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    • 专利摘要:
    Use of a semi-crystalline thermoplastic polyester for the production of bi-stretched hollow bodies, said polyester comprising at least one 1,4: 3,6-dianhydrohexitol (A) unit, at least one alicyclic diol unit (B) other than the 1,4: 3,6-dianhydrohexitol (A) units, at least one terephthalic acid unit (C), in which the molar ratio (A) / [(A) + (B)] is at least 0.05; and not more than 0.30, said polyester being free from non-cyclic aliphatic diol units or comprising a molar amount of non-cyclic aliphatic diol units, based on all the monomer units of the polyester, of less than 5%, and whose reduced solution viscosity (25 ° C, phenol (50% m): ortho-dichlorobenzene (50% m), 5 g / L polyester) is greater than 50 mL / g.
    公开号:FR3054830A1
    申请号:FR1657491
    申请日:2016-08-02
    公开日:2018-02-09
    发明作者:Helene Amedro；Rene Saint Loup
    申请人:Roquette Freres SA；
    IPC主号:
    专利说明:

    © Publication no .: 3,054,830 (use only for reproduction orders)
    ©) National registration number: 16 57491 ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY
    COURBEVOIE © Int Cl 8 : B 65 D 1/02 (2017.01), C 08 L 67/02, B 29 C 49/04, 49/06
    A1 PATENT APPLICATION
    ©) Date of filing: 02.08.16.(© Priority: (© Applicant (s): ROQUETTE FRERES Société anonyme - FR. ©) Date of availability of the request: 09.02.18 Bulletin 18/06. @ Inventor (s): AMEDRO HELENE and SAINT LOUP RENE. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ©) Holder (s): ROQUETTE FRERES Société anonyme. ©) Extension request (s): © Agent (s): CABINET PLASSERAUD.
    SEMI-CRYSTALLINE THERMOPLASTIC POLYESTER FOR THE MANUFACTURE OF HOLLOW HOLLOW BODIES.
    FR 3 054 830 - A1 _ Use of a semi-crystalline thermoplastic polyester for the production of bi-drawn hollow bodies, said polyester comprising at least one 1,4: 3,6-dianhydrohexitol unit (A), at least one unit alicyclic diol (B) other than 1,4: 3,6-dianhydrohexitol units (A), at least one terephthalic acid unit (C), in which molar ratio (A) / [(A) + (B)] being at least 0.05 and at most 0.30, said polyester being free of non-cyclic aliphatic diol units or comprising a molar amount of non-cyclic aliphatic diol units, relative to all of the polyester monomer units, at 5%, and whose reduced viscosity in solution (25 ° C; phenol (50% m): ortho-dichlorobenzene (50% m); 5 g / L of polyester) is greater than 50 mL / g.

    i
    Field of the invention
    The present invention relates to the use of a semi-crystalline thermoplastic polyester comprising at least one 1,4: 3,6-dianhydrohexitol unit for the manufacture of bi-drawn hollow bodies.
    Technological background of the invention
    Plastics have become essential for the mass production of objects. Indeed, their thermoplastic nature allows these materials to be transformed at high speed into all kinds of objects.
    Certain thermoplastic aromatic polyesters have thermal properties allowing them to be used directly for the manufacture of materials. They include aliphatic diol and aromatic diac units. Among these aromatic polyesters, mention may be made of polyethylene terephthalate (PET), which is a polyester comprising ethylene glycol and terephthalic acid units, used for example in the manufacture of films.
    However, for certain applications or under certain conditions of use, it is necessary to improve certain properties, in particular impact resistance or thermal resistance. This is how modified glycol PET (PETg) was developed. These are generally polyesters comprising, in addition to ethylene glycol and terephthalic acid units, cyclohexanedimethanol units (CHDM). The introduction of this diol in PET allows it to adapt the properties to the intended application, for example to improve its impact resistance or its optical properties.
    Other modified PETs have also been developed by introducing 1,4: 3,6-dianhydrohexitol units into the polyester, in particular isosorbide (PEIT). These modified polyesters have higher glass transition temperatures than unmodified PETs or PETg comprising CHDM. In addition, 1,4: 3,6-dianhydrohexitols have the advantage that they can be obtained from renewable resources such as starch.
    Another problem with these PEITs is that they may have insufficient impact resistance properties. In addition, the glass transition temperature may be insufficient for the manufacture of certain plastic objects.
    To improve the impact resistance properties of polyesters, it is known in the prior art to use polyesters whose crystallinity has been reduced. As regards polyesters based on isosorbide, mention may be made of application US2012 / 0177854 which describes polyesters comprising terephthalic acid units and diol units comprising from 1 to 60% by moles of isosorbide and from 5 to 99% 1,4-cyclohexanedimethanol which have improved impact resistance properties. As indicated in the introductory part of this application, it is a question of obtaining polymers from which the crystallinity is eliminated by the addition of comonomers, and therefore here by the addition of 1,4-cyclohexanedimethanol. In the examples section, the manufacture of various poly (ethylene-co-1,4-cyclohexanedimethylene-coisosorbide) terephthalates (PECIT) is described as well as an example of poly (1,4cyclohexanedimethylene-co-isosorbide) terephthalate (PCIT).
    It can also be noted that, while PECIT type polymers have been the subject of commercial developments, this is not the case with PCITs. In fact, their manufacture was hitherto considered to be complex, the isosorbide having a low reactivity as a secondary diol. Yoon et al. (Synthesis and Characteristics of a Biobased High-Tg Terpolyester of Isosorbide, Ethylene Glycol, and 1,4-Cyclohexane Dimethanol: Effect of Ethylene Glycol as a Chain Linker on Polymerization, Macromolecules, 2013, 46, 7219-7231) have thus shown that the synthesis of PCIT is much more difficult to achieve than that of PECIT. This document describes the study of the influence of the rate of ethylene glycol on the manufacturing kinetics of PECIT.
    In Yoon et al., An amorphous PCIT (which contains about 29% isosorbide and 71% CHDM compared to the sum of the diols), is made in order to compare its synthesis and its properties with those of PECIT polymers. The use of high temperatures during the synthesis induces a thermal degradation of the polymer formed if one refers to the first paragraph of the Synthesis part of page 7222, this degradation being notably linked to the presence of cyclic aliphatic diols such as isosorbide . Therefore, Yoon et al. have used a process in which the polycondensation temperature is limited to 270O. Yoon et al. have found that even by increasing the polymerization time, the process also does not provide a polyester with sufficient viscosity. Thus, without adding ethylene glycol, the viscosity of the polyester remains limited, despite the use of extended synthesis times.
    Thus, despite the modifications made to PETs, there is still a constant need for new polyesters having improved properties.
    In the field of plastics, and in particular for the manufacture of hollow bodies, it is necessary to have semi-crystalline thermoplastic polyester with improved properties, in particular having a high glass transition temperature, which ultimately allow hot filling at high temperatures.
    Document US 6126992 discloses objects made from polymers having terephthalic acid units, ethylene glycol units and isosorbide units and optionally another diol (for example 1,4-cyclohexanedimethanol). All of the polymers obtained thus have ethylene glycol units because it is widely accepted that these are necessary for the incorporation of isosorbide and for obtaining a high glass transition temperature.
    Document US6063465 describes polyester containers made from a polymer having isosorbide units, terephthalic acid units, and ethylene glycol units. The containers thus produced are adapted to contain liquids as well as solids. Examples 1 and 2 show the synthesis of polyester based on dimethyl terephthalate, isosorbide and ethylene glycol. The polymer obtained according to Example 2 is prepared in the same way as that of Example 1 but has a higher level of isosorbide.
    However, the containers made from these polymers exhibit, when filled at a temperature of up to 92 ° C., a shrinkage of the order of 1 to 10%, or even worse, deform at a temperature of 95 ° C as is the case for the polymer having a higher level of isosorbide (Example 2).
    Thus, there is still today the need for thermoplastic polyesters containing 1,4: 3,6-dianhydrohexitol units for the production of hollow bodies, said polyesters therefore having improved mechanical properties, which can be easily shaped, and having a thermal resistance allowing hot filling with high temperatures.
    It is therefore to the credit of the Applicant to have found that this objective could be achieved, against all odds, with a semi-crystalline thermoplastic polyester based on isosorbide not having ethylene glycol when it was known until now that the latter was essential for the incorporation of said isosorbide. Indeed, the semi-crystalline thermoplastic polyester used according to the present invention, thanks to a viscosity and a ratio in particular pattern, has improved properties for use according to the invention in the manufacture of bi-drawn hollow bodies.
    Summary of the invention
    The subject of the invention is therefore the use of a semi-crystalline thermoplastic polyester for the manufacture of bi-drawn hollow bodies, said polyester comprising:
    • at least one 1,4: 3,6-dianhydrohexitol unit (A);
    • at least one alicyclic diol unit (B) other than the 1,4: 3,6-dianhydrohexitol units (A);
    • at least one terephthalic acid unit (C);
    wherein the molar ratio (A) / [(A) + (B) j being at least 0.05 and at most 0.30, said polyester being free of non-cyclic aliphatic diol units or comprising a molar amount of non-cyclic aliphatic diol units, with respect to all of the monomeric units of polyester, of less than 5%, and whose reduced viscosity in solution (25 ° C; phenol (50% m): ortho-dichlorobenzene (50% m) ; 5 g / L of polyester) is greater than 50 mL / g.
    These polyesters have improved thermal and mechanical properties and in particular good thermal resistance due to a high glass transition temperature, which is particularly advantageous for the manufacture of bi-drawn hollow bodies. Indeed, the bi-stretched hollow bodies made from said polyester can in particular be filled hot at temperatures up to 105 ° C.
    A second object of the invention relates to a method of manufacturing a bi-stretched hollow body based on the semi-crystalline thermoplastic polyester described above.
    Finally, a third object of the invention relates to a bi-drawn hollow body comprising the semi-crystalline thermoplastic polyester as previously described.
    Detailed description of the invention
    The subject of the invention is therefore the use of a semi-crystalline thermoplastic polyester for the manufacture of bi-drawn hollow bodies, said polyester comprising:
    • at least one 1,4: 3,6-dianhydrohexitol unit (A);
    • at least one alicyclic diol unit (B) other than the 1,4: 3,6-dianhydrohexitol units (A);
    • at least one terephthalic acid unit (C);
    wherein the molar ratio (A) / [(A) + (B) j being at least 0.05 and at most 0.30 and the reduced viscosity in solution greater than 50 mL / g.
    The semi-crystalline thermoplastic polyester is free from or comprises a small amount of non-cyclic aliphatic diol units.
    By “low molar quantity of non-cyclic aliphatic diol units” is meant in particular a molar quantity of non-cyclic aliphatic diol units of less than 5%. According to the invention, this molar amount represents the ratio of the sum of the non-cyclic aliphatic diol units, these units possibly being identical or different, relative to all of the monomeric units of the polyester.
    By “molar ratio (A) / [(A) + (B)] >> is meant the ratio of 1,4: 3,6-dianhydrohexitol units (A) / sum of 1,4: 3,6-dianhydrohexitol units (A) and alicyclic diol units (B) other than 1,4: 3,6-dianhydrohexitol units (A).
    A non-cyclic aliphatic diol can be a linear or branched non-cyclic aliphatic diol. It can also be a saturated or unsaturated non-cyclic aliphatic diol. In addition to ethylene glycol, the saturated linear non-cyclic aliphatic diol can for example be 1,3propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and / or 1,10-decanediol. As an example of a saturated branched non-cyclic aliphatic diol, mention may be made of 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1, 3propanediol, propylene glycol and / or neopentylglycol. As an example of an unsaturated aliphatic diol, mention may, for example, be made of cis-2-butene-1,4-diol.
    This molar amount of non-cyclic aliphatic diol unit is advantageously less than 1%. Preferably, the polyester is free of non-cyclic aliphatic diol unit and more preferably, it is free of ethylene glycol.
    Despite the small amount of non-cyclic aliphatic diol, and therefore ethylene glycol, used for the synthesis, there is surprisingly obtained a semi-crystalline thermoplastic polyester having a reduced viscosity in high solution and in which the isosorbide is particularly well incorporated. Without being bound by any theory, this would be explained by the fact that the reaction kinetics of ethylene glycol is much higher than that of 1,4: 3,6-dianhydrohexitol which strongly limits the integration of this last in polyester. The resulting polyesters therefore have a low integration rate of 1,4: 3,6-dianhydrohexitol and therefore a relatively low glass transition temperature.
    The monomer (A) is a 1,4: 3,6-dianhydrohexitol can be isosorbide, isomannide, isoidide, or a mixture thereof. Preferably, 1,4: 3,6-dianhydrohexitol (A) is isosorbide.
    Isosorbide, isomannide and isoidide can be obtained by dehydrating sorbitol, mannitol and iditol, respectively. As regards isosorbide, it is marketed by the Applicant under the brand name POLYSORB® P.
    The alicyclic diol (B) is also called the aliphatic and cyclic diol. It is a diol which can in particular be chosen from 1,4-cyclohexanedimethanol, 1,2cyclohexanedimethanol, 1,3-cyclohexanedimethanol or a mixture of these diols. Preferably, the alicyclic diol (B) is 1,4-cyclohexanedimethanol.
    The alicyclic diol (B) can be in the cis configuration, in the trans configuration or can be a mixture of diols in the cis and trans configuration.
    The molar ratio of 1,4: 3,6-dianhydrohexitol units (A) / sum of 1,4: 3,6dianhydrohexitol units (A) and alicyclic diol units (B) other than 1,4: 3,6dianhydrohexitol units ( A), or (A) / [(A) + (B)], is at least 0.05 and at most 0.30. Advantageously, this ratio is at least 0.1 and at most 0.28, and more particularly this ratio is at least 0.15 and at most 0.25.
    A semi-crystalline thermoplastic polyester particularly suitable for the production of bi-drawn hollow bodies comprises:
    • a molar quantity of 1,4: 3,6-dianhydrohexitol (A) units ranging from 2.5 to 14 mol%;
    • a molar amount of alicyclic diol units (B) other than the 1,4: 3,6-dianhydrohexitol units (A) ranging from 31 to 42.5% mol;
    • a molar quantity of terephthalic acid units (C) ranging from 45 to 55% mol.
    The amounts of different units in the polyester can be determined by 1 H NMR or by chromatographic analysis of the mixture of monomers resulting from a methanolysis or from a complete hydrolysis of the polyester, preferably by 1 H NMR.
    Those skilled in the art can easily find the analysis conditions for determining the amounts in each of the polyester patterns. For example, from an NMR spectrum of a poly (1,4-cyclohexanedimethylene-co-isosorbide terephthalate), the chemical shifts relative to 1,4-cyclohexanedimethanol are between 0.9 and 2.4 ppm and 4 , 0 and 4.5 ppm, the chemical shifts relating to the terephthalate cycle are between 7.8 and 8.4 ppm and the chemical shifts relating to the isosorbide are between 4.1 and 5.8 ppm. The integration of each signal makes it possible to determine the quantity of each pattern of the polyester.
    The semi-crystalline thermoplastic polyesters used according to the invention have a melting temperature ranging from 210 to 295 ° C, for example from 240 to 285 ° C.
    In addition, the semi-crystalline thermoplastic polyesters have a glass transition temperature ranging from 85 to 120 ° C, for example from 90 to 115 ° C.
    The glass transition and melting temperatures are measured by conventional methods, in particular by using differential scanning calorimetry (DSC) using a heating rate of 10 ° C./min. The experimental protocol is detailed in the examples section below.
    Advantageously, the semi-crystalline thermoplastic polyester has a heat of fusion greater than 10 J / g, preferably greater than 20 J / g, the measurement of this heat of fusion consisting in subjecting a sample of this polyester to a heat treatment at 170 ° C for 16 hours then evaluate the heat of fusion by DSC by heating the sample to 10 ° C / min.
    The semi-crystalline thermoplastic polyester used according to the invention has in particular a clarity L * greater than 40. Advantageously, the clarity L * is greater than 55, preferably greater than 60, most preferably greater than 65, for example greater than 70. The L * parameter can be determined using a spectrophotometer, using the CIE Lab model.
    Finally, the reduced viscosity in solution of said semi-crystalline thermoplastic polyester is greater than 50 ml / g and preferably less than 120 ml / g, this viscosity being able to be measured using an Ubbelohde capillary viscometer at 25 ° C. in an equimassic mixture of phenol and ortho-dichlorobenzene after dissolution of the polymer at 130 ° C. with stirring, the concentration of polymer introduced being 5 g / L.
    This test for measuring reduced viscosity in solution is, by the choice of solvents and the concentration of polymers used, perfectly suited for determining the viscosity of the viscous polymer prepared according to the process described below.
    The semi-crystalline nature of the thermoplastic polyesters used according to the present invention is characterized when the latter, after a heat treatment of 16 h at 170 ° C., exhibit X-ray diffraction lines or an endothermic melting peak in Scanning Differential Calorimetric Analysis ( DSC).
    The semi-crystalline thermoplastic polyester as defined above has many advantages for the production of bi-drawn hollow bodies.
    Indeed, thanks in particular to the molar ratio of 1,4: 3,6-dianhydrohexitol units (A) / sum of the 1,4: 3,6-dianhydrohexitol units (A) and alicyclic diol units (B) other than units 1 , 4: 3,6-dianhydrohexitol (A) of at least 0.05 and at most 0.30 and at a reduced viscosity in solution greater than 50 ml / g and preferably less than 120 ml / g, the semi-crystalline thermoplastic polyesters have a better thermal resistance which allows hollow bodies made from these to be able to be filled in particular hot at temperatures up to 95 ° C or even up to 105 ° C without deformation and without running away.
    A bi-stretched hollow body within the meaning of the present invention is a hollow body essentially made of plastic and may for example be a bottle, a bottle, a can, a barrel or even a reservoir. Preferably the hollow body is a bottle.
    The bi-drawn hollow bodies according to the invention can be directly manufactured from the molten state after polymerization of the semi-crystalline thermoplastic polyester.
    According to an alternative, the semi-crystalline thermoplastic polyester can be packaged in an easily manipulated form such as pellets or granules before being used for the manufacture of hollow bodies. Preferably, the semi-crystalline thermoplastic polyester is packaged in the form of granules, said granules being advantageously dried before processing into the form of a hollow body. The drying is carried out so as to obtain granules having a residual moisture content of less than 300 ppm, preferably less than 200 ppm, for example around 134 ppm.
    The manufacture of bi-drawn hollow bodies can be done by techniques known to those skilled in the art such as, for example, extrusion-blowing with bi-drawing or injection-blowing.
    Preferably the manufacture is carried out by injection-blowing. According to this method, the semi-crystalline thermoplastic polyester is injected to form a preform. The neck of the preform already has its final shape and constitutes the part which is used to maintain the future hollow body during the blowing operation. If necessary, the preform is reheated and enclosed in a blow mold having the desired shape. The mold can be formed of two half-shells having imprints on the inner face making it possible to give the future hollow body particular surface aspects.
    When the preform is introduced into the mold, a stretching rod comes to stretch the material axially, and a pre-blowing is carried out at a few bars of pressure. The final blowing is carried out by injection of compressed air. Thus, the polymer chains are oriented both along a longitudinal axis of the future hollow body and both radially and the polyester cools on contact with the mold, which freezes the hollow body in its final form. This biorientation makes it possible to obtain bi-oriented hollow bodies with improved mechanical properties.
    The shape and volume of the bi-stretched hollow body produced are a function of the characteristics of the mold used for blowing. Regarding the volume, it can vary from a few cm 3 to a few dm 3 , in particular from 50 cm 3 to 5000 cm 3 and preferably from 100 cm 3 to 2500 cm 3 and even more particularly from 500 cm 3 to 2000 cm 3 , as for example 1500 cm 3 .
    According to a particular embodiment, the semi-crystalline thermoplastic polyester previously defined is used in combination with one or more additional polymer for the production of bi-drawn hollow bodies.
    The additional polymer can be chosen from polyamides, polyesters other than polyester according to the invention, polystyrene, styrene copolymers, styrene-acrylonitrile copolymers, styrene-acrylonitrile-butadiene copolymers, polymethyl methacrylates, copolymers acrylics, poly (ether-imides), polyphenylene oxides such as poly (2,6-dimethylphenylene), phenylene polysulfate, poly (ester-carbonates), polycarbonates, polysulfones, polysulfone ethers, polyether ketones and mixtures of these polymers.
    The additional polymer can also be a polymer making it possible to improve the impact properties of the polymer, in particular functional polyolefins such as functionalized ethylene or propylene polymers and copolymers, core-shell copolymers or block copolymers.
    One or more additives can be added during the production of bi-drawn hollow bodies from the semi-crystalline thermoplastic polyester in order to give it specific properties.
    Thus, by way of example of an additive, mention may be made of opacifying agents, dyes and pigments. They can be chosen from cobalt acetate and the following compounds: HS325 Sandoplast® RED BB (which is a compound carrying an azo function also known under the name Solvent Red 195), HS-510 Sandoplast® Blue 2B which is an anthraquinone, Polysynthren® Blue R, and Clariant® RSB Violet.
    The additive can also be a UV resistance agent such as, for example, benzophenone or benzotriazole type molecules, such as the Tinuvin ™ range from BASF: tinuvin 326, tinuvin P or tinuvin 234 for example or hindered amines such as the Chimassorb ™ range BASF: Chimassorb 2020, Chimasorb 81 or Chimassorb 944 for example.
    The additive can also be a flame retardant or flame retardant, such as for example halogenated derivatives or non-halogenated flame retardants (for example phosphorous derivatives, such as Exolit® OP) or as the range of melamine cyanurates (for example melapur ™ example: melapur 200) or aluminum or magnesium hydroxides.
    The use according to the present invention of semi-crystalline thermoplastic polyester for the manufacture of bi-drawn hollow bodies is particularly advantageous.
    Indeed, the bi-stretched hollow bodies thus manufactured from semi-crystalline thermoplastic polyester as previously described, with in particular a molar ratio of 1,4: 3,6dianhydrohexitol (A) units / sum of 1,4: 3,6- units dianhydrohexitol (A) and alicyclic diol units (B) other than 1,4: 3,6-dianhydrohexitol (A) units of at least 0.05 and at most 0.30 and reduced viscosity in higher solution at 50 mL / g, have remarkable properties, in particular with regard to hot filling.
    Thus, the bi-drawn hollow bodies produced can be filled hot, without deformation or leaking, up to temperatures of 105 ° C.
    A second object of the invention relates to a process for manufacturing a bi-stretched hollow body, said process comprising the following steps:
    - Supply of a semi-crystalline thermoplastic polyester as defined below.
    Preparation of said bi-oriented from the semi-crystalline thermoplastic polyester obtained in the previous step.
    The preparation step can be carried out according to methods known to a person skilled in the art conventionally used for the manufacture of bi-drawn hollow bodies.
    Thus, by way of example, the preparation can be carried out by extrusion-blowing with bi-drawing or by injection-blowing. Preferably, the production is carried out by blowing injection.
    A third object of the invention relates to bi-drawn hollow bodies comprising the semi-crystalline thermoplastic polyester described above. The bi-stretched hollow bodies according to the invention may also comprise an additional polymer and / or one or more additives as defined above.
    The semi-crystalline thermoplastic polyester which is particularly suitable for the production of bi-drawn hollow bodies can be prepared by a synthesis process comprising:
    • a step of introduction into a monomer reactor comprising at least one
    1,4: 3,6-dianhydrohexitol (A), at least one alicyclic diol (B) other than 1,4: 3,6dianhydrohexitols (A) and at least one terephthalic acid (C), the molar ratio ((A ) + (B)) / (C) ranging from 1.05 to 1.5, said monomers being free of non-cyclic aliphatic diol or comprising, relative to all of the monomers introduced, a molar amount of non-cyclic aliphatic diol units less than 5%;
    • a step of introducing a catalytic system into the reactor;
    A step of polymerizing said monomers to form polyester, said step consisting of:
    a first oligomerization stage during which the reaction medium is stirred under an inert atmosphere at a temperature ranging from 265 to 280O, advantageously from 270 to 280 ° C, for example 275 ° C;
    a second stage of condensation of the oligomers during which the oligomers formed are stirred under vacuum at a temperature ranging from 278 to
    300 ° C in order to form the polyester, advantageously from 280 to 290 ° C., for example 285 ° C;
    • a stage of recovery of the semi-crystalline thermoplastic polyester.
    This first stage of the process takes place in an inert atmosphere, that is to say in an atmosphere of at least one inert gas. This inert gas can in particular be dinitrogen. This first stage can be carried out under a gas flow and it can also be carried out under pressure, for example at a pressure of between 1.05 and 8 bars.
    Preferably, the pressure ranges from 3 to 8 bars, most preferably from 5 to 7.5 bars, for example 6.6 bars. Under these preferred pressure conditions, the reaction of all of the monomers with one another is favored by limiting the loss of monomers during this stage.
    Prior to the first stage of oligomerization, a stage of deoxygenation of the monomers is preferably carried out. It can be done for example once the monomers have been introduced into the reactor, by producing a vacuum and then introducing an inert gas such as nitrogen. This vacuum-introduction cycle of inert gas can be repeated several times, for example from 3 to 5 times. Preferably, this vacuum-nitrogen cycle is carried out at a temperature between 60 and 80 ° C. so that the reagents, and in particular the diols, are completely melted. This deoxygenation step has the advantage of improving the coloring properties of the polyester obtained at the end of the process.
    The second stage of condensation of the oligomers takes place under vacuum. The pressure can decrease during this second stage continuously by using pressure drop ramps, in stages or by using a combination of pressure drop ramps and steps. Preferably, at the end of this second stage, the pressure is less than 10 mbar, most preferably less than 1 mbar.
    The first stage of the polymerization stage preferably has a duration ranging from 20 minutes to 5 hours. Advantageously, the second stage has a duration ranging from 30 minutes to 6 hours, the start of this stage consisting in the moment when the reactor is placed under vacuum, that is to say at a pressure of less than 1 bar.
    The method further includes a step of introducing a catalytic system into the reactor. This step can take place before or during the polymerization step described above.
    The term “catalytic system” is understood to mean a catalyst or a mixture of catalysts, optionally dispersed or fixed on an inert support.
    The catalyst is used in suitable quantities to obtain a high viscosity polymer in accordance with the use according to the invention for the manufacture of hollow bodies.
    An esterification catalyst is advantageously used during the oligomerization stage. This esterification catalyst can be chosen from tin, titanium, zirconium, hafnium, zinc, manganese, calcium, strontium derivatives, organic catalysts such as para-toluene sulfonic acid (APTS ), methane sulfonic acid (AMS) or a mixture of these catalysts. By way of example of such compounds, mention may be made of those given in application US2011282020A1 in paragraphs [0026] to [0029], and on page 5 of application WO 2013/062408 A1.
    Preferably, a zinc derivative or a manganese derivative of tin or germanium is used during the first transesterification stage.
    As an example of mass quantities, it is possible to use from 10 to 500 ppm of metal contained in the catalytic system during the oligomerization stage, relative to the quantity of monomers introduced.
    At the end of transesterification, the catalyst of the first stage can be optionally blocked by the addition of phosphorous acid or phosphoric acid, or else as in the case of tin (IV) reduced by phosphites such as phosphite triphenyl or phosphite tris (nonylephenyle) or those cited in paragraph [0034] of the application
    US2011282020A1.
    The second stage of condensation of the oligomers can optionally be carried out with the addition of a catalyst. This catalyst is advantageously chosen from tin derivatives, preferably tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc, cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of these catalysts. Examples of such compounds can be, for example, those given in patent EP 1 882 712 B1 in paragraphs [0090] to [0094],
    Preferably, the catalyst is a derivative of tin, titanium, germanium, aluminum or antimony.
    As an example of mass quantities, it is possible to use from 10 to 500 ppm of metal contained in the catalytic system during the stage of condensation of the oligomers, relative to the quantity of monomers introduced.
    Most preferably, a catalytic system is used during the first stage and the second stage of polymerization. Said system advantageously consists of a tin-based catalyst or a mixture of tin, titanium, germanium and aluminum catalysts.
    By way of example, a mass quantity of 10 to 500 ppm of metal contained in the catalytic system can be used, relative to the quantity of monomers introduced.
    According to the preparation process, an antioxidant is advantageously used during the monomer polymerization step. These antioxidants make it possible to reduce the coloration of the polyester obtained. The antioxidants can be primary and / or secondary antioxidants. The primary antioxidant can be a sterically hindered phenol such as the compounds Hostanox® 0 3, Hostanox® 0 10, Hostanox® 0 16, Ultranox® 210, Ultranox®276, Dovernox® 10, Dovernox® 76, Dovernox® 3114 , Irganox® 1010, Irganox® 1076 or a phosphonate such as Irgamod® 195. The secondary antioxidant can be trivalent phosphorus compounds such as Ultranox® 626, Doverphos® S-9228, Hostanox® P-EPQ, or the Irgafos 168.
    It is also possible to introduce, as polymerization additive into the reactor, at least one compound capable of limiting the parasitic etherification reactions such as sodium acetate, tetramethylammonium hydroxide or tetraethylammonium hydroxide.
    Finally, the synthesis process includes a step of recovering the polyester at the end of the polymerization step. The semi-crystalline thermoplastic polyester thus recovered can then be shaped as described above.
    According to a variant of the synthesis process, a step of increasing molar mass is carried out after the step of recovering the semi-crystalline thermoplastic polyester.
    The step of increasing the molar mass is carried out by post-polymerization and can consist of a step of polycondensation in the solid state (PCS) of the semi-crystalline thermoplastic polyester or in a step of reactive extrusion of the semi-thermoplastic polyester crystalline in the presence of at least one chain extender.
    Thus, according to a first variant of the manufacturing process, the post-polymerization step is carried out by PCS.
    The PCS is generally carried out at a temperature between the glass transition temperature and the polymer melting temperature. Thus, to achieve PCS, it is necessary that the polymer is semi-crystalline. Preferably, the latter has a heat of fusion greater than 10 J / g, preferably greater than 20 J / g, the measurement of this heat of fusion consisting in subjecting a sample of this polymer of reduced viscosity in lower solution a heat treatment at 170 ° C. for 16 hours then evaluating the heat of fusion by DSC by heating the sample to 10 K / min.
    Advantageously, the PCS stage is carried out at a temperature ranging from 190 to 280 ° C., preferably ranging from 200 to 250 ° C., this stage must imperatively be carried out at a temperature below the melting temperature of the semi-crystalline thermoplastic polyester.
    The PCS stage can be carried out in an inert atmosphere, for example under nitrogen or argon or under vacuum.
    According to a second variant of the manufacturing process, the post-polymerization step is carried out by reactive extrusion of the semi-crystalline thermoplastic polyester in the presence of at least one chain extender.
    The chain extender is a compound comprising two functions capable of reacting, in reactive extrusion, with functions, alcohol, carboxylic acid and / or carboxylic acid ester of the semi-crystalline thermoplastic polyester. The chain extender can, for example, be chosen from compounds comprising two isocyanate, isocyanurate, lactam, lactone, carbonate, epoxy, oxazoline and imide functions, said functions being able to be identical or different. The chain extension of the thermoplastic polyester can be carried out in all reactors capable of mixing a very viscous medium with sufficiently dispersive stirring to ensure a good interface between the molten material and the gas overhead of the reactor. A reactor particularly suitable for this treatment stage is extrusion.
    The reactive extrusion can be carried out in an extruder of any type, in particular a single-screw extruder, a co-rotating twin-screw extruder or a counter-rotating twin-screw extruder. However, it is preferred to carry out this reactive extrusion using a co-rotary extruder.
    The reactive extrusion step can be done by:
    • introducing the polymer into the extruder so as to melt said polymer;
    • then introducing the chain extender into the molten polymer;
    • then reacting the polymer in the extruder with the chain extender;
    • then recovering the semi-crystalline thermoplastic polyester obtained in the extrusion step.
    During extrusion, the temperature inside the extruder is adjusted to be above the melting temperature of the polymer. The temperature inside the extruder can range from 150 to 320 ° C.
    The invention will be better understood with the aid of the examples and figures below which are intended to be purely illustrative and in no way limit the scope of the protection.
    Examples
    The properties of polymers have been studied with the following techniques:
    Reduced viscosity in solution
    The reduced viscosity in solution is evaluated using an Ubbelohde capillary viscometer at 25 ° C in an equimassic mixture of phenol and ortho-dichlorobenzene after dissolution of the polymer at 130 ° C with stirring, the concentration of polymer introduced being 5g / L.
    DSC
    The thermal properties of the polyesters were measured by differential scanning calorimetry (DSC): The sample is firstly heated under nitrogen in an open crucible from 10 to 320 ° C (10 ° C.min-1) , cooled to 10 ° C (10 ° C.min-1) then reheated to 320 ° C under the same conditions as the first step. The glass transition temperatures were taken at the mid-point of the second heating. The possible melting temperatures are determined on the endothermic peak (start of the peak (onset)) at the first heating.
    Similarly, the determination of the enthalpy of fusion (area under the curve) is carried out on the first heating.
    For the illustrative examples presented below, the following reagents were used:
    1,4-Cyclohexane dimethanol (purity 99%, mixture of cis and trans isomers)
    Isosorbide (purity> 99.5%) Polysorb® P from Roquette Frères
    Terephthalic acid (purity 99 +%) from Acros
    Irganox® 1010 from BASF AG
    Dibutyltin oxide (purity 98%) from Sigma Aldrich
    Example 1: Preparation of a semi-crystalline thermoplastic polyester P1 and use for the manufacture of bottles.
    A: polymerization
    To a 7.5 L reactor are added 1432 g (9.9 mol) of 1,4-cyclohexanedimethanol, 484 g (3.3 mol) of isosorbide, 2000 g (12.0 mol) of terephthalic acid, 1.65 g of Irganox 1010 (antioxidant) and 1.39 g of dibutyltinoxide (catalyst). To extract the residual oxygen from the isosorbide crystals, 4 vacuum-nitrogen cycles are carried out once the temperature of the reaction medium is between 60 and 80 ° C.
    The reaction mixture is then heated to 275 ° C (4 ° C / min) under 6.6 bar of pressure and with constant stirring (150 rpm) until an esterification rate of 87% is obtained. The esterification rate being estimated from the mass of distillate collected. Then, the pressure is reduced to 0.7 mbar in 90 minutes according to a logarithmic ramp and the temperature brought to 285 O.
    These vacuum and temperature conditions were maintained until an increase in torque of 12.1 Nm was obtained compared to the initial torque.
    Finally, a rod of polymer is poured through the bottom valve of the reactor, cooled in a tank of water temperature controlled at 15 ° C and cut into the form of granules of about 15 mg.
    The resin thus obtained has a reduced viscosity in solution of 80.1 ml / g.
    Analysis by 1 H NMR of the polyester shows that the final polyester contains 17.0% mol of isosorbide relative to the diols.
    With regard to thermal properties, polyester P1 has a glass transition temperature of 96 ° C, a melting temperature of 253 ° C with an enthalpy of fusion of 23.2 J / g.
    B: Injection blow molding with bi-stretch mold
    The polyester granules P1 obtained in step A of polymerization are dried under vacuum at 140 ° C for 3 hours in order to reach a residual moisture level of less than 300 ppm, in this example, the residual moisture level of the granules is 134 ppm.
    The injection is carried out on a Husky single-cavity press with shutters.
    The granules, maintained in anhydrous condition, are then introduced into the hopper of the injection press in order to obtain the preforms.
    The injection parameters are detailed in Table 1 below:
    Settings Units Value Introductory zone temperature ° C 230 Temperature of the plastic in the molten state (nozzle / sheath) 285/280/280/270 Mold temperature ° C 50 Injection speed mm / s 80 Holding pressure bar 29 Duration of maintenance s 20 Cooling time s 20
    TABLE 1
    The preforms obtained from polyester P1 have a weight of approximately 23 g after injection and have a reinforced neck specific for hot filling.
    The preforms thus injected are then blown into a blowing carousel of the SBO series 2 brand from the company SIDEL: BO rate 11.51: 3.59 in radial and 3.20 in axial with a rate of 1550 bottle / hour / mold.
    For blowing in the carousel, the latter preheats the preforms to 150 ° C at heart through infrared lamps in the thermal conditioning zone under air flow at room temperature. The preform is positioned within the mold which is at a temperature of 170Ό and the latter is then closed.
    The injection of compressed air is carried out via a cannula which ensures bi-stretching of the bottle.
    Demoulding is done automatically and a bi-stretched bottle is obtained at the exit of the carousel.
    The bottles thus formed have a uniform material distribution and a volume of 500 ml.
    Example 2: Preparation of a semi-crystalline thermoplastic polyester P2 and use for the manufacture of bottles.
    A second semi-crystalline thermoplastic polyester for use according to the invention was also prepared. The protocol is described below. Unlike polyester P1, this polyester P2 has undergone a step of increase in molar mass by post condensation.
    A: polymerization
    To a 7.5L reactor are added 1194 g (8.3 mol) of 1,4-cyclohexanedimethanol, 726 g (5.0 mol) of isosorbide, 2000 g (12.0 mol) of terephthalic acid, 1 , 65 g of Irganox 1010 (antioxidant) and 1.39 g of dibutyltinoxide (catalyst). To extract the residual oxygen from the isosorbide crystals, 4 vacuum-nitrogen cycles are carried out once the temperature of the reaction medium is between 60 and 80 ° C. The reaction mixture is then heated to 275 ° C (4 ° C / min) under 6.6 bar of pressure and with constant stirring (150 rpm). The esterification rate is estimated from the amount of distillate collected. Then, the pressure is reduced to 0.7 mbar in 90 minutes according to a logarithmic ramp and the temperature brought to 285 ° C.
    These vacuum and temperature conditions were maintained until an increase in torque of 11.1 Nm was obtained compared to the initial torque.
    Finally, a polymer rod is poured through the bottom valve of the reactor, cooled in a tank of water temperature controlled at 15 ° C and cut into the form of granules of about 15 mg.
    The resin thus obtained has a reduced viscosity in solution of 66.2 ml / g 1 .
    Analysis by 1 H NMR of the polyester shows that the final polyester contains 30.2 mol% of isosorbide relative to the diols.
    The granules are then crystallized for 5 hours at a temperature of 150 ° C. under nitrogen and then a post-condensation stage in solid phase was carried out on 25 kg of these granules for 20 hours at 210 ° C. under a flow of nitrogen (1500 L / h) to increase the molar mass. The resin after condensation in the solid phase has a reduced viscosity in solution of
    94 mL.g 1 .
    With regard to thermal properties, polyester P2 has a glass transition temperature of 113 ° C, a melting temperature of 230 ° C with a melting enthalpy of 22 J / g.
    B- Injection-blowing with bi-stretch in mold
    The polyester granules P2 obtained in step A of polymerization are dried under vacuum at 140 ° C. in order to reach a residual moisture level of less than 300 ppm, in this example, the residual moisture level of the granules is 172 ppm.
    The injection is carried out on a Husky single-cavity press with shutters.
    The granules, maintained in anhydrous condition, are introduced into the hopper of the injection press in order to obtain the preforms.
    The other steps are similar to those of Example 1 except for modifications in the injection parameters where the barrel temperatures are slightly higher. The injection parameters are detailed in Table 2 below:
    Settings Units Value Introductory zone temperature Ό 230 Temperature of the plastic in the molten state (nozzle / sheath) Ό 275/270/270/260 Mold temperature Ό 50 Injection speed mm / s 80 Holding pressure bar 35 Duration of maintenance s 15 Cooling time s 20
    TABLE 2
    The preforms obtained from polyester P2 have a weight of approximately 23 g after injection and have a reinforced neck specific for hot filling.
    The preforms thus injected are then blown in a blowing carousel of the brand SBO series 2 from the company SIDEL: BO rate 11.51: 3.59 in radial and 3.20 in axial with a rate of 1550 bottle / hour / mold and a mold temperature of 170 O.
    For blowing in the carousel, the latter preheats the preforms to 140 ° C. at heart through infrared lamps in the thermal conditioning zone under air flow at room temperature. The preform is positioned within the mold which is at a mold temperature of 170 ° C and the latter is then closed. The injection of compressed air is carried out via a cannula which ensures bi-stretching of the bottle.
    Demoulding is done automatically and a bi-stretched bottle is obtained at the exit of the carousel.
    The bottles thus formed have a uniform material distribution and a volume of 500 ml.
    Example 3: Preparation of an amorphous thermoplastic polyester P3 and use for the manufacture of bottles by blow molding.
    Unlike polyesters P1 and P2, polyester P3 is a polyester used for comparison and thus has a molar ratio [A] / ([A] + [B]) of 0.44.
    A: Polymerization
    In a 7.5 L reactor are added 859 g (6 mol) of 1,4-cyclohexanedimethanol, 871 g (6 mol) of isosorbide, 1800 g (10.8 mol) of terephthalic acid, 1.5 g of Irganox 1010 (antioxidant) and 1.23 g of dibutyltinoxide (catalyst). To extract the residual oxygen from the isosorbide crystals, 4 vacuum-nitrogen cycles are carried out once the temperature of the reaction medium is between 60 and 80 ° C.
    The reaction mixture is then heated to 275 ° C (4 ° C / min) under 6.6 bar of pressure and with constant stirring (150 rpm). The esterification rate is estimated from the amount of distillate collected. Then, the pressure is reduced to 0.7 mbar in 90 minutes according to a logarithmic ramp and the temperature brought to 285O. These vacuum and temperature conditions were maintained until an increase in torque of 10 Nm compared to the initial torque was obtained. Finally, a polymer rod is poured through the bottom valve of the reactor, cooled in a tank of water temperature-controlled to 15 ° C and cut into the form of granules of approximately 15 mg.
    The resin thus obtained with this polyester P3 has a reduced viscosity in solution of 54.9 5 ml / g.
    Analysis by 1 H NMR of the polyester shows that the final polyester contains 44 mol% of isosorbide relative to the diols. As regards the thermal properties (recorded on the second heating), the polymer has a glass transition temperature of 125 ° C.
    B: Production of hollow bodies by parison extrusion
    The granules of polyester P3 obtained in step A of polymerization are dried under vacuum at 110 ° C. in order to reach residual moisture levels of less than 300 ppm, in this example, the water content of the granules is 230 ppm. . The granules, maintained in a dry atmosphere, are introduced into the hopper of the extruder.
    The extrusion is carried out on a HESTA HV200 blower and the settings are grouped in table 1 below:
    Denomination Units Values Temperature of plastic in the statemelted (extruder / die) Ό 250/250/260/260/270/270 Mold temperature Ό 50 Injection speed rpm 100 Blowing time dry 7 Control time S 1 Allowable pressure drop mbar 5 Cycle time S 15 Cadence Bodytrough / hour 240
    TABLE 3
    Thanks to an annular die, a parison is continuously extruded. The mold closes around the parison, a blade cuts the parison on the top of the mold thus forming the preform and the latter is transferred to a second work station.
    At that time, a blowing rod injects compressed air inside the preform in order to bi-stretch it and press it against the walls of the mold.
    Finally, after opening the mold, the part is ejected and the mold returns to its initial position to close on a new preform.
    The amorphous hollow body thus formed has a weight of 23 g and the absence of X-ray diffraction lines confirms its amorphous nature.
    Example 4: Hot filling test of bottles obtained with the semi-crystalline thermoplastic polyesters P1 and P2 and the amorphous thermoplastic polyester P3 (comparison).
    A: Hot filling with water at 90 ° C
    The bottles obtained by blowing from the preforms manufactured with polyesters P1 and P2 were filled hot with water at a temperature of 90 ° C with the objective of a dimensional deformation of less than 2% maximum.
    The dimensional stability is measured by measuring the diameter and the height at 3 points: neck, center and base of the hollow body, before filling and 24 hours after hot filling. The percentage corresponds to an average of deformation on each of these dimensions.
    In the case of polyester P3, the bottle undergoes deformation and collapse as soon as the first volumes of liquid are introduced at 90 ° C. It was therefore not possible on the bottle made of polymer P3 to perform a hot filling.
    The measurements show that the bottles made from polyesters P1 and P2 have a dimensional deformation of less than 1% after filling.
    The thermoplastic polyesters according to the invention are therefore particularly advantageous for use in the manufacture of hollow bodies, in particular of bottles, requiring good resistance to deformation during hot filling.
    B: Hot filling with 105Ό oil
    The bottles obtained by blowing from the preforms manufactured with polyesters P1, P2 and P3 were filled hot with oil at a temperature of 105 ° C with the objective of a dimensional deformation of less than 2% maximum.
    The bottles obtained with polyester P1 and P3 undergo deformations and sag as soon as the first volumes of liquid are introduced at 105 ° C.
    This is explained by the fact that the glass transition temperature of polyester P1 is lower than the temperature of the oil used for filling and by the fact that polyester P3 is an amorphous polyester. Thus, it was therefore not possible to obtain a dimensional deformation of less than 2% for the bottles obtained from polyesters P1 and P3 during hot filling at 105 ° C.
    Conversely, the measurements show that the bottles made from polyester P2 have a dimensional deformation of less than 1.3% after filling.
    The thermoplastic polyesters according to the invention are therefore particularly advantageous for use in the manufacture of bi-drawn hollow bodies, in particular of bottles, io requiring good resistance to deformation during hot filling.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    1. Use of a semi-crystalline thermoplastic polyester for the manufacture of bi-drawn hollow bodies, said polyester comprising:
    • at least one 1,4: 3,6-dianhydrohexitol unit (A);
    • at least one alicyclic diol unit (B) other than the 1,4: 3,6dianhydrohexitol units (A);
    • at least one terephthalic acid unit (C);
    wherein the molar ratio (A) / [(A) + (B)] being at least 0.05 and at most 0.30;
    said polyester being free of non-cyclic aliphatic diol units or comprising a molar quantity of non-cyclic aliphatic diol units, relative to the totality of the monomeric units of polyester, of less than 5%, and whose reduced viscosity in solution (25 ° C; phenol (50% m): ortho-dichlorobenzene (50% m); 5 g / L of polyester) is greater than 50 mL / g.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that the alicyclic diol (B) is a diol chosen from 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3cyclohexanedimethanol or a mixture of these diols, very preferably 1,4cyclohexanedimethanol.
    [3" id="c-fr-0003]
    3. Use according to one of claims 1 or 2, characterized in that 1,4: 3,6dianhydrohexitol (A) is isosorbide.
    [4" id="c-fr-0004]
    4. Use according to one of claims 1 to 3, characterized in that the polyester is free of non-cyclic aliphatic diol unit or comprises a molar amount of non-cyclic aliphatic diol unit, relative to the totality of the monomeric units of polyester, less than 1%, preferably the polyester is free of non-cyclic aliphatic diol unit.
    [5" id="c-fr-0005]
    5. Use according to one of claims 1 to 4, characterized in that the molar ratio (3,6-dianhydrohexitol unit (A) + alicyclic diol unit (B) other than 1,4: 3,6-dianhydrohexitol units (A)) / (terephthalic acid unit (C)) is 1.05 to 1.5.
    [6" id="c-fr-0006]
    6. Use according to one of claims 1 to 5, characterized in that the bi-stretched hollow body comprises one or more additional polymers and / or one or more additives.
    [7" id="c-fr-0007]
    7. Bi-drawn hollow body comprising a semi-crystalline thermoplastic polyester comprising:
    • at least one 1,4: 3,6-dianhydrohexitol unit (A);
    • at least one alicyclic diol unit (B) other than the 1,4: 3,6dianhydrohexitol units (A);
    • at least one terephthalic acid unit (C);
    wherein the molar ratio (A) / [(A) + (B)] being at least 0.05 and at most 0.30;
    said polyester being free of non-cyclic aliphatic diol units or comprising a molar quantity of non-cyclic aliphatic diol units, relative to the totality of the monomeric units of polyester, of less than 5%, and whose reduced viscosity in solution (25 ° C; phenol (50% m): ortho-dichlorobenzene (50% m); 5 g / L of polyester) is greater than 50 mL / g.
    [8" id="c-fr-0008]
    8. Bi-drawn hollow body according to claim 7, characterized in that the alicyclic diol (B) is a diol chosen from 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or a mixture of these diols, very preferably 1,4cyclohexanedimethanol.
    [9" id="c-fr-0009]
    9. bi-drawn hollow body according to one of claims 7 or 8, characterized in that the 1,4: 3,6-dianhydrohexitol (A) is isosorbide.
    [10" id="c-fr-0010]
    10. Bi-drawn hollow body according to one of claims 7 to 9, characterized in that the polyester is free of non-cyclic aliphatic diol unit or comprises a molar amount of non-cyclic aliphatic diol units, relative to all of the units polyester monomers, less than 1%, preferably the polyester is free of non-cyclic aliphatic diol unit.
    [11" id="c-fr-0011]
    11. Bi-stretched hollow body according to one of claims 7 to 10, characterized in that the molar ratio (3,6-dianhydrohexitol unit (A) + alicyclic diol unit (B) other than 1,4: 3 units , 6-dianhydrohexitol (A)) / (terephthalic acid unit (C)) is 1.05 to 1.5.
    [12" id="c-fr-0012]
    12. Bi-drawn hollow body according to one of claims 7 to 11, characterized in that the bi-drawn hollow body comprises one or more additional polymers and / or one or more additives.
    [13" id="c-fr-0013]
    13. Method for manufacturing a bi-stretched hollow body comprising the following steps:
    • Supply of a semi-crystalline thermoplastic polyester comprising at least one 1,4: 3,6-dianhydrohexitol unit (A), at least one alicyclic diol unit (B) other than 1,4: 3,6-dianhydrohexitol units (A), at least one terephthalic acid unit (C), in which the molar ratio (A) / [(A) + (B)] being at least 0.05 and at most 0.30, said polyester being free of non-cyclic aliphatic diol units or comprising a molar quantity of non-cyclic aliphatic diol units, relative to the totality of the monomeric units of polyester, of less than 5%, and whose reduced viscosity in solution (25 ° C.; phenol (50% m): ortho-dichlorobenzene (50% m); 5 g / L of polyester) is greater than 50 ml_ / g.
    • Preparation of said bi-oriented hollow body from the semi-crystalline thermoplastic polyester obtained in the previous step.
    [14" id="c-fr-0014]
    14. The manufacturing method according to claim 13, characterized in that the preparation step is carried out by extrusion-blowing with bi-stretching or by injection-blowing.
    [15" id="c-fr-0015]
    15. The manufacturing method according to claims 13 or 14, characterized in that the alicyclic diol (B) is a diol chosen from 1,4-cyclohexanedimethanol, 1,2cyclohexanedimethanol, 1,3-cyclohexanedimethanol or a mixture of these diols, very preferably 1,4-cyclohexanedimethanol.
    [16" id="c-fr-0016]
    16. Manufacturing process according to any one of claims 13 to 15, characterized in that the 1,4: 3,6-dianhydrohexitol (A) is isosorbide.
    [17" id="c-fr-0017]
    17. Manufacturing process according to any one of claims 13 to 16, characterized in that the polyester is free of non-cyclic aliphatic diol unit or comprises a molar amount of non-cyclic aliphatic diol unit, relative to all of the monomeric units polyester, less than 1%, preferably the polyester is free of non-cyclic aliphatic diol unit.
    [18" id="c-fr-0018]
    18. Manufacturing process according to any one of claims 13 to 17, characterized in that the molar ratio (3,6-dianhydrohexitol unit (A) + alicyclic diol unit (B) other than 1,4: 3 units, 6-dianhydrohexitol (A)) / (terephthalic acid unit (C)) is 1.05 to 1.5.
    [19" id="c-fr-0019]
    19. The manufacturing method according to any one of claims 13 to 18, characterized in that the bi-stretched hollow body comprises one or more additional polymers and / or one or more additives.
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    同族专利:
    公开号 | 公开日
    WO2018024988A1|2018-02-08|
    CN109496220A|2019-03-19|
    EP3494160B1|2022-03-02|
    CA3031888A1|2018-02-08|
    KR20190038816A|2019-04-09|
    EP3494160A1|2019-06-12|
    FR3054830B1|2020-12-11|
    US20190169366A1|2019-06-06|
    CN109496220B|2022-02-18|
    JP2019529600A|2019-10-17|
    MX2019001447A|2019-06-20|
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    EP2771382B1|2011-10-24|2018-01-03|Synvina C.V.|A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications|FR3054804B1|2016-08-05|2019-07-12|Roquette Freres|USE OF A THERMOPLASTIC POLYESTER FOR THE MANUFACTURE OF INJECTED PARTS|
    FR3065958B1|2017-05-05|2020-09-04|Roquette Freres|METHOD OF MANUFACTURING A COMPOSITE MATERIAL|
    FR3081871B1|2018-05-31|2020-11-27|Roquette Freres|PROCESS FOR CRYSTALLIZING A POLYESTER CONTAINING AT LEAST ONE 1,4: 3,6-DIANHYDROHEXITOL PATTERN.|
    法律状态:
    2017-08-31| PLFP| Fee payment|Year of fee payment: 2 |
    2018-02-09| PLSC| Publication of the preliminary search report|Effective date: 20180209 |
    2018-08-30| PLFP| Fee payment|Year of fee payment: 3 |
    2019-08-30| PLFP| Fee payment|Year of fee payment: 4 |
    2020-08-31| PLFP| Fee payment|Year of fee payment: 5 |
    2021-08-31| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1657491|2016-08-02|
    FR1657491A|FR3054830B1|2016-08-02|2016-08-02|SEMI-CRYSTALLINE THERMOPLASTIC POLYESTER FOR MANUFACTURING TWO-STRETCH HOLLOW BODIES|FR1657491A| FR3054830B1|2016-08-02|2016-08-02|SEMI-CRYSTALLINE THERMOPLASTIC POLYESTER FOR MANUFACTURING TWO-STRETCH HOLLOW BODIES|
    US16/321,305| US20190169366A1|2016-08-02|2017-08-02|Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies|
    JP2019505458A| JP2019529600A|2016-08-02|2017-08-02|Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies|
    PCT/FR2017/052169| WO2018024988A1|2016-08-02|2017-08-02|Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies|
    MX2019001447A| MX2019001447A|2016-08-02|2017-08-02|Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies.|
    CA3031888A| CA3031888A1|2016-08-02|2017-08-02|Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies|
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