylene (PP) and poly(hydroxybutyrate) (PHB).
  • PCL, PHB and PLA are polyesters.
  • the non-algal polymer is PCL, the PCL may have a number average molecular weight of between about 50,000-100,000, or about 80,000.
  • the one or more additives when present, may serve to improve the elongation properties of the composition without reducing its tensile strength. Without wishing to be bound by theory, the inventors believe that the additives may form ester or amide bonds with the caprolactone and/or or the algal biomass or algae-derived material which alter the strength and elongation properties of the resulting composition, for example by cross-linking. Alternatively or additionally, the inventors believe that the additives may function as plasticisers.
  • the one or more additives may be selected from the group consisting of polyethylene glycol, citric acid, polyethylene glycol dimethacrylate, urea, glycerol, choline chloride, a beeswax product, and palmitic acid.
  • the composition may comprise combinations of additives such as polyethylene glycol and citric acid, urea and choline chloride, or urea and glycerol.
  • additives such as polyethylene glycol and citric acid, urea and choline chloride, or urea and glycerol.
  • each component may be included in equal amounts.
  • the one or more additives are a combination of urea and choline chloride, the urea and choline chloride may be included in a molar ratio of 2:1.
  • the one or more additives may be palmitic acid.
  • the one or more additives may be a beeswax product.
  • the beeswax product may be, for example, a mixture of fatty acid triglycerides, limonene and beeswax, in particular a mixture of about 70-80% w/w fatty acid triglycerides, about 15-20% w/w limonene and about 5% w/w beeswax.
  • the composition may not be in the form of a film, a microbead, a nanoparticle or a fiber.
  • a microbead refers to a bead having a diameter between 1 pm and 1 mm.
  • a nanoparticle refers to a particle having a diameter less than 1 pm.
  • the composition may be provided in the form a block or a pellet, or a plurality of blocks or pellets. Blocks or pellets can then be subject to further processing such as moulding or 3D printing.
  • the composition may have a tensile strength of at least about 3 MPa, as measured by ASTM D638.
  • the composition may have a tensile strength of at least about 4, 5, 6, 7, 8, 9, or about 10 MPa.
  • the composition may have tensile strength of about 5-20 MPa, or about 5-10, 5-15, 10-15, 10-20, or about 15-20 MPa.
  • the composition may have tensile strength of about 5-15 MPa.
  • the composition may have a tensile strength of about 5 MPa, or about 6, 7, 8, 9, 10, 11 , 12 ,13, 14, 15, 16, 17, 18, 19, or about 20 MPa.
  • the composition may have an elongation at break of at least about 2%, as measured by ASTM D638.
  • the composition may have an elongation at break of at least about 5, 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750 or at least about 800%.
  • the composition may have an elongation at break of about 100-800%, or about 2-100, 2-200, 2-300, 2-400, 2-500, 2-600, 2-700, 2-800, 100-200, 100-300, 100-400, 100-500, 100-600, 100-700, 200-300, 200-400, 200-500, 200-600, 200-700, 200-800, 300-400, 300-500, 300- 600, 300-700, 300-800, 400-500, 400-600, 400-700, 400-800, 500-600, 500-700, 500-800, 600-700, 600-800, or about 700-800%.
  • the composition may have an elongation at break of about 100-500%.
  • the composition may have an elongation at break of about 2,% or about 5, 10, 50, 100, 200, 300, 400, 500, 600, 700, or about 800%.
  • composition comprising or consisting of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives.
  • the algal biomass or algae-derived material may be obtained from any suitable algae, such as a microalgae or a macroalgae (i.e. seaweed).
  • suitable algae include algae of the genus Ulva, such as Ulva ohnoi or Ulva lactuca, algae of the genus Kappaphycus, such as Kappaphycus alverizii, algae of the genus Chlorella, such as Chlorella vulgaris, algae of the genus Scenedesmus, algae of the genus Phaeodactylum, such as Phaeodactylum tricornutum.
  • a method of preparing a composition comprising a non-algal polymer, algal biomass or an algae-derived material, and optionally one or more additives, the method comprising:
  • step (i) of the second aspect of the disclosure may be carried out using any suitable means of achieving comprehensive mixing of the components of the composition.
  • step (i) may be carried out in a twin-screw extruder, internal mixer, two roll mill, or single screw extruder.
  • step (i) may be carried out in a twin- screw extruder.
  • step (i) may be repeated once to ensure sufficient mixing. That is, the composition formed in the twin-screw extruder may be fed back in to the hopper of the twin-screw extruder and mixed a second time.
  • step (i) is carried out in a single- or twin- screw extruder, the screw L/D ratio, screw design, and nozzle design can be varied to improve mixing efficiency.
  • the mixing step of step (i) of the second aspect of the disclosure may be carried out at elevated temperature.
  • the elevated temperature may be below 180 °C.
  • the elevated temperature may be about 80-150 °C, or about 80-90, 80-100, 80-110, 80-120, 80-130, 80- 140, 90-100, 90-1 10, 90-120, 90-130, 90-140, 90-150, 100-1 10, 100-120, 100-130, 100-140, 100-150, 110-120, 110-130, 110-140, 110-150, 120-130, 120-140, 120-150, 130-140, 130- 150, or about 140-150 °C.
  • the elevated temperature may be between about 90-130 °C.
  • the non-algal polymer, algal biomass or algae-derived material, and optionally one or more additives may be passed through different zones of the twin screw extruder having different temperatures.
  • the zones may have increasing temperatures in the range of 80-150 °C.
  • the zones may have increasing temperatures in the range of 90-130 °C.
  • the non-algal polymer, algal biomass or algae-derived material, and optionally one or more additives are passed through a first zone at 90 °C, followed by a second zone at 100 °C, followed by a third zone at 1 10 °C, followed by a fourth zone at 120 °C, followed by a fifth zone at 130 °C.
  • the rotation speed of the twin screw extruder may be about 20-120 rpm, or about 20-40, 20-60, 20-80, 20- 100, 40-60, 40-80, 40-100, 40-120, 60-80, 60-100, 60-120, 80-100, 80-120, or about 100-120 rpm.
  • the rotation speed of the twin screw extruder may be about 40-60 rpm.
  • the rotation speed of the twin screw extruder may be about 100-120 rpm.
  • the rotation speed of the twin screw extruder may be about 100-1 10 rpm.
  • the rotation speed of the twin screw extruder may be about 20 rpm, or about 30, 40, 50, 60, 70, 80, 90, 100, 110 or about 120 rpm.
  • the rotation speed of the twin screw extruder may be about 50 rpm.
  • the rotation speed of the twin screw extruder may be about 100 rpm.
  • the rotation speed of the twin screw extruder may be about 110 rpm.
  • the components of the composition may be passed through the twin screw extruder at 1 10 pm, followed by passing the composition through the twins screw extruder a second time at 100 rpm.
  • the rotation speed of the extruder may be reduced to ensure enhanced reactive extrusion or mixing and incorporation of the additive into the composition.
  • the rotation speed of the twin screw extruder may be about 40-60 rpm, or about 50 rpm.
  • the rotation speed of the twin screw extruder may be about 100-120 rpm, or about 100-1 10 rpm.
  • the composition may be extruded and then formed into pellets.
  • the composition may be, in a step (ii), extruded through a die to form a strand of the composition.
  • the strand is formed into pellets, for example by cutting the strand into pellets. Pellets form a convenient substrate for further processing.
  • the method of the second aspect of the disclosure may thus further comprise a step (iv.a.) of compression moulding, injection moulding, thermoforming, blow moulding, calendaring, or extruding the composition in a desired shape, or alternatively, the method may further comprise a step (iv.b.) of 3D printing the composition in a desired shape.
  • the nature of the non-algal polymer, algal biomass or an algae-derived material, and one or more additives, and the amounts thereof in the composition are as described above in relation to the first aspect of the disclosure.
  • a method of preparing a composition comprising a non-algal polymer, algal biomass or an algae-derived material, and optionally one or more additives, the method comprising:
  • the algal biomass or algae-derived material may be obtained from any suitable algae, such as a microalgae or a macroalgae (i.e. seaweed).
  • suitable algae include algae of the genus Ulva, such as Ulva ohnoi or Ulva lactuca, algae of the genus Kappaphycus, such as Kappaphycus alverizii, algae of the genus Chlorella, such as Chlorella vulgaris, algae of the genus Scenedesmus, algae of the genus Phaeodactylum, such as Phaeodactylum tricornutum.
  • composition prepared according to the method of the second aspect of the disclosure.
  • a composition comprising or consisting of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives, wherein the algal biomass or algae-derived material are obtained from an algae selected from Kappaphycus alvarezii and Euchema denticulatum.
  • composition of form 1 consisting of: about 40-60% w/w of a non-algal polymer; and about 40-60% w/w of algal biomass or an algae-derived material.
  • composition of form 1 or form 2 consisting of: about 40% w/w of a non-algal polymer; and about 60% w/w of algal biomass or an algae-derived material.
  • composition of form 1 or form 2 consisting of: about 50% w/w of a non-algal polymer; and about 50% w/w of algal biomass or an algae-derived material.
  • composition of form 1 or form 2 consisting of: about 60% w/w of a non-algal polymer; and about 40% w/w of algal biomass or an algae-derived material.
  • composition of form 1 consisting of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • composition of form 1 or form 6 consisting of: about 30-70% w/w of a non-algal polymer; about 30-70% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • composition of any one of forms 1 , 6, and 7, consisting of: about 30-70% w/w of a non-algal polymer; about 30-70% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • composition of any one of forms 1 , and 6 to 8, consisting of: about 60-70% w/w of a non-algal polymer; about 30-40% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • composition of any one of forms 1 , and 6 to 9, consisting of: about 60% w/w of a non-algal polymer; about 35% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • the composition of form 11 wherein the sulfated polysaccharide is selected from the group consisting of carrageenan, ulvan, and fucoidan.
  • composition of form 11 or form 12, wherein the sulfated polysaccharide is carrageenan.
  • composition of any one of forms 1 to 14, wherein the non-algal polymer is selected from the group consisting of polycaprolactone (PCL), poly(lactic acid) (PLA), low density polyethelene (LDPE), polypropylene (PP) and poly(hydroxybutyrate) (PHB).
  • PCL polycaprolactone
  • PLA poly(lactic acid)
  • LDPE low density polyethelene
  • PP polypropylene
  • PHB poly(hydroxybutyrate)
  • composition of form 16 wherein the PCL has a number average molecular weight of between about 50,000 and 100,000.
  • composition of form 16 or form 17, wherein the PCL has a number average molecular weight of about 80,000.
  • composition of any one of forms 1 to 18, wherein the one or more additives are selected from the group consisting of polyethylene glycol, citric acid, polyethylene glycol dimethacrylate, urea, glycerol, choline chloride, a beeswax product, and palmitic acid.
  • composition of any one of forms 1 to 21 wherein the composition is not in the form of a film, a microbead, a nanoparticle or a fiber.
  • a method of preparing a composition comprising a non-algal polymer, algal biomass or an algae-derived material, and optionally one or more additives, the method comprising:
  • step (i) is carried out in a twin screw extruder.
  • composition comprises or consists of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 0-20% w/w of one or more additives.
  • composition consists of: about 40-60% w/w of a non-algal polymer; and about 40-60% w/w of algal biomass or an algae-derived material.
  • composition consists of: about 40% w/w of a non-algal polymer; and about 60% w/w of algal biomass or an algae-derived material.
  • composition consists of: about 50% w/w of a non-algal polymer; and about 50% w/w of algal biomass or algae-derived material.
  • composition consists of: about 60% w/w of a non-algal polymer; and about 40% w/w of algal biomass or an algae-derived material.
  • composition consists of: about 20-80% w/w of a non-algal polymer; about 20-80% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • composition consists of: about 30-70% w/w of a non-algal polymer; about 30-70% w/w of algal biomass or an algae-derived material; and about 2-10% w/w of one or more additives.
  • composition consists of: about 30-70% w/w of a non-algal polymer; about 30-70% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • any one of forms 26 to 32, and 37 to 39, wherein the composition consists of: about 60-70% w/w of a non-algal polymer; about 30-40% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • 41 The method of any one of forms 26 to 32, and 37 to 40, wherein the composition consists of: about 60% w/w of a non-algal polymer; about 35% w/w of algal biomass or an algae-derived material; and about 5% w/w of one or more additives.
  • non-algal polymer is selected from the group consisting of polycaprolactone (PCL), poly(lactic acid) (PLA), low density polyethelene (LDPE), polypropylene (PP), and poly(hydroxybutyrate) (PHB).
  • PCL polycaprolactone
  • PLA poly(lactic acid)
  • LDPE low density polyethelene
  • PP polypropylene
  • PHB poly(hydroxybutyrate)
  • any one of forms 26 to 49, wherein the one or more additives are selected from the group consisting of polyethylene glycol, citric acid, polyethylene glycol dimethacrylate, urea, glycerol, choline chloride, a beeswax product, and palmitic acid.
  • Carrageenan was extracted from Kappaphycus alverizii according to the procedure of Carbohydrate Polymers, 136 (2016), p. 930-935. Briefly, the algae was treated with a deep eutectic solution (ethylene glycol: choline chloride in 2:1 molar ratio) in an autoclave at 120 °C and 1 psi pressure for 20 minutes. The solids were then washed thoroughly with water and dried in oven till no further weight loss is noted. This dried mass was powdered in a grain grinder and sieved through 2-micron sieve.
  • a deep eutectic solution ethylene glycol: choline chloride in 2:1 molar ratio
  • Ulvan was extracted from Ulva lactuca according to the procedure of J. Phycol. 45 (2009), p. 962-973. Briefly, the algae was refluxed in sodium oxalate (0.5 M) at 85 °C for 2 hours. The solids were then filtered and washed.
  • Algal biomass was prepared by washing harvested algae and drying. The dried algae was powdered and sieved, for example with a 2 pm sieve. Algal biomass may also be obtained following extraction of harvested algae using the methods described above, or following extraction with acetone or ethanol.
  • Blends were prepared according to Table 1 below and passed twice through a Collin ZK 12X 24D twin screw extruder. The initial pass was carried out at 110 rpm with zone temperature of 90/100/110/120/130 °C. The extruded strand was cooled and pelletised. The pellets were fed back into the hopper and a second pass was carried out at 100 rpm with zone temperature of 90/100/110/120/130 °C. The extruded strand following the second pass was again cooled and pelletised. The pellets were used for compression moulding or 3D printing as described below.
  • composition were prepared as above, except that mixing speed was reduced to 50 rpm.
  • Compression moulding was carried out in a 30-ton machine with heated platens. The pellets obtained above were preheated to 1 10 °C and the mould closed. Pressure (100 bar) was applied for five minutes. The mould was cooled to 35 °C and parts were ejected. Compression moulded blocks are depicted in Figure 1. 3D Printing
  • Testing was carried out in accordance with ASTM D638.
  • Dumbbell specimens of ASTM Type IV dimensions were compression moulded as described above.
  • the test specimens were loaded in a Shimadzu AGS-X universal testing machine. Testing was carried out at a speed of 10 mm/s with a 10 kN load cell.
  • the tensile strength and elongation at break were calculated from the raw data obtained from the machine.
  • Tensile strength at break measures the maximum stress a plastic specimen can withstand while being stretched before breaking and is measured as the force per unit cross sectional area (MPa or psi).
  • the elongation at break or ultimate elongation is the percentage increase in length that occurs before it breaks under tension and is expressed in % with respect to the initial length.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

La présente invention concerne une composition comprenant ou constituée par environ 20 à 80 % p/p d'un polymère non algal ; d'environ 20 à 80 % p/p de biomasse algale ou d'une matière dérivée d'algues ; et d'environ 0 à 20 % p/p d'un ou plusieurs additifs, la biomasse algale ou la matière dérivée d'algues étant obtenue à partir d'algues choisies parmi Kappaphycus alvarezii et Euchema denticulatum, ainsi que son procédé de préparation.
PCT/AU2023/051293 2022-12-14 2023-12-13 Composite algal Ceased WO2024124291A1 (fr)

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AU2022903824A AU2022903824A0 (en) 2022-12-14 Algal composite

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060117999A1 (en) * 2004-12-03 2006-06-08 Council Of Scientific & Industrial Research Process of preparation of biodegradable films from semi refined kappa carrageenan
WO2021186477A1 (fr) * 2020-03-19 2021-09-23 Sea6 Energy Pvt. Ltd. Composite, procédé de préparation du composite et sa mise en œuvre
WO2022043691A1 (fr) * 2020-08-26 2022-03-03 Solublue Ltd Matériau composite biodégradable
GB2620613A (en) * 2022-07-14 2024-01-17 Notpla Ltd Methods

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8524811B2 (en) * 2009-04-28 2013-09-03 Kimberly-Clark Worldwide, Inc. Algae-blended compositions for thermoplastic articles
FR3012817B1 (fr) * 2013-11-07 2017-03-24 Super Film Ambalaj San Tic A S Composition a base de polymeres pour la fabrication de produits plastiques degradables dans l'environnement et produits plastiques obtenus
FR3041351B1 (fr) * 2015-09-17 2020-01-24 Eranova Procede de preparation d'une poudre d'algues a teneur reduite en proteines et composition bioplastique formulee a partir d'une telle poudre

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060117999A1 (en) * 2004-12-03 2006-06-08 Council Of Scientific & Industrial Research Process of preparation of biodegradable films from semi refined kappa carrageenan
WO2021186477A1 (fr) * 2020-03-19 2021-09-23 Sea6 Energy Pvt. Ltd. Composite, procédé de préparation du composite et sa mise en œuvre
WO2022043691A1 (fr) * 2020-08-26 2022-03-03 Solublue Ltd Matériau composite biodégradable
GB2620613A (en) * 2022-07-14 2024-01-17 Notpla Ltd Methods

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