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WO2024201311A1 - Matériau composite biocompatible - Google Patents

Matériau composite biocompatible Download PDF

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Publication number
WO2024201311A1
WO2024201311A1 PCT/IB2024/052930 IB2024052930W WO2024201311A1 WO 2024201311 A1 WO2024201311 A1 WO 2024201311A1 IB 2024052930 W IB2024052930 W IB 2024052930W WO 2024201311 A1 WO2024201311 A1 WO 2024201311A1
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WO
WIPO (PCT)
Prior art keywords
starch
corn
hydrolyzed collagen
composite material
pop
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.)
Pending
Application number
PCT/IB2024/052930
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English (en)
Inventor
Riccardo ARDICCIONI
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Individual
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Individual
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Filing date
Publication date
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Publication of WO2024201311A1 publication Critical patent/WO2024201311A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/02—Shellac
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L99/00—Compositions of natural macromolecular compounds or of derivatives thereof not provided for in groups C08L89/00 - C08L97/00

Definitions

  • the present invention relates to a new biocompatible composite material that can be used in manufacturing molded articles used, for example, for packaging, in the automotive industry (for interiors and exteriors), as sound-absorbers, for thermal insulation or in the consumer goods industry.
  • the subject biocompatible composite material of the present invention enables to achieve molded items with extremely easy, low-cost, productive systems, items with good and excellent mechanical strength properties, thermal and acoustic insulation, with improved lightness, and fully made of renewable raw materials, since they are biocompatible, such as starch, preferably corn starch, hydrolyzed collagen, pop-corn and shellac.
  • the molded items are mainly made of polypropylene, polyethylene, polyvinyl chloride and polystyrene, four families of plastics which, despite having positive properties such as low-density hydro- phobic surface, good workability and low thermal conductivity, have also negative properties such as brittleness, only one single chemical resistance and a very low softening temperature. Furthermore, the products made of these plastics have often shown a very low melting temperature, which causes the plastic to melt and drip while burning at temperatures slightly higher than 100 °C. This drops can ignite and contribute to spreading the fire. Flammability can be reduced by using suitable, but very often toxic, flame-retardants. Brominated additives (di-phenyl polybromurate or hexabrom ine-cyclo-dodecane ethers) have been used so far, which are extremely harmful to environment and health.
  • Incineration releases carbon dioxide, the plastic particles become part of the food chain and the decomposition releases polluting substances.
  • Organizations such as the EU and the United Nations remark that if the economic growth continues and the consumption pattern remains the same, the environmental issues connected to plastic will continue to increase. Due to these health and environmental issues, which are generally known, the request of new alternative materials in manufacturing formed items has become stronger and stronger.
  • thermoplastic resin performs a binding action, gives appropriate mechanical strength, hydrophobicity and prevents the degradation thereof into popped corn flakes which, when mixed with said resins, formed by heating the mold (USE 3,51 1 ,899).
  • Such a material does not have a full biocompatibility and arrangement to be capable of being loaded in pre-formed molds of any shape mixing the materials to each other with noncompatible aggregation states: the solid seeds and the thermoplastic resin melted in a suitable sol- vent.
  • said technology was resumed and modified in order to obtain molded items by mixing starch flakes, obtained by popping the corn beads or seeds, with at least a polymer, and optionally a binder, in order to coat the single starch flakes with a hydrophobic resin or polymer and at the same time promoting the adherence to each other within the forming mold of the item intended to be made (US 2022/0040933A1 ).
  • these materials and the related molded items are not fully biocompatible.
  • plastic such as polypropylene, polyethylene, polyvinyl chloride and polystyrene, in particular and mainly polystyrene foam, in the scope of manufacturing molded items, which come to be only made of fully biocompatible materials, yet keeping good and improved mechanical strength properties and physicochemical properties of thermal and acoustic insulation.
  • biocompatible composite material comprising starch and hydrolyzed collagen mixed with each other, said biocompatible composite material optionally, but preferably, comprising also pop-corn mixed with starch and hydrolyzed collagen, all of it, optionally, but preferably, continuously coated by a shellac layer, which has mechanical strength properties, such as resistance to compression stresses and the modulus of elasticity parameter, and physicochemical property of thermal and acoustic insulation such to make it comparable to polystyrol, in particular polystyrol foam, but with the great advantage, compared to the latter, to be made of fully biocompatible and biodegradable materials such as, indeed, starch, preferably corn starch, hydrolyzed collagen and, when present, the pop-corn, preferably popped corn, mixed with starch and hydrolyzed collagen and/or the shellac coating.
  • molded items can be manufactured, exactly during forming and hardening biocompatible composite material according to the present invention, such to keep in all respects the improved physicochemical and mechanical properties of said material.
  • the biocompatible composite material according to the present invention and that forms the molded items, only consists of renewable raw materials, i.e. starch, preferably corn starch, hydrolyzed collagen and when present pop-corn, preferably popped corn/maize and/or shellac.
  • renewable raw materials i.e. starch, preferably corn starch, hydrolyzed collagen and when present pop-corn, preferably popped corn/maize and/or shellac.
  • a new process of preparing the biocompatible composite material comprising starch, and hydrolyzed col- lagen, optionally, but preferably, continuously coated with shellac comprising the steps of: a) Providing starch; b) Providing hydrolyzed collagen; c) Mixing starch and hydrolyzed collagen until a homogeneous mixture is obtained; d) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e) Drying until constant weight of the biocompatible composite material thereby obtained is achieved; f) Optionally, continuously coating the biocompatible composite material obtained in step e) with shellac.
  • a further equally preferred embodiment of the present invention is the method for preparing the biocompatible composite material according to the present invention such as the biocompatible composite material comprising starch, preferably corn starch, hydrolyzed collagen and pop-corn, preferably popped corn, said pop-corn mixed with starch and hydrolyzed collagen, all of it optionally, but preferably, continuously coated with shellac, said method comprising the following steps: a’) Providing starch; b’) Providing hydrolyzed collagen; bi ’) Providing pop-corn; c’) Mixing starch, hydrolyzed collagen and pop-corn until a homogeneous mixture is obtained; d’) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e’) Drying until constant weight of the biocompatible composite material thereby obtained is achieved; f’) Optionally, continuously
  • a biocompatible composite material comprising starch and hydrolyzed collagen mixed to each other, said biocompatible composite material optionally continuously coated by a shellac layer;
  • a biocompatible composite material according to embodiment 1 wherein, when continuously coated by a shellac layer, being 100 the sum by weight of the combination of starch, hydrolyzed collagen and shellac, the % by weight of shellac is 1 to 6% by weight, by weight of the combination of starch, hydrolyzed collagen and shellac.
  • biocompatible composite material in the form of molded item selected from the group comprising panels, bars, storage or packaging boxes or cases, etc., consumer items, such as toys, sport equipment components, yoga mats, insulating mats, etc. components for the automotive industry, such as items for both interior and exterior, such as car sunshades, headrests, infant car seats, etc., electrical insulating panels, etc., pieces of furniture or in the form of grain/granule/granulate/grains.
  • biocompatible composite material for general thermal insulation of coatings, thermal insulation for cavity walls, thermal insulation of level or tilted coatings, thermal insulation for floorings and floors, preferably in the form of panels and/or slabs and or granule/s.
  • biocompatible composite material for general thermal insulation of coatings, thermal insulation for cavity walls, thermal insulation of level or tilted coatings, thermal insulation for floorings and floors, preferably in the form of panels and/or slabs and or granule/s.
  • biocompatible composite material according to any one of embodiments 1 - 6 for pack- ing/packaging preferably in the form of boxes, enclosures, cases, containers, either open or closed.
  • biocompatible composite material preferably in the form of boxes, enclosures, cases, containers, either open or closed.
  • the starch selected according to the present invention is starch selected among corn starch, starch such as corn, wheat, rice, potato starches, preferably corn starch, preferably in the form of powder, promptly available on the market.
  • the hydrolyzed collagen is obtained through hot acid hydrolysis processes, for examples aqueous environment with hot acetic acid, at lower temperatures than the boiling temperature, preferably at temperatures not higher than 65°C, of animal glue, isinglass, bone glue from several sources, preferably mammal bones, a promptly available raw material on the market.
  • the shellac is applied as a continuous coating on the biocompatible composite material according to the present invention, both when made of a starch mix, preferably corn starch, and hydrolyzed collagen, and when made also of pop-corn mixed with starch, preferably corn starch and hydrolyzed collagen.
  • Said processing allows to give the biocompatible composite material under preparation and the related molded item made of such a material water resistance properties while enabling transpiration and vapor permeability, in order to prevent moulds and condensate from forming and therefore the long-term degradation of the material object of the present invention.
  • pop-corn/popcorn is meant to comprise in particular popped/puffed starch meaning starch flakes that is such as popped-puffed corn flakes/puffed- popped maize or popped corn/maize beads/seeds (Zea mays, convar. Microsperma) - possibly after suitable greasing - wherein the seeds or beads explode when quickly heated at high temperatures, the water in the seeds evaporates abruptly, it transforms the starch contained in the seed into flake giving the starch a spongy texture or similar to foam, which can then be defined as a popped/puffed starch.
  • starch flakes such as popped-puffed corn flakes/puffed- popped maize or popped corn/maize beads/seeds (Zea mays, convar. Microsperma) - possibly after suitable greasing - wherein the seeds or beads explode when quickly heated at high temperatures, the water in the seeds evaporates abruptly, it transforms the starch contained in the seed into flake giving the starch a
  • the pop-corn/popcorn increases the lightness of the biocompatible composite material and the molded item comprising or made of such biocompatible composite material comprising the pop-corn/popcorn or popped/puffed starch.
  • the popcorn is used in its entirety, that is, the entire beads and/or seeds are caused to explode/expand and the popcorn obtained thereby is mixed in combination with starch and hydrolyzed collagen, or as a further equally preferred embodiment the pop- corn/popcorn is also totally or partially crushed before being mixed in combination with starch and hydrolyzed collagen.
  • biocompatible composite material according to the present invention wherein both pop-corn/popcorn in its entirety and crushed pop-corn/popcorn are mixed in combination with starch and hydrolyzed collagen.
  • popcorn is used which was produced from previously crushed raw material (for example corn flour).
  • the composite material according to the present invention comprises pop-corn, preferably popped corn beans or seeds, the flakes of which are mixed, or in a mixture, with starch and hydrolyzed collagen, such that the pop-corn is, or the flakes thereof are, substantially enclosed, coated by the starch, preferably corn starch, mixture, combined with the hydrolyzed collagen, hydro-soluble and/or hydro-compatible substances.
  • the popped/puffed pop-corn or starch preferably popped corn
  • the popped/puffed pop-corn or starch is present mixed with starch and hydrolyzed collagen and being 100 the sum by weight of the combination of starch, hydrolyzed collagen and pop-corn
  • the % by weight of pop-corn is 50 to 75% by weight of the combination of starch, hydrolyzed collagen and pop-corn.
  • the popped/puffed pop-corn or starch, preferably popped corn can be used in addition as such also as a starch source, by being crushed and powdered.
  • molded item with (various) geometric shapes, such as panels, bars, storage or packaging boxes or cases, etc., and (various) sizes, as well as various imaginary shapes, forced by the mold used for the relative shaping, such as consumer goods, for example toys, sport equipment components, yoga mats, insulating mats, etc. both interior and exterior components for the automotive industry: car sunshades, headrests, infant car seats, electrical insulating panels, etc., pieces of furniture and of a number of different sizes
  • the method for preparing the biocompatible composite material according to the present invention such as the biocompatible composite material comprising starch, preferably corn starch, and hydrolyzed collagen, optionally, but preferably, continuously coated with shellac, said method comprising the steps of: a) Providing starch; b) Providing hydrolyzed collagen; c) Mixing starch and hydrolyzed collagen until a homogeneous mixture is obtained; d) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e) Drying until constant weight of the biocompatible composite material thereby obtained is achieved; f) Optionally, continuously coating the biocompatible composite material obtained in step e) with shellac.
  • a further equally preferred embodiment of the present invention is the method for preparing the biocompatible composite material according to the present invention such as the biocompatible composite material comprising starch, preferably corn starch, hydrolyzed collagen and popped/puffed pop-corn or starch, preferably popped corn, said pop-corn mixed with starch and hydrolyzed collagen, all of it optionally, but preferably, continuously coated with shellac, said method comprising the following steps: a’) Providing starch; b’) Providing hydrolyzed collagen; bi ’) Providing pop-corn; c’) Mixing starch, hydrolyzed collagen and pop-corn until a homogeneous mixture is obtained; d’) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e’) Drying until the constant weight of the biocompatible composite material thereby obtained is achieved
  • the method for preparing a molded article comprising the/or made of the biocompatible composite material according to the present invention, such as the biocompatible composite material comprising starch, preferably corn starch, and hydrolyzed collagen, optionally, but preferably, continuously coated with shellac
  • said method for preparing a molded article comprising the steps of: a) Providing starch; b) Providing hydrolyzed collagen; c) Mixing starch, hydrolyzed collagen and hydrolyzed collagen until a homogeneous mixture is obtained; d) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e) Drying until constant weight of the molded item thereby obtained is achieved; f) Optionally, continuously coating the molded item obtained in step e) with shellac.
  • a further equally preferred embodiment of the present invention is the method for preparing a molded item comprising the/or made of the biocompatible composite material according to the present invention such as the biocompatible composite material comprising starch, preferably corn starch, hydrolyzed collagen and popped/puffed pop-corn or starch, preferably popped corn, said pop-corn mixed with starch and hydrolyzed collagen, all of it optionally, but preferably, continuously coated with shellac, said method comprising the following steps: a’) Providing starch; b’) Providing hydrolyzed collagen; bi ’) Providing pop-corn; c’) Mixing starch, hydrolyzed collagen and pop-corn until a homogeneous mixture is obtained; d’) Pouring the homogeneous mixture in a specific mold operating at a pressure ranging from 1 bar to 5 bar and a temperature ranging from room temperature up to 70 - 100 °C, preferably under stepped increase of pressure and/or temperature, until hardened; e’) Drying until constant weight
  • Steps a) and a’ which are the same, imply retrieving and supplying starch, such as corn, wheat, rice, potato starch, preferably corn starch, preferably in a powdered form, promptly available on the market.
  • starch such as corn, wheat, rice, potato starch, preferably corn starch, preferably in a powdered form, promptly available on the market.
  • Steps b) and b’ which are the same, imply finding and making available the hydrolyzed collagen achievable through hot acid hydrolysis processes, for examples aqueous environment hydrolysis with hot acetic acid, at lower temperatures than the boiling temperature, preferably at temperatures not higher than 65°C, of animal glue, such as isinglass, bone glue from several sources, preferably mammal bones, a raw material promptly available on the market.
  • animal glue such as isinglass, bone glue from several sources, preferably mammal bones, a raw material promptly available on the market.
  • Step bi implies finding and making available pop-corn/popcorn, to be understood according to the present invention, preferably finding on the market and manufacturing in situ popped or puffed starch, as stated according to the present invention, preferably popped corn, through the traditional heating techniques with abrupt increase of temperature in order to cause a sudden evaporation of the water in the seed of corn or rice, or maize, etc., in order to transform the starch within the seed, giving it a spongy texture or similar to foam.
  • Steps c) and c’ which are the same except for the further presence of pop-corn, mixed with starch, preferably corn starch and hydrolyzed collagen, in step c’) in respect to the equivalent step c), result in the intimate mixing of the components described in steps c) and c’), respectively, to give respective homogeneous, semi-fluid mixtures, thereby meaning an homogeneous distribution of the components intimately mixed with each other: in step c) starch, preferably corn starch, with hydrolyzed collagen, in step c’) the popped starch pop-corn flakes, preferably popped corn, homogeneously distributed in the homogeneous starch mix, preferably corn starch and hydrolyzed collagen which cover, surround and enclose the pop-corn, or popped starch flakes.
  • Steps d) and d’ which are the same, imply forming in a specific mold, to give, where the desired shape is required, the biocompatible composite material/molded item, at given pressure and temperature values, until the hardening thereof.
  • Steps e) and e’ which are the same, involve drying the hardened and formed biocompatible composite material/molded item according to the any desired form, until its constant weight is achieved, being able to operate at both room pressure and temperature and under several conditions of forced drying in ventilated or static dryers at programmable and variable temperatures, lowering the drying times.
  • Steps f) and f’ which are the same, imply the application of a continuous shellac coating on the surface of the biocompatible composite material/molded item via the traditional coating application techniques in resin material, applied to surfaces to be processed by means of highly volatile solvent vehicle, for example spray deposition of an alcohol solution where shellac is dispersed.
  • a molded item comprising or made of the biocompatible composite material according to any one of the embodiments described herein, said molded item selected from the group comprising panels, bars, storage or packaging boxes or cases, etc., consumer items, such as toys, sport equipment components, yoga mats, insulating mats, etc. components, items for both interior and exterior, for the automotive industry, such as car sunshades, headrests, infant car seats, electrical insulating panels, etc., pieces of furniture.
  • Some specimens of the biocompatible composite material according to the present invention have been prepared, some coated with shellac, some not, all of them prepared operating at room temperature and pressure, according to the process described herein. All of them have undergone a preliminary check of their mechanical properties of compressive strength and the measurement of the modulus of elasticity according to the standard ASTM D1621 .
  • the average value of the compressive strength of the uncoated specimens according to the present invention is 140 Kpa, whereas for those coated with shellac is 160 Kpa, i.e. comparable values as to the magnitude to those of polystyrene, in particular polystyrene foam, specimens.
  • E modulus modulus of elasticity

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dermatology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un matériau composite biocompatible comprenant de l'amidon et du collagène hydrolysé mélangés l'un à l'autre, ledit matériau composite biocompatible, éventuellement, mais de préférence, comprenant également du maïs à éclater mélangé avec de l'amidon et du collagène hydrolysé, le tout étant revêtu en continu par une couche de gomme laque.
PCT/IB2024/052930 2023-03-31 2024-03-27 Matériau composite biocompatible Pending WO2024201311A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102023000006405 2023-03-31
IT102023000006405A IT202300006405A1 (it) 2023-03-31 2023-03-31 Materiale composito biocompatibile

Publications (1)

Publication Number Publication Date
WO2024201311A1 true WO2024201311A1 (fr) 2024-10-03

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Application Number Title Priority Date Filing Date
PCT/IB2024/052930 Pending WO2024201311A1 (fr) 2023-03-31 2024-03-27 Matériau composite biocompatible

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IT (1) IT202300006405A1 (fr)
WO (1) WO2024201311A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5208061A (en) * 1990-12-13 1993-05-04 Cerestar Holding B.V. Starch composition
US5294249A (en) * 1987-03-27 1994-03-15 Luisi Pier L Blendpolymers
US5719203A (en) * 1994-08-27 1998-02-17 Metraplast H. Jung Gmbh Biodegradable composition comprising regenerative raw material and method of producing the same
WO2005074953A1 (fr) * 2004-02-03 2005-08-18 Universidad Austral De Chile Composition de diterpenes du type labdane extraite de andrographis paniculata, utilisee pour traiter les maladies auto-immunes et la maladie d'alzheimer par activation des recepteurs ppr-gamma

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511899A (en) 1967-07-20 1970-05-12 Gen Motors Corp Method of making a popcorn energy absorber
DE102018132738A1 (de) 2018-12-18 2020-06-18 Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts Einsatz von expandiertem und hydrophobem Popcorn zur Herstellung von dreidimensionalen Formteilen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5294249A (en) * 1987-03-27 1994-03-15 Luisi Pier L Blendpolymers
US5208061A (en) * 1990-12-13 1993-05-04 Cerestar Holding B.V. Starch composition
US5719203A (en) * 1994-08-27 1998-02-17 Metraplast H. Jung Gmbh Biodegradable composition comprising regenerative raw material and method of producing the same
WO2005074953A1 (fr) * 2004-02-03 2005-08-18 Universidad Austral De Chile Composition de diterpenes du type labdane extraite de andrographis paniculata, utilisee pour traiter les maladies auto-immunes et la maladie d'alzheimer par activation des recepteurs ppr-gamma

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KUMAR RAJ ET AL: "Biodegradable composite films/coatings of modified corn starch/gelatin for shelf life improvement of cucumber", JOURNAL OF FOOD SCIENCE AND TECHNOLOGY, vol. 58, no. 4, 1 April 2021 (2021-04-01), pages 1227 - 1237, XP037388512, ISSN: 0022-1155, DOI: 10.1007/S13197-020-04685-Y *

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