Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
  • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
  • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/80—Solid-state polycondensation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films

Definitions

• 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.
• plastics 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.
• 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.
• PET polyethylene terephthalate
• 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.
• PET modified glycols PET modified glycols
• CHDM cyclohexanedimethanol
• modified PETs have also been developed by introducing into the polyester units 1,4: 3,6-dianhydrohexitol, especially isosorbide (PEIT).
• PEIT isosorbide
• These modified polyesters have higher glass transition temperatures than unmodified PETs or PETgs comprising CHDM.
• 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.
• the glass transition temperature may be insufficient for certain applications.
• polyesters whose crystallinity has been reduced.
• 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.
• 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.
• polyesters comprising 1,4-3,6-dianhydrohexitol units, and in particular isosorbide units, are relatively low.
• rate of incorporation of these units remains relatively low.
• a high degree of incorporation of 1,4-3,6-dianhydrohexitol units is desirable to achieve thermal performance, more particularly a glass transition temperature, which is sufficient for various applications such as in the packaging sector.
• thermoplastic polyesters comprising 1,4-3,6-dianhydrohexitol units having a high heat resistance which can be efficiently prepared and which advantageously have at the same time gas barrier properties. , especially oxygen, carbon dioxide and / or water vapor.
• thermoplastic polyesters comprising 1,4-3,6-dianhydrohexitol units and which are free of ethylene glycol units and terephthalic acid units.
• thermoplastic polyester comprising:
• 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) selected from 2,5-dicarboxylic acid furan, naphthalene dicarboxylic acid and isophthalic acid units, said monomers being free of ethylene glycol and terephthalic acid.
• A 1,4: 3,6-dianhydrohexitol
• B alicyclic diol
• C dicarboxylic acid
• This process comprises a step of polymerization at a high temperature of said monomers to form the polyester, said step consisting of:
• a first oligomerization stage during which the reaction mixture is first stirred under inert atmosphere at a temperature ranging from 120 to 250 ° C, preferably from 125 to 210, more preferably 130 to 200 ° C and then brought to a temperature ranging from 210 to 300 ⁇ , preferably from 220 to 280 ⁇ C, more preferably 225-265 ⁇ C;
• 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 Polyesters resulting therefrom thus 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.
• thermoplastic polyester comprising:
• the polyester according to the invention has a high glass transition temperature.
• it has a glass transition temperature of at least 95 ° C., preferably at least 100 ° C., more preferably at least 110 ° C. and even more preferably at least 120 ° C.
• the polyester according to the invention has a glass transition temperature ranging from 95 ° C to ' ⁇ 55 ° C, preferably of OO'C to ôO'C, more preferably from 1 10 ⁇ 147 ° C, even more preferably from 120 to ⁇ ' ⁇ 45 ° C.
• the glass transition temperature is measured by conventional methods, especially using differential scanning calorimetry (DSC) using a heating rate of 1 O'C / min.
• DSC differential scanning calorimetry
• 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.
• gases especially oxygen, carbon dioxide and / or water vapor.
• the barrier properties can be evaluated on gas-based films respectively according to ASTM D1434, ASTD3985 and ASTM F1249.
• the unit (A) is 1, 4: 3,6-dianhydrohexitol.
• the 1,4, 3,6-dianhydrohexitols have the disadvantage of being secondary diols that are not very reactive in the manufacture of polyesters.
• 1,4: 3,6-Dianhydrohexitol (A) may be isosorbide, isomannide, isoidide, or a mixture thereof.
• 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.
• 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 can be determined by H-NMR or by chromatographic analysis of the monomer mixture resulting from methanolysis or complete hydrolysis of the polyester, preferably by RMN H.
• 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 configuration c / 's, in the trans configuration or may be a mixture of diols configuration cis and trans. In a particular embodiment, a cis / trans mixture of 1,4-cyclohexanedimethanol is used.
• 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.
• 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.
• 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 ortho-chlorophenol at ISO'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%;
• the quantities in different units in the polyester may be determined by H NMR or by chromatographic analysis of the monomer mixture resulting from a methanolysis or complete hydrolysis of the polyester, preferably by H.sym.
• the polyester according to the invention can be semi-crystalline or amorphous.
• 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.
• the polyester according to the invention when it 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 1 O / min.
• DSC differential scanning calorimetry
• the invention also relates to a method of manufacturing the polyester according to the invention. This process comprises:
• 3,6-dianhydrohexitol A
• at least one alicyclic diol B
• 3,6-dianhydrohexitols A
• at least one diacid C
• 2,5-furan acid dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and isophthalic acid said monomers being free of ethylene glycol and terephthalic acid;
• a step of polymerizing said monomers to form the polyester consisting of:
• a first oligomerization stage during which the reaction mixture is first stirred under inert atmosphere at a temperature ranging from 120 to 250 ° C, preferably from 125 to 210, more preferably 130 to 200 ° C and then brought to a temperature ranging from 210 to 300 ⁇ , preferably from 220 to 280 ⁇ C, more preferably 225-265 ⁇ C;
• 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 by example of nitrogen (N 2 ), and at a temperature of 5 to 30 ° C below the melting point of the polyester.
• an inert gas such as by example of nitrogen (N 2 )
• catalytic system 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].
• 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.
• 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.
• 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® 31 14, 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.
• 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.
• charges or fibers of organic or inorganic nature 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, 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 include 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 shaping equipment, 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.
• 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.
• 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.
• 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.
• the plasticizer may be water or a polyol, in particular glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol or else urea.
• 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.
• 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, particularly 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.
• fibers or son of techniques well known to those skilled in the art such as spin-drawing, electrospinning for example
• 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 may also be a hollow article, in particular 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 being aerosols, dishes, for example for ready meals, microwavable 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.
• 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.
• a coextrusion step in the case where the materials of the different layers are brought into contact in the molten state.
• the articles 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 properties of the polymers were 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%: (10 ⁇ 0.min-1), cooled to 10%: (10%: min-1) then heated to 320%: under the same conditions as the first stage.
• 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 35% Ubbelohde capillary viscometer.
• the polymer is dissolved beforehand in 130% ortho-chlorophenol: 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.
• the following reagents were used:
• the polymer obtained is a semi-crystalline material whose glass transition is 1 1 1, its crystallization temperature of 175 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.
• the polyester of Example 1 is used in a post-condensation step in the solid state.
• the polymer is crystallized for 2 hours in a vacuum oven at 170.
• the polymer crystallized 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 (ratio cis / trans: 70/30), 1 1, 0 g of isosorbide and 20 mg of Germanium oxide. The mixture is stirred by mechanical stirring at 150 rpm and is heated to 130 ° C in 10 minutes under a stream of nitrogen. Still under a stream of nitrogen and mechanical stirring, the reaction medium is then maintained at 140 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.
• the polymer obtained is an amorphous material whose glass transition is 123% 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.
• the polymer obtained is an amorphous material whose glass transition is 97 ° C. and a viscosity number of 46.8 ml / g (concentration at 5 g / l in 2-chlorophenol at 35 ° C.).
• the analysis of Final polyester by NMR shows that 29% of Isosorbide (relative to the diols) were introduced into the polymer chains.
• the resulting polymer is a semicrystalline material with a glass transition is 140 ⁇ , a crystallization temperature of 221 ° C, a melting temperature of 272 ⁇ € 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.
• the polyester of Example 4 is used in a post-condensation step in the solid state.
• the polymer is crystallized for 2 hours in a vacuum oven at 190.
• 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.

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• 2015
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