WO2024102010A1 - Composition de polymère thermoplastique biodégradable et ses procédés de fabrication - Google Patents

Composition de polymère thermoplastique biodégradable et ses procédés de fabrication Download PDF

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Publication number
WO2024102010A1
WO2024102010A1 PCT/PL2023/050092 PL2023050092W WO2024102010A1 WO 2024102010 A1 WO2024102010 A1 WO 2024102010A1 PL 2023050092 W PL2023050092 W PL 2023050092W WO 2024102010 A1 WO2024102010 A1 WO 2024102010A1
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Prior art keywords
starch
composition
gum rosin
substances
mixture
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PCT/PL2023/050092
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English (en)
Inventor
Maciej Sienkiewicz
Justyna Kucinska-Lipka
Robert SZWABIS
Piotr Nadolski
Edyta PILAT
Przemyslaw GNATOWSKI
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Lab Bio Sp. Z O.O.
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Publication of WO2024102010A1 publication Critical patent/WO2024102010A1/fr

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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
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • C08L5/04—Alginic acid; Derivatives thereof
    • 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
    • C08L5/06—Pectin; Derivatives thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates

Definitions

  • the object of the invention is a biodegradable thermoplastic polymer composition based on starch reinforced with natural cellulose fillers and methods for its manufacture, applicable to the production of disposable and reusable products or packaging materials in particular for food contact.
  • Polish patent Pat.216930 discloses a method for manufacturing thermoplastic starch for disposable packaging by mixing corn starch in the amount of 50-80 parts by weight with plasticizer in the form of glycerin in the amount of 20-50 parts by weight, heating the mixture obtained in this way to a temperature of 60-100°C and draining the water. The premix is conditioned for 24 h, then plasticized by shear forces at 130-150°C, extruded in the temperature range of 150-180°C, and granulated.
  • Polish patent application no. P.433862 discloses a method of manufacturing thermoplastic starch for industrial applications in the production of utility products by injection molding and blow molding.
  • the method consists in mixing starch, with at least one plasticizer from the group including citric acid, water, glycerol, sorbitol for a time covering the range from 1 to 9 h at 60-120°C, with the content of citric acid in the mixture being at most 5 wt.%.
  • the applied ratio of starch to plasticizer varies between 2:1 and 20:1.
  • the method sequentially involves extrusion of the pre-mix directly after mixing (in the temperature range of 130-150°C) without conditioning, cooling of the extrudate and optional granulation.
  • thermoplastic starch which causes esterification and crosslinking of starch, thus increasing the brittleness of the resulting product.
  • citric acid in a preferably variant of the invention significantly limits the possibility of using the thermoplastic starch obtained in this way to form its compositions with other biopolymers, since citric acid decomposes at a temperature of about 175°C, which is below the processing temperature of most compostable polyesters such as PLA (polylactide), for example, or PBAT (polybutylene adipate terephthalate). This decomposition probably manifests itself as outgassing and mechanical weakening of injection moldings or extrusions after the extrusion process.
  • An inconvenience in the method according to the invention is also the requirement to mix native starch with the plasticizer at temperatures above 60°C, which can cause an uncontrolled reaction of starch cross-linking by citric acid (multi-carboxylic acid) through polycondensation, consequently making it more difficult to process by increasing melt flow rates and causing difficulties in the possible recycling of usable products made with it.
  • Polish Patent Description Pat.207301 discloses a method of manufacturing a biodegradable polymer material based on renewable raw materials for disposable packaging.
  • Thermoplastic starch granulate is obtained by mixing (heat-dynamic treatment) starch with a plasticizer from the polyol group: glycerin, esters, preferably citric acid esters, glycol, as well as water at an ascending temperature from 40 to 170°C. It is then subjected to shear and pressure at 120-190°C, carried out into a melt, extruded and granulated.
  • Starch granulate is mixed, with at least two thermoplastic polymers, preferably ethylene-acrylic acid copolymer or polyethylene grafted with maleic anhydride (at the temperature at which they form a melt), extruded and subjected to granulation.
  • Processing auxiliaries are also used: lubricants - favorably from 0.05 to 0.25% of oleamide, from 0.1 to 0.5% of magnesium, zinc and calcium stearate, from 0.1 to 0.15% of tri-alkolphenols.
  • Polish patent Pat.214329 discloses a method of obtaining a biodegradable polymer material based on thermoplastic starch and polylactide, preferably amorphous polylactide.
  • the starch preferably potato or corn starch
  • polylactide preferably amorphous polylactide.
  • the starch preferably potato or corn starch
  • glycerin preferably glycerin
  • the finished melt is extruded at 130-150°C.
  • the polylactide is mixed with maleic anhydride and a free radical initiator in an extruder and extruded at 100-140°C.
  • the starch granulate is then mixed with PLA granulate and PLA granulate grafted with maleic anhydride in a 1 :1 ratio, containing PLA grafted with maleic anhydride at 60% of the mixture (or 40 parts by weight of modified starch and 55 or 57.5 parts by weight of the PLA mixture with 5 or 2.5 parts by weight of auxiliaries to improve the compatibility, such as gluten), and carries out the extrusion process at 80-150°C.
  • European patent application EP 2467418A1 describes a method for obtaining a blend of thermoplastic starch with synthetic polymers.
  • dry starch e.g. corn, potato, rice or wheat
  • a plasticizer in the form of a polyol: glycerol, sorbitol, polyethylene glycol, their mixture or, for example, urea, formamide.
  • the plasticizer is glycerol and/or sorbitol in an amount of 5 to 40% by weight.
  • the extrusion process leads to obtaining TPS thermoplastic starch.
  • a polymer is then introduced in dry form, such as a pellet of a substance from a group including polyethylene, polypropylene, polylactide, polycaprolactone, polybutylene succinate, or mixtures thereof, to produce the right blend.
  • the ratio of starch to synthetic polymer is preferably between 10 and 90%.
  • compatibilizers preferably unsaturated carboxylic acid anhydrides.
  • thermoplastic starch is blended at high speed with a plasticizer such as ethylene glycol at a ratio of 1 :0.2-0.5 for 10-30 minutes at a mixing speed of 2000 to 4000 rpm and conditioned for 24 hours.
  • a plasticizer such as ethylene glycol
  • the mixture is heated to 120- 140°C, cooled and granulated to obtain thermoplastic starch.
  • Gum rosin is heated under a nitrogen atmosphere to 150-200°C, gradually mixed with polyol, catalyst and antioxidant, then subjected to reaction at 240-280°C for 5-10 hours and mixed with thermoplastic starch for 20-30 minutes, and cooled in the final stage.
  • solid paraffin is used as a compounding agent.
  • the actual mixture is obtained by mixing gum rosin with starch granules and a mixture enhancer in a ratio of 1 :0.43 ⁇ 2.3:0.15 ⁇ 0.33.
  • CN1115966C From the Chinese patent description CN1115966C is known the method of obtaining a biodegradable foaming material based on vegetable protein, modified starch and a filler in the form of cellulose fibers with metal salt hydrate, added to improve the mechanical properties of the product, and based on citric acid and sodium bicarbonate acting as endothermic blowing agents.
  • the mixture preferably contains from 10 to 46 % by weight of vegetable protein - soy or animal protein in the form of casein, albumin, gelatin, collagen, keratin, or mixtures thereof, from 20 to 46% starch in the form of native starch, or chemically modified starch, or mixtures thereof.
  • native starches are corn starch, potato starch, sweet potato starch, tapioca starch, sorghum starch or a mixture of the above.
  • the content of the plasticizer preferably in the form of ethyl glycol or glycerol, is in the range of 5 to 25%, water in the range of 8 to 20%, while the hydrate of salts such as calcium, sodium, potassium, among others, is in the range of 0.5 to 5% by weight.
  • Natural cellulose fibers represent 5 to 25% by weight of the blend. Chemical or physical phosphors, nucleating agents, lubricants in the form of vegetable oils and other modifiers are also used.
  • the mixture is produced in one of the ways by mixing, extrusion with a single or twin screw extruder to produce granulate, and processing by injection or extrusion.
  • glutaraldehyde is also used to cross-link the protein and possibly bind it to starch and cellulose.
  • the introduction of glutaraldehyde into the composition of the material presents the danger of its unreacted residues penetrating into the environment.
  • U.S. patent US11 ,168,203B2 discloses a method for obtaining thermoplastic starch. Starch, e.g.
  • corn, potato, tapioca or rice starch is blended with polyol, mono-, disaccharide, fatty alcohol or a mixture thereof (for example: polyethylene glycol, glycerol, sorbitol) in an amount of 10-25% by weight and epoxidized vegetable oil (e.g. soybean, flaxseed, sunflower) in an amount of 0.1 to 6%, preferably in an amount of 2.5 to 3.5%.
  • polyol mono-, disaccharide, fatty alcohol or a mixture thereof
  • epoxidized vegetable oil e.g. soybean, flaxseed, sunflower
  • an acid is used, preferably a carboxylic acid from the group: citric acid, malic acid or tartaric acid in an amount of 0.1 -0.5% by weight.
  • the mixture is obtained by extrusion using a twin screw extruder in the temperature range of 100-175°C, at the speed of 250 rpm. The product is subsequently subjected to granulation.
  • US5451673A discloses a method of obtaining films from aqueous solutions based on a mixture of pectin, without the addition of calcium cations, with starch and an optional plasticizer.
  • the starch is mixed with water and gelatinized at the boiling point of the water under pressure, then cooled (e.g., in a water bath) and mixed with the pectin solution for about 1 hour.
  • the material is poured to produce films that have been vacuum dried.
  • U.S. patent application US2012/0283364A1 discloses a method of obtaining a polymer blend with thermoplastic starch for processing by extrusion or injection molding.
  • the first step is to obtain thermoplastic starch by mixing starch, water and plasticizer and undergoing mechanical and thermal processing, as well as draining the water.
  • a blend of synthetic polymers e.g. PHBV and PVOH
  • PHBV and PVOH synthetic polymers
  • European Patent EP2473542B1 discloses a method for obtaining a biodegradable polymer blend with a thermoplastic starch, which includes mixing the pre-mix with one or more biodegradable polyesters having a melt flow index (MFI) of not more than 5 g/10 min, preferably a polymer of the group: PCL, PBAT, PHBV, PES and PBS, with the pre-mix consisting of polyalkylene carbonate, thermoplastic starch, a polymer containing carboxylic acid groups and a transesterification catalyst such as sodium or potassium hydroxide.
  • MFI melt flow index
  • the starch can be corn starch, potato starch, wheat starch, tapioca starch, soybean starch or a mixture thereof, while the plasticizer is preferably glycerin and/or sorbitol.
  • the ratio of starch to plasticizer is 2:1 to 3:1.
  • U.S. patent description US 8852747B2 discloses a method of obtaining thermoplastic multilayer products obtained by co-extruding a layer obtained from polymer A in the form of a renewable/biodegradable, polylactide, homopolymers or poly hydroxyalkanoate copolymers e.g. PHB, PHBV, polyalkylene succinates e.g. PBS. PBS, which are grafted with a monomer from the group of unsaturated carboxylic acids; a layer composed of polymer B, which is identical to polymer A, but is not grafted, the composition of the multilayer product also includes component C - a plasticizer from the group of polymers, oligomers or prepolymers, e.g. polyethylene glycol multilayer product, and there is also a starch material D in the form of thermoplastic starch.
  • the product is manufactured by co-extrusion on a twin screw extruder.
  • the composition consists, preferably, of at least one biodegradable rigid polymer, preferably from the group of, among others, polyesteramides, lactic acid-based polymers, and also consists of polyhydroxybutyrate or starch, also consists of at least one biodegradable flexible polymer (preferably, among others, PHBV, PCL, PBS) and optionally a filler (e.g., talc, silica).
  • a biodegradable rigid polymer preferably from the group of, among others, polyesteramides, lactic acid-based polymers, and also consists of polyhydroxybutyrate or starch, also consists of at least one biodegradable flexible polymer (preferably, among others, PHBV, PCL, PBS) and optionally a filler (e.g., talc, silica).
  • a filler e.g., talc, silica
  • US patent US 5756194 A discloses a method of obtaining a biodegradable water-resistant material consisting of a core made of gelled starch and a layer of gum rosin, which is an intermediate layer between the starch and a coating made of biodegradable polyester, e.g. PLA, PHBV, PCL.
  • a layer made of gum rosin is obtained by spraying an alcoholic gum rosin solution on the starch product, and then coating it with a suitable solution of the selected polyester, for example, in tetra hydrofuran.
  • European patent EP3 064542B1 discloses a method for manufacturing a biodegradable composition based on TPS thermoplastic starch and PLA polylactide.
  • the thermoplastic starch blend is obtained by mixing native starch with a plasticizer, such as glycerin, and extruding using a single- or twin-screw extruder in a thermomechanical process, with starch accounting for 30 to 80.8 percent by weight, glycerin 10 to 48.5 percent by weight, and modifying additives in the form of agar 2 to 20 percent by weight and/or epoxidized vegetable oil 0.5 to 10 percent by weight and/or gum arabic 0.5 to 10 percent by weight.
  • the resulting TPS is then granulated, mixed with PLA granulate at a ratio of 7:1 to 1 :7, and extruded.
  • thermoplastic starch that contained 10 wt.%. of various pine resin derivatives: gum rosin, disproportionated gum rosin, modified gum rosin with maleic anhydride, pentaerythritol gum rosin esters and gum rosin glycerol esters.
  • Thermoplastic starch was obtained by mixing native starch with plasticizer - glycerin, water and appropriate modifiers, and then the mixtures were extruded.
  • the invention disclosed in international patent application WO2009155511A2 relates to a method for producing a meat food product having a casing, which method includes the step of applying a casing paste containing alginate and a hard-soluble calcium salt by co-extrusion to the outside of the meat material, to be cased to form a water-resistant product, also relates to a method of obtaining a co-extruded meat product whose water resistance is obtained by contacting the co-extruded product with a solution containing calcium ions, thereby causing the alginate to gel on the surface of the meat material.
  • U.S. patent description US9770044B2 discloses an edible chewing product for pets containing 10%-30% by weight of meat component and 20%-50% by weight of vegetable starch, said chewing product further comprising the addition of compounds from the group of: thickeners (including, but not limited to. vegetable proteins, pectin gum arabic, potassium alginate, gelatin, agar, gum arabic, sodium carboxymethylcellulose), humectants (e.g. glycerin, vegetable proteins), emulsifiers (e.g.
  • the product is a product obtained by extrusion, whereby the said material is heat-treated to at least 40°C and formed into a sheet before extrusion.
  • the document did not disclose the addition of calcium salts to physically cross-link the mixture of proteins, starches and pectins to increase their water resistance.
  • thermoplastic expanded food composition containing, at a minimum, insoluble milk protein (casein) and non-bull starch, as well as preservatives, flavors, food colorants, vitamins, food acids, phosphates or mixtures thereof, and optionally calcium salts in the role of a nucleating agent designed to accelerate the boiling of water in the extrudate, in a manner that is more controlled than if the nucleating agent were not present.
  • a nucleating agent designed to accelerate the boiling of water in the extrudate, in a manner that is more controlled than if the nucleating agent were not present.
  • no glycerin was used as a plasticizer, as a result, the product after extrusion was in the form of a stiff and brittle foam, the usefulness of which is limited to food purposes only.
  • US patent application US5451673A discloses an invention for films made from aqueous solutions of pectin-starch mixtures and glycerol, as a plasticizer to increase the flexibility of the film.
  • Films obtained by the method according to the invention have a high elastic modulus are flexible and self-supporting, and have the advantage that all materials are derived from plant products.
  • US patent application US5523293A reveals a method for obtaining biodegradable thermoplastic compositions made from the reaction product of soy protein and a starch filler, a reducing agent from the group of sulfites, nitrates and sulfur compounds, and the reaction of a plasticizer in the form of glycerol, water and possible additives, if desired.
  • the composition has a high degree of fluidity for processing by extrusion and injection molding into solid articles that are biodegradable and have a high degree of tensile strength and water resistance.
  • thermoplastic starch is currently one of the few types of biodegradable polymers, of natural origin, that can be successfully converted into usable products using processing technologies specific to thermoplastics.
  • TPS is not free of disadvantages, among which are its high hygroscopicity and susceptibility to dissolution in water, as well as its low mechanical strength and brittleness.
  • Increasing the mechanical resistance of TPS can be realized by increasing the proportion of native starch, relative to the plasticizer, but this comes at the expense of increasing susceptibility to brittle fracture.
  • increasing the proportion of plasticizer in the composition of TPS allows to obtain flexible products, but characterized by very low tensile strength, high plasticity and high susceptibility to swelling and dissolution in water.
  • thermoplastic starch Also known from the prior art are ways to increase the mechanical strength and water resistance of thermoplastic starch by creating various types of TPS polymer biocompositions involving compostable polylactide (PLA), poly[adipate-co-terephthalate- 1 ,4-butylene] (PBAT), polybutylene succinate (PBS) or polycaprolactone (PCL).
  • PLA compostable polylactide
  • PBAT poly[adipate-co-terephthalate- 1 ,4-butylene]
  • PBS polybutylene succinate
  • PCL polycaprolactone
  • the aforementioned plastics are synthetically or semi-synthetically derived materials and have poor biodegradability in the aquatic environment, as well as in the soil.
  • increasing the proportion of thermoplastic starch in such compositions above 50 wt. % makes these materials susceptible to swelling and disintegration when exposed to water.
  • plastics of this type must be characterized by high water resistance, mechanical strength, allowing them to be used in the production of consumer products without the need for changes in existing processing technologies relating to thermoplastics.
  • Biodegradable thermoplastic polymeric composition constituting a mixture containing native starch and additives in the form of plasticizers, gelling agents, proteins, substances modifying physical properties, hydrophobizing substances, fillers enhancing mechanical strength, compatibilizers and possibly polyester of natural origin is characterized according to the invention in that, on a total weight basis, the composition contains from 42.7 wt.% to 70.2 wt.% native starch, from 19.0 wt.% to 32.5 wt.% of plasticizer, advantageously glycerol, from 0.1 wt.% to 20.0 wt.% of proteins advantageously containing in their structure substances selected from the group comprising amino acids such as glutamic acid, aspartic acid, advantageously in the form of gluten, casein, potato protein isolate, pea protein isolate, soy protein isolate, gelatin, collagen, or a mixture thereof, from 0.1 wt.% to 10.0 wt.% of natural polyester, to 10.0 wt.% of natural gelling substances selected from the group including pec
  • hydrophobizing substances of natural origin selected from the group including gum rosin, glycerin esters of gum rosin, pentaerythritol esters of gum rosin, gum rosin dimers, stearic acid esters preferably glycerol monostearate, salts of stearic acid, preferably magnesium stearate, calcium stearate, zinc stearate, vegetable oils, preferably soybean oil, sunflower oil, rapeseed oil, linseed oil, olive oil, powder hydrophobizing substances, preferably amber dust, or mixtures thereof, from 0.1wt.% to 20.0 wt.% of natural mechanical strength enhancing fillers selected from the group including cellulose fibers, wood dust, cork dust, pulp, from 0.1 w
  • the native starch is potato and/or corn starch.
  • the calcium salt is calcium chloride.
  • it additionally contains from 12.5 wt.% to 87.5 wt.% poly hydroxyalkanoates preferably poly(3-hydroxybutyrate-co-3-hydroxyvalerate) on the final weight of the composition.
  • a method for manufacturing a biodegradable thermoplastic composition constituting a mixture containing native starch and additives in the form of plasticizers, gelling agents, proteins, substances modifying physical properties, hydrophobizing substances, fillers enhancing mechanical strength, compatibilizers and possibly polyester of natural origin involving the steps of mixing, extrusion, cooling and granulation is characterized according to the invention in that it is carried out in two stages.
  • the first step using a mechanical mixer, at a temperature in the range of 20-60°C, advantageously at 25°C, is mixed on a total weight basis from 42.7 wt.% to 70.2 wt.% of native starch, from 19.0 wt.% to 32.5 wt.
  • plasticizer advantageously glycerol
  • proteins advantageously containing in their structure substances selected from the group comprising amino acids such as glutamic acid, aspartic acid, advantageously in the form of gluten, casein, potato protein isolate, pea protein isolate, soy protein isolate, gelatin, collagen, or mixtures thereof from 0.1 wt.% to 10.0 wt.% of natural gelling substances selected from the group including pectin, sodium salt of alginic acid, from 0.1 wt.% to 5.0 wt.% of physical ionic modifier, a physical ionic modifier in the form of a carrier of at least divalent metal cations, preferably calcium salts, from 0.1 wt.% to 12.0 wt.%.
  • hydrophobizing substances of natural origin selected from the group including gum rosin, gum rosin glyceryl esters, gum rosin pentaerythritol esters, gum rosin dimers, stearic acid esters advantageously glycerol monostearate, stearic acid salts, favorably magnesium stearate, calcium stearate, zinc stearate, vegetable oils, favorably soybean oil, sunflower oil, rapeseed oil, linseed oil, olive oil, powder hydrophobizing substances, favorably amber dust, or mixtures thereof, from 0.1 wt.% to 2.5 wt.% of cellulose filler compatibilizer and hydrogen interaction inducer with components containing polar functional groups, in the form of sodium tetraborate.
  • the starch mixture obtained in the first stage is subjected to extrusion immediately after it is made with the extruder while maintaining the temperature of the heating zones of the plasticizing system in the range from 100°C to 190°C, preferably in the range from 100°C to 165°C with simultaneous degassing of volatile parts, and then the obtained extrudate is cooled by forced air circulation to room temperature and subjected to granulation.
  • the native starch is potato and/or corn starch.
  • the calcium salt is calcium chloride.
  • polyhydroxyalkanoates preferably poly(3- hydroxybutyrate-co-3-hydroxyvalerate) are added to the extruder hopper on the final weight of the composition.
  • 12.5 wt% to 87.5 wt% of polyhydroxyalkanoates preferably poly(3-hydroxybutyrate-co-3-hydroxyvalerate) are added to the extruder in a stream of plasticized starch mixture at least half the length of the plasticizing zone (L/2) by means of a side dispenser, per final weight of the composition.
  • the extruder is an extrusion device divided into temperature-controlled heating zones including the hopper, plasticizing system and head, preferably a single screw or multi screw device.
  • Another invention is a method for obtaining a biodegradable thermoplastic composition constituting a mixture containing native starch and additives in the form of plasticizers, gelling agents, proteins, substances modifying physical properties, hydropho- bizing substances, fillers enhancing mechanical strength, compatibilizers and possibly polyester of natural origin comprising the steps of mixing, extrusion, cooling and granulation characterized in that it is carried out in one step using an extruder.
  • Into the extruder in the feed zone is dosed, on a total weight basis, from 42.7 wt.% to 70.2 wt.% of native starch, from 19.0 wt.% to 32.5 wt.% of plasticizer, advantageously glycerol, from 0.1 wt.
  • proteins advantageously containing substances in their structure, selected from the group including amino acids such as glutamic acid, aspartic acid, advantageously in the form of gluten, casein, potato protein isolate, pea protein isolate, soy protein isolate, gelatin, collagen, or a mixture thereof, from 0.1 wt.% to 10.0 wt.% of natural gelling agents selected from the group including pectin, alginic acid sodium salt, from 0.1 wt.% to 5.0 wt.% of a physical ionic modifier in the form of a carrier of at least divalent metal cations, preferably calcium salts, from 0.1 wt.% to 12.0 wt.%.
  • amino acids such as glutamic acid, aspartic acid
  • natural gelling agents selected from the group including pectin, alginic acid sodium salt
  • a physical ionic modifier in the form of a carrier of at least divalent metal cations, preferably calcium salts, from 0.1 wt.% to 12.0 wt.%
  • hydrophobizing substances of natural origin selected from the group including gum rosin, gum rosin glyceryl esters, gum rosin pentaerythritol esters, gum rosin dimers, stearic acid esters advantageously glycerol monostearate, stearic acid salts, favorably magnesium stearate, calcium stearate, zinc stearate, vegetable oils, favorably soybean oil, sunflower oil, rapeseed oil, linseed oil, olive oil, powder hydrophobizing substances, favorably amber dust, or mixtures thereof, from 0.1 wt.% to 20.0 wt.% of natural mechanical strength enhancing fillers selected from the group including cellulose fibers, wood dust, cork dust, pulp, from 0.1 wt.% to 2.5 wt.% of cellulose filler compatibilizer and hydrogen interaction inducer with components containing polar functional groups, in the form of sodium tetraborate.
  • the plasticizer or hydrophobizing substance is in liquid form, it is dosed in the first zone of the plasticizing system, located directly behind the bulk component backfill zone.
  • the temperatures of the heating zones of the plasticizing system are maintained in the range from 100°C to 190°C, preferably from 100°C to 165°C with simultaneous degassing of volatile parts, and then the thermoplastic extrudate thus obtained is cooled with air to room temperature and subjected to granulation.
  • the native starch is potato and/or corn starch.
  • the calcium salt is calcium chloride.
  • polyhydroxyalkanoates preferably poly(3-hydroxybutyrate-co-3- hydroxyvalerate) are added to the extruder hopper on a final weight basis.
  • polyhydroxyalkanoates are added to the extruder in a stream of plasticized starch mixture at least half the length of the plasticizing zone (L/2) by means of a side dispenser preferably poly(3-hydroxybutyrate-co- 3-hydroxyalkanoate) on a final weight basis.
  • the extruder is an extrusion device divided into temperature-controlled heating zones including the hopper, plasticizing system and head, preferably a single screw or multi screw device.
  • rhTPS stands for reinforced and hydrophobized thermoplastic starch
  • ST starch
  • GL stands for vegetable glycerin
  • BRX sodium tetraborate (borax)
  • GEL stands for natural gelling agents, which include PEC -pectins, sodium salt of alginic acid
  • P stands for proteins advantageously containing in their structure amino acids such as glutamic acid and/or aspartic acid with active carboxyl groups to which include CAS - casein (milk protein), VPI - vegetable protein isolate (potato, pea, soybean), GET - food gelatin
  • FM - stands for physical ionic modifier in the form of calcium chloride (CaCI2)
  • H stands for hydrophobizing substances which include gum rosin (RO), gum rosin pentaerythritol esters (RPE), gum rosin glycerin esters (RGE), gum rosin dim
  • rhTPS and the rhTPS/PHA biocomposition that is the subject of the invention are of natural origin, including plant, animal and bacterial, and some of them may be derived from renewable sources.
  • thermoplastic starch Modification of the physical properties of thermoplastic starch and its compatibility with cellulose fillers is realized by means of sodium tetraborate (borax) mediated by which physical hydrogen interactions between -OH groups contained in starch and -OH groups present in cellulose are induced.
  • Sodium tetraborate will also make it possible to induce physical hydrogen interactions between starch, other components such as gelling agents and proteins.
  • polyhydroxyalkanoate preferably polyhydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), more preferably poly(3-hydroxybutyrate-co-3- hydroxy valerate) (PHBV) in the composition according to the invention
  • PHA polyhydroxyalkanoate
  • PVB polyhydroxybutyrate
  • PV poly-3-hydroxyvalerate
  • PHBV poly(3-hydroxybutyrate-co-3- hydroxy valerate)
  • rhTPS starch reinforced and hydrophobized with natural compounds
  • the role of PHA in composition with rhTPS is also to induce a barrier to water access.
  • PHAs including PHBV
  • PHBV is one of the few biopolymers that is biodegradable in seawater, freshwater and soil without being composted under industrial conditions.
  • the obtained biodegradable material is characterized by desirable processing and physical and mechanical properties, as well as the usability of products made from it, i.e. disposable and reusable products or packaging materials, etc.
  • the purpose of the invention is to obtain, based on the components used, which are of natural origin or obtained from natural raw materials, a thermoplastic starch showing high barrier to water access and high resistance to dissolution in water.
  • gelling agents used in the food industry in the form of pectin, or optionally using modification products of natural gelling agents, such as alginic acid sodium salt, in combination with proteins, advantageously containing in their structure amino acids such as glutamic acid and/or aspartic acid with a free carboxyl group, advantageously in the form of, for example, gluten, and/or casein (whey protein) and/or potato protein isolate and/or pea protein isolate and/or soy protein isolate and/or dietary gelatin and/or collagen.
  • the combination of gelling carbohydrates and starch with proteins enables the formation of interpenetrating protein-polysaccharide polymer networks in the rhTPS mass, in which there are strong interactions based on coacervation, i.e. adsorption of a negatively charged anionic polysaccharide, mainly a gelling polysaccharide, on the su rface of a positively charged protein.
  • coacervation i.e. adsorption of a negatively charged anionic polysaccharide, mainly a gelling polysaccharide, on the su rface of a positively charged protein.
  • Coacervation is the process of physically binding a protein-polysaccharide system into a stiffened polymer network, dependent on maintaining the appropriate pH level in the starch material.
  • thermoplastic starch the dry gelling agent and the dry ionic modifier are mixed with the thermoplastic starch in its molten state, as a result of which they are well dispersed throughout its volume.
  • the system is also environmentally safe, as the gelling agents used are fully biodegradable and compostable, and in the case of thermoplastic starch biodegradation in water, the first step is desorption of metal cations into water, followed by polysaccharide biodegradation, with the process being much faster in the case of seawater, due to the desorption and ion exchange of cations occurring via sodium ions and chloride anions.
  • the invention uses stearic acid derivatives in the form of magnesium stearate and/or calcium stearate and/or zinc stearate, as well as pine gum rosin and/or its derivatives in the form of gum rosin pentaerythritol esters, gum rosin glycerin esters and gum rosin dimers, which are non-toxic, biodegradable and used in the food industry, among others.
  • hydrophobic cyclic rings of gum rosin acids ensure good interaction with a hydrophobic polyester, such as PHA, and water resistance of the biocompositions obtained by the method according to the invention.
  • the resulting "bridging" effect provides the basis for interfacial compatibilization of rhTPS with PHA, mediated by salts of stearic acid and gum rosin and its derivatives, also providing increased water resistance of rhTPS.
  • thermoplastic starch allows the compatibility of rhTPS with PHA, advantageously PHBV or other types of hydrophobic polyesters such as PLA, PBT, PSB, for example, which has a significant effect on increasing the strength of the compositions and improving their processing properties.
  • amphiphilic structure of the natural oil which has areas of high hydrophilicity in the molecule that allow it to induce hydrogen interactions with polar rhTPS components and hydrophobic areas that interact with hydrophobic polyesters in the composition.
  • amber dust with high hydrophobicity and the ability to generate negatively polarized electrical charges on the surface of the grains makes it possible, on the one hand, to excite the hydrophobic character of rhTPS and to induce induced interactions with other components and electrostatic interactions with positively charged protein molecules in an environment below their pH(l) isoelectric point.
  • thermoplastic starch as well as its composition with PHA in the invention, is realized by using cellulose fillers in the form of cellulose fibers, and/or cellulose dust, and/or shredded vegetable pulp as reinforcement.
  • the invention uses cellulose fibers as reinforcement.
  • Cellulose fibers due to their hydrophilic nature and ability to interact with water, are added to rhTPS and its composition with PHA in combination with gum rosin, which is capable of compatibilizing cellulose with a hydrophobic polyester like PHA. Gum rosin, as well as the method of obtaining rhTPS, also makes it possible to achieve the effect of impregnating cellulose fibers with it.
  • the biodegradable, thermoplastic, reinforced and hydrophobic starch-based polymer composition according to the invention consists exclusively of components of natural origin and/or components obtained from renewable raw materials. It is obtained in the dry state without the operation of dissolving components and intermediates in water, undergoes physical self-reinforcement in contact with water under the influence of divalent and/or trivalent metal ions. It is stable during use, and the products made from it are fully biodegradable, including in fresh and seawater and soil, while maintaining the desired physical, mechanical and functional properties.
  • a biocomposition composed of thermoplastic starch and polyhydroxyalkanoates (PHAs) of natural origin is obtained according to the invention so that no chemical modification of the starch is used, and its composition is chosen to induce interaction between the individual components solely through physical interactions.
  • the invention is explained in more detail in the presented manufacturing examples, which include a planetary mixer, an extruder equipped with modular heating zones and a heated head and granulator knife, an injection molding machine using which paddleshaped samples with dimensions in accordance with PN- ISO 37:2007 were obtained.
  • the specimens obtained according to the examples were subjected to tests of their tensile strength and elongation at rupture according to PN- ISO 37:2007 standard, and the wetting angle was determined for them using a goniometer (Rame-Hart instrument).
  • potato starch (NOWAMYL" S.A.), corn starch (Biomus sp. z o.o.), vegetable glycerol 99.5% (TechlandLab sp. z o.o.), glycerol monostearate (LOUIS FRANQOIS), calcium stearate (Warchem Sp. z o.o.), magnesium stearate (Europharma invest Sp. z o.o. ), zinc stearate (Warchem Sp. z o.o.), soybean oil (Heuschen & Schrouff), sunflower oil (Golden Eggs), rapeseed oil (ZT Kruszwica S.A.
  • pea protein isolate Medicaline
  • potato protein ALAMYL S.A.
  • soy protein isolate SFD S.A.
  • casein ARTE METAL STYLE POLSKA Spolka z o.o.
  • wheat gluten Kol-Pol
  • food grade gelatin Mr Cook Corp.
  • collagen Kol-Pol
  • gum rosin PinoPine
  • gum rosin pentaerythritol ester PinoPine
  • gum rosin glycerin ester PinoPine
  • dimerized gum rosin PinoPine
  • coffee grounds Starbucks Gdansk
  • sterilized rice husk ROBNET Robert Kwiecinski
  • cork dust KORK.
  • a potato starch composition of 65.6 wt.%, 21.9 wt.% glycerol, 0.5 wt.% pectin, 10 wt.% gluten, 0.25 wt.% calcium chloride, 0.5 wt.% gum rosin, 1.0 wt.% cellulose fibers and 0.25 wt.% sodium tetraborate was prepared.
  • the mixing process of all ingredients was carried out in a standard mechanical mixer for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 60-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 1 .
  • a potato starch composition of 58.7 wt.%, with 29.3 wt.% glycerol, and with 0.5 wt.% pectin, 1.0 wt.% gluten, 0.25 wt.% calcium chloride, 5.0 wt.% gum rosin dimer, 5.0 wt.% wood flour and 0.25 wt.% sodium tetraborate was prepared.
  • the mixing process of all ingredients was carried out in a standard mechanical mixer for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of a co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the range of 100-175°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 2.
  • a potato starch composition of 58.7 wt% was prepared, with 29.3 wt% glycerol, and 0.5 wt % pectin, 1.0 wt% gluten, 0.25 wt% calcium chloride, 5.0 wt% gum rosin, 5.0 wt% cellulose fibers and 0.25 wt% sodium tetraborate.
  • the mixing process of all ingredients was carried out in a standard mechanical mixer for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 60-185°C and a screw speed of 100 rpm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 3.
  • a potato starch composition of 57.0 wt.%, with 19.0 wt.% glycerol, and with 10.0 wt.% pectin, 1.0 wt.% gluten, 5.0 wt.% calcium chloride, 0.5 wt.% glycerol monostearate, 5.0 wt. % cellulose fibers and 2.5 wt.% sodium tetraborate was prepared.
  • the mixing process was carried out in a standard mechanical mixer for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of a co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the range of 60-190°C and a screw speed of 100 rpm. It was further proceeded as in Example 1. As a result of the high pectin and calcium chloride content, the resulting extrudate was highly rigid and foamy, allowing it to be used as a waterproof filling for mail parcels. Table 1 shows the properties of the thermoplastic starch obtained according to Example 4.
  • a potato starch composition of 49.0 wt.%, with 24.5 wt.% glycerol, and with 0.5 wt.% pectin, 0.5 wt.% gluten, 0.25 wt.% calcium chloride, 5.0 wt.% glycerol monostearate, 20.0 wt.% cellulose fibers and 0.25 wt.% sodium tetraborate was prepared.
  • the mixing process was carried out in a standard mechanical mixer for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 5.
  • a 42.7 wt.% potato starch composition was prepared in a standard mechanical mixer, with 21.3 wt.% glycerol and 0.5 wt.% pectin, 10.0 wt.% gluten, 0.25 wt.% calcium chloride, 5.0 wt.% pentaerythritol gum rosin ester, 20.0 wt.% wood dust and 0.25 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 6.
  • a potato starch composition of 42.7 wt.% was prepared in a standard mechanical mixer, with 21 .3 wt.% glycerol and 0.5 wt.% pectin, 10.0 wt.% gluten, 0.25 wt.% calcium chloride, 5.0 wt.% gum rosin glycerin ester, 20.0 wt.% wood dust and 0.25 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 7.
  • a 48.1 wt.% potato starch composition was prepared in a standard mechanical mixer, with 24.0 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 7.5 wt. % gum rosin, 20.0 wt.% wood dust and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 8.
  • a 65.1 wt.% corn starch composition was prepared in a standard mechanical mixer, with 32.5 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 1.0 wt. % magnesium stearate, 1.0 wt.% cork dust and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of th e device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 9.
  • a 65.0 wt.% potato starch composition was prepared in a standard mechanical mixer with 32.5 wt.% glycerol, along with 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 1.0 wt.% magnesium stearate, 1.0 wt.% amber dust, 0.1 wt.% wood dust and O.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 10.
  • a composition consisting of 65.1 wt% potato starch with 32.5 wt% glycerol and 0.1 wt% sodium alginate, 1.0 wt% collagen, 0.1 wt% calcium chloride, 1.0 wt% magnesium stearate, 0.1 wt% cellulose fibers and 0.1 wt% sodium tetraborate was prepared in a standard mechanical mixer. The mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm. It was further proceeded as in example 1.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 11.
  • a 65.1 wt.% potato starch composition was prepared in a standard mechanical mixer, with 32.5 wt.% glycerol, and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 1.0 wt.% magnesium stearate, 1.0 wt. rice husk and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the planetary extruder and subjected to the extrusion process, maintaining the temperature in the successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 12.
  • a 59.1 wt.% potato starch composition was prepared in a standard mechanical mixer, with 29.5 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 1.0 wt. % magnesium stearate, 10.0 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the single-screw extruder and subjected to the extrusion process, maintaining the temperature in the successive heating zones of the device in the following range of 100-165°C and the screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 13.
  • a corn starch composition of 59.1 wt.%, with 29.5 wt.% glycerol, and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 1.0 wt.% calcium stearate, 10.0 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate were prepared in a standard mechanical mixer. The mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the planetary extruder and subjected to the extrusion process, maintaining the temperature in the successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 14.
  • a 56.4 wt.% potato starch composition was prepared in a standard mechanical mixer, with 28.2 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 5.0 wt. % gum rosin, 10.0 wt.% coffee grounds and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the single-screw extruder and subjected to the extrusion process, maintaining the temperature in the successive heating zones of the device in the following range of 100-165°C and the screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 15.
  • a 62.6 wt.% potato starch composition was prepared in a standard mechanical mixer, with 25.0 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 2.0 wt. % glycerol monostearate, 10.0 wt.% glycerol, rice husk and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the planetary extruder and subjected to the extrusion process, maintaining the temperature in the successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 16.
  • a 70.2 wt.% potato starch composition was prepared in a standard mechanical mixer, with 23.4 wt.% glycerol and 0.1 wt.% pectin, 4.0 wt.% gelatin, 0.1 wt.% calcium chloride, 2.0 wt.% glycerol monostearate, 0.1 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 17.
  • a potato starch composition of 61.9 wt.% was prepared with 24.7 wt.% glycerol and 0.1 wt.% pectin, 0.1 wt.% gelatin, 0.1 wt.% calcium chloride, 3.0 wt.% glycerol monostearate, 10.0 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter of grains in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 18.
  • a composition consisting of 61.2 wt.% potato starch, 24.5 wt.% glycerol, and 2.0 wt.% pectin, 0.1 wt.% gluten, 2.0 wt.% calcium chloride, 0.1 wt.% glycerol monostearate, 10.0 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate was prepared in a standard mechanical mixer. The mixing process was carried out for 15 minutes at 20+5 °C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 19.
  • a composition was prepared in a standard mechanical mixer, consisting of 60.1 wt.% potato starch mixed with 24.1 wt.% glycerol and 5.0 wt.% pectin, 10.0 wt.% gelatin, 0.1 wt % calcium chloride, 0.1 wt.% glycerol monostearate, 0.1 wt.% cellulose fibers and 0.5 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20+5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with diameter of grains in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 20.
  • a composition was prepared in a standard mechanical mixer, consisting of 59.7 wt.% potato starch, 29.9 wt.% glycerol, and 5.0 wt.% sodium alginate, 0.1 wt.% gluten, 5.0 wt.% calcium chloride, 0.1 wt.% glycerol monostearate, 0.1 wt.% cellulose fibers and O.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100 - 165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 21.
  • a composition was prepared in a standard mechanical mixer, consisting of 62.5 wt.% potato starch with 31.2 wt.% glycerol, as well as 2.0 wt.% sodium alginate, 2.0 wt.% potato protein, 2.0 wt.% calcium chloride, 0.1 wt.% glycerol monostearate, 0.1 wt.% cellulose fibers and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with diameter of grains in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 22.
  • a composition consisting of 59.1 wt% potato starch with 29.5 wt% glycerol was prepared, along with 0.1 wt% pectin, 10.0 wt% casein, 0.1 wt% calcium chloride, 1.0 wt% gum rosin, 0.1 wt% cellulose fibers and 0.1 wt% sodium tetraborate.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 23.
  • a composition was prepared in a standard mechanical mixer, consisting of 63.1 wt.% potato starch, 31.5 wt.% glycerol, and 0.1 wt.% pectin, 2.5 wt.% gelatin, 0.1 wt.% calcium chloride, 0.1 wt.% gum rosin, 0.1 wt.% cellulose fibers and 2.5 wt.% sodium tetraborate.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 60-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 24.
  • a composition consisting of 59.1 wt% potato starch, 29.5 wt% glycerol, and 0.1 wt% pectin, 10 wt% casein, 0.1 wt% calcium chloride, 1.0 wt% gum rosin, 0.1 wt% cellulose fibers and 0.1 wt% sodium tetraborate was prepared in a standard mechanical mixer. The mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 25.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the corotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granules of modified thermoplastic starch with a grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 26.
  • a composition consisting of 52.7 wt.% potato starch, 26.4 wt.% glycerol, and 0.1 wt.% pectin, 10.0 wt.% gelatin, 10.0 wt.% gluten, 0.1 wt.% calcium chloride, 0.1 wt.% gum rosin, 0.1 wt.% cellulose fibers and 0.5 wt.% sodium tetraborate was prepared in a standard mechanical mixer. The mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 27.
  • a composition was prepared consisting of 62.2 wt.% potato starch, 24.9 wt.% glycerol, and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 5.0 wt.% magnesium stearate, 5.0 wt.% gum rosin pentaerythritol ester, 2.5 wt.% cork dust and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granules of modified thermoplastic starch with a grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 28.
  • a composition was prepared consisting of 67.5 wt.% potato starch, 27.0 wt.% glycerol, and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 5.0 wt.% gum rosin glycerol ester, 0.1 wt.% cellulose fiber and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 29.
  • a composition was prepared consisting of 67.5 wt.% potato starch, 27.0 wt.% glycerol, and 0.1 wt.% pectin, 0.1 wt.% gluten, 0.1 wt.% calcium chloride, 5.0 wt.% gum rosin pentaerythritol ester, 0.1 wt.% cellulose fiber and 0.1 wt.% sodium tetraborate.
  • the mixing process was carried out for 15 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the starch mixture obtained in this way was introduced immediately after mixing into the hopper of the co-rotating twin screw extruder and subjected to the extrusion process, maintaining the temperature in successive heating zones of the device in the following range of 100 - 165°C and a screw speed of 100 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granules of modified thermoplastic starch with a grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 30.
  • a composition consisting of potato starch in an amount representing 58.3% of the final weight of the product and pectin in an amount representing 0.1% of the final weig ht of the product and gluten in an amount representing 0.1 % of the final weight of the product was continuously dosed into the hopper of the twin screw extruder using screw dispensers, calcium chloride in an amount representing 0.1 % of the final weight of the product, gum rosin in an amount representing 5% of the final weight of the product, zinc stearate in an amount representing 5% of the final weight of the product, cellulose fibers in an amount representing 0.1% of the final weight of the product, and sodium tetraborate in an amount representing 0.1 % of the final weight of the product.
  • liquid glycerol in an amount of 29.2% of the final weight of the product and soybean oil in an amount of 2% of the final weight of the product were dosed continuously by means of a peristaltic pump.
  • the extrusion process was carried out by maintaining the temperature in successive heating zones of the device in the following range of 100 -165°C and a screw speed of 50 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 31.
  • liquid glycerol in an amount of 23.1 % of the final weight of the product and sunflower oil in an amount of 3.75% of the final weight of the product were dosed continuously by means of a peristaltic pump.
  • the extrusion process was carried out by maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 50 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 32.
  • a composition consisting of potato starch in an amount accounting for 42.7% of the final weight of the product and pectin in an amount accounting for 0.5% of the final weight of the product and gluten in an amount accounting for 10% of the final weight of the product was continuously dosed into the hopper of the twin-screw extruder by means of screw dispensers, calcium chloride in an amount representing 0.25% of the final weight of the product, gum rosin glycerin ester in an amount representing 5% of the final weight of the product, cellulose fibers in an amount representing 20% of the final weight of the product, and sodium tetraborate in an amount representing 0.25% of the final weight of the product.
  • liquid glycerol was continuously dosed by means of a peristaltic pump in an amount accounting for 21.3% of the final weight of the product.
  • the extrusion process was carried out by maintaining the temperature in successive heating zones of the device in the following range of 100-165°C and a screw speed of 50 rpm.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining granulate of modified thermoplastic starch with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the thermoplastic starch obtained according to Example 33.
  • the method of manufacturing the rhTPS/PHI002 composition according to Example 34 is carried out in two steps.
  • potato starch was mixed in a standard mechanical mixer with glycerol pectin, gluten, calcium chloride, gum rosin, cellulose fibers and sodium tetraborate, which are the raw materials for obtaining rhTPS.
  • the mixing process was carried out for 30 minutes at 20 ⁇ 5°C, with the stirrer speed in the range of 50-150 rpm.
  • the resulting mixture was then dosed in a second stage using a screw feeder into the hopper of a co-rotating twin screw extruder.
  • Poly (3- hydroxybutyrate-co-3-hydroxyvalerate) granules (PHI002, NaturePlast) were also dosed into the hopper via another screw feeder in an amount that made it possible to achieve a mass ratio of rhTPS to PHA in the resulting composition equal to 1/7, which corresponds to an amount of rhTPS equal to 12.5 wt.% and an amount of PHI002 equal to 87.5 wt.% on the final weight of the composition.
  • potato starch in the amount of 7.93 wt.%, glycerol in the amount of 3.97 wt.% were used to obtain rhTPS on the final mass of the rhTPS/PHI002 composition, pectin in an amount of 0.13 wt.%, gluten in an amount of 0.01 wt.%, calcium chloride in an amount of 0.01 wt.%, gum rosin in an amount of 0.31 wt.%, wood flour in an amount of 0.13 wt.%, and sodium tetraborate (borax) in an amount of 0.01 wt.%.
  • the components dosed into the hopper were then subjected to extrusion while maintaining the extruder head temperature in the range of 165- 175°C and the temperature of the heating zones of the extruder plasticizing system in the range of 60°C to 190°C, with simultaneous degassing of the volatile parts.
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 34.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 35 is carried out in the same way, in two stages, and using the same materials, with the same mass ratio of rhTPS/PHI002 as described in Example 34 except that the content in the composition of potato starch was 6.35 wt.%, glycerol was 3.18 wt.%, pectin was 0.13 wt. %, gluten was 0.01 wt.%, calcium chloride was 0.01 wt.%, gum rosin was 0.31 wt.%, wood flour was 2.5 wt.% and borax was 0.01 wt.%. Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 35.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 36 is carried out in the same way, in two stages, and using the same materials as described in Example 34 except that the mass ratio of rhTPS/PHI002 is 7/1 , which corresponds to an amount of rhTPS equal to 87.5 wt.% and an amount of PHI002 equal to 12.5 wt.% in terms of the final weight of the composition, while the content in the composition of potato starch was 55.53 wt.%, glycerol was 27.77 wt.%, pectin was 0.86 wt.%, gluten was 0.09 wt.%, calcium chloride was 0.09 wt.%, gum rosin was 2.19 wt.%, wood flour was 0.88 wt.% and borax was 0.09 wt.%.
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 36.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 37 is carried out in the same way, in two stages, and using the same materials as described in Example 34 except that the mass ratio of rhTPS/PHI002 is 7/1 , which corresponds to an amount of rhTPS equal to 87.5 wt.% and an amount of PHI002 equal to 12.5 wt.% on the final weight of the composition, while the content in the composition of potato starch was 44.45 wt.%, glycerol was 22.23 wt.%, pectin was 0.86 wt.%, gluten was 0.09 wt.%, calcium chloride was 0.09 wt.%, gum rosin was 2.19 wt.%, wood flour was 17.5 wt.% and borax was 0.09 wt.%.
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 37.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 38 is carried out in one step with a mass ratio of rhTPS/PHI002 equal to 1/7.
  • PHI002 granulate in an amount constituting 87.5% of the final weight of the rhTPS/PHI002 composition, was continuously dosed into the hopper of the twin-screw extruder by means of screw dispensers, potato starch in an amount constituting 8.05% of the final weight of the product and pectin in an amount constituting 0, 01 % of the final product weight, and gluten in an amount representing 0.01% of the final product weight, calcium chloride in an amount representing 0.01% of the final product weight, gum rosin in an amount representing 0.125% of the final product weight, wood flour in an amount representing 0.13% of the final product weight, and sodium tetraborate in an amount representing 0.01% of the final product weight.
  • liquid glycerol in an amount of 4.03% of the final weight of the product and canola oil in an amount of 0.125% of the final weight of the product were dosed continuously by means of a peristaltic pump.
  • the extrusion process was carried out by maintaining the temperature in successive heating zones of the device in the following range of 100-180°C.
  • an extrudate was obtained, which was cooled by forced air circulation to room temperature and subjected to granulation, thus obtaining rhTPS/PHI002 composition granules with grain diameter in the range of 3-5mm.
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 38.
  • the method of manufacturing the rhTPS/PHI002 composition according to Example 39 is carried out in the same way, in one step, with the same mass ratio of rhTPS/PHI002 as described in Example 38 except that the content in the composition of corn starch was 6.47 wt.%, glycerol was 3.24 wt%, pectin was 0.01 wt%, gluten was 0.01 wt%, calcium chloride was 0.01 wt%, gum rosin was 0.125 wt%, olive oil was 0.125 wt%, wood flour was 2.5 wt% and borax was 0.01 wt%.
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 39.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 40 is carried out in the same way, in one step, as described in Example 38 except that the mass ratio of rhTPS/PHI002 is 7/1 , which corresponds to an amount of rhTPS equal to
  • Table 1 shows the properties of the rhTPS/PHI002 composition obtained according to Example 40.
  • the method of obtaining the rhTPS/PHI002 composition according to Example 41 is carried out in the same way, in one step, as described in Example 38 except that the mass ratio of rhTPS/PHI002 is 7/1 , which corresponds to an amount of rhTPS equal to
  • thermoplastic biodegradable materials obtained according to each of examples 1 to 41 were subjected to tests of their tensile strength, elongation at break according to PN- ISO 37:2007 standard, and were subjected to water wetting angle tests, and the results are shown in Table 1.
  • test results of the materials obtained according to examples 1-33 relating to biodegradable thermoplastic starch indicate that they have an ultimate tensile strength in the range of 5.5-24.0 MPa and an elongation at break in the range of 48- 457%, as well as a contact angle in the range of 31-83°. Based on them, it can be concluded that under the influence of the applied set of modifiers, there was an increase in the ultimate tensile strength of rhTPS, compared to unmodified TPS, and the greatest effect on the increase in tensile strength was due to the addition of reinforcing fillers.
  • thermoplastic polymer As for the rhTPS/PHI compositions, a significant effect of bacterial thermoplastic polymer (PHI) on their improvement of mechanical properties is evident, while the increase in the value of their contact angle depends on the content of PHI in the composition of these materials.

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Abstract

L'invention concerne une composition de polymère thermoplastique biodégradable qui est un mélange contenant, sur la base du poids total de la composition, de 42,7 % en poids à 70,2 % en poids d'amidon natif, de 19,0 % en poids à 32,5 % en poids de plastifiant, de 0,1 % à 20 % en poids de protéine, de 0,1 % en poids à 10,0 % en poids d'agents gélifiants naturels choisis dans un groupe comprenant la pectine, un sel de sodium d'acide alginique de 0,1 % en poids à 5,0 % d'un modificateur ionique physique sous la forme d'un support d'au moins des cations métalliques divalents, de 0,1 % en poids à 12,0 % en poids de substances hydrophobes d'origine naturelle, de 0,1 % à 20,0 % en poids de charges de renforcement naturelles, de 0,1 % à 2,5 % en poids de tétraborate de sodium. Un objet de l'invention est également une composition avec l'addition de polyhydroxyalcanoates, ainsi que des procédés de fabrication de ces compositions. Les compositions sont utilisées pour la fabrication de produits en contact avec des aliments.
PCT/PL2023/050092 2022-11-11 2023-11-11 Composition de polymère thermoplastique biodégradable et ses procédés de fabrication WO2024102010A1 (fr)

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US6231970B1 (en) * 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
WO2008090195A2 (fr) * 2007-01-26 2008-07-31 Obtusa Investimentos E Gestao Limidada Compositions à base d'amidon et utilisation relative et procédé d'obtention
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PL207301B1 (pl) * 2005-09-09 2010-11-30 Inst Chemii Przemysłowej Im Prof Ignacego Mościckiego Sposób wytwarzania biodegradowalnegomateriału polimerowego
CN104877180A (zh) * 2015-05-25 2015-09-02 苏州市贝克生物科技有限公司 水溶性食品包装膜及其制备方法
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WO2008090195A2 (fr) * 2007-01-26 2008-07-31 Obtusa Investimentos E Gestao Limidada Compositions à base d'amidon et utilisation relative et procédé d'obtention
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