FR2973386A1 - USE OF A BIODEGRADABLE LACTIDE OLIGOMER AS PLASTIFIERS - Google Patents
USE OF A BIODEGRADABLE LACTIDE OLIGOMER AS PLASTIFIERS Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08K5/00—Use of organic ingredients
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08K5/00—Use of organic ingredients
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Abstract
L'objet de l'invention est l'utilisation d'un oligomère de lactide biodégradable, obtenu par un procédé comprenant au moins une étape de polymérisation du lactide par ouverture de cycle en présence d'un agent di-fonctionnel, en tant que plastifiant pour des formulations à base de polymères biodégradables et/ou de farines végétales.The object of the invention is the use of a biodegradable lactide oligomer obtained by a process comprising at least one step of polymerization of lactide by ring opening in the presence of a di-functional agent, as plasticizer. for formulations based on biodegradable polymers and / or vegetable flours.
Description
UTILISATION D'UN OLIGOMERE DE LACTIDE BIODEGRADABLE COMME PLASTIFIANT USE OF A BIODEGRADABLE LACTIDE OLIGOMER AS A PLASTIFIANT
La présente invention se rapporte à un procédé de fabrication d'un oligomère biodégradable de lactide. L'invention couvre aussi le produit obtenu et son utilisation en tant que plastifiant de polymères ou de composites polymères/farines végétales. The present invention relates to a process for producing a biodegradable oligomer of lactide. The invention also covers the product obtained and its use as a plasticizer for polymers or polymer composites / vegetable meals.
Actuellement on assiste à un développement industriel considérable des matériaux biodégradables. Les matériaux à biodégradabilité contrôlée sont de plus en plus recherchés, en particulier les matériaux aptes à se dégrader en milieu naturel, sans nécessiter d'apport spécifique de micro-organismes. Ces matériaux, à base de polymères biodégradables ou de mélanges de polymères biodégradables et de farines végétales, sont généralement utilisés par la mise en oeuvre de techniques de type injection, extrusion soufflage, extrusion gonflage, calandrage, etc., qui demandent une fluidité importante à l'état fondu. Or, les polymères biodégradables et les mélanges polymères biodégradables/farines végétales présentent une fluidité faible à l'état fondu. Currently there is considerable industrial development of biodegradable materials. Controlled biodegradability materials are more and more sought after, in particular materials capable of degrading in the natural environment, without the need for a specific supply of microorganisms. These materials, based on biodegradable polymers or biodegradable polymer blends and vegetable flours, are generally used by the implementation of techniques of the injection, extrusion blowing, extrusion inflating, calendering, etc. type, which require a high degree of fluidity. the melted state. However, the biodegradable polymers and the biodegradable polymer / vegetable meal mixtures have a low melt flowability.
Une solution utilisée pour améliorer la fluidité de ces matériaux est de leur ajouter un plastifiant, par exemple un phtalate, un benzoate, un époxyde, etc., qui permet de générer un produit flexible, résistant et plus facile à manipuler. Toutefois les plastifiants actuellement employés dans l'industrie des polymères sont d'origine pétrochimique, non renouvelables, et ne sont pas biodégradables. A solution used to improve the fluidity of these materials is to add a plasticizer, for example a phthalate, a benzoate, an epoxide, etc., which generates a flexible product, resistant and easier to handle. However plasticizers currently used in the polymer industry are of petrochemical origin, non-renewable, and are not biodegradable.
On se retrouve donc au final avec des matériaux qui ne sont pas écologiques et qui ne se dégradent pas entièrement. So we end up with materials that are not environmentally friendly and do not degrade entirely.
Il existe donc un besoin pour un produit capable d'améliorer la fluidité à l'état fondu des polymères biodégradables et des formulations à base de polymères biodégradables, en conservant leurs propriétés mécaniques et leur caractère dégradable. There is therefore a need for a product capable of improving the melt flowability of biodegradable polymers and formulations based on biodegradable polymers, retaining their mechanical properties and their degradability.
C'est ce à quoi répond la présente invention en proposant un procédé de fabrication d'un oligomère biodégradable de lactide, utilisable en tant que plastifiant biodégradable. Le procédé d'obtention selon l'invention comprend au moins une étape de polymérisation par ouverture de cycle en présence d'une agent di-fonctionnel. This is what the present invention provides by proposing a process for producing a biodegradable oligomer of lactide, which can be used as a biodegradable plasticizer. The obtaining process according to the invention comprises at least one step of ring-opening polymerization in the presence of a di-functional agent.
L'oligomère à base de lactide, obtenu par la mise en oeuvre du procédé selon l'invention, est utilisable comme plastifiant biodégradable pour améliorer la fluidité à l'état fondu des formulations à base de polymères biodégradables et/ou de farines végétales. Avantageusement, cet oligomère à base de lactide est dégradable en milieu 15 naturel et n'est pas néfaste pour l'environnement. D'autres caractéristiques et avantages ressortiront de la description en détail du procédé d'obtention selon l'invention qui va suivre, suivant un mode de réalisation, non limitatif, illustré de deux exemples particuliers. The oligomer based on lactide, obtained by the implementation of the process according to the invention, can be used as a biodegradable plasticizer to improve the melt flowability of formulations based on biodegradable polymers and / or vegetable flours. Advantageously, this oligomer based on lactide is degradable in a natural medium and is not harmful to the environment. Other features and advantages will emerge from the description in detail of the method of production according to the invention which follows, according to one embodiment, not limiting, illustrated by two particular examples.
20 I. Procédé d'obtention d'un oligomère à base de lactide selon l'invention Le procédé selon l'invention consiste à polymériser le lactide par ouverture de cycle en présence d'un agent di-fonctionnel pour former un oligomère fonctionnalisé. Le rapport molaire lactide / agent di-fonctionnel est compris entre 10 et 1000. 25 Selon un mode de réalisation préféré, le procédé selon l'invention consiste à polymériser le lactide par ouverture de cycle en présence d'un composé diol ou diacide pour former un oligomère fonctionnalisé. La réaction qui se produit est la suivante : X-R-X Lactide X-R- --- X X= OH ou Oligomère X= COOH I. Process for Obtaining a Lactide Oligomer According to the Invention The process according to the invention consists in polymerizing lactide by ring opening in the presence of a di-functional agent to form a functionalized oligomer. The molar lactide / di-functional agent ratio is between 10 and 1000. According to a preferred embodiment, the process according to the invention consists in polymerizing lactide by ring opening in the presence of a diol or diacid compound to form a functionalized oligomer. The reaction that occurs is as follows: X-R-X Lactide X-R- X X = OH or Oligomer X = COOH
De manière préférentielle, on utilise comme lactide le L-lactide, le D-lactide ou 5 le LD-lactide ou un mélange des trois isomères. Preferably, L-lactide, D-lactide or LD-lactide or a mixture of the three isomers is used as lactide.
La polymérisation est effectuée sous vide à haute température : The polymerization is carried out under vacuum at high temperature:
la pression est comprise entre 1 et 900mbar, plus particulièrement entre 20 et 600mbar, the pressure is between 1 and 900mbar, more particularly between 20 and 600mbar,
la température est comprise entre 100 et 200°C, plus particulièrement 10 entre 140 et 200°C. the temperature is from 100 to 200 ° C, more preferably from 140 to 200 ° C.
Préférentiellement, la polymérisation est réalisée en présence de catalyseurs, qui permettent d'augmenter la vitesse de la réaction. Preferably, the polymerization is carried out in the presence of catalysts, which make it possible to increase the speed of the reaction.
Parmi les catalyseurs susceptibles d'être utilisés pour la présente invention, on peut citer les métaux des groupes I, II, III et IV du tableau périodique, ou des Among the catalysts which can be used for the present invention, mention may be made of the metals of groups I, II, III and IV of the periodic table, or
15 sels à base de ces métaux. En particulier, on peut citer l'octoate d'étain, le dichlorure d'étain, l'acide sulfurique, le butoxyde de titane, l'isopropoxyde de titane, l'oxyde d'étain, l'oxyde d'antimoine, le dilaurate de dibutylétain et l'acétylacétonate de zircon. Salts based on these metals. In particular, there may be mentioned tin octoate, tin dichloride, sulfuric acid, titanium butoxide, titanium isopropoxide, tin oxide, antimony oxide, dibutyltin dilaurate and zircon acetylacetonate.
De manière préférentielle, on utilise l'acide succinique ou l'acide adipique, comme 20 diacide, ou le 1,4-butanediol comme diol. Preferably, succinic acid or adipic acid, such as diacid, or 1,4-butanediol as the diol is used.
On obtient ainsi un oligomère fonctionnalisé acide ou hydroxyle. II. Caractérisation des oligomères à base de lactide obtenus selon l'invention An acid or hydroxyl functionalized oligomer is thus obtained. II. Characterization of the oligomers based on lactide obtained according to the invention
Les oligomères fonctionnalisés obtenus selon l'invention sont biodégradables et 25 présente : The functionalized oligomers obtained according to the invention are biodegradable and exhibit:
une masse molaire moyenne en nombre faible comprise entre 500 et 5000 g/mol, un indice de polydispersité faible, généralement compris entre 1 et 2, et une structure amorphe avec une température de transition vitreuse comprise entre 10 et 70 °C. a low number average molar mass of between 500 and 5000 g / mol, a low polydispersity index, generally between 1 and 2, and an amorphous structure with a glass transition temperature of between 10 and 70 ° C.
Ces oligomères peuvent être utilisés pour améliorer la fluidité à l'état fondu de polymères ou de composites polymères/farines végétales. A titre d'exemple, les polymères peuvent être choisis parmi : l'amidon et les mélanges d'amidon, les polypeptides, le polyvinylalcool, les polyhydroxyalkanoates, po lydroxybutyrates et po lyhydroxyvalerates, - l'acide polylactique et les polylactates, le polychlorure de vinyle, et les polyoléfines, les dérivés cellulosiques comme l'acétate de cellulose, et les polyesters. Les farines végétales peuvent être choisies parmi : - les farines céréalières amylacées, telles que les farines de blé, mais ou 20 seigle, les farines de protéines, telles que les farines de féverole, lupin, colza, tournesol, soja ou caséine, et - les farines lignocellulosiques, telles que des fibres du bois, chanvre ou lin. These oligomers can be used to improve the melt flowability of polymers or polymer / vegetable meal composites. By way of example, the polymers may be chosen from: starch and starch mixtures, polypeptides, polyvinylalcohol, polyhydroxyalkanoates, hydroxybutyrates and polyhydroxyvalerates, polylactic acid and polylactates, polyvinylchloride vinyl, and polyolefins, cellulosic derivatives such as cellulose acetate, and polyesters. Vegetable flours may be chosen from: - starchy cereal flours, such as wheat flour, but or rye flours, protein flours, such as faba bean, lupine, rapeseed, sunflower, soy or casein, and - lignocellulosic flours, such as wood fibers, hemp or flax.
III. Exemples : oligomères de lactide Pour les deux exemples qui suivent : - les indices d'acide, définis par la masse de potasse nécessaire à la neutralisation de 1g de polymère, ont été déterminés par dosage de la norme DIN 53402, - les propriétés thermiques des matériaux ont été obtenues par calorimétrie par balayage différentiel, les caractéristiques en traction des matières plastiques ont été déterminées selon la norme I50/R 527, et l'indice de fluidité à l'état fondu des matières plastiques suit la norme I50 1133. III. Examples: oligomers of lactide For the following two examples: the acid values, defined by the mass of potash necessary for the neutralization of 1 g of polymer, were determined by assay of the standard DIN 53402, the thermal properties of the Materials were obtained by differential scanning calorimetry, the tensile characteristics of plastics were determined according to I50 / R 527, and the melt flow index of plastics follows I50 1133.
III.1. Exemple 1 a - Procédé d'obtention d'un oligomère d'acide lactique On chauffe entre 160 et 190°C un ballon contenant un mélange de L-lactide, d'acide succinique (entre 1 et 4% molaire vis-à-vis de l'acide lactique) et d'octoate d'étain (entre 0,1 et 2% massique de la masse totale), et on le connecte à un évaporateur rotatif. III.1. EXAMPLE 1a Process for Obtaining a Lactic Acid Oligomer A flask containing a mixture of L-lactide and succinic acid (between 1 and 4 mol% vis-a-vis) is heated between 160 and 190 ° C. lactic acid) and tin octoate (between 0.1 and 2% by weight of the total mass), and is connected to a rotary evaporator.
Le montage est placé sous pression réduite afin d'éliminer l'eau produite par les réactions de condensation. A t=0, le mélange est placé à 800mbar. Après trente minutes, la pression est diminuée progressivement jusqu'à 25mbar. The assembly is placed under reduced pressure in order to eliminate the water produced by the condensation reactions. At t = 0, the mixture is placed at 800mbar. After thirty minutes, the pressure is gradually decreased to 25mbar.
La réaction est arrêtée après 3 heures, et on récupère un oligomère. L'oligomère obtenu présente les caractéristiques suivantes : - il est amorphe avec une température de transition vitreuse de 43°C, et - il possède un indice d'acide de 30 mg KOH/g. b - Utilisation de l'oligomère d'acide lactique dans une formulation à base d'acide polylactique (PLA) On réalise le mélange A suivant : 75% en masse d'acide polylactique, 20% en masse de farine de blé, et 5% en masse de glycérol. On réalise le mélange B suivant : 75% en masse d'acide polylactique, 20% en masse de farine de blé, 6,6 % en masse de glycérol, et - 5% en masse de l'oligomère de lactide obtenu selon le procédé III.1.a. Les mélanges A et B sont extrudés à 180°C à l'aide d'une extrudeuse 15 bivis corotative. Les composés (A) et (B) obtenus par granulation des mélanges A et B sont injectés sur une presse afin de déterminer leurs caractéristiques de traction et leur indice de fluidité à l'état fondu. Les résultats obtenus pour le composé (B) contenant l'oligomère de 20 lactide selon l'invention sont présentés dans le tableau ci-dessous, les caractéristiques du composé (A) étant utilisées comme référence en base 100 : 10 Composé (A) Composé (B) (contenant l'oligomère de lactide) Indice de fluidité à l'état 100 2000 fondu (g/l0min, 2,16Kg/190°C) Contrainte maximale (MPa) 100 90 Allongement à contrainte 100 160 maximale (%) Contrainte à la rupture (MPa) 100 95 Allongement à la rupture (%) 100 180 Module de traction (MPa) 100 80 On constate que l'ajout d'un oligomère de lactide obtenu selon l'invention permet d'augmenter très sensiblement la fluidité à l'état fondu tout en diminuant la rigidité du mélange PLA-farine. L'oligomère de lactide obtenu selon l'invention joue donc bien un rôle de plastifiant. De plus, des études de biodégradabilité ont montré que le composé (B) présente des caractéristiques de biodégradabilité analogues à celles du composé (A). Ainsi l'ajout d'un oligomère de lactide obtenu selon l'invention conserve le caractère biodégradable du mélange PLA-farine. The reaction is stopped after 3 hours, and an oligomer is recovered. The oligomer obtained has the following characteristics: it is amorphous with a glass transition temperature of 43 ° C., and it has an acid number of 30 mg KOH / g. b - Use of the oligomer of lactic acid in a formulation based on polylactic acid (PLA) The following mixture A is carried out: 75% by weight of polylactic acid, 20% by weight of wheat flour, and % by weight of glycerol. The following mixture B is produced: 75% by weight of polylactic acid, 20% by weight of wheat flour, 6.6% by weight of glycerol, and -5% by weight of the lactide oligomer obtained by the process. III.1.a. Blends A and B are extruded at 180 ° C using a twin-screw corotative extruder. The compounds (A) and (B) obtained by granulation of the mixtures A and B are injected on a press in order to determine their tensile characteristics and their melt index. The results obtained for the compound (B) containing the lactide oligomer according to the invention are presented in the table below, the characteristics of the compound (A) being used as reference in base 100: Compound (A) Compound (B) (containing lactide oligomer) Melt flow rate at 100 2000 melt (g / 10 min, 2.16 Kg / 190 ° C) Maximum stress (MPa) 100 90 Stretch elongation 100 160 maximum (%) Stress at Break (MPa) 100 95 Elongation at Break (%) 100 180 Traction Module (MPa) 100 80 It is found that the addition of a lactide oligomer obtained according to the invention makes it possible to increase very substantially the melt flow while decreasing the rigidity of the PLA-flour mixture. The oligomer of lactide obtained according to the invention therefore plays a role of plasticizer. In addition, biodegradability studies have shown that the compound (B) has biodegradability characteristics similar to those of the compound (A). Thus, the addition of a lactide oligomer obtained according to the invention retains the biodegradable character of the PLA-flour mixture.
III.2. Exemple 2 a - Procédé d'obtention d'un oligomère d'acide lactique On chauffe entre 160 et 190°C un ballon contenant un mélange de L-lactide, d'acide succinique (entre 1 et 4% molaire vis-à-vis de l'acide lactique) et d'octoate d'étain (entre 0,1 et 2% massique de la masse totale), et on le connecte à un évaporateur rotatif. Le montage est placé sous pression réduite afin d'éliminer l'eau produite par les réactions de condensation. A t=0, le mélange est placé à 800mbar. III.2. EXAMPLE 2a Process for Obtaining a Lactic Acid Oligomer A flask containing a mixture of L-lactide and succinic acid (between 1 and 4 mol% vis-à-vis between 1 and 4 mol%) is heated between 160 and 190 ° C. lactic acid) and tin octoate (between 0.1 and 2% by weight of the total mass), and is connected to a rotary evaporator. The assembly is placed under reduced pressure in order to eliminate the water produced by the condensation reactions. At t = 0, the mixture is placed at 800mbar.
Après une heure, la pression est diminuée progressivement jusqu'à 25mbar. La réaction est arrêtée après 6 heures, et on récupère un oligomère : L'oligomère obtenu présente les caractéristiques suivantes : - il est amorphe avec une température de transition vitreuse de 46°C, et - il possède un indice d'acide de 22mg KOH/g. b - Utilisation de l'oligomère de lactide dans une formulation à base d'acide polylactique On réalise le mélange A suivant : - 50% en masse d'acide polylactique, 45% en masse de farine de blé, et 5% en masse de glycérol. On réalise le mélange B suivant : - 50% en masse d'acide polylactique, 45% en masse de farine de blé, 5% en masse de l'oligomère d'acide lactique obtenu selon le procédé III.2.a. Les mélanges A et B sont extrudés à 170°C à l'aide d'une extrudeuse bivis corotative. Les composés (A) et (B) obtenus par granulation des mélanges A et B sont injectés sur une presse afin de déterminer leurs caractéristiques de traction et leur indice de fluidité à l'état fondu. Les résultats obtenus pour le composé (B) contenant l'oligomère de lactide selon l'invention sont présentés dans le tableau ci-dessous, les caractéristiques du composé (A) étant utilisées comme référence en base 100 : Composé (A) Composé (B) (contenant l'oligomère de lactide) Indice de fluidité à l'état 100 400 fondu (g/10min, 2,16 Kg/190°C) Contrainte maximale (MPa) 100 95 Allongement à contrainte 100 80 maximale (%) Contrainte à la rupture (MPa) 100 110 Allongement à la rupture (%) 100 80 Module de traction (MPa) 100 95 On constate que l'ajout d'un oligomère d'acide lactique obtenu selon l'invention permet d'augmenter la fluidité à l'état fondu, d'augmenter les contraintes et de diminuer les allongements du mélange acide polylactique-farine. L'oligomère de lactide obtenu selon l'invention joue donc bien un rôle de plastifiant. De plus, des études de biodégradabilité ont montré que le composé (B) présente des caractéristiques de biodégradabilité analogues à celles du composé (A). Ainsi l'ajout d'un oligomère de lactide obtenu selon l'invention conserve le caractère biodégradable du mélange acide polylactique-farine. After one hour, the pressure is gradually decreased to 25mbar. The reaction is stopped after 6 hours, and an oligomer is recovered: The oligomer obtained has the following characteristics: - it is amorphous with a glass transition temperature of 46 ° C., and - it has an acid number of 22 mg KOH /boy Wut. b-Use of the oligomer of lactide in a formulation based on polylactic acid The following mixture is carried out as follows: 50% by weight of polylactic acid, 45% by weight of wheat flour, and 5% by weight of glycerol. The following mixture B is carried out: 50% by weight of polylactic acid, 45% by weight of wheat flour, 5% by weight of the lactic acid oligomer obtained according to process III.2.a. Blends A and B are extruded at 170 ° C using a corotative twin-screw extruder. The compounds (A) and (B) obtained by granulation of the mixtures A and B are injected on a press in order to determine their tensile characteristics and their melt index. The results obtained for the compound (B) containing the lactide oligomer according to the invention are presented in the table below, the characteristics of the compound (A) being used as reference in base 100: Compound (A) Compound (B) ) (containing lactide oligomer) Melt flow rate at 100 400 melt (g / 10min, 2.16 Kg / 190 ° C) Maximum stress (MPa) 100 95 Stretch elongation 100 80 maximum (%) Constraint at break (MPa) 100 110 Elongation at break (%) 100 80 Traction module (MPa) 100 95 It is found that the addition of a lactic acid oligomer obtained according to the invention makes it possible to increase the fluidity in the molten state, to increase the stresses and decrease the elongations of the polylactic acid-flour mixture. The oligomer of lactide obtained according to the invention therefore plays a role of plasticizer. In addition, biodegradability studies have shown that the compound (B) has biodegradability characteristics similar to those of the compound (A). Thus, the addition of a lactide oligomer obtained according to the invention retains the biodegradable character of the polylactic acid-flour mixture.
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| FR1152525A FR2973386B1 (en) | 2011-03-28 | 2011-03-28 | USE OF A BIODEGRADABLE LACTIDE OLIGOMER AS PLASTIFIERS |
| PCT/FR2012/050647 WO2012131252A1 (en) | 2011-03-28 | 2012-03-28 | Use of a biodegradable lactide oligomer as plasticizer |
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| US5180765A (en) * | 1988-08-08 | 1993-01-19 | Biopak Technology, Ltd. | Biodegradable packaging thermoplastics from lactides |
| WO2009148581A1 (en) * | 2008-06-03 | 2009-12-10 | Qlt Usa, Inc. | Biocompatible oligomer-polymer compositions |
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| EP1587443A4 (en) * | 2003-01-24 | 2006-04-05 | Tyco Healthcare | Bioabsorbable composition and coatings including same |
| US8980300B2 (en) * | 2004-08-05 | 2015-03-17 | Advanced Cardiovascular Systems, Inc. | Plasticizers for coating compositions |
| BRPI0600787A (en) * | 2006-02-24 | 2007-11-20 | Phb Ind Sa | environmentally degradable polymer composition and its method of obtaining |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180765A (en) * | 1988-08-08 | 1993-01-19 | Biopak Technology, Ltd. | Biodegradable packaging thermoplastics from lactides |
| WO2009148581A1 (en) * | 2008-06-03 | 2009-12-10 | Qlt Usa, Inc. | Biocompatible oligomer-polymer compositions |
Non-Patent Citations (1)
| Title |
|---|
| LEMMOUCHI Y ET AL: "Plasticization of poly(lactide) with blends of tributyl citrate and low molecular weight poly(d,l-lactide)-b-poly(ethylene glycol) copolymers", EUROPEAN POLYMER JOURNAL, PERGAMON PRESS LTD. OXFORD, GB, vol. 45, no. 10, 1 October 2009 (2009-10-01), pages 2839 - 2848, XP026612028, ISSN: 0014-3057, [retrieved on 20090714], DOI: 10.1016/J.EURPOLYMJ.2009.07.006 * |
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