FR3128222A1 - Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, process for preparing said composition and corresponding consumable filament for 3D printing. - Google Patents
Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, process for preparing said composition and corresponding consumable filament for 3D printing. Download PDFInfo
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- FR3128222A1 FR3128222A1 FR2111063A FR2111063A FR3128222A1 FR 3128222 A1 FR3128222 A1 FR 3128222A1 FR 2111063 A FR2111063 A FR 2111063A FR 2111063 A FR2111063 A FR 2111063A FR 3128222 A1 FR3128222 A1 FR 3128222A1
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- pha
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
- C12P7/625—Polyesters of hydroxy carboxylic acids
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
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- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
Abstract
L’invention concerne des compositions de filaments consommables pour impression 3D comprenant au moins polyhydroxyalcanoate. L’invention concerne également un procédé de préparation de telles compositions. L’invention concerne encore des filaments consommables pour impression 3D comprenant de telles compositions.The invention relates to consumable filament compositions for 3D printing comprising at least polyhydroxyalkanoate. The invention also relates to a process for the preparation of such compositions. The invention also relates to consumable filaments for 3D printing comprising such compositions.
Description
La présente invention appartient au domaine technique des compositions pour impression 3D.The present invention belongs to the technical field of compositions for 3D printing.
Plus particulièrement, l’invention concerne des compositions de filaments consommables pour impression 3D comprenant au moins polyhydroxyalcanoate. L’invention concerne également un procédé de préparation de telles compositions. L’invention concerne encore des filaments consommables pour impression 3D comprenant de telles compositions.More particularly, the invention relates to compositions of consumable filaments for 3D printing comprising at least polyhydroxyalkanoate. The invention also relates to a process for the preparation of such compositions. The invention also relates to consumable filaments for 3D printing comprising such compositions.
Art antérieurPrior art
Les polyhydroxyalcanoates (PHA) sont des polyesters de type thermoplastiques naturels qui peuvent être utilisés en remplacement des plastiques conventionnels dans différents domaines d’application, tels que les emballages de consommation, les doublures de couches jetables et les sacs poubelles, les produits alimentaires et médicaux, etc. Les efforts initiaux se sont concentrés sur leur utilisation pour des applications de moulage ou de thermoformage, en particulier pour des articles d'emballage de consommation tels que des bouteilles, des récipients pour cosmétiques, des stylos ou encore des tees de golf.Polyhydroxyalkanoates (PHA) are naturally occurring thermoplastic type polyesters that can be used as a replacement for conventional plastics in different application areas, such as consumer packaging, disposable diaper liners and trash bags, food and medical products , etc. Initial efforts have focused on their use for molding or thermoforming applications, particularly for consumer packaging items such as bottles, cosmetic containers, pens, and golf tees.
Une des propriétés les plus utiles des PHA, qui les distingue facilement des polymères dérivés de la pétrochimie, est leur origine naturelle et leur biodégradabilité, par exemple en compost domestique, industriel, dans les eaux douces ou dans l’eau de mer, et plus généralement dans tout milieu dans lequel un écosystème vivant et actif est présent.One of the most useful properties of PHAs, which easily distinguishes them from polymers derived from petrochemicals, is their natural origin and their biodegradability, for example in domestic compost, industrial compost, in fresh water or in sea water, and more. generally in any environment in which a living and active ecosystem is present.
La vitesse de biodégradation de ces PHA va dépendre de différents facteurs. La présence de microorganismes, la température, le pH, le poids moléculaire et la cristallinité en sont les principaux.The rate of biodegradation of these PHAs will depend on various factors. The presence of microorganisms, temperature, pH, molecular weight and crystallinity are the main ones.
Les PHA sont synthétisés naturellement par certains microorganismes lorsque l’environnement naturel est défavorable. Ce sont des molécules de réserves permettant au microorganisme de survivre.PHAs are synthesized naturally by certain microorganisms when the natural environment is unfavourable. These are reserve molecules allowing the microorganism to survive.
La production de ces PHA par voie biotechnologique utilise notamment des biofermenteurs qui permettent de contrôler parfaitement les conditions de production de ce biopolymère.The production of these PHAs by biotechnological means uses in particular biofermentors which make it possible to perfectly control the conditions of production of this biopolymer.
La structure chimique d’un PHA est un polyester caractérisé par la longueur de la chaîne latérale en nombre de carbone. Il existe donc différentes structures chimiques de PHA :
- les PHA scl, qui comprennent de 3 à 5 carbones ;
- les PHA mcl, qui comprennent de 6 à 14 carbones ; et
- les PHA lcl, qui comprennent un nombre supérieur à 14 carbones.The chemical structure of a PHA is a polyester characterized by the length of the side chain in carbon number. There are therefore different chemical structures of PHA:
- scl PHAs, which comprise from 3 to 5 carbons;
- mcl PHAs, which comprise from 6 to 14 carbons; And
- the PHA lcl, which comprise a number greater than 14 carbons.
Il existe actuellement des compositions pour la fabrication de filaments 3D contenant des PHA. Ce sont principalement des PHB (PHA scl ayant 4 carbones) utilisés en faible quantités en formulation avec d’autres polymères qui ne sont pas des biopolymères (acide polylactique (PLA) principalement) ou des additifs (charges et fibres principalement). De telle compositions de l’art antérieur comprennent par exemple 20% de PHA pour 80% de PLA.There currently exist compositions for the manufacture of 3D filaments containing PHAs. These are mainly PHBs (PHA scl with 4 carbons) used in small quantities in formulations with other polymers that are not biopolymers (mainly polylactic acid (PLA)) or additives (mainly fillers and fibers). Such compositions of the prior art comprise for example 20% PHA for 80% PLA.
Contre toute attente, les inventeurs de la présente invention ont réussi à mettre au point des filaments 3D composés majoritairement de biopolymères PHA. Ces PHA peuvent être intégrés soit seuls en formulation dans la fabrication de ces filaments, soit avec des fibres et/ou charges, en proportion minoritaire.Against all expectations, the inventors of the present invention succeeded in developing 3D filaments composed mainly of PHA biopolymers. These PHAs can be integrated either alone in the formulation in the manufacture of these filaments, or with fibers and/or fillers, in a minority proportion.
Description de l'inventionDescription of the invention
L’invention consiste donc en des compositions comprenant au moins un PHA en tant qu’ingrédient majoritaire. Ces compositions sont adaptées à la fabrication de filaments pouvant être utilisés en impression 3D. Une technique d’impression 3D qui met en œuvre ces compositions est par exemple l’impression 3D par dépôt de matière fondue, qui consiste à déposer un matériau fondu, type plastique, par couches successives via une extrudeuse qui se déplace et construit un objet physique en suivant un dessin défini par un fichier de conception assistée par ordinateur.The invention therefore consists of compositions comprising at least one PHA as major ingredient. These compositions are suitable for the manufacture of filaments that can be used in 3D printing. A 3D printing technique that implements these compositions is, for example, 3D printing by deposition of molten material, which consists of depositing a molten material, such as plastic, in successive layers via an extruder which moves and builds a physical object. following a drawing defined by a computer-aided design file.
Ainsi, un premier objet selon l’invention concerne une composition de filaments consommables pour impression 3D comprenant une teneur de 50 à 99% en poids, par rapport au poids total de ladite composition, d’au moins un polyhydroxyalcanoate (PHA).Thus, a first object according to the invention relates to a composition of consumable filaments for 3D printing comprising a content of 50 to 99% by weight, relative to the total weight of said composition, of at least one polyhydroxyalkanoate (PHA).
L’invention repose sur une approche tout à fait nouvelle et originale de fabriquer des filaments pour impression 3D. De telles compositions selon l’invention comprenant des PHA en tant qu’ingrédients majoritaires, biopolymères d’origine naturelle et biodégradables, sont avantageuses d’un point vue écologique et économique.The invention is based on a completely new and original approach to manufacturing filaments for 3D printing. Such compositions according to the invention comprising PHAs as major ingredients, biopolymers of natural origin and biodegradable, are advantageous from an ecological and economic point of view.
Selon un mode de réalisation, l’au moins un PHA est choisi parmi le groupe comprenant : PHA scl, PHA mcl, PHA lcl, et leur combinaison.According to one embodiment, the at least one PHA is chosen from the group comprising: PHA scl, PHA mcl, PHA lcl, and their combination.
L’utilisation de ces différents types de PHA permet de moduler les paramètres physiques et chimiques des compositions au regard des divers systèmes de fabrication additive dans lesquels elles peuvent être utilisées, ainsi que des divers objets imprimables.The use of these different types of PHA makes it possible to modulate the physical and chemical parameters of the compositions with regard to the various additive manufacturing systems in which they can be used, as well as the various printable objects.
Selon un mode de réalisation, une telle composition comprend en outre au moins un additif.According to one embodiment, such a composition also comprises at least one additive.
Il est donc avantageusement possible de rajouter différents types d’additifs pour que la composition soit davantage adaptée à une extrusion de filament 3D.It is therefore advantageously possible to add different types of additives so that the composition is more suitable for 3D filament extrusion.
Selon un mode de réalisation, cet au moins un additif est choisi parmi les fibres, les charges et leur combinaison.According to one embodiment, this at least one additive is chosen from fibers, fillers and their combination.
Selon un mode de réalisation, une telle composition comprend une teneur de 0,01% à 10% en poids de fibres, par rapport au poids total de la composition et/ou une teneur de 0,01% à 40% en poids de charges, par rapport au poids total de la composition.According to one embodiment, such a composition comprises a content of 0.01% to 10% by weight of fibers, relative to the total weight of the composition and/or a content of 0.01% to 40% by weight of fillers , relative to the total weight of the composition.
Ces gammes de valeurs acceptables pour l’intégration d’additifs dans les compositions selon l’invention permettent d’adapter encore davantage ces compositions en fonction de l’environnement d’impression 3D.These ranges of acceptable values for the integration of additives in the compositions according to the invention make it possible to adapt these compositions even further according to the 3D printing environment.
Selon un mode de réalisation, l’au moins un PHA est issu de bactéries choisies parmi un groupe comprenant les bactéries de souche CNCM I-5658 et les bactéries de souche CNCM I-5079.According to one embodiment, the at least one PHA is derived from bacteria chosen from a group comprising bacteria of strain CNCM I-5658 and bacteria of strain CNCM I-5079.
Un deuxième objet selon l’invention concerne un procédé de préparation d’une composition selon l’invention, ce procédé comprenant les étapes suivantes :
-culture de bactéries productrices de PHA ;
-concentration d’une biomasse cellulaire créée par cette culture de bactéries ;
-séchage de la biomasse cellulaire ;
-extraction du PHA de la biomasse ;
-purification du PHA ;
la composition comprenant une teneur de 50 à 99% en poids du PHA, par rapport au poids total de la composition.A second object according to the invention relates to a method for preparing a composition according to the invention, this method comprising the following steps:
-culture of PHA-producing bacteria;
-concentration of a cellular biomass created by this culture of bacteria;
- drying of the cellular biomass;
- extraction of the PHA from the biomass;
-purification of the PHA;
the composition comprising a content of 50 to 99% by weight of the PHA, relative to the total weight of the composition.
Ce procédé, qui permet de préparer une composition selon l’invention, met en œuvre des étapes classiques de préparation de PHA, qui ne nécessitent nullement un matériel difficile à se procurer.This process, which makes it possible to prepare a composition according to the invention, implements conventional PHA preparation steps, which in no way require equipment that is difficult to obtain.
Selon un mode de réalisation, l’au moins un PHA extrait et mis en œuvre dans ce procédé est choisi parmi le groupe comprenant : PHA scl, PHA mcl, PHA lcl, et leur combinaison.According to one embodiment, the at least one PHA extracted and used in this method is chosen from the group comprising: PHA scl, PHA mcl, PHA lcl, and their combination.
Selon un mode de réalisation, la composition préparée par ce procédé comprend en outre au moins un additif, lequel est choisi parmi les fibres et les charges.According to one embodiment, the composition prepared by this process also comprises at least one additive, which is chosen from fibers and fillers.
Un troisième objet selon l’invention concerne un filament consommable pour impression 3D qui comprend une composition telle que décrite précédemment.A third object according to the invention relates to a consumable filament for 3D printing which comprises a composition as described previously.
Claims (10)
-culture de bactéries productrices de PHA ;
-concentration d’une biomasse cellulaire créée par ladite culture de bactéries ;
-séchage de ladite biomasse cellulaire ;
-extraction dudit PHA de ladite biomasse ;
-purification dudit PHA ;
caractérisé en ce que ladite composition comprend une teneur de 50 à 99% en poids dudit PHA, par rapport au poids total de la composition.Process for the preparation of a composition according to claims 1 to 6 comprising the following steps:
-culture of PHA-producing bacteria;
-concentration of a cellular biomass created by said culture of bacteria;
- drying of said cellular biomass;
-extraction of said PHA from said biomass;
- purification of said PHA;
characterized in that said composition comprises a content of 50 to 99% by weight of said PHA, relative to the total weight of the composition.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2111063A FR3128222A1 (en) | 2021-10-18 | 2021-10-18 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, process for preparing said composition and corresponding consumable filament for 3D printing. |
| FR2112967A FR3128221A1 (en) | 2021-10-18 | 2021-12-03 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, formulations comprising said compositions, process for preparing said formulations and corresponding consumable filament for 3D printing. |
| EP22202335.0A EP4166612A1 (en) | 2021-10-18 | 2022-10-18 | Polyhydroxyalkanoate compositions for making 3d printing filaments, formulations including same, method of making same and consumable filament for 3d printing |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2111063A FR3128222A1 (en) | 2021-10-18 | 2021-10-18 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, process for preparing said composition and corresponding consumable filament for 3D printing. |
| FR2111063 | 2021-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR3128222A1 true FR3128222A1 (en) | 2023-04-21 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR2111063A Pending FR3128222A1 (en) | 2021-10-18 | 2021-10-18 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, process for preparing said composition and corresponding consumable filament for 3D printing. |
| FR2112967A Pending FR3128221A1 (en) | 2021-10-18 | 2021-12-03 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, formulations comprising said compositions, process for preparing said formulations and corresponding consumable filament for 3D printing. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR2112967A Pending FR3128221A1 (en) | 2021-10-18 | 2021-12-03 | Compositions based on polyhydroxyalkanoate(s) for producing 3D printing filaments, formulations comprising said compositions, process for preparing said formulations and corresponding consumable filament for 3D printing. |
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| FR (2) | FR3128222A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016058097A1 (en) * | 2014-10-15 | 2016-04-21 | Terraverdae Bioworks Inc. | Biodegradable polymer filament |
| US11407168B2 (en) * | 2018-06-11 | 2022-08-09 | Tepha, Inc. | Methods for 3D printing of poly-4-hydroxybutyrate and copolymers |
-
2021
- 2021-10-18 FR FR2111063A patent/FR3128222A1/en active Pending
- 2021-12-03 FR FR2112967A patent/FR3128221A1/en active Pending
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| Publication number | Publication date |
|---|---|
| FR3128221A1 (en) | 2023-04-21 |
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