COMPOSITION MODIFYING THE MECHANICAL PROPERTIES OF A THERMOPLASTIC POLYMER

Abstract

The use of a composition including at least one saturated free fatty acid and at least one unsaturated free fatty acid as additive, for modifying the mechanical properties of a thermoplastic polymer material. An additivated thermoplastic polymer material and a process for producing same are also described.

Claims

1-15. (canceled)

16. Method for manufacturing an additivated thermoplastic polymer material which comprises a step of additivation at least one thermoplastic polymer material with a composition comprising at least one saturated free fatty acid and at least one unsaturated free fatty acid, as an additive, in order to modify the mechanical properties of said at least one thermoplastic polymer material.

17. Method according to claim 16, wherein the thermoplastic polymer material comprises at least one thermoplastic polymer chosen from poly(vinyl chloride), a polyamide or a polyester.

18. Method according to claim 17, wherein the polyester is a polyester from the family of polyethylene terephthalates or a biodegradable polyester.

19. Method according to claim 16, wherein the thermoplastic polymer material is polylactic acid, polylactide or one of the copolymers thereof.

20. Method according to claim 16, wherein the composition comprising at least one saturated free fatty acid and at least one unsaturated free fatty acid is comprised in a vegetable oil deodorization condensate.

21. Method according to claim 20, wherein the thermoplastic polymer material is additivated with a mass proportion of vegetable oil deodorization condensate ranging from 1 to 30%, preferentially from 5 to 15%, by weight with respect to the total weight of the additivated thermoplastic polymer material by said vegetable oil deodorization condensate.

22. Method according to claim 20, wherein the vegetable oil is chosen from soy oil, olive oil, palm oil, rapeseed oil, peanut oil, almond oil, sunflower oil, oleic sunflower oil, palm kernel oil, grape seed oil, pumpkin seed oil, corn oil, walnut oil, wheat germ oil, borage oil, hazelnut oil, cameline oil, hemp oil, macadamia oil, primrose oil.

23. Method according to claim 20, wherein the vegetable oil deodorization condensate is obtained during the step of deodorization of a method of physical or chemical refining of a vegetable oil, by distillation of fatty acids, with said vegetable oil being agitated with a quantity of injected steam ranging from 7.5 to 8.5 kg/h, at a temperature ranging from 180 to 260 C., and under an absolute pressure less than 5 mBar.

24. Method according to claim 23, wherein the vegetable oil deodorization condensate is obtained by physical refining at a temperature ranging from 240 to 260 C.

25. Method according to claim 20, wherein the vegetable oil deodorization condensate comprises a mass proportion of free fatty acids with respect to the total weight of the vegetable oil deodorization condensate ranging from 15 to 100%.

26. Additivated thermoplastic polymer material comprising at least one thermoplastic polymer chosen from poly(vinyl chloride), polyesters from the polyethylene terephthalate family and biodegradable polyesters, wherein the thermoplastic polymer is additivated by at least one vegetable oil deodorization condensate.

27. Additivated thermoplastic polymer material according to claim 26, wherein the thermoplastic polymer is a biodegradable material consisting of polylactic acid, polylactide and/or one of the copolymers thereof.

28. Additivated thermoplastic polymer material according to claim 27, wherein the mass proportion of the vegetable oil deodorization condensate with respect to the total weight of the additivated thermoplastic material ranges from 5 to 30%, with said material having the following mechanical properties, measured in uniaxial traction according to the standard ISO 527-2: a breaking elongation ranging from 30 to 300%, a Young's modulus greater than 1200 MPa, a yield stress greater than 15 MPa, said material further having a glass transition temperature, measured by TMDSC (temperature modulated differential scanning calorimetry) ranging from 45 to 55 C. at atmospheric pressure.

29. Food packaging carried out in an additivated thermoplastic polymer material according to claim 26.

30. Food packaging carried out in an additivated thermoplastic polymer material according to claim 27.

31. Food packaging carried out in an additivated thermoplastic polymer material according to claim 28.

32. Method for manufacturing an additivated thermoplastic polymer material according to claim 26, which comprises a step of additivation of at least one thermoplastic polymer material with a vegetable oil deodorization condensate.

33. Method for manufacturing an additivated thermoplastic polymer material according to claim 27, which comprises a step of additivation of at least one thermoplastic polymer material with a vegetable oil deodorization condensate.

34. Method for manufacturing an additivated thermoplastic polymer material according to claim 28, which comprises a step of additivation of at least one thermoplastic polymer material with a vegetable oil deodorization condensate.

Description

FIGURES

[0148] FIG. 1: 1A: diagram showing the value of breaking elongation (%) for the additivated PLA from left to right of ATBC, DOA, PEG 400 (petrosourced additives), palm oil and olive oil deodorization condensate (biosourced additives according to the invention) in mass proportions of (for each group from left to right) 0, 5, 10 and 15%; 1B: diagram showing the value of Young's modulus to (MPa) for the additivated PLA from left to right of ATBC, DOA, PEG 400 (petrosourced additives), palm oil and olive oil deodorization condensate (biosourced additives according to the invention) in mass proportions of (for each group from left to right) 0, 5, 10 and 15%; 1C: diagram showing the value of the yield stress (MPa) for the additivated PLA from left to right of ATBC, DOA, PEG 400 (petrosourced additives), palm oil and olive oil deodorization condensate (biosourced additives according to the invention) in mass proportions of (for each group from left to right) 0, 5, 10 and 15%.

[0149] FIG. 2: 2A diagram showing the value of the glass transition temperature (Tg in C.) for the additivated PLA from left to right of ATBC, DOA, PEG 400 (petrosourced additives), palm oil and olive oil deodorization condensate (biosourced additives according to the invention) in mass proportions of (for each group from left to right) 0, 5, 10 and 15%; 2B: Comparison of the glass transition temperature (Tg) at 20 (light gray) and 170 days (dark gray) of PLA additivated with a palm oil deodorization condensate in mass proportions (from left to right) of 0, 5, 10, 15 or 20% by weight with respect to the total weight of the mixture. 2C: Comparison of the glass transition temperature (Tg) at 10 (light gray) and 290 days (dark gray) of PLA additivated with an olive oil deodorization condensate (2C) in mass proportions (for each one of the 5 groups from left to right) of 0, 5, 10, 15 or 20% by weight with respect to the total weight of the mixture.

[0150] FIG. 3: 3A-D diagrams showing the value of breaking elongation (%) (3A), the value of Young's modulus (MPa) (3B), the value of the yield stress (MPa) (3C) and the glass transition temperature (Tg in C.) (3D) for the additivated PLA from left to right of palm, olive, rapeseed oil deodorization condensate and in mass proportions of (for each group from left to right) 0, 5, 10 and 15%.

[0151] FIG. 4: 4A-D diagrams showing the value of breaking elongation (%) (4A), the value of Young's modulus (MPa) (4B), and the glass transition temperature (Tg in C.) (4C) for the non-additivated PLA (composition 1) or additivated with different formulations of free fatty acids (compositions 2 to 7)

EXAMPLES

[0152] Equipment and Methods:

[0153] The examples of deodorization condensates used in the experimental results described hereinafter were recovered during the step of deodorization of a method for the physical refining of olive, soy, rapeseed, palm or sunflower oil.

[0154] The step of deodorization was carried out in the following conditions: a temperature between 240 and 260 C., an absolute pressure less than 5 mbar, a duration between 2 and 3 h and with a quantity of injected steam of about 8 kg/h. The composition of the oil deodorization condensates obtained was analyzed using gas chromatography.

[0155] These condensates have a great variability in their composition in fatty acids. They are described for the purposes of illustration and the results show that the presence of a mixture of saturated and unsaturated free fatty acids, regardless of the exact composition in fatty acids makes it possible to obtain an improvement in the ductility of the polymer tested.

[0156] 1) Soy oil condensates: average composition

TABLE-US-00001 Analysis Results Unit Method Acid index 68.43 mg KOH/g NF EN ISO 660 Saponification 157.9 mg KOH/g NF EN ISO index 3657 Fatty acid 76 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 43.08 % IUPAC composition acids 6.002 and Mono 2.92 % NF EN glycerides 14105 Cholesterol 1.05 % Sterols 8.69 % Di glycerides 8.96 % Tri glycerides 16.84 % Squalene + 13.78 % hydrocarbons Unidentified 4.59 %

[0157] Composition in fatty acids (NF EN 12966-2)

TABLE-US-00002 FATTY ACID Usual name % C12:0 Lauric acid 0.8 C14:0 Myristic acid 0.4 C16:0 Palmitic acid 12.3 C18:0 Stearic Acid 4.1 C18:1 cis Oleic Acid 21.7 C18:2 cis Linoleic Acid 49.7 C18:3 trans 0.4 C18:3 cis Linolenic Acid 6.0 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.2 C22:0 Behenic Acid 0.5 C24:0 Lignoceric Acid 0.2 unidentified 3.4

[0158] 2) Palm oil condensate: average composition

TABLE-US-00003 Analysis Results Unit Method Acid index 201.03 mg KOH/g NF EN ISO 660 Saponification 205.7 mg KOH/g NF EN ISO index 3657 Fatty acid 100 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 95.37 % IUPAC composition acids 6.002 and Mono 1.66 % NF EN glycerides 14105 Cholesterol 0 % Sterols 0 % Di glycerides 2.24 % Tri glycerides 0.65 % Fatty acid 0 % esters Unidentified 0 %

[0159] Composition in fatty acids (NF EN 12966-2)

TABLE-US-00004 FATTY ACID Usual name % C12:0 Lauric acid 0.4 C14:0 Myristic acid 1.3 C16:0 Palmitic acid 49.8 C16:1 Palmitoleic acid 0.2 C18:0 Stearic Acid 4.1 C18:1 trans 0.2 C18:1 cis Oleic Acid 35.0 C18:2 trans 0.1 C18:2 cis Linoleic Acid 7.7 C18:3 cis Linolenic Acid 0.3 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.1 unidentified 0.7

[0160] 3) Rapeseed oil condensate: average composition

TABLE-US-00005 Analysis Results Unit Method Acid index 65.29 mg KOH/g NF EN ISO 660 Saponification 125.1 mg KOH/g NF EN ISO index 3657 Fatty acid 67.6 g/100 g of NF EN ISO content product 12966-2

[0161] Composition in fatty acids (NF EN ISO 12966-2):

TABLE-US-00006 FATTY ACID Usual name % C16:0 Palmitic acid 7.4 C18:0 Stearic Acid 3.4 C18:1 cis Oleic Acid 27.3 C18:2 cis Linoleic Acid 41.7 C18:3 trans 0.7 C18:3 cis Linolenic Acid 1.5 C20:0 Arachidic Acid 0.5 C20:1 Eicosenoic Acid 0.3 C22:0 Behenic Acid 1.0 C24:0 Lignoceric Acid 0.5 unidentified 15.9

[0162] 4) Olive oil condensate: average composition

TABLE-US-00007 Analysis Results Unit Method Acid index 47.73 mg KOH/g NF EN ISO 660 Saponification 162.2 mg KOH/g NF EN ISO index 3657 Fatty acid 79.3 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 39.24 % IUPAC composition acids and 6.002 and associated NF EN compounds 14105 Mono 15.05 % glycerides + squalene Cholesterol 0 % Sterols 1.63 % Di glycerides 8.44 % Tri glycerides 33.37 % Fatty acid 1.07 % esters Unidentified 1.20 %

[0163] Composition in fatty acids (NF EN ISO 12966-2)

TABLE-US-00008 FATTY ACID Usual name % C10:0 Capric Acid 0.1 C16:0 Palmitic acid 11.3 C18:0 Stearic Acid 2.5 C18:1 trans 1.2 C18:1 cis Oleic Acid 68.3 C18:2 trans 0.1 C18:2 cis Linoleic Acid 10.8 C18:3 cis Linolenic Acid 0.6 C20:0 Arachidic Acid 0.4 C20:1 Eicosenoic Acid 0.4 C24:0 Lignoceric Acid 0.1 unidentified 4.3

[0164] 5) Sunflower oil condensate: composition of an example of a batch of sunflower oil condensate

TABLE-US-00009 Analysis Results Unit Method Acid index 187.7 mg KOH/g NF EN ISO 660 Saponification 194 mg KOH/g NF EN ISO index 3657 Fatty acid 93.6 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 98.9 % IUPAC composition acids 6.002 and Mono 0 % NF EN glycerides 14105 Cholesterol 0 % Sterols 0.9 % Di glycerides 0 % Tri glycerides 0 % Fatty acid 0 % esters Unidentified 0.3 %

[0165] Composition in fatty acids (NF EN ISO 12966-2) batch E14-9234

TABLE-US-00010 FATTY ACID Usual name % C12:0 Lauric acid 0.2 C14:0 Myristic acid 0.1 C16:0 Palmitic acid 8.4 C16:1 Palmitoleic acid 0.2 C17:1 <0.1 C18:0 Stearic Acid 3.9 C18:1 cis Oleic Acid 26.6 C18:2 cis Linoleic Acid 56.6 C18:3 cis Linolenic Acid 0.2 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.2 C22:0 Behenic Acid 0.4 C24:0 Lignoceric Acid 0.1

[0166] 6) Carrying out of mixtures and measurements of the mechanical and thermal properties of the polymer

[0167] Additivated granulates were carried out using polylactide and polylactic acid (PLA) and additive (chosen from an olive oil, soy, rapeseed or palm deodorization condensate,) via a method of granulation extrusion via the use of a conventional two-screw extruder provided with interpenetrated co-rotating co-driving screws. Such a method allows for the obtaining of additivated PLA granulates containing an average additive content that is known and controlled. In this particular case, the PLA was additivated with mass proportions in additives ranging from 5 to 20% by weight of additive with respect to the total weight of the additivated PLA.

[0168] For the purposes of comparison, PLA additivated with mass proportions of plasticizing additive known in prior art consisting of ATBC (acetyl tributyl citrate), DOA (Dioctyl Adipate) or PEG (polyethylene glycol) 400 ranging from 5 to 20% were also carried out.

[0169] The measurements of mechanical properties: breaking elongation, Young's modulus and yield stress were carried out according to the standard ISO 527-2, describing in particular the use of shouldered specimens of the 5A type of a thickness of about 1 mm; a prior conditioning before study of 72 h at 23 C. under 50% relative humidity; a traction speed of 25 mm/min as well as a temperature of 23 C. and a relative humidity of 50% during the measurement. The values indicated (tables 1 and 2) correspond to the average values obtained over 10 trials.

[0170] The measurement of the glass transition temperature was carried out by the temperature modulated differential scanning calorimetry method (TMDSC), with a heating speed of 2 C./min, a temperature modulation amplitude of 0.318 C. and a modulation period of 60 s. The measurements are usually taken under a nitrogen atmosphere at 50 ml/min. The values indicated for the glass transition temperature (table 3) correspond to the average values obtained over three trials.

[0171] The measurements of the global migration rates of the compounds forming the vegetable oil deodorization condensates, in the foods concerned were taken according to the global migration tests of EU regulations (EU Regulation No. 10/2011 of the Commission of Jan. 14, 2011 concerning materials and objects made of plastic material intended to come into contact with items of food) for three food simulants.

[0172] The measurements of the mechanical properties and of the glass transition temperatures for the various additivated PLAs were taken on films (or plates) having a thickness of about 1 mm obtained via thermocompression of the additivated granulates. The measurements of the migration rates in simulants for food contact as well as Robinson tests characterizing the possible impact of the packaging material on the organoleptic perception of the food were carried out on films having a thickness of about 50 m obtained via single-screw extrusion with flat die then calendering of the additivated granulates.

[0173] For the additivated PLA with the sunflower condensate, the PLA condensate mixture (10%) was carried out in a two-screw extruder (PTW 16/40D Thermo Haake). The granulates were then thermo-compressed in order to obtain plates (Thermocompression with Gibrite press).

[0174] A heat-compressed plate was carried out and on this plate 4 specimens of the 5A type were cut in order to carry out the traction tests according to standard ISO 527-2.

[0175] The traction test is carried out on an Instron 4507, with a traction cell of 5 kN. The speed of traction for all of the trials is 5 mm/min.

[0176] Results:

[0177] 1) Effect of the additivation with a deodorization condensate on the mechanical properties of the PLA

TABLE-US-00011 TABLE 1 Ductility PLA (breaking elongation) - ISO 527-2 - 25 mm/min Palm Olive Soy Rapeseed Sunflower conden- conden- conden- conden- conden- sate sate sate sate sate Average Average Average Average Average (%) (%) (%) (%) (%) 0% 6 5 6 5 6.4 additive by weight 5% 51 50 30 23 additive by weight 10% 132 85 73 56 100 additive by weight 15% 179 88 79 66 additive by weight 20% 84 67 52 73 additive by weight

[0178] As shown in the table 1, as well as in FIG. 1A, the adding of a mass proportion of vegetable oil deodorization condensate ranging from 5 to 15% makes it possible to increase the breaking elongation of the PLA by a factor of 4 on the average, for a mass proportion of 5% of rapeseed condensate by a factor of 30 for a mass proportion of 15% of palm oil deodorization condensate, i.e. breaking elongation values from 22 to 178%. Regardless of the vegetable oil used, the use of a vegetable oil deodorization condensate in mass proportions from 10 to 15% makes it possible to obtain an increase in the breaking elongation of the PLA at least multiplied by 6, even multiplied by 10, in relation to non-additivated PLA with a deodorization condensate, i.e. a value for breaking elongation for the additivated PLA with a deodorization condensate at least equal to 40%, even 55%.

[0179] The use of vegetable oil condensates containing a substantial content in fatty acids (in particular greater than 70%) and in particular in free fatty acids (in particular greater than 35%) makes it possible to improve the plasticizing effectiveness of the condensate and in particular the effect of increasing the effect on the breaking elongation of the polymer. The palm oil condensate containing a proportion of fatty acids close to 100% and a content in free fatty acids of about 95% as such makes it possible to obtain the best effects with increases in the ductility of the PLA ranging from 10 to about 30 times for mass proportions of 5 or 15%.

[0180] As such the invention makes it possible to obtain additivated PLA, of which the breaking elongation is at least equal to 20%, in particular greater than 50 or 60% for mass proportions of additive ranging from 10 to 15%. The use of a palm oil deodorization condensate in mass proportions from 10 to 15% makes it possible in particular to obtain a breaking elongation at least equal to 50% even greater than 130%.

[0181] FIG. 1 also makes it possible to show that the use of vegetable oil deodorization condensates and in particular of palm oil or olive oil, and more particularly palm oil deodorization condensate, makes it possible to obtain results on the increase of the breaking elongation of the PLA, of the same magnitude as those obtained with a conventional plasticizer such as DOA (Dioctyl Adipate) (see FIG. 3A). Palm oil deodorization condensate makes it possible to obtain a more substantial increase in the breaking elongation for lower mass proportions, in particular for a mass proportion of 10%. The PEG 400 is actually effective on the increase in ductility only for mass proportions of 10 or 15%. Finally ATBC, a biodegradable and relatively non-toxic plasticizer, used in particular in nail polishes, makes it possible to obtain a breaking elongation greater than 300% but it induces a significant effect only for a minimum mass proportion of about 15%.

TABLE-US-00012 TABLE 2 Young's modulus PLAS - ISO 527-2 25 mm/min Palm Olive Soy Rapeseed condensate condensate condensate condensate Average Average Average Average (Mpa) (Mpa) (Mpa) (Mpa) 0% 1680 1738 1694 1658 additive by weight 5% 1713 1430 1550 1536 additive by weight 10% 1458 1495 1516 1494 additive by weight 15% 1179 1360 1344 1380 additive by weight 20% 1133 1374 1216 1267 additive by weight

TABLE-US-00013 TABLE 3 (PLA4060D + PLA4060D 10% wt) (Average) E (MPa) 1518 1307 .sub.E (MPa) 56.6 20.9 A.sub.E (%) 4.8 2.3 .sub.R (MPa) 50.7 20.0 A.sub.R (%) 6.4 100.3

[0182] The analysis of the other mechanical properties of the PLA mixed with variable proportions of additives (see table 2 hereinabove) shows that the use of a vegetable oil deodorization condensate according to the invention makes it possible to maintain the values of Young's modulus (see also FIGS. 1B and 3B). Indeed, regardless of the vegetable oil used, the use of a vegetable oil deodorization condensate in order to increase the ductility of the PLA does not decrease Young's modulus by more than about 35%. In particular, for mass proportions of additive ranging from 5 to 15%, vegetable oil deodorization condensates reduce Young's modulus by less than 30% and makes it possible to obtain a mixture of additivated PLA of which Young's modulus is greater than 1200 MPa.

[0183] The results of table 3, obtained with additivated PLA by a sunflower oil deodorization condensate, have the same conclusions. The use of a sunflower oil deodorization condensate, in order to increase the ductility of the PLA does not decrease Young's modulus by more than about 20% and makes it possible to obtain a mixture of additivated PLA of which Young's modulus is greater than 1300 MPA.

[0184] FIG. 1B shows that only DOA makes it possible to maintain the value of Young's modulus, for mass proportions wherein these additives are effective. Indeed, ATBC produces a significant increase in the ductility only for a mass proportion at least equal to 15%, a proportion at which it indices a drastic decrease in Young's modulus for PLA.

[0185] FIG. 1C shows that the use of deodorization condensates according to the invention, and in particular of olive oil and palm oil deodorization condensate makes it possible to obtain additivated PLA of which the yield stress is greater than 20 MPa for mass proportions of additives ranging from 5 to 15%. For mass proportions of 10 or 15%, the values of yield stress for the additivated PLA with the vegetable oil deodorization condensates of the invention are similar to those obtained with DOA or PEG 400. The ATBC makes it possible to obtain a PLA additivated with a yield stress greater than 50 MPa for mass proportions of 5 or 10%. As indicated hereinabove, for a mass proportion of 15%, effective on the increase of the ductility (breaking elongation), the yield stress of the additivated PLA is less than 10 MPa. These results are similar regardless of the vegetable oil from which the vegetable oil deodorization condensate is obtained (FIG. 3C).

[0186] 2) Effect of the additivation with a vegetable oil condensate on the thermal properties of the PLA

TABLE-US-00014 TABLE 4 Glass Transition Temperature PLA - TM-DSC 2 C. min Palm Olive Soy Rapeseed condensate condensate condensate condensate Average Average Average Average ( C.) ( C.) ( C.) ( C.) 0% 54.7 55.4 55.1 55.3 additive by weight 5% 50.2 49.6 51.4 51.8 additive by weight 10% 49.4 49.4 49.7 49.7 additive by weight 15% 49.1 48.7 49.5 49.1 additive by weight 20% 49 48.8 48 48.6 additive by weight

[0187] As shown in table 4, as well as in FIG. 2A, the use of vegetable oil deodorization condensate makes it possible to obtain additivated PLA of which the breaking elongation is at least equal to 20% (see table 1) and of which the glass transition temperature (Tg) is greater than 48 C. These values are compatible with a use as food packaging, in particular as a plastic bag and make it possible in particular to prevent the softening of the packaging carried out using additivated PLA according to the invention, at normal temperatures of use (conventionally less than 40 C.).

[0188] During the additivation of the PLA with a sunflower condensate, in a mass proportion of 10%, a value of glass transition temperature Tg similar to that of palm, olive, rapeseed or soy condensates is obtained. This value varies between 48 and 52 C. according to the batch of condensate used.

[0189] On the other hand, as shown in FIG. 2A, PLA additivated with plasticizing additives of prior art has a glass transition temperature less than 40 C., for proportions of additives of 5, 10 or 15%. As such PLA additivated with a mass proportion of 15% of ATBC, a biodegradable and non-toxic plasticizer, has a Tg less than 25 C. The additivated PLA of DOA, a conventional plasticizer with an adipate base, in proportions of 5, 10 or 15% has a Tg less than 40 C. Finally the additivated PLA of PEG 400 in a mass proportion of 15%, has a Tg less than 20 C. These results are similar regardless of the vegetable oil from which the vegetable oil deodorization condensate is obtained (FIG. 3D)

[0190] The stability of the additivated PLA granulates of olive or palm oil deodorization condensate, shown by the glass transition temperature, was compared to 20 days and 170 or 290 days, as shown in FIGS. 2B and 2C.

[0191] The results show that the glass transition temperature is not modified over this period, and regardless of the vegetable oil (palm or olive) and the mass proportion of vegetable oil deodorization condensate added to the PLA (from 5 to 15%).

[0192] Finally, the results of the global migration tests carried out on the films of additivated PLA from 5 to 10% by weight of palm oil deodorization condensates show that the total concentration in compounds forming said condensates in food simulant environments is less than the regulatory migration threshold, i.e. 60 mg/kg of food simulant. Such results predict a stability of the film carried out in additivated PLA according to the invention with food contact for one year, at ambient temperature.

[0193] Furthermore, regulations in terms of food packaging impose a non-alteration of the olfactory and organoleptic properties of the food with contact. A Robinson test, conducted on a panel of persons on the films of additivated PLA of 5 and 10% by weight in palm oil deodorization condensate did not reveal any alteration on the taste or in the odor.

[0194] All of these results show that PLA additivated with a deodorization condensate globally has mechanical properties and a glass transition temperature higher than PLA mixed with additives known in prior art. All of these qualities make it possible to obtain a biosourced and biodegradable plastic material that can be used as packaging, in particular for food.

[0195] 3) Synergistic effect of a deodorization condensate on the improvement of the ductility of the PLA

[0196] The comparison of different compositions of free fatty acids shows also that a vegetable oil deodorization condensate induces a superior effect on the increase in the ductility of the polymer with respect to a simple mixture of fatty acids that it is comprised of. These results (see table 4 hereinbelow and FIG. 4 A-C) strongly suggest a synergistic effect of the various compounds of the condensate with respect to the mixture of free fatty acids.

[0197] For the purposes of this comparison, 7 compositions were prepared. For compositions 2 to 7, 10% by weight of additive were added, with respect to the total weight of the composition, were added to PLA4060D. The composition 1 corresponds to PLA4060D without additive.

[0198] composition 1: PLA4060D

[0199] composition 2: PLA4060D+10% palmitic acid (100%)

[0200] composition 3: PLA4060D+10% oleic acid (100%)

[0201] composition 4: PLA4060D+10% Hydrogenated palm oil [10% diglycerides (DG)+90% triglycerides (TG) such as estimated according to the method described in standard NFEN 14105]

[0202] composition 5: PLA4060D+10% [50% wt palmitic acid+50% wt oleic acid]

[0203] composition 6: PLA4060D+10% [95% wt mixture of free fatty acids (50% wt palmitic acid+50% wt Oleic acid)+5% wt hydrogenated palm oil (10% DG+90% TG]

[0204] composition 7: PLA4060D+10% Palm oil deodorization condensate [95.4% of free fatty acids (of which 49.8% palmitic acid+35% oleic acid+7.7% linoleic acid+4.1% stearic acid+1.3% Myristic acid+others) and 4.6% of glycerides (of which 1.7% monoglycerides (MG)+2.2% DG+0.7% triglycerides TG)].

TABLE-US-00015 TABLE 5 COMPOSITION 1 2 3 4 5 6 7 Breaking 5 4 16 9 45 74 132 elongation (%) Young's 1709 1722 1440 1540 1593 1549 1458 Modulus (MPa) Glass transition 55.7 49.0 44.6 48.6 45.9 44.6 44.9 temperature ( C.)

[0205] The mechanical properties were measured according to the methods and standards defined hereinabove. The glass transition temperature was measured by non-modulated DSC (Differential Scanning calorimetry), with a heating speed of 10 C./min.

[0206] The results show that for this example, the adding in the composition of a mixture constituted of a saturated free fatty acid (palmitic acid) and of an unsaturated free fatty acid (oleic acid) makes it possible to obtain an increase by a factor of 10 of the breaking elongation. Such a mixture represents about 80% of the composition of a palm oil deodorization condensate. The closer the mixture used is to the final composition of the palm oil condensate, the more substantial the increase in the breaking elongation observed is. As such PLA additivated with the composition 6, which has about 85% of similarity of composition with the palm oil deodorization condensate, has an increase in the breaking elongation of more than 10 times with respect to the control PLA (composition 1). The use of the palm oil deodorization condensate makes it possible to obtain the best result, i.e. a breaking elongation for the PLA of about 130% i.e. an increase by practically a factor of 25. These results demonstrate the superiority of the natural deodorization condensate of complex composition concerning the improvement in the ductility, compared to the isolated use of a type of molecules present in the natural product. The cocktail/synergistic effect between the various organic molecules naturally present appears to be a determining factor.

[0207] The composition of the additive (composition 2 to 7) does not significantly modify the glass transition temperature and Young's modulus.

[0208] 4) Variability of the batches of palm condensate on the mechanical and thermal properties of PLA

[0209] The composition of a deodorization condensate of a given oil is able to vary according to the batches. As shown hereinbelow the variability between the various batches does not modify the results obtained with regards to the mechanical and thermal properties of the additivated polymer obtained.

[0210] CP1=Palm Condensate of the 1st batch (E 12-1822)

[0211] CP2=Palm Condensate of the 2nd batch (E 14-5299)

[0212] CP3=Palm Condensate of the 3rd batch (E 14-5903)

[0213] Composition of the palm deodorization condensate batch E12-1822

TABLE-US-00016 Analysis Results Unit Method Acid index 201 mg KOH/g NF EN ISO 660 Saponification 205.7 mg KOH/g NF EN ISO index 3657 Fatty acid 100 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 95.3 % IUPAC composition acids 6.002 and Mono 1.7 % NF EN glycerides 14105 Cholesterol 0 % Sterols 0 % Di glycerides 2.2 % Tri glycerides 0.7 % Fatty acid 0 % esters Unidentified 0 %

[0214] Composition in fatty acids (NF EN ISO 12966-2) batch E12-1822

TABLE-US-00017 FATTY ACID Usual name % C8:0 Caprylic Acid <0.1 C10:0 Capric Acid <0.1 C12:0 Lauric acid 0.4 C14:0 Myristic acid 1.3 C16:0 Palmitic acid 49.8 C16:1 Palmitoleic acid 0.2 C17:1 <0.1 C18:0 Stearic Acid 4.1 C18:1 trans 0.2 C18:1 cis Oleic Acid 35 C18:2 trans 0.1 C18:2 cis Linoleic Acid 7.7 C18:3 trans <0.1 C18:3 cis Linolenic Acid 0.3 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.1 C22:0 Behenic Acid 0.1 C24:0 Lignoceric Acid <0.1 unidentified 0.7

[0215] Composition palm oil deodorization condensate E14-5299

TABLE-US-00018 Analysis Results Unit Method Acid index 187.8 mg KOH/g NF EN ISO 660 Saponification 202 mg KOH/g NF EN ISO index 3657 Fatty acid 100 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 96 % IUPAC composition acids 6.002 and Mono 1.3 % NF EN glycerides 14105 Cholesterol 0 % Sterols 0.9 % Di glycerides 2 % Tri glycerides 0.4 % Fatty acid 0 % esters Unidentified 0.3 %

[0216] Composition in fatty acids (NF EN ISO 12966-2)

TABLE-US-00019 FATTY ACID Usual name % C8:0 Caprylic Acid <0.1 C10:0 Capric Acid <0.1 C12:0 Lauric acid 0.2 C14:0 Myristic acid 1.1 C16:0 Palmitic acid 46.4 C16:1 Palmitoleic acid 0.2 C17:1 <0.1 C18:0 Stearic Acid 4.3 C18:1 trans 0.1 C18:1 cis Oleic Acid 37.6 C18:2 trans 0.1 C18:2 cis Linoleic Acid 8.9 C18:3 trans <0.1 C18:3 cis Linolenic Acid 0.4 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.1 C22:0 Behenic Acid 0.1 C24:0 Lignoceric Acid <0.1 unidentified <0.1

[0217] Composition palm oil deodorization condensate E14-5903

TABLE-US-00020 Analysis Results Unit Method Acid index 181.9 mg KOH/g NF EN ISO 660 Saponification 206 mg KOH/g NF EN ISO index 3657 Fatty acid 99.8 g/100 g of NF EN ISO content product 12966-2 Glyceride Free fatty 93.3 % IUPAC composition acids 6.002 and Mono 3.0 % NF EN glycerides 14105 Cholesterol 0 % Sterols 0 % Di glycerides 3.2 % Tri glycerides 0.4 % Fatty acid 0 % esters Unidentified 0.1 %

[0218] Composition in fatty acids (NF EN ISO 12966-2)

TABLE-US-00021 FATTY ACID Usual name % C8:0 Caprylic Acid 0.1 C10:0 Capric Acid 0.1 C12:0 Lauric acid 0.8 C14:0 Myristic acid 1.4 C16:0 Palmitic acid 50.6 C16:1 Palmitoleic acid 0.2 C17:1 <0.1 C18:0 Stearic Acid 4.1 C18:1 trans 0.2 C18:1 cis Oleic Acid 32.9 C18:2 trans 0.1 C18:2 cis Linoleic Acid 8.5 C18:3 trans <0.1 C18:3 cis Linolenic Acid 0.3 C20:0 Arachidic Acid 0.3 C20:1 Eicosenoic Acid 0.1 C22:0 Behenic Acid 0.1 C24:0 Lignoceric Acid <0.1 unidentified <0.1

[0219] Conditions for implementation and testing

[0220] Mixtures carried out with a two-screw extruder PTW 16-40D Thermo Haake

[0221] The granulates are then thermocompressed in order to obtain plates. (Thermocompression on Gibrite press). Carrying out of several thermocompressed plates and on each plate several specimens of the 5A type were cut in order to carry out the tests of traction according to the standard ISO 527-2.sup.(2).

[0222] Traction test: Instron 4301 of the PIMM, with a traction cell of 5 kN of the CNAM. The traction speed for all of the trials is 5 mm/min

[0223] Results:

[0224] The results of the mechanical properties of the additivated PLAs with the three batches of palm condensates are shown in Table 6 hereinbelow.

[0225] For the two mixtures CP2 and CP3, the traction specimens were cut in three plates carried out with the same parameters for thermocompression.

TABLE-US-00022 TABLE 6 CP1 CP2 CP3 Composition Glycerides Free fatty acids 95.37 96 93.3 (% wt) Mono glycerides 1.66 1.3 3 Di glycerides 2.24 2 3.2 Tri glycerides 0.65 0.4 0.4 Fatty Palmitic acid 49.8 46.4 50.6 acids Oleic Acid 35 37.6 32.9 Linoleic Acid 7.7 8.9 8.5 Stearic Acid 4.1 4.3 4.1 Mechanical E (MPa) 1460 1210 1300 properties .sub.E (MPa) 24 19.4 21.6 A.sub.E (%) 2.1 1.9 2.1 .sub.R (MPa) 17.5 18.9 A.sub.R (%) 132.0 113.6 117.1

[0226] 5) Thermal properties of the PLA: variability of the batches of palm condensate

[0227] The characteristics of the mixtures were determined using the DSC TA Q1000. The method used for all of the samples was as follows:

[0228] A first heating at 10 C./min to 120 C.

[0229] An isotherm at 120 C. for 2 minutes

[0230] A cooling at 10 C./min to 50 C.

[0231] An isotherm at 50 C. for 2 minutes

[0232] A second heating at 10 C./min to 120 C.

TABLE-US-00023 TABLE 7 Thermal properties (glass transition Tg) of the PLA in the presence of the various batches of palm deodorization condensates. PLA/additive Tg ( C.) PLA4060D + 10% wt CP1 * 49.4 PLA4060D + 10% wt CP2 38.3 PLA4060D + 10% wt CP3 40.1

[0233] Table 7 shows that the variability in the composition of the batches of palm condensates does not affect the value of the glass transition temperature of the additivated PLA. This temperature is lowered slightly by the adding of vegetable oil deodorization condensate and as such remains above ambient temperature.

[0234] 6) Polymer material: mixture of PLA4060D 90%+PHBV 10%

[0235] Conditions for implementation and testing

[0236] The mixtures of PLA4060D with 10% CP1 then with PHBV 10%, were obtained in a two-screw extruder or as a dry blend mixture then the films were produced via cast extrusion or via blow-film extrusion with extruder MAPRE 30-33D.

[0237] On the films produced, traction specimens were cut using a punch. These are standardized specimens of the 5A type according to the standard ISO 527-2.sup.(2).

[0238] Traction test: Instron 4507, with a traction cell of 5 kN of the CNAM. The traction speed for all of the trials is 5 mm/min

[0239] Results

TABLE-US-00024 TABLE 8 Mechanical properties of the films of mixtures PLA + 10% PHBV additivated with 10% of palm oil deodorization condensate (CP1) produced via cast extrusion and blow-film extrusion E (MPa) A.sub.R (%) PLA4060D + 10% PHBV Extrusion cast 1640 16 PLA4060D + 10% CP1 Blow-film extrusion 2226 87 (90 PLA4060 + 10 CP1) + PHBV 2032 112 Dry blend + Extrusion cast (90 PLA4060 + 10 CP1) + PHBV 1410 132 Dry blend + Blow-film extrusion (90 PLA4060 + 10 CP1) + PHBV 1086 78 Two-screw + Extrusion cast (90 PLA4060 + 10 CP1) + PHBV 2560 128 Two-screw + Blow-film extrusion

[0240] The virgin PLA4060D can be formed via cast extrusion but cannot be formed by blow-film extrusion due to its low melt strength. Indeed, the values of A.sub.R for a virgin PLA vary between 5 and 9% for a film obtained as cast extrusion or via thermocompression.

[0241] The results of Table 8 confirm the improvement of the properties of breaking deformation for a film of PLA +10% CP product either by blow-film extrusion or by cast extrusion. The values of A.sub.R (breaking elongation) vary between 87% and 141%,

[0242] As such only the adding of the vegetable oil condensate (here the CP) in the PLA, via its effect on the increase in ductility (increased breaking elongation), allows for the forming via blow-film extrusion. Via blow-film extrusion, the films coming from the mixture of (PLA+10% CP1) and of PHBV show breaking elongations that vary between 128 and 144%. An effect of the condensate on the mechanical properties, at ambient temperature, but also in melted state, is therefore observed.

[0243] 7) Incorporation of the palm condensate in polyester other than PLA

[0244] PHB and PHBV

[0245] Two biosourced and biodegradable polyesters of the family of PHAs were tested for the incorporation of the palm oil condensate. This is PHB: Poly (3-hydroxybutyrate) and PHBV: Poly (3-hydroxybutyrate-co Hydroxyvalerate)

[0246] Conditions for Forming and Testing:

[0247] Mixtures carried out with internal mixer Haake with 10% palm condensate CP1

[0248] The granulates are then thermocompressed in order to obtain plates. (Thermocompression Gibrite of the PIMM). A heat-compressed plate was manufactured on each mixture and several specimens of the 5A type were cut on the plate in order to conduct the traction tests.

[0249] Traction test: Instron 4507 of the CNAM, with a traction cell of 5 kN of the CNAM.

[0250] The traction speed for all of the trials is 5 mm/min

[0251] Results

TABLE-US-00025 TABLE 9 Mechanical properties of the two grades of virgin and additivated PHB and PHBV with the palm oil deodorization condensate (batch CP1) (n = 4) PHB (biomer 310 2013) PHBV (PHI003) +10% wtCP1 +10% wtCP1 E (MPa) 900 599 835 785 .sub.E (MPa) 30.3 20.4 18.5 16.9 A.sub.E (%) 6.0 6.0 2.4 3.2 .sub.R (MPa) 30.2 20.0 18.3 15.9 A.sub.R (%) 6.1 6.2 2.5 4.6

[0252] The PHA of grade PHI003 (PHBV) shows a very slight reduction in Young's modulus and an increase of the breaking elongation of 86% (increase by at least a factor of 1.5).

[0253] PHB shows on the contrary a maintaining of the breaking elongation and a significant decrease in Young's modulus by at least 30%. Such a modification of the properties of the additivated polymer makes it possible to obtain a more flexible material of which the processability is improved.

[0254] Polyamide

[0255] Conditions for Implementation and Testing:

[0256] A mixture of PA11 and of 10% of palm condensate (CP1) was manufactured by internal mixer. The granulates were then thermocompressed, and specimens were cut using these plates. The traction tests were carried out on Instron 4507 of the Cnam with a traction cell of 5 KN. The traction speed is 5 mm/min

[0257] Results:

TABLE-US-00026 TABLE 10 mechanical properties and glass transition temperature (Tg) of the PA11 in the presence of a palm oil deodorization condensate PA11 (PA11 + 10% wtCP1) E (MPa) 652 297 .sub.E (MPa) 34.9 34.3 20 A.sub.E (%) 8.9 74.6 .sub.R (MPa) 40.7 40.8 A.sub.R (%) 280 302 Tg ( C.) 50 30

[0258] An increase of 8% in the factor A.sub.R (breaking elongation) of the additivated PA11 is measured with regards to the virgin PA11 (non-additivated). The glass transition of the PA11 is lowered to 30 C. with 10% of palm condensate. The results on PLA11 also show that Young's modulus (E) decreases by half, and that the 2 stresses .sub.E (yield stress) and .sub.R (breaking stress) do not vary. Finally a very significant increase, by a factor of 8, in the breaking elongation (A.sub.E) is measured. This shows that the palm oil deodorization condensate makes it possible to increase the deformation to yield of the PA11, without decreasing the yield stress. Such a modification makes it possible to obtain a much more elastic material that makes it possible to consider applications in the fields that are usually covered by elastomers and rubbers, which are generally penalized by their low glass transition temperatures while in the case of the additivated PA11, the glass transition is beyond the ambient temperature.

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