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    • 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 cyclic diol unit (B) other than cyclohexanedimethanol units and the 1,4: 3,6-dianhydrohexitol (A) units; at least one aromatic dicarboxylic acid unit (C); said polyester being free of ethylene glycol units, its manufacture and use.
    公开号:FR3044667A1
    申请号:FR1651205
    申请日:2016-02-15
    公开日:2017-06-09
    发明作者:Nicolas Jacquel；Gabriel Degand；Loup Rene Saint
    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 optical articles.
    Technological background of the invention
    Optical glass and transparent optical resins are used for the manufacture of optical lenses in various optical devices, such as cameras, cameras, telescopes, magnifiers, binoculars or projectors. Transparent optical resins also find an application in the form of an optical film, for example for screens of electronic devices.
    Optical glass has excellent properties of heat resistance, transparency, dimensional stability and chemical resistance. However, its cost is high and it can not or only very difficult to be processed by molding. Unlike optical glass, a lens made from a transparent optical resin, particularly a thermoplastic transparent resin, has the advantage that it can easily be mass produced by injection molding.
    Examples of transparent optical resins include polycarbonates and polymethyl methacrylate (PMMA). However, these resins have several defects. The high viscosity of the polycarbonates causes problems in their shaping. In addition, the polycarbonates have limited UV light resistance. With regard to polymethyl methacrylate, it has limitations in optical applications subjected to high temperatures, such as for example projector lenses or screens of electronic devices, because of its low thermal resistance.
    Thus, there is still to date the need to find new transparent resins with interesting optical properties, can easily be shaped and having a thermal resistance and a high impact resistance.
    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 units of a cyclic diol other than cyclohexanedimethanol units and units. , 4: 3,6-dianhydrohexitol. 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 cyclic diol unit (B) other than cyclohexanedimethanol units and the 1,4: 3,6-dianhydrohexitol units (A); At least one aromatic dicarboxylic acid unit (C); said polyester being free of ethylene glycol units.
    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 cyclic diol (B). other than cyclohexanedimethanol and 1,4: 3,6-dianhydrohexitols (A) and at least one aromatic dicarboxylic acid (C), said monomers being free of ethylene glycol.
    This process comprises a polymerization step in the presence of a catalyst system and 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 150 to 250 ° C, advantageously from 170 to 240 ° C, more preferably from 180 to 235 ° C, and then raised to a temperature of from 230 to 300 ° C, advantageously from 240 to 290 ° C, more preferably 245 to 270 ° C; a second oligomer condensation step wherein the oligomers formed are vacuum stirred at 240 to 320 ° C to form the polyester, preferably 275 to 310 ° C, more preferably 289 to 310 ° 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.
    Due to the absence of ethylene glycol units, 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 molding, especially injection molding. It also has interesting optical properties for manufacturing optical lenses having high refractive indices and an Abbe number (variation of the refractive index with the wavelength) high compared to conventional polyesters. Its high glass transition temperature makes it particularly suitable for applications in the field of optics subjected to high temperatures.
    In addition, the polyesters according to the invention have interesting optical properties, in particular as regards their transmittance, refractive index and Abbe number. They are characterized in fact by a high transparency a high refractive index and Abbe number higher than the usual polyesters.
    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 cyclic diol unit (B) other than cyclohexanedimethanol units and the 1,4: 3,6-dianhydrohexitol units (A); At least one aromatic dicarboxylic acid unit (C); said polyester being free of ethylene glycol 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 ° C and more preferably still at least 120 ° C. In a particular embodiment, the polyester according to the invention has a glass transition temperature ranging from 95 ° C. to 155 ° C., preferably from 100 ° C. to 150 ° C., more preferably from 110 ° C. 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 10 ° C / min. The experimental protocol is detailed in the examples section below.
    The polyester according to the invention advantageously has a transmittance greater than 88%, preferably greater than 90%.
    Advantageously, the polyester according to the invention has a haze of less than 2%, preferably less than 1%.
    The haze and the transmittance of the sample are measured according to the ASTM D1003 and ASTM D1003-95 methods on a polyester injected part according to the invention.
    Preferably, the refractive index of the polyester according to the invention is greater than 1.50, more preferably greater than 1.55. It can be measured on a thick injected part (for example 3mm thick). The refractive index is then measured at 589 nm (D line of sodium).
    The Abbe number of the polyester according to the invention is preferably greater than 30, more preferably greater than 50.
    The number of ABBE is calculated according to the formula below from three refractive index measurements taken at 589 nm (nD: sodium D-line), 486 nm (nF: hydrogen F-line) and 656 nm (nC: C line of hydrogen). v = "p-1 nF - nc
    Advantageously, the polyesters according to the invention have a high impact resistance. Preferably, the impact strength of the polyester according to the invention measured at ambient temperature is greater than 100 kJ / m 2 for a non-notched specimen and greater than 5 kJ / m 2 for a notched specimen. It can be evaluated using a Charpy shock test according to ISO 179 (Not notched: ISO 179 1eU, Notched: ISO 179 1eA).
    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. 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 1%, preferably at least 2%, more preferably at least 5% and even more preferably at least 10% 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 can 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 (spiroglycol-co-isosorbide terephthalate), the chemical shifts relative to spiroglycol are between 0.7 and 0.9 ppm, between 3.1 and 3.6 ppm and between 4.1 and 4.3 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 relative quantity of a pattern with respect to all of the two diol units.
    The cyclic diol (B) may be chosen from spiroglycol, tricyclo [5.2.1.02.6] decane dimethanol (TCDDM), 2,2,4,4-tetramethyl-1,3-cyclobutandiol, tetrahydrofuranedimethanol (THFDM) , furanedimethanol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cycloheptanediol, 1,5-naphthalenediol, 2,7-cyclohexanediol, naphthalenediol, 1,4-naphthalenediol, 2,3-naphthalenediol, 2-methyl-1,4-naphthalenediol, 1,4-benzylediol, octahydronaphthalene-4,8-diol, dioxane glycol (DOG ), norbornane diols, adamanthanediols, pentacyclopentadecane dimethanols.
    In a preferred embodiment, the cyclic diol (B) is spiroglycol, tricyclo [5.2.1.02.6] decane dimethanol (TCDDM) or a mixture of these two diols.
    Advantageously, the polyester according to the invention is free of cyclohexanedimethanol units.
    The aromatic dicarboxylic acid unit (C) is advantageously chosen from terephthalic acid, 2,5-furan dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, isophthalic acid units and mixtures of two or more of these acidic units.
    According to one embodiment, the polyester according to the invention contains only one type of aromatic dicarboxylic acid unit. In other words, according to this embodiment, the polyester of the invention advantageously contains at least one terephthalic acid unit, 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 35 ° C. The polymer is dissolved beforehand in orthochlorophenol at 130 ° C. 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 quantity of cyclic diol units (B) other than cyclohexanedimethanol units and 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 (spiroglycol-co-isosorbide terephthalate), the chemical shifts relative to spiroglycol are between 0.7 and 0.9 ppm, between 3.1 and 3.6 ppm. and between 4.1 and 4.3 ppm, the chemical shifts relating to the terephthalate ring are between 7.8 and 8.4 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 175 to 250 ° C., preferably from 190 to 220 ° C., for example from 195 to 215 ° 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.
    Crystallization and melting temperatures are measured by conventional methods, including 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 dihydrohexitols (A) and at least one dicarboxylic acid (C), said monomers being free of ethylene glycol; 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 150 to 250 ° C., advantageously from 170 to 250 ° C. at 240 ° C, more preferably from 180 to 235 ° C, then raised to a temperature of from 230 to 300 ° C, preferably from 240 to 290 ° C, more preferably from 245 to 270 ° C; a second oligomer condensation step wherein the oligomers formed are vacuum stirred at 240 to 320 ° C to form the polyester, preferably 275 to 310 ° C, more preferably 289 to 310 ° 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 point 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 polyesters. 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, there may be mentioned charges or fibers of organic or inorganic nature, nanometric or non-functional, functionalized or not. 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 optical articles, in particular for the manufacture of optical lenses or optical films. It can also be used for the manufacture of multilayer articles. 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 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 article according to the invention may also be a multilayer article, 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 blowing hollow body, coextrusion inflation also called blowing film (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 orthochlorophenol 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
    - Spiroglycol (purity> 97%) of TCI - Tricyclo [5.2.1.02,6] decane dimethanol (TCDDM, purity 96%) of Sigma-Aldrich - Isosorbide (purity> 99,5%) Polysorb® P from Roquette Frères - Acid terephthalic acid (purity 99 +%) of Accros - 2,5-furan dicarboxylic acid (99.7% purity)) from Satachem - isophthalic acid (99% purity) from Sigma-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
    25 g of dimethylterephthalate, 2.4 g of Isosorbide, 67.5 g of Spiroglycol and 20 mg of tin dibutyl dioxide are introduced into a reactor. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190 ° C in 15 min under nitrogen flow. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 190 ° C for 5 minutes before being heated again to 265 ° C in 10 minutes. This temperature is maintained for 3 hours.
    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 3 hours.
    The polymer obtained is a semi-crystalline material whose glass transition is 130 ° C., a crystallization temperature of 200 ° C., a melting temperature of 281 ° C. and a reduced viscosity of 63.8 ml / g (concentration at 5 g). / L in 2-chlorophenol at 35 ° C). Analysis of the final polyester by NMR shows that 5% 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. 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 270 ° C. and a nitrogen flow of 3.3 L / min. After 25 hours of post condensation, the polymer will have a reduced solution viscosity of 105.8 ml / g.
    Example 2
    25 g of dimethylterephthalate, 10.5 g of Isosorbide, 50.8 g of Spiroglycol and 20 mg of tin dibutyl dioxide are introduced into a reactor. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190 ° C in 15 min under nitrogen flow. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 190 ° C for 5 minutes before being heated again to 265 ° C in 10 minutes. This temperature is maintained for 4 hours.
    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 4 hours.
    The polymer obtained is an amorphous material whose glass transition is 149 ° C. and the reduced viscosity is 54.9 ml / g (concentration at 5 g / l in 2-chlorophenol at 35 ° C.). Analysis of the final polyester by NMR shows that 27% of Isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 3
    25 g of 2,6-naphthalene dicarboxylic acid, 4.0 g of Isosorbide, 33.3 g of Spiroglycol and 20 mg of tin dibutyl dioxide are introduced into a reactor. The mixture is stirred by mechanical stirring at 150 rpm and is heated at 230 ° C in 15 min under nitrogen flow. Still under nitrogen flow and mechanical stirring, the reaction medium is then maintained at 230 ° C for 5 minutes before being heated again to 265 ° C in 10 minutes. This temperature is maintained for 4 hours.
    Following this, the temperature is raised to 310 ° 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 4 hours.
    The polymer obtained is a semi-crystalline material whose glass transition is 169 ° C., a crystallization temperature of 210 ° C., a melting temperature of 292 ° C. and a reduced viscosity of 49.4 ml / g (concentration at 5 g). / L in 2-chlorophenol at 35 ° C). Analysis of the final polyester by NMR shows that 17% of Isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 3a:
    The polyester of Example 3 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 270 ° C. and a nitrogen flow of 3.3 L / min. After 28 hours of post condensation, the polymer will have a reduced solution viscosity of 78.2 ml / g.
    Example 4
    25 g of dimethylterephthalate, 42.2 g of 4,8-tricyclo [5.2.1.02.6] decane dimethanol (mixture of isomers), 4.2 g of isosobide and 17.9 mg of oxide are introduced into a reactor. dibutyl tin. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190 ° C in 10 min under nitrogen flow. Still under a stream of nitrogen and mechanical stirring, the reaction medium is then maintained at 190 ° C. for 5 minutes before being heated again to 250 ° C. in 20 minutes. This temperature is maintained 120 minutes.
    Following this, the temperature is raised to 280 ° 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 an amorphous material whose glass transition is 119 ° C., and a reduced viscosity of 58.4 ml / g (concentration at 5 g / l in 2-chlorophenol at 35 ° C.). Analysis of the final polyester by NMR shows that 11% of Isosorbide (relative to the diols) were introduced into the polymer chains.
    Example 5
    25 g of dimethylterephthalate, 33.5 g of 4,8-tricyclo [5.2.1.02.6] decane dimethanol (mixture of isomers), 10.7 g of isosobide and 17.9 mg of oxide are introduced into a reactor. dibutyl tin. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 190 ° C in 10 min under nitrogen flow. Still under a stream of nitrogen and mechanical stirring, the reaction medium is then maintained at 190 ° C. for 5 minutes before being heated again to 250 ° C. in 20 minutes. This temperature is maintained 180 minutes.
    Following this, the temperature is raised to 280 ° 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 4:30.
    The polymer obtained is an amorphous material whose glass transition is 135 ° C., and a reduced viscosity of 51.3 ml / g (concentration at 5 g / l in 2-chlorophenol at 35 ° C.). Analysis of the final polyester by NMR shows that 27% of Isosorbide (relative to the diols) were introduced into the polymer chains.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    A thermoplastic polyester comprising: at least one 1,4: 3,6-dianhydrohexitol unit (A); at least one cyclic diol unit (B) other than cyclohexanedimethanol units and the 1,4: 3,6-dianhydrohexitol (A) units; at least one aromatic dicarboxylic acid unit (C); said polyester being free of ethylene glycol 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 according to any one of claims 1 or 2, wherein the cyclic diol (B) is selected from spiroglycol, tricyclo [5.2.1.02.6] decane dimethanol (TCDDM), 2,2,4, 4-tetramethyl-1,3-cyclobutandiol, tetrahydrofuranedimethanol (THFDM), furanedimethanol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1, 2-cycloheptanediol, 1,5-naphthalenediol, 2,7-naphthalenediol, 1,4-naphthalenediol, 2,3-naphthalenediol, 2-methyl-1,4-naphthalenediol, 1,4-benzylediol, octahydronaphthalene-4,8-diol, dioxane glycol (DOG), norbornane diols, adamanthanediols, pentacyclopentadecane dimethanols.
    [5" id="c-fr-0005]
    5. Polyester according to one of the preceding claims, characterized in that it is free of cyclohexanedimethanol units.
    [6" id="c-fr-0006]
    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 cyclic diol units (B) other than cyclohexanedimethanol units and 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%.
    [7" id="c-fr-0007]
    7. Polyester according to one of the preceding claims, characterized in that it is amorphous.
    [8" id="c-fr-0008]
    8. Polyester according to one of claims 1 to 6, characterized in that it is semi-crystalline.
    [9" id="c-fr-0009]
    9. A method of manufacturing the polyester according to one of the preceding claims, said method 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: 3,6-dianhydrohexitols (A) and at least one dicarboxylic acid (C), said monomers being free of ethylene glycol; a step of introduction into the reactor of a catalytic system; a step of polymerization of said monomers to form the polyester, said step consisting in: a first oligomerization stage during which the reaction medium is first agitated under an inert atmosphere at a temperature ranging from 150 to 250 ° C., advantageously from 170 to 250 ° C. at 240 ° C, more preferably from 180 to 235 ° C, then raised to a temperature of from 230 to 300 ° C, preferably from 240 to 290 ° C, more preferably from 245 to 270 ° C; a second oligomer condensation step wherein the oligomers formed are vacuum stirred at 240 to 320 ° C to form the polyester, preferably 275 to 310 ° C, more preferably 289 to 310 ° C; and; a step of recovering the polyester.
    [10" id="c-fr-0010]
    The process according to claim 9, wherein the polyester is semi-crystalline and the process comprises a post-condensation step in the solid state under vacuum or under an inert gas sweep and at a temperature below 5 to 30 ° C at the melting temperature of the polyester.
    [11" id="c-fr-0011]
    11. Polyester obtainable by the process according to claim 9 or 10.
    [12" id="c-fr-0012]
    12. A polyester composition comprising a polyester according to one of claims I to 8 or 11.
    [13" id="c-fr-0013]
    13. Use of the polyester of one of claims 1 to 8 or 11 or a composition according to claim 12, in the field of optical articles or multilayer plastic articles.
    [14" id="c-fr-0014]
    Plastic article comprising a polyester according to one of claims 1 to 8 or II or a composition according to claim 12.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3044667A1|2017-06-09|AROMATIC THERMOPLASTIC COPOLYESTERS COMPRISING 1,4: 3,6-DIANHYDROHEXITOL AND VARIOUS CYCLIC DIOLS
    CA2986103A1|2016-12-01|High-viscosity polyester with improved impact properties
    CA3006898A1|2017-06-08|Thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various aromatic diacids
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    EP3861050A1|2021-08-11|Method for preparing a polyester of the poly| type
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    EP3494158B1|2020-06-10|Semi-crystalline thermoplastic polyester for producing bioriented films
    EP3494417B1|2021-02-24|Amorphous thermoplastic polyester for the production of optical articles
    FR3054551B1|2019-08-02|POLYMER COMPOSITION COMPRISING A THERMOPLASTIC POLYESTER
    WO2022008096A1|2022-01-13|Thermoplastic polyester for producing 3d-printed objects
    WO2022008097A1|2022-01-13|Thermoplastic polyester for producing 3d-printed objects
    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
    同族专利:
    公开号 | 公开日
    CN108431078B|2021-08-06|
    JP2018536073A|2018-12-06|
    US20180362707A1|2018-12-20|
    FR3044667B1|2020-02-14|
    MX2018006685A|2018-08-24|
    CN108431078A|2018-08-21|
    KR20180089418A|2018-08-08|
    FR3044665A1|2017-06-09|
    EP3383932A1|2018-10-10|
    CA3006905A1|2017-06-08|
    WO2017093685A1|2017-06-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1322671A|1961-05-26|1963-03-29|Atlas Chem Ind|Improved polyester resins and process for their preparation|
    DE19704506A1|1997-02-06|1998-08-13|Basf Ag|Chiral nematic polyester|
    EP0924283A1|1997-12-20|1999-06-23|Clariant GmbH|Organic material with metallic glare|
    WO1999054119A1|1998-04-23|1999-10-28|E.I. Du Pont De Nemours And Company|Isosorbide containing polyesters and methods for making same|
    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|
    TWI383003B|2005-02-02|2013-01-21|Mitsubishi Gas Chemical Co|Polyester film, the process thereof, and the use thereof|
    EP2650317A1|2010-12-10|2013-10-16|Mitsubishi Gas Chemical Company, Inc.|Polyester resin and optical lens|
    KR101775620B1|2011-04-06|2017-09-07|에스케이케미칼주식회사|Polyester binder resin for coating application and coating composition including the same|
    US20130095271A1|2011-10-14|2013-04-18|Eastman Chemical Company|Polyester compositions containing furandicarboxylic acid or an ester thereof, ethylene glycol and cyclohexanedimethanol|KR20170093011A|2016-02-04|2017-08-14|에스케이케미칼주식회사|Polyester resin having excellent heat-resistance and solvent-solubility and coating composition comprising same|
    FR3065958B1|2017-05-05|2020-09-04|Roquette Freres|METHOD OF MANUFACTURING A COMPOSITE MATERIAL|
    CH715228A1|2018-08-02|2020-02-14|Alpla Werke Alwin Lehner Gmbh & Co Kg|Preform made of polyester.|
    CN111072940B|2019-11-28|2021-09-28|中国科学院宁波材料技术与工程研究所|Copolyester based on spiro ethylene glycol and preparation method and product thereof|
    CN111303394A|2020-04-20|2020-06-19|河南功能高分子膜材料创新中心有限公司|Preparation method of modified high-temperature-resistant polyester and modified high-temperature-resistant polyester|
    CN111471167A|2020-05-12|2020-07-31|河南功能高分子膜材料创新中心有限公司|Modified high-temperature-resistant hydrolysis-resistant copolyester|
    法律状态:
    2017-02-28| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-09| PLSC| Search report ready|Effective date: 20170609 |
    2018-02-26| PLFP| Fee payment|Year of fee payment: 3 |
    2019-02-28| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-28| PLFP| Fee payment|Year of fee payment: 5 |
    2021-02-26| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1561753A|FR3044665A1|2015-12-02|2015-12-02|AROMATIC THERMOPLASTIC COPOLYESTERS COMPRISING 1,4: 3,6-DIANHYDROHEXITOL AND VARIOUS CYCLIC DIOLS|
    FR1561753|2015-12-02|CN201680070741.4A| CN108431078B|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters containing 1,4:3, 6-dianhydrohexitol and various cyclic diols|
    KR1020187015250A| KR20180089418A|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4: 3,6-dianhydrohexitol and various cyclic diols|
    PCT/FR2016/053180| WO2017093685A1|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various cyclic diols|
    JP2018528647A| JP2018536073A|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters containing 1,4: 3,6-dianhydrohexitol and various cyclic diols|
    EP16819348.0A| EP3383932A1|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various cyclic diols|
    US15/781,387| US20180362707A1|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4:3,6-dianhydrohexitol and various cyclic diols|
    MX2018006685A| MX2018006685A|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various cyclic diols.|
    CA3006905A| CA3006905A1|2015-12-02|2016-12-02|Aromatic thermoplastic copolyesters comprising 1,4 : 3,6-dianhydrohexitol and various cyclic diols|
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