• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to an at least partially biodegradable and at least partially biosourced polymeric material which comprises: a) a matrix of a polyester, for example polybutylene succinate; b) a biodegradable and biosourced reinforcing agent, for example polylactic acid, lignin, cellulose, cellulose ethers; c) an ionic liquid. The invention also relates to a film (for example a stretchable film), a bag or an article of crockery which is wholly or partly constituted of said material.
    公开号:FR3060014A1
    申请号:FR1662369
    申请日:2016-12-13
    公开日:2018-06-15
    发明作者:Sebastien Livi；Jannick DUCHET-RUMEAU；Jean-Francois Gerard
    申请人:Centre National de la Recherche Scientifique CNRS；Universite Claude Bernard Lyon 1 UCBL；Institut National des Sciences Appliquees de Lyon ；Universite Jean Monnet Saint Etienne；
    IPC主号:
    专利说明:

    Holder (s): NATIONAL INSTITUTE OF APPLIED SCIENCES OF LYON, CLAUDE BERNARD LYON 1 UNIVERSITY, NATIONAL CENTER OF SCIENTIFIC RESEARCH, JEAN MONNET SAINT ETIENNE UNIVERSITY.
    Extension request (s)
    Agent (s): LTL SAS.
    BIODEGRADABLE POLYMERIC MATERIAL AND BIOSOURCE.
    FR 3 060 014 - A1
    The invention relates to an at least partially biodegradable and at least partially biobased polymeric material which comprises:
    a) a matrix of a polyester, for example polybutylene succinate;
    b) a biodegradable and biobased reinforcing agent, for example polylactic acid, lignin, cellulose, cellulose ethers;
    c) an ionic liquid.
    The invention also relates to a film (for example a stretch film), a bag or a tableware which is made wholly or partly of said material.
    i
    The invention relates to an at least partially biodegradable and at least partially biobased polymeric material.
    In the context of the present invention, the term “at least partially biodegradable material” means a material capable of being totally or if not at least partially degraded by living organisms, in particular bacteria, so as to produce water, carbon dioxide and / or methane and possibly by-products such as residues or new biomass that are non-toxic to the environment.
    In the context of the present invention, the term "at least partially biobased material" means a material which comes in whole or in part from a biomass. In other words, it is a material at least partially if not totally organic, of plant origin (which notably includes algae and micro-algae), animal, bacterial or fungal, in the wild or cultivated state. Said material can thus be chosen from the materials resulting from a culture, but also its waste and / or its residues. Thus, if the material is biobased, it means that it is a completely organic material of plant, animal, bacterial or fungal origin.
    In the current context of environmental issues, intensive research is being carried out to develop new polymeric materials intended for various applications such as packaging (in particular plastic bags and films for the transport of goods), the manufacture of objects everyday life (e.g. disposable dishes).
    For example, plastic checkout bags are generally made of polyethylene, that is to say a material derived from petrochemicals. These plastic bags are the source of ecological problems: not only during their production due to the consumption of petroleum resources, but also after their use. Indeed, these bags cause environmental damage to flora and fauna when they are abandoned in a wild way. In addition, their treatment in recycling centers is complicated and costly and poses problems of emission of carbon dioxide and polluting fumes which must also be reprocessed.
    In an eco-design approach, we seek to develop plastic materials that have a small environmental footprint, so as to protect the environment and reduce the greenhouse effects with the reduction in the production of carbon dioxide.
    Research work has been undertaken to find alternatives to polymeric materials derived from petrochemicals.
    In this regard, as an example of an alternative material, mention may be made of the publication entitled “Phosphonium ionic liquids as new compatibilizing agents of biopolymer blends composed of poly (butylene-adipate-co-terephthalate) / poly (lactic acid) (PBAT / PLA) de Lins et al., RSC Adv., 2015, 5, 59082-59092, which describes materials comprising a matrix of poly (butylene adipate-co-terephthalate) (hereinafter abbreviated PBAT), namely a biodegradable but synthetic polymer, of polylactic acid (hereinafter abbreviated as PLA) as a reinforcing agent, as well as an ionic liquid.
    In addition, the publication entitled "Ionie liquids - lignin combination: an innovative way to improve mechanical behavior and water vapor permeability of eco-designed biodegradable polymer blends" by Livi et al., RCS Adv., 2015, 5, 19891998, describes materials also comprising a matrix of PBAT, PLA and lignin as reinforcing agents, as well as an ionic liquid.
    Such alternative materials described in these two publications have the following drawbacks:
    they include a matrix based on PBAT, which is a non-bio-based polymer; their mechanical properties are not as efficient as those of polymeric materials derived from petrochemicals. In addition, they can be disparate depending on the choice of reinforcing agents and ionic liquids.
    Also, there is a need for at least partially biodegradable and at least partially biobased materials having mechanical properties that are as efficient, or even better, than the materials known from the prior art; it would also be advantageous if these materials could be used during the manufacture of objects such as those mentioned above according to the same processability as materials from petrochemicals.
    The inventors of the present invention have developed polymeric materials which at least partially, if not completely, fulfill these objectives.
    The subject of the present invention is a polymeric material at least partially biodegradable and at least partially biobased which is characterized in that it comprises:
    a) a matrix comprising at least one polyester chosen from the group consisting of polybutylene succinate (hereinafter abbreviated as PBS), polybutylene terephthalate (hereinafter abbreviated as PBT), polybutylene succinate co-adipate (hereinafter abbreviated as PBSA) ), polymethylene adipate / terephthalate (hereinafter abbreviated as PTMAT), polyethylene isosorbide terephthalate (hereinafter abbreviated as PEIT) and poly (butylene succinate-coterephthalate (hereinafter abbreviated as PBST);
    b) at least one biodegradable and biobased reinforcing agent;
    c) at least one ionic liquid.
    The at least partially biodegradable and at least partially biobased polymeric material according to the invention has perfectly advantageous mechanical properties from a processability point of view by the conventional techniques for shaping polymeric materials, such as extrusion / stretching. , extrusion / blowing, extrusion / inflation, injection and thermoforming.
    Indeed, said material has a rigidity characterized by a Young's modulus and by a percentage of deformation at break which is in line with the required rigidity of the polymeric materials which are shaped by the aforementioned techniques.
    In addition, the material according to the invention has excellent fire-fighting and water vapor barrier properties. This water vapor barrier property is particularly advantageous when the polymeric material according to the invention is intended for the manufacture of packaging, in particular food packaging. Indeed, this property increases the shelf life of foodstuffs.
    The material according to the invention also has good gas barrier properties.
    In one embodiment of the invention, the matrix comprises at least one partially biobased polyester which is PBT or PEIT.
    In one embodiment of the invention, the matrix comprises at least one biodegradable polyester which is chosen from PBS, PBSA, PTMAT and PBST. PBS is also a bio-based polymer.
    Preferably, the polyester is chosen from PBS, PBT and PEIT. Even more preferably, it is PBS which is biodegradable and bio-based.
    In one embodiment of the invention, the polymeric material comprises a single reinforcing agent.
    In another embodiment of the invention, the polymeric material comprises two reinforcing agents.
    The biodegradable and biobased reinforcing agent can be chosen from the group consisting of polylactic acid (abbreviated PLA), polyhydroxyalkanoate (hereinafter abbreviated PHA), polyhydroxybutyrate (hereinafter abbreviated
    PHB), polyhydroxyvalerate (hereinafter abbreviated as PHV), lignin, cellulose, cellulose ethers such as methyl cellulose (hereinafter abbreviated as MC), hydroxyethyl cellulose (hereinafter abbreviated as HEC), carboxymethyl cellulose (hereinafter abbreviated as CMC) and methylhydroxy propyl cellulose (hereinafter abbreviated as MHPC).
    Advantageously, the reinforcing agent is chosen from PLA, lignin, cellulose and cellulose ethers.
    Preferably, the lignin is a lignosulfonate. For example, it may be an ammonium, calcium, magnesium, sodium or potassium lignosulfonate.
    Lignin, cellulose and cellulose ethers are renewable materials. Indeed, they come from co-products or waste, for example waste from the paper industry. This is why, when the polymeric material according to the invention comprises these constituents as a recovery agent, this is particularly advantageous from an environmental point of view. Indeed, the material according to the invention has the advantage of recycling waste.
    In the context of the present invention, the term “ionic liquids” is understood to mean salts having a melting temperature below 100 ° C. and which are, for the most part, liquid at a temperature close to ambient temperature (approximately 25 ° C. ). These salts consist of organic cations complexed with inorganic or organic anions.
    The anion can be selected from the group consisting of dialkyl phosphate anions, dialkylphosphinate, dicyanamide, bis (trifluoromethylsulfonyl) imide, bis (trifluoromethane) sulfonimide, alkyl carboxylate, hexafluorophosphate, sulfonate, sulfate, tetrafluoroborate, trifluoromethanesulfonate, [C 4 F g SO 3] , [CF 3 CO 2 ], [(CF 3 SO 2 ) 3 C] “, [(CF 3 SO 2 ) 2 N]“, nitrate, [CIO 4 ], F, Br, Cl, Γ, [AI 2 CI 7 ], chloroaluminate, [CuCI 2 ], [AuCI 4 ], [ZnCI 3 ], [SnCI 3 ], as well as their mixtures.
    Preferably, the anion is chosen from the group comprising the dialkylphosphate, dialkylphosphinate, dicyanamide, alkylcarboxylate anions and their mixtures, where the alkyl group is linear or branched and comprises from 1 to 12, preferably from 2 to 8, carbon atoms .
    The organic cation can be chosen from the group consisting of the tetraalkylphosphonium, Ν, Ν-dialkylimidazolium, N-alkylpyridinium, Ndialkylpiperidinium, N-dialkylpyrrolidinium, tetraalkylammonium, pyrazolium, Nalkylthiazolium, trialkylsulfonium cations.
    Preferably, the ionic liquid is formed from a tetraalkylphosphonium cation, the alkyl group of which is advantageously linear and contains from 1 to 18, preferably from 4 to 14 carbon atoms.
    The ionic liquid (abbreviated L1) can be chosen from the group consisting of trihexyl (tetradecyl) phosphonium bistriflimide (abbreviated LI-TFSI), trihexyl (tetradecyl) phosphonium chloride (abbreviated LI-CI), trihexyl (tetradecyl) phosphonium bromide (abbreviated L1-Br), trihexyl (tetradecyl) phosphonium bis-2,4,4,4 (trimethylpentyl) phosphinate (abbreviated LITMP), trihexyl (tetradecyl) phosphonium bis-2- (ethylhexyl) phosphate (abbreviated LlEHP), trihexyl (tetradecyl) phosphonium 2-ethylhexanoate (abbreviated LI-EHT) and tributylethylphosphonium diethylphosphate (abbreviated L1-Ph).
    Preferably, the ionic liquid is chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    lignin and / or cellulose and / or at least one cellulose ether and / or PLA;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    lignin and / or PLA;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    lignin and cellulose;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    lignin and at least one cellulose ether;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    PLA and cellulose;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    In one embodiment of the invention, the polymeric material comprises at least:
    - duPBS;
    PLA and at least one cellulose ether;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    The at least partially biodegradable and at least partially biobased polymeric material can comprise, in mass percentages expressed relative to the total mass of said material:
    at) between 10% and 80%, preferably between 50% preferentially between 50% and 70%, of the matrix, and 80%, again more b) between 10% and 80%, preferably between 10% and 50%, again more preferably between 10% and 30%, of the agent of enhancement biodegradable and bio-based, vs) between 0.5% and 5%, preferably between 0.5% and 2%, again more
    preferably between 0.5% and 1%, of the ionic liquid.
    The polymeric material according to the invention can also comprise at least one optional compound chosen from:
    fillers, in particular reinforcing fillers (which are different from the reinforcing agents that said material comprises), opacifying fillers and conductive fillers, for example carbon nanotubes, carbon fibers, carbon black, fibers glass, silica, titanium or clays; flame retardants;
    anti-ultraviolet agents; thermal stabilizers; pigments and / or dyes; bactericidal agents; and catalysts;
    taken alone or in mixtures.
    The present invention also relates to a process for manufacturing the polymeric material as described above which is characterized in that it comprises at least one step consisting in the preparation of a mixture containing at least the matrix, the agent reinforcement and the ionic liquid as described above.
    The inventors have found that the ionic liquid promotes the dispersion of the reinforcing agent in the matrix and also acts as a compatibilizing agent for the latter, in the case where the reinforcing agent is a polymer normally immiscible with the matrix polymer. When the reinforcing agent is lignin, cellulose or a cellulose ether, the ionic liquid promotes the dissolution of this reinforcing agent in the matrix.
    Thus, the presence of the ionic liquid in the material according to the invention promotes mixing of the compounds present and makes it possible to obtain a perfectly homogeneous material.
    The mixing can be carried out with stirring, the speed of which is advantageously between 50 revolutions / minute and 300 revolutions / minute, preferably between 80 revolutions / minute and 200 revolutions / minute, at a temperature advantageously between 150 ° C and 190 ° C , preferably between 150 ° C and 170 ° C.
    The mixture may further comprise the optional compounds which have been described above.
    The order of incorporation of the various constituents in the mixture does not matter.
    In one embodiment of the invention, the matrix and the ionic liquid are first mixed together, then the reinforcing agent is added thereto.
    In another embodiment of the invention, a premix is prepared containing the ionic liquid and the reinforcing agent. Then, this premix is added to the matrix so as to obtain said mixture.
    The mixing can be carried out in any polymer kneading device, for example a twin screw mixer. These devices are perfectly within the reach of those skilled in the art. For example, it may be the device marketed by the company THERMOFISHER under the trade name HAAKE MiniCTW®.
    The manufacture of the polymeric material according to the invention is perfectly within the reach of a person skilled in the art who masters the techniques of polymeric blends. Thus, the stirring and temperature parameters of the mixture which have been detailed above are perfectly within the reach of those skilled in the art.
    The polymeric material according to the invention can then be shaped by different techniques perfectly within the reach of those skilled in the art, such as extrusion, extrusion / inflation, extrusion / blowing, extrusion / drawing. , injection and thermoforming.
    The subject of the invention is also a film, preferably a stretch film, consisting wholly or in part of the polymeric material as described above. This film may have been manufactured using conventional stretch film manufacturing techniques such as extrusion / stretching and inflation extrusion. These techniques are perfectly mastered by those skilled in the art.
    In one embodiment of the invention, the film is a mulching film.
    The subject of the invention is also a bag made entirely or in part of the film as described above.
    The subject of the invention is also an article of tableware, in particular disposable tableware, which is made wholly or in part of the polymeric material at least partially biodegradable and at least partially biosourced as described above. This article can be a goblet, a cup, a plate, a glass, a fork, a spoon or a knife. Said tableware article may have been manufactured using conventional techniques for manufacturing such articles, for example by injection or thermoforming. These techniques are perfectly mastered by those skilled in the art.
    EXPERIMENTAL PART :
    Experiments were carried out on polymeric materials according to the invention in order to determine their mechanical properties and to compare them with those of other so-called "comparative" materials whose matrix consisted of P BAT.
    PBAT is a biodegradable but synthetic polymer, that is to say not biobased.
    Within the framework of these experiments, the following mechanical properties were determined:
    a) Young's modulus expressed in MPa (hereinafter abbreviated as “Module”);
    b) the percentage of deformation at break (hereinafter abbreviated as “Deformation”);
    c) the stress expressed in MPa.
    The Young's modulus, the percentage of deformation at break and the stress were determined by implementing the operating mode as described in the European standards NF EN ISO 527-1: 1996 and NF EN ISO 527-2: 1996.
    All the polymeric materials according to the invention were prepared in the following manner:
    Was mixed in a twin-screw mixer sold by the company DSM XPLORE under the trade name "Xplore® MC 15" at a temperature of 160 ° C. and with stirring at 100 revolutions / minute, according to the quantities indicated below for each of the materials, a matrix (PBS or PBAT), a reinforcing agent (PLA or lignin), and if necessary an ionic liquid (LI-TMP or LI-EHT or LI-CI or Li-Ph or Ll-Br).
    The mixture thus obtained was then shaped with a micro-injection molding device sold by the company DSM XPLORE under the trade name "Xplore® IM 12" to obtain polymeric materials having the shape of a dumbbell test tube of 2 mm of thickness in accordance with the dumbbell test pieces detailed in the above-mentioned standards.
    I - Comparison of the mechanical properties of polymeric materials according to the invention, the matrix of which is PBS and the reinforcing agent is PLA with those of so-called “comparative” materials, the matrix of which is PBAT:
    The following polymeric materials according to the invention were prepared. The percentages indicated are the mass contents of each of the constituents relative to the total mass of said material:
    79.2% PBS, 19.8% PLA and 1% LI-TMP (hereinafter abbreviated: PBS / PLA / LI-TMP);
    - 79.2% PBS, 19.8% PLA and 1% LI-EHP (hereinafter abbreviated:
    PBS / PLA / LI-EHP);
    79.2% PBS, 19.8% PLA and 1% LI-CI below abbreviated:
    PBS / PLA / LI-CI).
    In addition, a material comprising, in mass contents relative to the total mass of said material: 80% PBS and 20% PLA was prepared. This material is abbreviated below PBS / PLA.
    Table 1 details below the mechanical properties of the dumbbell test pieces made of these different materials, as well as those made only of PBS or PLA.
    ίο
    Samples Module (MPa) Deformation (%) Constraint (Mpa) PLA 2507 4 70 PBS 377 370 39.5 PBS / PLA 450 595 38 PBS / PLA / LI-TMP 500 680 38 PBS / PLA / LI-EHP 460 550 36 PBS / PLA / LI-CI 560 560 36
    Table 1 detailing the mechanical properties of PLA, PBS, a PBS / PLA material and 3 polymeric motérioux according to the invention.
    PLA is a very rigid polymer (Young's modulus of 2507 MPa) but also very brittle (4% deformation at break). This is why, in view of the mechanical properties of PBS / PLA, it is noted that PLA brings to PBS a significant increase in Young's Modulus (450 instead of 377 MPa).
    When the materials also comprise 1% of ionic liquid (namely the materials according to the invention), according to the results in Table 1, a slight increase in rigidity is observed in all cases and in particular for IL-TMP and IL-CI with increases of 10% and 25% of the Young's Modulus, while retaining a deformation greater than 500% except in the case of LI-TMP where a clearer increase in the deformation at break is observed going from 595% to 680%.
    In other words, the materials according to the invention have better rigidity than the material containing only PBS and that containing a mixture of PBS / PLA, and this while retaining a percentage of deformation at break. This is advantageous for the techniques for forming polymeric materials which have been detailed above. The increase in Young's modulus is particularly advantageous for the applications for which the polymeric materials according to the invention are intended.
    Next, the mechanical properties of these polymeric materials according to the invention were compared with those of a polymeric material which had PBAT as its matrix.
    The following comparative polymeric materials were prepared. The percentages indicated are the mass contents of each of the constituents relative to the total mass of said material:
    79.2% PBAT, 19.8% PLA and 1% LI-TMP (hereinafter abbreviated:
    PBAT / PLA / LI-TMP);
    - 79.2% of PBAT, 19.8% of PLA and 1% of LI-EHP (hereinafter abbreviated: PBAT / PLA / LI-EHP);
    79.2% PBAT, 19.8% PLA and 1% LI-CI hereinafter abbreviated: PBAT / PLA / LI-CI);
    - 79.2% of PBAT, 19.8% of PLA and 1% of LI-TFSI hereinafter abbreviated: PBAT / PLA / LI-TFSI).
    - 79.2% of PBAT, 19.8% of PLA and 1% of LI-EHT hereinafter abbreviated: PBAT / PLA / LI-EHT).
    In addition, a polymeric material comprising, in mass contents relative to the total mass of said material: 80% of PBAT and 20% of PLA was prepared. This material is abbreviated below PBAT / PLA.
    Table 2 details below the mechanical properties of these various so-called comparative polymer materials, as well as those of PBAT and PLA.
    Samples Module (MPa) Deformation (%) Stress (MPa) PLA 2507 4 70 PBAT 38 582 20 PBAT / PLA 115 540 23 PBAT / PLA / LI-TMP 165 910 28 PBAT / PLA / LI-EHP 135 915 26 PBAT / PLA / LI-CI 140 1000 24 PBAT / PLA / LI-TFSI 138 675 22 PBAT / PLA / LI-EHT 215 620 28
    Table 2 detailing the mechanical properties of PLA, PBAT, a PBAT / PLA material and comparative polymeric materials
    In view of the results expressed in table 2 above, in particular by comparing with the values of the PBAT / PLA material, it is noted that for polymeric materials whose matrix is PBAT, the presence of the ionic liquid certainly increases the modulus of Young and the percentage of the strain at break. However, in comparison with the values detailed in table 1, the values of the Young's moduli of these polymeric materials of the order of 115-215 MPa are much lower (by more than half) than those of the polymeric materials according to the invention which are of the order of 500 MPa.
    Thus, the polymeric materials according to the invention have better rigidity than the polymeric materials whose matrix is PBAT.
    II - Comparison of the mechanical properties of materials according to the invention whose matrix is PBS and the reinforcing agent is lignin with those of so-called “comparative” materials whose matrix is PBAT:
    The following polymeric materials according to the invention were prepared. The percentages indicated are the mass contents of each of the constituents relative to the total mass of said material:
    79.2% PBS, 19.8% lignin and 1% LI-CI (hereinafter abbreviated: PBS / 20% lignin / 1% LI-CI);
    78.4% PBS, 19.6% lignin and 2% LI-CI (hereinafter abbreviated: PBS / 20% lignin / 2% LI-CI);
    76.2% PBS, 19% lignin and 4.8% LI-CI (hereinafter abbreviated: PBS / 20% lignin / 5% LI-CI);
    78.4% PBS, 19.6% lignin and 2% LI-TMP (hereinafter abbreviated: PBS / 20% lignin / 2% LI-TMP);
    78.4% PBS, 19.6% lignin and 2% LI-TFSI (hereinafter abbreviated: PBS / 20% lignin / 2% LI-TFSI);
    57.1% PBS, 38.1% lignin and 4.8% LI-CI (hereinafter abbreviated: PBS / 40% lignin / 5% LI-CI);
    57.1% PBS, 38.1% lignin and 4.8% Ll-Br (hereinafter abbreviated: PBS / 40% lignin / 5% Ll-Br).
    In addition, polymeric materials comprising, in mass contents relative to the total mass of said material respectively 80% PBS and 20% lignin and 60% PBS and 40% lignin were prepared. These materials are abbreviated below respectively PBS / 20% lignin and PBS / 40% lignin.
    Table 3 details the mechanical properties of these various polymeric materials below, as well as those of PBS.
    Sample Module (MPa) Rupture deformation (%) Stress (MPa) PBS 377 370 39.5 PBS / 20% lignin 450 380 31 PBS / 20% lignin / 1% LI-CI 430 400 36 PBS / 20% lignin / 2% LI-CI 475 350 31 PBS / 20% lignin / 5% LI-CI 465 290 29 PBS / 20% lignin / 2% LI-TMP 515 21 29 PBS / 20% lignin / 2% LI-TFSI 560 30 28 PBS / 40% lignin 625 8 26 PBS / 40% lignin / 5% LI-CI 595 6 22 PBS / 40% lignin / 5% Ll-Br 785 4 23
    Table 3 detailing the mechanical properties of PBS, PBS / lignin materials,
    PBS / 40% lignin and 7 polymeric materials according to the invention.
    In view of the results detailed in Table 3, it is noted that the addition of 20% of lignin in a PBS matrix leads to an increase in rigidity of the order of 19% compared to the rigidity of the material consisting of a matrix of PBS and makes it possible to keep an identical deformation at break. This shows that it is possible to add lignin without observing any loss of mechanical properties in uniaxial traction.
    When 40% lignin is added to the PBS matrix, an increase in Young's modulus is observed (of the order of 66%). In addition, a significant reduction in the deformation is obtained: indeed, one passes from a deformation of 380% to a deformation of 8%.
    Thus, in the polymeric material according to the invention, lignin contributes to increasing the Young's modulus of said material; which is very advantageous for the applications mentioned above for which said material is intended.
    When the polymeric material according to the invention comprises 1% of LI-CI, a very slight decrease in the Young's modulus is observed and a slight increase in the deformation is obtained. And when the polymeric material according to the invention comprises 2%, and even 5% of LI-CI, a conservation of the mechanical properties is observed in terms of Young's moduli and deformation at break.
    When the nature of the ionic liquid in the polymeric material according to the invention is changed, increases in Young's modulus are observed (plus 14% for LI-TMP and plus 25% for LI-TFSI) which are coupled with decreases in the strain at break from 380% to 25-30%. Due to the high Young's modulus, these polymeric materials according to the invention have very advantageous mechanical properties for the shaping techniques mentioned above (for example injection and thermoforming).
    Thus, depending on the intended application, by varying the nature of the ionic liquid, it is possible to increase either the deformation at break or the rigidity.
    For polymeric materials according to the invention comprising 40% of lignin, an increase in rigidity compared to PBS of 66% is obtained. When the polymeric material according to the invention comprises 5% of LI-TFSI, an increase of 108% is obtained with modules of 625 and 785 MPa compared to the value of 377 MPa.
    Next, the mechanical properties of the polymeric materials according to the invention were compared with those of materials having a PBAT matrix.
    The following comparative polymeric materials were prepared. The percentages indicated are the mass contents of each of the constituents relative to the total mass of said material:
    79.2% PBAT, 19.8% lignin and 1% Ll-Ph (hereinafter abbreviated: PBAT / 20% lignin / 1% Ll-Ph);
    78.4% PBAT, 19.6% lignin and 2% Ll-Ph (hereinafter abbreviated: PBAT / 20% lignin / 2% Ll-Ph);
    76.2% PBAT, 19% lignin and 4.8% Ll-Ph (hereinafter abbreviated: PBAT / 20% lignin / 5% Ll-Ph);
    69.3% PBAT, 29.7% lignin and 1% Ll-Ph (hereinafter abbreviated: PBAT / 30% lignin / 1% Ll-Ph);
    68.6% PBAT, 29.4% lignin and 2% Ll-Ph (hereinafter abbreviated: PBAT / 30% lignin / 2% Ll-Ph);
    66.7% PBAT, 28.5% lignin and 4.8% Ll-Ph (hereinafter abbreviated: PBAT / 30% lignin / 5% Ll-Ph);
    79.2% PBAT, 19.8% lignin and 1% LI-CI (hereinafter abbreviated: PBAT / 20% lignin / 1% LI-CI);
    78.4% PBAT, 19.6% lignin and 2% LI-CI (hereinafter abbreviated: PBAT / 20% lignin / 2% LI-CI);
    76.2% PBAT, 19% lignin and 4.8% LI-CI (hereinafter abbreviated: PBAT / 20% lignin / 5% LI-CI);
    69.3% PBAT, 29.7% lignin and 1% LI-CI (hereinafter abbreviated: PBAT / 30% lignin / 1% LI-CI);
    68.6% PBAT, 29.4% lignin and 2% LI-CI (hereinafter abbreviated: PBAT / 30% lignin / 2% LI-CI);
    66.7% PBAT, 28.5% lignin and 4.8% LI-CI (hereinafter abbreviated: PBS / 30% lignin / 5% LI-CI).
    Table 4 details below the mechanical properties of these various so-called comparative polymer materials, as well as those of PBAT.
    Sample Module(MPa) Rupture deformation (%) Constraint(MPa) PBAT 38 582 20 PBAT / 20% lignin / 1% Ll-Ph 49 749 19 PBAT / 20% lignin / 2% Ll-Ph 55 745 14 PBAT / 20% lignin / 5% Ll-Ph 44 617 17 PBAT / 30% lignin / 1% Ll-Ph 61 483 13 PBAT / 30% lignin / 2% Ll-Ph 58 401 12 PBAT / 30% lignin / 5% Ll-Ph 40 561 16 PBAT / 20% Lignin / 1% LI-CI 36 532 23 PBAT / 20% Lignin / 2% LI-CI 39 549 20 PBAT / 20% Lignin / 5% LI-CI 38 642 20 PBAT / 30% Lignin / 1% LI-CI 54 455 17 PBAT / 30% Lignin / 2% LI-CI 38 551 19 PBAT / 30% Lignin / 5% LI-CI 61 459 14
    Table 4 detailing the mechanical properties of PBAT and comparative polymeric materials
    In view of the results of Table 4 and in comparison with those of Table 3, it is noted that these comparative polymeric materials have a Young's modulus approximately 10 times lower than that of the polymeric materials according to the invention.
    Unlike the polymeric materials according to the invention, these comparative polymeric materials do not have a satisfactory rigidity for their shaping according to the techniques detailed above (namely extrusion / inflation, extrusion / blowing, extrusion / stretching, injection and thermoforming).
    权利要求:
    Claims (11)
    [1" id="c-fr-0001]
    1. Polymeric material at least partially biodegradable and at least partially biobased, characterized in that it comprises at least:
    a) a matrix comprising at least one polyester chosen from the group consisting of polybutylene succinate (abbreviated PBS), polybutylene terephthalate (abbreviated PBT), polybutylene succinate co-adipate (abbreviated PBSA), polymethylene adipate / terephthalate (abbreviated PTMAT), polyethylene isosorbide terephthalate (abbreviated PEIT) and poly (butylene succinate-co-terephthalate (abbreviated PBST);
    b) at least one biodegradable and biobased reinforcing agent;
    c) at least one ionic liquid.
    [2" id="c-fr-0002]
    2. Polymeric material according to claim 1, characterized in that the polyester is chosen from PBS, PBT and PEIT.
    [3" id="c-fr-0003]
    3. Polymeric material according to claim 1 or 2, characterized in that the reinforcing agent is chosen from the group consisting of polylactic acid (abbreviated PLA), polyhydroxyalkanoate (abbreviated PHA), polyhydroxybutyrate (abbreviated PHB), polyhydroxyvalerate (abbreviated PHV), lignin, cellulose and cellulose ethers.
    [4" id="c-fr-0004]
    4. Polymeric material according to claim 3, characterized in that the reinforcing agent is chosen from PLA, lignin, cellulose and cellulose ethers.
    [5" id="c-fr-0005]
    5. Polymeric material according to any one of claims 1 to 4, characterized in that the ionic liquid is chosen from the group consisting of
    trihexyl (tetradecyl) phosphonium bistriflimide (abbreviated LI-TFSI), the trihexyl (tetradecyl) phosphonium chloride (abbreviated LI-CI), the trihexyl (tetradecyl) phosphonium bromide (abbreviated Ll-Br), the
    trihexyl (tetradecyl) phosphonium bis-2,4,4,4 (trimethylpentyl) phosphinate (abbreviated LITMP), trihexyl (tetradecyl) phosphonium bis-2- (ethylhexyl) phosphate (abbreviated LlEHP), trihexyl (tetradecyl) phosphonium 2- ethylhexanoate (abbreviated LI-EHT) and tributylethylphosphonium diethylphosphate (abbreviated LI-Ph).
    [6" id="c-fr-0006]
    6. Polymeric material according to any one of claims 1 to
    5, characterized in that it comprises at least:
    - duPBS;
    lignin and / or PLA;
    at least one ionic liquid, preferably an ionic liquid chosen from LI-CI, LI-TMP and Ll-Ph.
    [7" id="c-fr-0007]
    7. Polymeric material according to any one of claims 1 to
    6, characterized in that it comprises, in percentages by mass expressed relative to the total mass of said material:
    a) between 10% and 80%, preferably between 50% and 80%, of the matrix,
    b) between 10% and 80%, preferably between 10% and 50%, of the biodegradable and biobased reinforcing agent,
    c) between 0.5% and 5%, preferably between 0.5% and 2%, of the ionic liquid.
    [8" id="c-fr-0008]
    8. Polymeric material according to any one of claims 1 to
    7, characterized in that it also comprises at least one optional compound chosen from fillers, flame retardants, anti-ultraviolet agents, thermal stabilizers, pigments and / or dyes, bactericidal agents and catalysts, taken alone or in mixtures.
    [9" id="c-fr-0009]
    9. Film, preferably stretch film, made wholly or partly of polymeric material according to any one of claims 1 to 8.
    [10" id="c-fr-0010]
    10. Bag made entirely or in part of the film according to claim
    [11" id="c-fr-0011]
    11. An article of dishes consisting entirely or in part of the polymeric material according to any one of claims 1 to 8.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3060014A1|2018-06-15|BIODEGRADABLE POLYMERIC MATERIAL AND BIOSOURCE
    Luo et al.2012|Effect of gelatinization and additives on morphology and thermal behavior of corn starch/PVA blend films
    JP4495535B2|2010-07-07|Polylactic acid biaxially stretched laminated film and use thereof
    US20070259195A1|2007-11-08|Polylactic acid composition, transparent heat resistant biodegradable molded article made of the same, and method for making the article
    Markarian2008|Biopolymers present new market opportunities for additives in packaging
    US20130220173A1|2013-08-29|Macrophyte-based bioplastic
    EP3298064A1|2018-03-28|High-viscosity polyester with improved impact properties
    TW201000540A|2010-01-01|Thermoformed article made from bio-based biodegradable polymer composition
    US8604123B1|2013-12-10|Biodegradable polymer composition with calcium carbonate and methods and products using same
    Pardo‐Ibáñez et al.2014|Keratin–polyhydroxyalkanoate melt‐compounded composites with improved barrier properties of interest in food packaging applications
    Falcão et al.2017|PBAT/organoclay composite films: preparation and properties
    EP3415565B1|2020-12-16|Biodegradable polyester resin composition and molded article formed from said resin composition
    Rojas-Lema et al.2020|Tailoring the properties of thermo-compressed polylactide films for food packaging applications by individual and combined additions of lactic acid oligomer and halloysite nanotubes
    US20120238673A1|2012-09-20|Bio-resins
    WO2012069721A1|2012-05-31|Biodegradable thermoplastic material
    JP4441210B2|2010-03-31|Biodegradable polyester resin composition
    CN102993653B|2014-08-20|Biodegradable heat-shrinkable material, biodegradable heat-shrinkable film and preparation method of biodegradable heat-shrinkable film
    CN110446754A|2019-11-12|It being capable of biodegradable film
    Rodrigues et al.2021|Preparation and characterization of polymeric films based on PLA, PBAT and corn starch and babassu mesocarp starch by flat extrusion
    EP2558535B1|2014-07-16|Composition of polymers derived from renewable resources
    FR3086663A1|2020-04-03|PROCESS FOR THE PREPARATION OF A POLYESTER OF THE POLY TYPE |
    EP3290477B1|2020-01-08|Recyclable, biodegradable and/or compostable food-grade plastic composition, rigid items derived from same, and corresponding methods and uses
    Ballesteros et al.2018|Processing, production methods and characterization of bio-based packaging materials
    Srivastava et al.2021|Biodegradable Fibre-Based Composites as Alternative Materials for Sustainable Packaging Design
    KR20210005851A|2021-01-15|Homogeneous polymer mixtures, methods related thereto, and uses thereof
    同族专利:
    公开号 | 公开日
    EP3555209A1|2019-10-23|
    WO2018108881A1|2018-06-21|
    FR3060014B1|2020-03-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN103352267B|2013-06-19|2015-05-13|东华大学|Preparation method for new type fully-degradable cellulose composite fiber with skin-core structures|
    FR3014885A1|2013-12-17|2015-06-19|Univ Reims Champagne Ardenne|COMPOSITION BASED ON AGRO-SOURCE AND BIODEGRADABLE POLYMERS|
    CN113166484A|2018-12-14|2021-07-23|三菱瓦斯化学株式会社|Resin composition, resin sheet, security card, and method for producing resin composition|
    CN110964301A|2019-11-15|2020-04-07|湖南骏泰新材料科技有限责任公司|Lignin-based flame-retardant biodegradable polylactic acid film and preparation method thereof|
    CN110819086A|2019-11-26|2020-02-21|卢贵宝|Preparation method of easily degradable plastic film|
    法律状态:
    2017-12-21| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-15| PLSC| Publication of the preliminary search report|Effective date: 20180615 |
    2019-12-19| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-23| PLFP| Fee payment|Year of fee payment: 5 |
    2021-12-28| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1662369A|FR3060014B1|2016-12-13|2016-12-13|BIODEGRADABLE POLYMERIC MATERIAL AND BIOSOURCE|
    FR1662369|2016-12-13|FR1662369A| FR3060014B1|2016-12-13|2016-12-13|BIODEGRADABLE POLYMERIC MATERIAL AND BIOSOURCE|
    PCT/EP2017/082375| WO2018108881A1|2016-12-13|2017-12-12|Biodegradable and biosourced polymeric material|
    EP17811609.1A| EP3555209A1|2016-12-13|2017-12-12|Biodegradable and biosourced polymeric material|
    [返回顶部]