• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a 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: 3,6-dianhydrohexitol (A) units; at least one dicarboxylic acid unit (C) chosen from the 2,5-dicarboxylic acid furan, 2,6-naphthalic acid and isophthalic acid units; said polyester having at least 10% 1,4: 3,6-dianhydrohexitol (A) units and being free of ethylene glycol units and terephthalic acid units, its manufacture and use.
    公开号:FR3044666A1
    申请号:FR1561757
    申请日:2015-12-02
    公开日:2017-06-09
    发明作者:Nicolas Jacquel；Gabriel Degand；Rene Saint-Loup
    申请人:Roquette Freres SA；
    IPC主号:
    专利说明:

    Field of the invention
    The present invention relates to a thermoplastic polyester free of ethylene glycol units and having a high degree of incorporation of 1,4: 3,6-dianhydrohexitol units. The invention also relates to a method of manufacturing said polyester and the use of this polyester for the manufacture of different articles.
    Technological background of the invention
    Because of their many advantages, plastics have become essential for the mass production of objects. Indeed, their thermoplastic nature allows these materials to be transformed at a high rate in all kinds of objects.
    Some thermoplastic aromatic polyesters have thermal properties allowing them to be used directly for the manufacture of materials. They comprise aliphatic diol and aromatic diacid monomer 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 for the manufacture of containers, packages, films or fibers.
    By "monomeric unit (s)" or "unit (s)" is meant according to the invention units included in the polyester that can be obtained after polymerization of a monomer. As regards the ethylene glycol and terephthalic acid units included in the PET, they may be obtained by esterification reaction of ethylene glycol and terephthalic acid, or by a trans-esterification reaction of ethylene glycol and terephthalic acid ester.
    However, for certain applications or under certain conditions of use, these polyesters do not have all the required properties, in particular optical properties, impact resistance or heat resistance. Thus, PET modified glycols (PETg) have been developed. These are generally polyesters comprising, in addition to ethylene glycol and terephthalic acid units, cyclohexanedimethanol (CHDM) units. The introduction of this diol in the PET allows it to adapt the properties to the intended application, for example to improve its impact resistance or its optical properties, especially when the PETg is amorphous. Other modified PETs have also been developed by introducing 1,4: 3,6-dianhydrohexitol units into the polyester, in particular isosorbide (PEU). These modified polyesters have higher glass transition temperatures than unmodified PETs or PETgs comprising CHDM. In addition, 1,4: 3,6-dianhydrohexitols have the advantage that they can be obtained from renewable resources such as starch. These modified polyesters are especially useful for the manufacture of bottles, films, thick sheets, fibers or articles requiring high optical properties.
    A problem with these PEITs is that they may have insufficient properties of impact resistance. In addition, the glass transition temperature may be insufficient for certain applications.
    To improve the impact properties of polyesters, it is known from the prior art to use polyesters whose crystallinity has been reduced. As regards isosorbide-based polyesters, US2012 / 0177854, which describes polyesters prepared from an acidic component consisting of terephthalic acid and possibly a minor amount of another aromatic diacid, may be cited. such as phthalic acid, isopthalic acid or a naphthalene acid and a diol component consisting of 1 to 60 mol% of isosorbide and 5 to 99% of 1,4-cyclohexanedimethanol and optionally other diols like ethylene glycol. As indicated in the introductory part of this application, it is a question of obtaining polymers whose crystallinity is eliminated by the addition of comonomers, and thus here by the addition of 1,4-cyclohexanedimethanol. In the examples part, the manufacture of various poly (ethylene-co-1,4-cyclohexanedimethylene-co-isosorbide) terephthalates (PECIT) and an example of poly (1,4-cyclohexanedimethylene-co-isosorbide) terephthalate ( CITP). However, this demand is completely silent with regard to the content of the various constituents in the final polyester.
    Alternatives to modified PET and PET based on 2,5-dicarboxylic furan acid have also been proposed. For example, patent application US 2013/0171397 discloses polyesters comprising ethylene glycol and 2,5-dicarboxylic furan (PEF) units as well as polyesters comprising ethylene glycol, isosorbide and 2,5-furan dicarboxylic acid units. (PEIF). The PEIF glass transition temperatures (Tg) remain relatively low with a maximum of 78 ° C compared to 74 ° C for PEF indicating that the incorporation rate of isosorbide in the polyester is well below the amount of isosorbide used.
    The patent application WO 2014/100257 provides a theoretical description of polyesters based on furan dicarboxylic acid and naphthalene dicarboxylic acid, comprising, in addition to these acidic units, isosorbide units and optionally another polyol unit. However, this patent application discloses no real embodiment. In general, a problem encountered for the manufacture of polyesters comprising 1,4: 3,6-dianhydrohexitols units, and in particular isosorbide units, is that the incorporation rate of these units remains relatively low. A high incorporation rate of 1,4: 3,6-dianhydrohexitol units is, however, desirable to achieve thermal performance, more particularly a glass transition temperature, sufficient for various applications such as in the packaging sector.
    Thus, to date, there is still a need to find novel thermoplastic polyesters comprising 1,4: 3,6-dianhydrohexitol units having a high heat resistance which can be prepared efficiently and which advantageously have at the same time gas barrier properties. , especially oxygen, carbon dioxide and / or water vapor.
    It is the merit of the Applicant to have found that this objective can be achieved with thermoplastic polyesters comprising 1,4: 3,6-dianhydrohexitol units and which are free of ethylene glycol units and terephthalic acid units. SUMMARY OF THE INVENTION The invention thus relates to a 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: 3,6-dianhydrohexitol (A) units; At least one dicarboxylic acid unit (C) chosen from 2,5-furahe dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and isophthalic acid units; said polyester having at least 10% 1,4: 3,6-dianhydrohexitol units (A) with respect to all of the diol units present in the polyester and being free of ethylene glycol units and terephthalic acid units.
    Despite the large amounts of 1,4: 3,6-dianhydrohexitol units known as coloring agents in polyesters during the polymerization, the Applicant has found that the polyesters according to the invention surprisingly exhibit a low color.
    This polymer may especially be obtained by a particular manufacturing process, comprising in particular a step of introducing into a monomer reactor comprising at least one 1,4: 3,6-dianhydrohexitol (A), at least one alicyclic diol (B). other than 1,4: 3,6-dianhydrohexitols (A) and at least one dicarboxylic acid (C) chosen from 2,5-dicarboxylic acid furan, naphthalene dicarboxylic acid and isophthalic acid units, said monomers being free of ethylene glycol and terephthalic acid.
    This process comprises a step of polymerization at a high temperature of said monomers to form the polyester, said step consisting in: a first oligomerization step during which the reaction medium is first stirred under an inert atmosphere at a temperature ranging from 120 to 250 C, preferably from 125 to 210 ° C, more preferably from 130 to 200, then brought to a temperature of from 210 to 300 ° C, preferably from 220 to 280 ° C, more preferably from 225 to 265: second stage of oligomeric condensation during which the oligomers formed are stirred under vacuum at a temperature of 240 to 320 ° C to form the polyester, preferably 255 to 310 ° C, more preferably 265 to 300 ° C; and a step of recovering the polyester.
    The Applicant has found against all odds that by not using ethylene glycol as the diol monomer, it is possible to obtain new thermoplastic polyesters having a high glass transition temperature. This is explained by the fact that the reaction kinetics of ethylene glycol is much higher than that of 1,4: 3,6-dianhydrohexitol which greatly limits the integration of the latter in the polyester. The resulting polyesters therefore have a low degree of integration of 1,4: 3,6-dianhydrohexitol and therefore a relatively low glass transition temperature.
    The polyester according to the invention has a high glass transition temperature and can be used in many tools for converting plastics, and in particular be easily converted by blowing. It also has excellent impact properties.
    Detailed description of the invention
    The polymer which is the subject of the invention is a 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: 3,6-dianhydrohexitol (A) units; At least one dicarboxylic acid unit (C) chosen from 2,5-furane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and isophthalic acid units; said polyester having at least 10% 1,4: 3,6-dianhydrohexitol units (A) with respect to all of the diol units present in the polyester and being free of ethylene glycol units and terephthalic acid units.
    As explained above, the polyester according to the invention has a high glass transition temperature. Advantageously, it has a glass transition temperature of at least 95 ° C, preferably at least 100 ° C, more preferably at least 110 ° and more preferably still at least 120 °. In a particular embodiment, the polyester according to the invention has a glass transition temperature ranging from 95 ° to 155 °, preferably from 100 ° to 150 ° C., more preferably from 110 ° to 147 ° C. more preferably still from 120 ° C to 145 ° C.
    The glass transition temperature is measured by conventional methods, especially using differential scanning calorimetry (DSC) using a heating rate of 100 / min. The experimental protocol is detailed in the examples section below.
    The polyester according to the invention also has good barrier properties to gases, especially oxygen, carbon dioxide and / or water vapor. Advantageously, a CO 2 permeability less than 0.30 bar, an oxygen permeability of less than 0.11 bar and a water vapor permeability of less than 370 bar. The barrier properties can be evaluated on gas-based films respectively according to ASTM D1434, ASTD3985 and ASTM F1249.
    The unit (A) is a 1,4: 3,6-dianhydrohexitol. As previously explained, 1,4: 3,6-dianhydrohexitols have the disadvantage of being secondary diols that are not very reactive in the manufacture of polyesters. The 1,4: 3,6-dianhydrohexitol (A) may be isosorbide, isomannide, isoidide, or a mixture thereof. Preferably, 1,4: 3,6-dianhydrohexitol (A) is isosorbide. Isosorbide, isomannide and isoidide can be obtained respectively by dehydration of sorbitol, mannitol and iditol or by isomerization of another of these dianhydrohexitols. As regards isosorbide, it is marketed by the Applicant under the brand name POLYSORB® P.
    The polyester according to the invention preferably has at least 12%, preferably at least 15%, more preferably at least 20% and even more preferably at least 30% of 1,4: 3,6-dianhydrohexitol (A) units. relative to all the diol units present in the polyester.
    The amount of 1,4: 3,6-dianhydrohexitol (A) units in the polyester may be determined by 1 H NMR or by chromatographic analysis of the monomer mixture resulting from methanolysis or complete hydrolysis of the polyester, preferably by 1H NMR. Those skilled in the art can readily find the assay conditions to determine the amount of 1,4: 3,6-dianhydrohexitol (A) units of the polyester. For example, from an NMR spectrum of a poly (1,4-cyclohexanedimethylene-co-isosorbide isophthalate), the chemical shifts relating to 1,4-cyclohexanedimethanol are between 0.9 and 2.4 ppm and 4 , 0 and 4.5 ppm and chemical shifts relative to isosorbide are between 4.1 and 5.8 ppm. The integration of each signal makes it possible to determine the relative amount of a pattern with respect to all of the two patterns.
    The alicyclic diol (B) is also called aliphatic and cyclic diol. It is a diol which can be chosen in particular from 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or a mixture of these diols. Most preferably the alicyclic diol (B) is 1,4-cyclohexanedimethanol. The alicyclic diol (B) may be in the c / s configuration, in the trans configuration or may be a mixture of diols in the cis and trans configuration. In a particular embodiment, a cis / trans mixture of 1,4-cyclohexanedimethanol is used.
    According to one embodiment, the polyester contains only one type of dicarboxylic acid unit (C) chosen from 2,5-furane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and isophthalic acid units. In other words, according to this embodiment, the polyester of the invention contains at least one 2,5-furan dicarboxylic acid unit or at least one 2,6-naphthalene dicarboxylic acid unit or at least one isophthalic acid unit.
    Advantageously, the polyester according to the invention has a reduced solution viscosity greater than 40 ml / g, preferably greater than 45 ml / g and more preferably greater than 50 ml / g. The reduced viscosity in solution is evaluated using a Ubbelohde capillary viscometer at 35¾. The polymer is dissolved beforehand in ortho-chlorophenol at 130 ° with magnetic stirring. For these measurements, the polymer concentration introduced is 5 g / l.
    The polyester of the invention may for example comprise: • a molar amount of 1,4: 3,6-dianhydrohexitol (A) units ranging from 5 to 45%; A molar amount of alicyclic diol units (B) other than the 1,4: 3,6-dianhydrohexitol (A) units ranging from 3 to 47%; • a molar amount of dicarboxylic acid units (C) ranging from 48 to 52%.
    The amounts of different units in the polyester may be determined by 1H NMR or by chromatographic analysis of the monomer mixture resulting from methanolysis or complete hydrolysis of the polyester, preferably by 1 H NMR. Those skilled in the art can easily find the conditions of analysis to determine the amounts in each of the patterns of the polyester. For example, from an NMR spectrum of a poly (1,4-cyclohexanedimethylene-co-isosorbide isophthalate), the chemical shifts relating to 1,4-cyclohexanedimethanol are between 0.9 and 2.4 ppm and 4 At 0 and 4.5 ppm, the chemical shifts relative to the isophthalate ring are between 7.1 and 9.0 ppm and the chemical shifts relative to 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 polyester according to the invention can be semi-crystalline or amorphous.
    When the polyester according to the invention is semi-crystalline, it advantageously has a crystallization temperature ranging from 150 to 250 ° C., preferably from 160 to 230 ° C., for example from 170 to 225 ° C.
    Preferably, when the polyester according to the invention is semi-crystalline, it has a melting point ranging from 210 to 320 ° C., for example from 225 to 310 ° C.
    The melting temperature is measured by conventional methods, especially using differential scanning calorimetry (DSC) using a heating rate of 10 ° C / min. The experimental protocol is detailed in the examples section below. The invention also relates to a method of manufacturing the polyester according to the invention. This process comprises: • a step of introducing into a monomer reactor comprising at least one 1,4: 3,6-dianhydrohexitol (A), at least one alicyclic diol (B) other than 1,4: 3,6 -dianhydrohexitols (A) and at least one diacid (C) selected from 2,5-furan dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and isophthalic acid, said monomers being free of ethylene glycol and terephthalic acid; A step of introducing into the reactor a catalytic system; A step of polymerization of said monomers to form the polyester, said step consisting in: a first oligomerization step during which the reaction medium is first agitated under an inert atmosphere at a temperature ranging from 120 to 250 ° C., advantageously 125 to 250 ° C. at 210 ° C, more preferably 130 to 200 ° C, and then raised to a temperature of 210 to 300 ° C, preferably 220 to 280 ° C, more preferably 225 to 265 ° C; a second oligomer condensation step wherein the oligomers formed are vacuum stirred at 240 to 320 ° C to form the polyester, preferably 255 to 310 ° C, more preferably 265 to 300 ° C; • a polyester recovery step.
    If the polyester according to the invention is semi-crystalline, this process may comprise a step of post-condensation in the solid state under vacuum or under a sweep of an inert gas such as, for example, nitrogen (N 2), and a temperature of 5 to 30 ° C lower than the melting temperature of the polyester.
    By catalytic system is meant a catalyst or a mixture of catalysts, optionally dispersed or fixed on an inert support.
    The catalytic system is advantageously chosen from the group consisting of tin derivatives, preferentially tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc , cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of two or more of these catalysts. Examples of such compounds may be, for example, those given in EP 1882712 B1 in paragraphs [0090] to [0094].
    Preferably, the catalyst is a tin, titanium, germanium, aluminum or antimony derivative, more preferably a tin derivative or a germanium derivative, for example tin dibutyl dioxide or germanium oxide.
    The catalyst system is used in catalytic amounts usually used for the production of aromatic polyester. By way of example of mass quantities, it is possible to use from 10 to 500 ppm of catalyst system during the condensation stage of the oligomers, with respect to the amount of monomers introduced.
    According to the process of the invention, an antioxidant is advantageously used during the polymerization step of the monomers. These antioxidants make it possible to reduce the coloring of the polyester obtained. The antioxidants may be primary and / or secondary antioxidants. The primary antioxidant can be a sterically hindered phenol such as the compounds Hostanox® 0 3, Hostanox® 010, Hostanox® 016, Ultranox® 210, Ultranox®276, Dovernox® 10, Dovernox® 76, Dovernox® 3114 Irganox® 1010, Irganox® 1076 or a phosphonate such as Irgamod® 195. The secondary antioxidant may 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 spurious etherification reactions, such as sodium acetate, tetramethylammonium hydroxide, or tetraethylammonium hydroxide.
    The method of the invention comprises a step of recovering the polyester at the end of the polymerization step. The polyester can be recovered by extracting it from the reactor in the form of a melted polymer rod. This ring can be converted into granules using conventional granulation techniques. The subject of the invention is also the polyester obtainable by the process of the invention. The invention also relates to a composition comprising the polyester according to the invention, this composition may also comprise at least one additive or at least one additional polymer or at least one mixture thereof.
    The polyester composition according to the invention may comprise the polymerization additives possibly used during the process. It may also comprise other additives and / or additional polymers which are generally added during a subsequent thermomechanical mixing step. As an example of an additive, mention may be made of fillers or fibers of organic or inorganic nature, nanometric or non-functionalized or non-functionalized. It can be silicas, zeolites, fibers or glass beads, clays, mica, titanates, silicates, graphite, calcium carbonate, carbon nanotubes, wood fibers, of carbon fibers, polymer fibers, proteins, cellulosic fibers, lignocellulosic fibers and non-destructured granular starch. These fillers or fibers can improve the hardness, rigidity or permeability to water or gases. The composition may comprise from 0.1 to 75% by weight filler and / or fibers relative to the total weight of the composition, for example from 0.5 to 50%. The additive useful for the composition according to the invention may also comprise opacifying agents, dyes and pigments. They can be selected from cobalt acetate and the following compounds: HS-325 Sandoplast® RED BB (which is a compound carrying an azo function also known as Solvent Red 195), HS-510 Sandoplast® Blue 2B which is an anthraquinone, Polysynthren® Blue R, and Clariant® RSB Violet.
    The composition may also comprise as an additive a process agent, or processing aid, to reduce the pressure in the processing tool. A release agent to reduce adhesion to polyester forming materials such as molds or calender rolls can also be used. These agents can be selected from esters and fatty acid amides, metal salts, soaps, paraffins or hydrocarbon waxes. Specific examples of these agents are zinc stearate, calcium stearate, aluminum stearate, stearamides, erucamides, behenamides, beeswax or candelilla waxes.
    The composition according to the invention may also comprise other additives such as stabilizing agents, for example light stabilizing agents, UV stabilizing agents and heat stabilizing agents, fluidifying agents, flame retardants and antistatic agents.
    The composition may further comprise an additional polymer, different from the polyester according to the invention. This polymer may be chosen from polyamides, polyesters other than the polyester according to the invention, polystyrene, styrene copolymers, styrene-acrylonitrile copolymers, styrene-acrylonitrile-butadiene copolymers, polymethyl methacrylates and acrylic copolymers. poly (ether-imides), phenylene polyoxides such as (2,6-dimethylphenylene) polyoxide, phenylene polysulphates, poly (ester-carbonates), polycarbonates, polysulfones, polysulfone ethers, polyether ketones and mixtures of these polymers.
    The composition may also comprise, as additional polymer, 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.
    The composition according to the invention may also comprise polymers of natural origin, such as starch, cellulose, chitosans, alginates, proteins such as gluten, pea proteins, casein, collagen, gelatin, lignin, these polymers of natural origin may or may not be physically or chemically modified. The starch can be used in destructured or plasticized form. In the latter case, the plasticizer may be water or a polyol, in particular glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol or else urea. In order to prepare the composition, use may especially be made of the process described in document WO 2010/010282 A1.
    The composition according to the invention can be manufactured by conventional methods of blending thermoplastics. These conventional methods include at least one step of melt blending or softening of the polymers and a step of recovering the composition. This method can be carried out in internal mixers with blades or rotors, external mixers, co-rotating or counter-rotating twin screw extruders. However, it is preferred to carry out this mixture by extrusion, in particular by using a co-rotating extruder.
    The mixture of the constituents of the composition can be carried out under an inert atmosphere.
    In the case of an extruder, the various constituents of the composition can be introduced by means of introducing hoppers located along the extruder. The invention also relates to the use of the polyester or the composition in the field of packaging, in particular for the manufacture of fibers and yarns, films, sheets or hollow bodies, or in the field of optical articles, in particular for the manufacture of lenses or optical films. The invention also relates to a plastic article, finished or semi-finished, comprising the polyester or the composition according to the invention.
    This article can be of any type and be obtained using conventional transformation techniques.
    It may be for example for the fibers or son of techniques well known to those skilled in the art such as spin-drawing, electrospinning for example,
    It may be for example a film or a sheet, especially for use in the field of packaging. These films or sheets can be manufactured by calendering, cast film extrusion, duct extrusion extrusion techniques followed or not by monoaxial or polyaxial drawing or orientation techniques. The article according to the invention can also be a hollow article, especially for use in the field of packaging. It may be bottles, for example bottles of sparkling water or not, bottles of juice, bottles of soda, bottles, bottles of alcoholic beverages, bottles, for example bottles of medicine, vials cosmetics, these bottles may be aerosols, dishes, for example for ready meals, microwave dishes, pots, for example yoghurt pots, compote or cosmetics, or lids. These containers can be of any size. They can be manufactured by extrusion blow molding, thermoforming or injection blow molding. The article according to the invention can also be an optical article, that is to say an article requiring good optical properties such as lenses, disks, transparent or translucent panels, light-emitting diode (LED) components. , optical fibers, films for LCD screens or windows. Thanks to the high glass transition temperature of the polyester according to the invention, the optical articles have the advantage of being able to be placed near sources of light and therefore of heat, while maintaining excellent dimensional stability and good resistance to light. light.
    The articles may also be multilayer articles, at least one layer of which comprises the polymer or the composition according to the invention. These articles can be manufactured by a process comprising a coextrusion step in the case where the materials of the different layers are brought into contact in the molten state. By way of example, mention may be made of tube coextrusion techniques, coextrusion of profiles, coextrusion blow molding (in English "blowmolding") of bottles, flasks or tanks, generally grouped under the term coextrusion blow molding of hollow bodies, coextrusion inflation also called blowing of sheath (in English "film blowing") and co-extrusion flat ("in English" cast coextrusion ").
    They can also be manufactured by a process comprising a step of applying a polyester layer in the molten state to a layer based on organic polymer, metal or adhesive composition in the solid state. This step may be carried out by pressing, overmolding, lamination or lamination, extrusion-rolling, coating, extrusion-coating or coating. The article according to the invention can also be a fiber, a wire or a filament. The filaments can be obtained by various processes such as wet spinning, dry spinning, melt spinning, spinning of a gel (spinning or dry-wet spinning gel). or electrospinning. Filaments obtained by spinning can also be stretched or oriented.
    The filaments, if desired, can be cut into short fibers, which allows these fibers to be mixed with other fibers to create blends and obtain a yarn.
    Yarns or filaments can also be woven for the manufacture of clothing fabrics, carpets, curtains, draperies, linens, wall coverings, boat sails, upholstery fabrics or straps. or seat belts.
    The yarns, fibers or filaments can also be used in technical applications as reinforcements such as in pipes, power belts, tires, or as reinforcement in any other polymer matrix.
    The yarns, fibers or filaments can also be assembled in the form of nonwovens (eg felts), in the form of ropes, or knitted in the form of nets. The invention will now be illustrated in the examples below. It is specified that these examples do not limit the present invention.
    Examples:
    The properties of polymers have been studied with the following techniques:
    The thermal properties of the polyesters were measured by differential scanning calorimetry (DSC): The sample is first heated under a nitrogen atmosphere in an open crucible of 10 to 320 ° C (10 ° C.min-1). cooled to 10 ° C. (10 ° C.min -1) and then heated to 320 ° C. under the same conditions as the first step. The glass transition temperatures were taken at the midpoint of the second heating. The possible crystallization temperatures are determined on the exothermic peak (onset of the peak). The possible melting temperatures are determined on the endothermic peak (onset of the peak) in the second heating. In the same way the determination of the enthalpy of fusion (area under the curve) is carried out at the second heating.
    The reduced viscosity in solution is evaluated using a Ubbelohde capillary viscometer at 35 ° C. The polymer is dissolved beforehand in ortho-chlorophenol at 130 ° C. with magnetic stirring. For these measurements, the polymer concentration introduced is 5 g / l.
    The isosorbide content of the final polyester was determined by 1 H NMR by integrating the signals relating to each pattern of the polyester.
    For the illustrative examples presented below the following reagents were used: - Ethylene glycol (purity> 99.8%) of Sigma-Aldrich - 1,4-cyclohexane dimethanol (purity 99%, mixture of cis and trans isomers) - Isosorbide (purity> 99.5%) Roquette Frères Polysorb® P - 2.5-furan dicarboxylic acid (purity 99.7%) from Satachem - isophthalic acid (99% purity) from Aldrich ...
    - 2,6-naphthalene dicarboxylic acid (purity 99.8%) BASF - germanium dioxide (> 99.99%) Sigma Aldrich - Dibutyl dioxide (purity 98%) by Sigma Aldrich
    Preparation of the polyesters:
    Example 1
    In a reactor are introduced 50 g of 2,5-furan dicarboxylic acid, 21.6 g of 1,4-cyclohexanedimethanol (cis / trans ratio: 70/30), 7.3 g of isosorbide and 15 mg of oxide. of Germanium. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 130 ° C. in 10 min under a stream of nitrogen. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 140 ° C. for 10 minutes before being heated again to 200 ° C. in 20 minutes. This temperature is maintained for 20 minutes. Then the temperature is again increased to 225 ° C in 20 minutes and is maintained for 2:30.
    Following this, the temperature is raised to 265 ° C, the pressure is reduced in 30 minutes to 0.7mbar and the stirring speed is reduced to 50 rpm. These conditions will be maintained for 3 hours.
    The polymer obtained is a semicrystalline material whose glass transition is 111 ° C., its crystallization temperature of 175 ° C. and its melting temperature of 229 ° C. and its viscosity number is 54.7 ml / g (concentration at 5 g / L in 2-chlorophenol at 35 ° C). Analysis of the final polyester by NMR shows that 23% of isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 1a.
    The polyester of Example 1 is used in a post-condensation step in the solid state. First, the polymer is crystallized for 2 hours in a vacuum oven at 170 ° C. The crystallized polymer is then introduced into an oil bath rotavapor equipped with a fluted balloon. The granules are then subjected to a temperature of 220 ° C. and a nitrogen flow of 3.3 L / min. After 31 hours of post condensation, the polymer will have a solution viscosity of 71.2 ml / g.
    Example 2
    In a reactor are introduced 50 g of 2,5-furan dicarboxylic acid, 17.3 g of 1,4-cyclohexanedimethanol (cis / trans ratio: 70/30), 11.0 g of isosorbide and 20 mg of oxide. of Germanium. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 130 ° C. in 10 min under a stream of nitrogen. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 140 ° C. for 10 minutes before being heated again to 200 ° C. in 20 minutes. This temperature is maintained for 20 minutes. Then the temperature is again increased to 225 ° C in 20 minutes and is maintained for 3:30.
    Following this, the temperature is raised to 265 ° C, the pressure is reduced in 30 minutes to 0.7mbar and the stirring speed is reduced to 50 rpm. These conditions will be maintained for 5 hours.
    The polymer obtained is an amorphous material whose glass transition is 123 ° C. and its viscosity number is 47.5 ml / g (concentration at 5 g / l in 2-chlorophenol at 35 ° C.). Analysis of the final polyester by NMR shows that 37% of isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 3
    25 g of isophthalic acid, 16.8 g of 1,4-cyclohexanedimethanol (cis / trans ratio: 70/30), 9.2 g of isosorbide and 17 mg of tin dibutyl dioxide are introduced into a reactor. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190¾ in 15 min under a stream of nitrogen. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 190¾ for 10 minutes before being heated again to 250¾ in 30 minutes. This temperature is maintained for 2h30. Following this, the temperature rose to 280¾. the pressure is reduced in 1 hour to 0.7mbar and the stirring speed is reduced to 50 rpm. These conditions will be maintained for 3 hours.
    The polymer obtained is an amorphous material whose glass transition is 97¾ and a viscosity number of 46.8 ml / g (concentration at 5 g / l in 2-chlorophenol at 35¾). Analysis of the final polyester by NMR shows that 29% of Isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 4
    25 g of 2,6-naphthalene dicarboxylic acid, 12 g of 1,4-cyclohexanedimethanol (cis / trans ratio: 70/30), 8 g of isosorbide and 27 mg of dibutyl dioxide are introduced into a reactor. tin. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190¾ in 15 min under a stream of nitrogen. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 190 ° C for 10 minutes before being heated again to 265 ° C in 30 minutes. This temperature is maintained for 3:30.
    Following this, the temperature is raised to 300 ° C, the pressure is reduced in 1 hour to 0.7mbar and the stirring speed is reduced to 50 rpm. These conditions will be maintained for 5 hours.
    The polymer obtained is a semi-crystalline material whose glass transition is 140 ° C., a crystallization temperature of 221 ° C., a melting point of 272 ° C. and a viscosity number of 43.5 ml / g. Analysis of the final polyester by NMR shows that 30% of isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 4a
    The polyester of Example 4 is used in a post-condensation step in the solid state. Firstly, the polymer is crystallized for 2 hours in a vacuum oven at 190 ° C. The crystallized polymer is then introduced into an oil bath rotavapor equipped with a fluted balloon. The granules are then subjected to a temperature of 260 ° C. and a nitrogen flow of 3.3 l / min. After 35 hours post condensation, the polymer will have a solution viscosity of 75.3 ml / g.
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    A 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: 3,6-dianhydrohexitol (A) units; at least one dicarboxylic acid unit (C) chosen from the 2,5-dicarboxylic acid furan, 2,6-naphthalic acid and isophthalic acid units; said polyester having at least 10% of 1,4: 3,6-dianhydrohexitol units (A) and being free of ethylene glycol units and terephthalic acid units.
    [2" id="c-fr-0002]
    2. Polyester according to claim 1 having a glass transition temperature of at least 95 ° C, preferably at least 100 ° C, more preferably at least 110 ° C and more preferably still at least 120 ° C. vs.
    [3" id="c-fr-0003]
    The polyester of any preceding claim, wherein the 1,4: 3,6-dianhydrohexitol (A) is isosorbide.
    [4" id="c-fr-0004]
    The polyester of any one of claims 1 or 2, wherein the alicyclic diol (B) is a diol selected from 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or a mixture thereof. of these diols, preferentially 1,4-cyclohexanedimethanol.
    [5" id="c-fr-0005]
    The polyester of any preceding claim, wherein the polyester comprises: - a molar amount of 1,4: 3,6-dianhydrohexitol (A) units ranging from 5 to 45%; a molar quantity of alicyclic diol units (B) other than the 1,4: 3,6-dianhydrohexitol (A) units ranging from 3 to 47%; a molar amount of dicarboxylic acid units (G) ranging from 48 to 52%.
    [6" id="c-fr-0006]
    6. Polyester according to one of the preceding claims, characterized in that it is amorphous.
    [7" id="c-fr-0007]
    7. Polyester according to one of claims 1 to 5, characterized in that it is semi-crystalline.
    [8" id="c-fr-0008]
    8. A method of manufacturing the polyester according to one of the preceding claims, said method comprising: - a step of introduction into a reactor of monomers comprising at least one 1,4: 3,6-dianhydrohexitol (A), at least one alicyclic diol (B) other than 1,4: 3,6-dianhydrohexitols (A) and at least one diacid (C) selected from 2,5-dicarboxylic furan acid, 2,6-naphthalic acid and isophthalic acid, said monomers being free of ethylene glycol and terephthalic acid; a step of introduction into the reactor of a catalytic system; a step of polymerizing said monomers to form the polyester, said step consisting in: a first oligomerization step during which the reaction medium is first agitated under an inert atmosphere at a temperature ranging from 120 to 250 ° C., advantageously 125 to 250 ° C. at 210 ° C, more preferably 130 ° C to 200 ° C, then heated to 210 ° C to 300 ° C, preferably 220 ° C to 280 ° C, more preferably 225 ° C to 265 ° C; a second oligomer condensation step wherein the formed oligomers are vacuum stirred at a temperature of from 240 to 320 ° to form the polyester, preferably 255 to 310 ° C, more preferably 265 to 300 ° C; and a step of recovering the polyester.
    [9" id="c-fr-0009]
    The process according to claim 8, wherein the polyester is semi-crystalline and the process comprises a step of post-condensation in the solid state under vacuum or under an inert gas sweep and at a temperature of 5 to 30 ° C at the melting point of the polyester.
    [10" id="c-fr-0010]
    10. Polyester obtainable by the process according to claim 8 or 9.
    [11" id="c-fr-0011]
    11. A polyester composition comprising a polyester according to one of claims 1 to 7 or 10.
    [12" id="c-fr-0012]
    12. Use of the polyester according to one of claims 1 to 7 or 10 or a composition according to claim 11, in the field of packaging or in the field of optical articles.
    [13" id="c-fr-0013]
    Plastic article comprising a polyester according to one of claims 1 to 7 or 10 or a composition according to claim 11.
    类似技术:
    公开号 | 公开日 | 专利标题
    CA2986103A1|2016-12-01|High-viscosity polyester with improved impact properties
    EP3383932A1|2018-10-10|Aromatic thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various cyclic diols
    CA2965900A1|2016-05-06|Method for producing a polyester containing at least one 1,4:3,6-dianhydrohexitol unit with improved colouring
    WO2017093684A1|2017-06-08|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids
    EP3494061B1|2021-11-17|Packaging method based on a semi-crystalline thermoplastic polyester
    EP3694903A1|2020-08-19|Thermoplastic polyester with high incorporation of1,4:3,6-dianhydro-l-iditol units
    CA3031882A1|2018-02-01|Thermoplastic polyester for producing 3d-printed objects
    WO2020070445A1|2020-04-09|Method for preparing a polyester of the poly| type
    WO2018015692A1|2018-01-25|Semi-crystalline thermoplastic polyester for producing fibres
    FR3105232A1|2021-06-25|Process for the manufacture of a polyester containing at least one 1,4: 3,6-dianhydrohexitol unit with reduced coloration and the rate of incorporation of said unit improved
    EP3494158B1|2020-06-10|Semi-crystalline thermoplastic polyester for producing bioriented films
    FR3054551B1|2019-08-02|POLYMER COMPOSITION COMPRISING A THERMOPLASTIC POLYESTER
    EP3755736A1|2020-12-30|Thermoplastic polyester having improved resistance to the phenomenon of cracking
    WO2022008096A1|2022-01-13|Thermoplastic polyester for producing 3d-printed objects
    同族专利:
    公开号 | 公开日
    MX2018006684A|2018-08-24|
    JP2018536072A|2018-12-06|
    CN108368242A|2018-08-03|
    US20180355101A1|2018-12-13|
    FR3044666B1|2020-10-30|
    CA3006898A1|2017-06-08|
    WO2017093684A1|2017-06-08|
    KR20180089419A|2018-08-08|
    EP3383933A1|2018-10-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1999054119A1|1998-04-23|1999-10-28|E.I. Du Pont De Nemours And Company|Isosorbide containing polyesters and methods for making same|
    US20130095263A1|2011-10-14|2013-04-18|Eastman Chemical Company|Polyester compositions containing furandicarboxylic acid or an ester thereof, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol|
    WO2014100257A2|2012-12-20|2014-06-26|Dow Global Technologies Llc|Fdca-based polyesters made with isosorbide|
    WO2015170050A1|2014-05-09|2015-11-12|Roquette Freres|Thermoplastic aromatic polyesters comprising tetrahydrofuran-dimethanol and furandicarboxylic acid motifs|
    US6914120B2|2002-11-13|2005-07-05|Eastman Chemical Company|Method for making isosorbide containing polyesters|ITUA20162764A1|2016-04-20|2017-10-20|Novamont Spa|NEW POLYESTER AND COMPOSITIONS THAT CONTAIN IT|
    CN109648966B|2018-12-27|2020-11-13|合肥乐凯科技产业有限公司|High-barrier polyester film|
    WO2022043501A1|2020-08-27|2022-03-03|Furanix Technologies B.V.|Preparing polyester comprising 2,5-furandicarboxylate units with germanium catalyst|
    法律状态:
    2016-12-29| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-09| PLSC| Publication of the preliminary search report|Effective date: 20170609 |
    2018-01-02| PLFP| Fee payment|Year of fee payment: 3 |
    2018-12-31| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-30| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-30| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1561757A|FR3044666B1|2015-12-02|2015-12-02|THERMOPLASTIC COPOLYESTERS INCLUDING 1,4: 3,6-DIANHYDROHEXITOL AND VARIOUS AROMATIC DIACIDS|FR1561757A| FR3044666B1|2015-12-02|2015-12-02|THERMOPLASTIC COPOLYESTERS INCLUDING 1,4: 3,6-DIANHYDROHEXITOL AND VARIOUS AROMATIC DIACIDS|
    JP2018528614A| JP2018536072A|2015-12-02|2016-12-02|Thermoplastic copolyester comprising 1,4: 3,6-dianhydrohexitol and various aromatic diacids|
    EP16819969.3A| EP3383933A1|2015-12-02|2016-12-02|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids|
    KR1020187015251A| KR20180089419A|2015-12-02|2016-12-02|1,4: 3,6-dianhydrohexitol and thermoplastic copolyesters comprising various aromatic diacids|
    CN201680070700.5A| CN108368242A|2015-12-02|2016-12-02|Containing 1,4:The thermoplastic copolyesters of 3,6- bis- dewatering hexitols and various aromatic diacids|
    CA3006898A| CA3006898A1|2015-12-02|2016-12-02|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids|
    PCT/FR2016/053179| WO2017093684A1|2015-12-02|2016-12-02|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids|
    US15/781,406| US20180355101A1|2015-12-02|2016-12-02|Thermoplastic copolyesters comprising 1,4:3,6-dianhydrohexitol and various aromatic diacids|
    MX2018006684A| MX2018006684A|2015-12-02|2016-12-02|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids.|
    [返回顶部]