EP3298064A1 - Polyester de haute viscosité aux propriétés choc améliorées - Google Patents
Polyester de haute viscosité aux propriétés choc amélioréesInfo
- Publication number
- EP3298064A1 EP3298064A1 EP16728066.8A EP16728066A EP3298064A1 EP 3298064 A1 EP3298064 A1 EP 3298064A1 EP 16728066 A EP16728066 A EP 16728066A EP 3298064 A1 EP3298064 A1 EP 3298064A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- units
- dianhydrohexitol
- molar amount
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- 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
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- 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
- C08G63/02—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
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- 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
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Definitions
- the present invention relates to a thermoplastic polyester of high viscosity, comprising at least one 1,4: 3,6-dianhydrohexitol unit, which can exhibit excellent properties of impact resistance and low coloring.
- the invention also relates to a method of manufacturing said polyester and the use of this polyester for the manufacture of different articles.
- 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 include aliphatic diol and aromatic diacid 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
- “Monomeric units” means, according to the invention, units included in the polyester which can be obtained after polymerization of a monomer.
- 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 transesterification 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). 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 particularly useful for the manufacture of bottles, films, thick sheets, fibers or articles requiring high optical properties.
- a problem encountered in the manufacture of polyesters comprising 1,4-3,6-dianhydrohexitol units, and in particular isosorbide units is that these polyesters generally have a coloration.
- polyesters comprising predominantly ethylene glycol and isosorbide are difficult to dry.
- the moisture can cause hydrolysis of said polyester.
- obtaining polyesters which are easier to dry could improve the stability of the polyester during its melt processing.
- Another 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 comprising terephthalic acid units, and diol units comprising from 1 to 60 mol% of isosorbide and from 5 to 99 % 1,4-cyclohexanedimethanol which have improved impact properties.
- comonomers comonomers
- 1,4-cyclohexanedimethanol 1,4-cyclohexanedimethanol
- the Applicant has found (see examples below) that the PCIT synthesized in this application US2012 / 0177854 has a reduced viscosity in solution which may be insufficient, for example, for the manufacture of films when they are produced by blowing sheath or for the manufacture of hollow bodies or son.
- its impact resistance is presented as improved, it is not at all the case of its resistance to cold shock.
- its glass transition temperature may be insufficient for certain applications (for example for hot filling or "hot-fill").
- the PECITs described in this document have much higher glass transition temperatures. Note that this document also mentions the phenomenon of polyester staining related to the presence of isosorbide in the starting monomers.
- thermoplastic polyesters having a sufficiently high viscosity for use in more applications.
- polymers which also have low color and / or good impact resistance properties, especially when cold.
- the Applicant has succeeded in obtaining a new high-viscosity polyester, which polyester may also have excellent properties of resistance to shock, low staining and / or ability to be easily dried.
- This polyester can be used in very different temperature conditions since it has excellent cold impact resistance, while having a high glass transition temperature.
- thermoplastic polyester comprising: at least one 1,4-4,6-dianhydrohexitol (A) unit;
- polyesters according to the invention can surprisingly present together a high viscosity and 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 terephthalic acid (C), said monomers being free from non-cyclic aliphatic diol or comprising a molar amount of non-cyclic aliphatic diol units of less than 5%, this amount being determined with respect to all the monomers introduced.
- 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 terephthalic acid (C), said monomers being free from non-cyclic aliphatic diol or comprising a
- 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 stage during which the reaction medium is stirred under an inert atmosphere at a temperature ranging from 265 to 280 ° C, preferably from 270 to 280 ° C, for example 275 ° C; ⁇ a second stage of condensation of the oligomers in which the oligomers formed are stirred under vacuum at a temperature ranging from 278 to 300 ° C to form the polyester, preferably 280 to 290 ° C, e.g. 285 ° C;
- the polyesters stain only if the diols used are mixtures of 1, 4: 3,6-dianhydrohexitols with non-cyclic aliphatic diols, and in particular when the molar amount of non-cyclic aliphatic diols is equal. at or above 5%. Without being bound by any particular theory, it appears that the degradation of 1,4: 3,6-dianhydrohexitols is increased during polymerization when non-cyclic aliphatic diols are included in the starting monomers.
- the polyester according to the invention has a reduced viscosity in high solution and can be used in many tools for converting plastics, and in particular be easily converted by blowing. It also has excellent impact properties. According to some embodiments of the invention, they can also have particularly high glass transition temperatures.
- the invention also relates to different processes for manufacturing this polyester.
- At least one terephthalic acid unit (C) is free from aliphatic non-cyclic diol units or comprises a small amount.
- low molar amount of non-cyclic aliphatic diol units is meant in particular a molar amount of non-cyclic aliphatic diol units of less than 5%. According to the invention, this molar amount represents the ratio of the sum of the non-cyclic aliphatic diol units, these units being able to be identical or different, with respect to all the monomeric units of the polyester.
- a non-cyclic aliphatic diol may be a linear or branched non-cyclic aliphatic diol. It can also be a saturated or unsaturated non-cyclic aliphatic diol.
- the saturated linear non-cyclic aliphatic diol may, for example, be 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-di- octanediol and / or 1,10-decanediol.
- saturated branched non-cyclic aliphatic diol mention may be made of 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, propylene glycol and / or neopentyl glycol.
- unsaturated aliphatic diol include, for example, cis-2-butene-1,4-diol.
- This molar amount of non-cyclic aliphatic diol unit is advantageously less than 1%.
- the polyester is free of non-cyclic aliphatic diol unit.
- the polyester has a reduced viscosity in high solution.
- This reduced viscosity in solution may be greater than 50 ml / g, this viscosity can be measured using a Ubbelohde capillary viscometer at 25 ° C. in an equimassic mixture of phenol and ortho-dichlorobenzene after dissolving the polymer. 130 ° C with stirring, the introduced polymer concentration being 5g / L.
- This test of reduced viscosity in solution is, by the choice of solvents and the concentration of the polymers used, perfectly suitable for determining the viscosity of the viscous polymer of the present invention. According to the present invention, it is considered that a polyester of reduced viscosity in solution greater than 50 ml / g and up to 70 ml / g is a "high viscosity polyester".
- polyester of very high viscosity means a polyester having a reduced viscosity in solution of greater than 70 ml / g, advantageously greater than 75 ml / g, preferably greater than 85 ml / g, and preferably greater than 85 ml / g. at 95 mL / g.
- the polyester according to the invention is a polyester of very high viscosity, it has excellent impact properties at room temperature but also good properties of cold impact resistance. As this polyester can be used and mechanically stressed at low temperature, this allows it to be used in many applications, in various industries such as for example automotive or household appliances.
- the monomer (A) is a 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.
- isosorbide it is marketed by the Applicant under the brand name POLYSORB® P.
- 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 c /' s and trans.
- the polyester of the invention may for example comprise: A molar amount of 1,4-3,6-dianhydrohexitol (A) units ranging from 1 to 54%;
- 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 chemical shifts relating to 1,4-cyclohexanedimethanol are between 0.9 and 2.4 ppm and 4.
- the chemical shifts relative 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.
- the semicrystalline nature of the polymer depends mainly on the amounts of each of the units in the polymer.
- the polymer according to the invention comprises large quantities of 1,4-3,6-dianhydrohexitol (A) units
- the polymer is generally amorphous, whereas it is generally semi-crystalline in the opposite case.
- the polyester according to the invention has a glass transition temperature ranging from 85 to 200 ° C.
- the polyester according to the invention comprises:
- a molar amount of 1,4-3,6-dianhydrohexitol (A) units ranging from 1 to 20%, advantageously from 5 to 15%;
- a molar amount of alicyclic diol units (B) other than the 1,4, 3,6-dianhydrohexitol (A) units ranging from 25 to 54%, advantageously from 30 to 50%;
- a molar amount of terephthalic acid (C) units ranging from 45 to 55%.
- the polyester is generally semi-crystalline.
- the Applicant has succeeded in obtaining polyesters having semi-crystalline properties, even when the molar amount of 1,4-3,6-dianhydrohexitols reaches 20%.
- This polyester has surprisingly excellent properties of impact resistance.
- the crystallization rate of these new polyesters is higher than that of PEIT and PEICT, which allows to transform them into articles with improved application properties.
- this semi-crystalline polyester has a particularly high thermomechanical behavior, due to its high glass transition temperature and the presence of crystallinity reinforcing the mechanical properties at high temperature.
- the polyester according to the invention when it is semi-crystalline, it has a melting point ranging from 210 to 295 ° C., for example from 240 to 285 ° C.
- the polyester according to the invention when it is semi-crystalline, it has a glass transition temperature ranging from 85 to 140 ° C., for example from 90 to 115 ° C.
- the glass transition and melting temperatures are measured by conventional methods, especially using differential scanning calorimetry (DSC) using a heating rate of 10 ° C / min.
- DSC differential scanning calorimetry
- the polyester according to the invention when it is semi-crystalline, it has a heat of fusion greater than 10 J / g, preferably greater than 30 J / g, the measurement of this heat of fusion consisting in subjecting a sample of this polyester heat treatment at 170 ° C for 10 hours and then evaluate the heat of fusion by DSC by heating the sample to 10 ° C / min.
- the polyester comprises: ⁇ a molar amount of 1,4-3,6-dianhydrohexitol (A) units ranging from 20 to 54%;
- a molar amount of terephthalic acid (C) units ranging from 45 to 55%.
- the polymer is generally amorphous.
- the polyester according to the invention when it is amorphous, it has a glass transition temperature ranging from 120 to 200 ° C., for example from 140 to 190 ° C.
- the polyester according to the invention may be of low color and in particular have a clarity L * greater than 50.
- the clarity L * is greater than 55, preferably greater than 60, most preferably greater than 65, for example greater than 70 .
- the L * parameter can be determined using a spectrophotometer, using the CIE Lab model.
- the polyester according to the invention especially that of very high viscosity, has a very good impact resistance, in particular a very good resistance to cold impact.
- the polyester according to the invention in particular that of very high viscosity, advantageously has a non-notched Charpy impact strength greater than 100 kJ / m 2 (25 ° C, ISO 179-1 / 1 eU: 2010).
- the polyester according to the invention advantageously has a Charpy impact strength with a notch greater than 5 kJ / m 2 , advantageously greater than 10 kJ / m 2 (-30 ° C., ISO 179-1 / 1 eA: 2010).
- the invention also relates to a method of manufacturing the polyester according to the invention.
- the Applicant has succeeded in obtaining a polyester, which may have a reduced viscosity in high solution, by a manufacturing process comprising:
- a step of polymerizing said monomers to form the polyester consisting of:
- a first oligomerization stage during which the reaction medium is stirred under inert atmosphere at a temperature ranging from 265 to 280 ° C, preferably from 270 to 280 ° C, e.g. 275 ° C; ⁇ a second stage of condensation of the oligomers in which the oligomers formed are stirred under vacuum at a temperature ranging from 278 to 300 ° C to form the polyester, preferably 280 to 290 ° C, e.g. 285 ° C; • a polyester recovery step.
- the polymer obtained can thus have at least a reduced viscosity in solution of greater than 50 ml / g.
- This first stage of this variant of the process is carried out in an inert atmosphere, that is to say under an atmosphere of at least one inert gas.
- This inert gas may especially be dinitrogen.
- This first stage can be done under gas flow. It can also be done under pressure, for example at a pressure of between 1.05 and 8 bar.
- the pressure ranges from 3 to 8 bar, most preferably from 5 to 7.5 bar, for example 6.6 bar. Under these preferred pressure conditions, the reaction of all the monomers with each other is facilitated by limiting the loss of monomers during this stage.
- a deoxygenation step of the monomers is preferably carried out prior to the first oligomerization step. It can be done for example by performing, after introducing the monomers into the reactor, a vacuum and then introducing an inert gas such as nitrogen into the reactor. This empty cycle-introduction of inert gas can be repeated several times, for example 3 to 5 times. Preferably, this vacuum-nitrogen cycle is carried out at a temperature between 60 and 80 ° C. so that the reagents, and in particular the diols, are totally melted.
- This deoxygenation step has the advantage of improving the coloring properties of the polyester obtained at the end of the process.
- the second stage of condensation of the oligomers is carried out under vacuum.
- the pressure can decrease during this second stage continuously using pressure drop ramps, stepwise or using a combination of pressure drop ramps and bearings.
- the pressure is less than 10 mbar, most preferably less than 1 mbar.
- the first stage of the polymerization stage preferably has a duration ranging from 20 minutes to 5 hours.
- the second stage has a duration ranging from 30 minutes to 6 hours, the beginning of this stage consisting of the moment when the reactor is placed under vacuum, that is to say at a pressure lower than 1 bar.
- the method of this first variant comprises a step of introducing into the reactor a catalytic system. This step may take place before or during the polymerization step described above.
- catalytic system means a catalyst or a mixture of catalysts, optionally dispersed or fixed on an inert support.
- the catalyst is used in suitable amounts to obtain a high viscosity polymer according to the invention.
- an esterification catalyst is used during the oligomerization stage.
- This esterification catalyst may be chosen from tin, titanium, zirconium, hafnium, zinc, manganese, calcium and strontium derivatives, organic catalysts such as para-toluenesulphonic acid (APTS ), methanesulfonic acid (AMS) or a mixture of these catalysts.
- APTS para-toluenesulphonic acid
- AMS methanesulfonic acid
- a titanium derivative, a zinc derivative or a manganese derivative is used.
- the catalyst of the first step may be optionally blocked by the addition of phosphorous acid or phosphoric acid, or else as in the case of tin (IV) reduced by phosphites such as phosphite triphenyl or phosphite tris (nonylphenyl) or those cited in paragraph [0034] of US201 application 1282020A1.
- the second stage of condensation of the oligomers may optionally be carried out with the addition of a catalyst.
- This catalyst is advantageously chosen from tin derivatives, preferably tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc, cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of these catalysts.
- tin derivatives preferably tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc, cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of these catalysts.
- tin derivatives preferably tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc, cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of these catalysts.
- examples of such compounds may be, for example, those given in EP 1882712 B1 in paragraphs [
- the catalyst is a derivative of tin, titanium, germanium, aluminum or antimony.
- 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.
- a catalyst system is used in the first stage and the second stage of polymerization.
- Said system advantageously consists of a tin-based catalyst or a mixture of catalysts based on tin, titanium, germanium and aluminum.
- tin-based catalyst or a mixture of catalysts based on tin, titanium, germanium and aluminum.
- mass quantity 10 to 500 ppm of catalyst system, relative to the quantity of monomers introduced.
- an antioxidant is advantageously used during the monomer polymerization step. 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 Nrgamod® 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 first variant 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 method of manufacturing the polyester comprises a step of increasing the molar mass by post-polymerization of a polymer of reduced viscosity in weaker solution, which comprises at least one unit 1, 4: 3,6-dianhydrohexitol (A), at least one alicyclic diol unit (B) other than the 1,4-3,6-dianhydrohexitol units (A) and at least one terephthalic acid unit (C), said lower viscosity in lower solution being free from non-cyclic aliphatic diol units or comprising a molar amount of non-cyclic aliphatic diol units, based on all the monomer units of the polymer, less than 5%.
- a polymer of reduced viscosity in weaker solution which comprises at least one unit 1, 4: 3,6-dianhydrohexitol (A), at least one alicyclic diol unit (B) other than the 1,4-3,6-dianhydrohexitol units (A) and at least
- reduced viscosity polymer in weaker solution means a polyester having a reduced viscosity in solution which is lower than that of the polyester obtained at the end of the post-polymerization stage.
- This polymer can be obtained according to the processes described in documents US2012 / 0177854 and Yoon et al., Using methods of manufacture using as monomers diols and diesters of terephthalic acid, or by using the method of the first variant described. previously.
- the post-polymerization step may consist of a solid state polycondensation (PCS) step of the reduced viscosity polymer in a lower solution or a reactive extrusion step of the reduced viscosity polymer in a lower solution in the presence of at least one chain extender.
- PCS solid state polycondensation
- PCS is generally performed at a temperature between the glass transition temperature and the polymer melting temperature.
- the reduced viscosity polymer in lower solution be semi-crystalline.
- the latter has a heat of fusion greater than 10 J / g, preferably greater than 30 J / g, the measurement of this heat of fusion consisting in subjecting a sample of this reduced viscosity polymer to a lower solution. heat treatment at 170 ° C for 10 hours and then evaluate the heat of fusion by DSC by heating the sample to 10 K / min.
- the reduced viscosity polymer in lower solution comprises:
- a molar amount of 1,4-3,6-dianhydrohexitol (A) units ranging from 1 to 20%, advantageously from 5 to 15%;
- a molar amount of alicyclic diol units (B) other than the 1,4, 3,6-dianhydrohexitol (A) units ranging from 25 to 54%, advantageously from 30 to 50%;
- a molar amount of terephthalic acid (C) units ranging from 45 to 55%.
- the PCS step is carried out at a temperature ranging from 190 to 300 ° C., preferably from 200 to 280 ° C.
- the PCS step can be carried out in an inert atmosphere, for example under nitrogen or under argon or under vacuum.
- the post-polymerization step is carried out by reactive extrusion of the reduced viscosity polymer in a lower solution in the presence of at least one chain extender.
- the chain extender is a compound comprising two functions capable of reacting, in reactive extrusion, with functions, alcohol, carboxylic acid and / or carboxylic acid ester of the reduced viscosity polymer in a lower solution.
- the chain extender may, for example, be chosen from compounds comprising two isocyanate, isocyanurate, lactam, lactone, carbonate, epoxy, oxazoline and imide functions, said functions possibly being identical or different.
- Reactive extrusion may be carried out in an extruder of any type, such as a single-screw extruder, a twin-screw co-rotating extruder or a twin-screw counter-rotating extruder. However, it is preferred to perform this reactive extrusion using a co-rotating extruder.
- the reactive extrusion step can be done in:
- the temperature inside the extruder is set to be at a temperature above the glass transition temperature if the polymer is amorphous and greater than the melting temperature if it is semi -cristallin.
- the temperature inside the extruder can range from 150 to 320 ° C.
- the invention also relates to the polyester obtainable by the method of the invention.
- the invention also relates to a composition comprising the polyester according to the invention, this composition may 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 can comprise from 0.1 to 75% by weight of 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 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, stearamide, erucamide, behenamide, 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.
- 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.
- the plasticizer may be water or a polyol, in particular glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol or else urea.
- glycerol polyglycerol
- isosorbide polyglycerol
- sorbitans sorbitol
- mannitol a polyol
- urea a polyol
- 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 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.
- This may be, for example, fibers or yarns useful for the textile industry or other industries. These fibers or yarns can be woven to form fabrics or nonwovens.
- the article according to the invention may also be a film or a sheet.
- 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. These sheets can be thermoformed or injected to be used for example for parts such as portholes or machine covers, the body of various electronic devices (telephones, computers, screens), or as impact-resistant windows.
- the article can also be processed by extrusion profiles which can find their application in the fields of building and construction.
- the article according to the invention may also be a container for transporting gases, liquids and / or solids. It may be bottles, gourds, bottles, for example bottles of sparkling water or not, bottles of juice, bottles of soda, bottles, bottles of alcoholic beverages, vials, for example bottles of medicine, bottles of cosmetic products, these bottles being aerosols, dishes, for example for ready meals, microwave dishes or lids.
- These containers can be of any size. They can be manufactured by extrusion blow molding, thermoforming or injection blow molding.
- These articles can also be optical articles, that is to say articles 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.
- 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.
- 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.
- They can also be manufactured according to a process comprising a step of applying a layer of polyester in the molten state to a layer based on an 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 reduced viscosity in solution is evaluated using a Ubbelohde capillary viscometer at 25 ° C. in an equimassic mixture of phenol and ortho-dichlorobenzene after dissolution of the polymer at 130 ° C. with magnetic stirring.
- the polymer concentration introduced is 5 g / l.
- the color of the polymer was measured on the granules (25 grams of granules in the measuring cell) using a Konica Minolta CM-2300d spectrophotometer.
- the impact strengths were determined as follows:
- test is carried out according to the ISO 179-1 1 eU standard at 25 ° C .;
- Germanium dioxide > 99.99%) from Sigma Aldrich
- the resin thus obtained has a reduced solution viscosity of 69.9 ml / g 1 .
- the H-NMR analysis of the polyester shows that the final polyester contains 3.2 mol% of isosorbide with respect to all the monomeric units.
- the polymer With regard to the thermal properties (recorded at the second heating), the polymer has a glass transition temperature of 91 ° C., a melting temperature of 276 ° C. with a melting enthalpy of 44.5 J / g.
- the mechanical properties of the polymer obtained are collated in Table 1.
- the clarity L * is 53.2.
- 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 ° 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 248 ° C. and a nitrogen flow of 3.3 L / min.
- the polymer of ex 1 was extruded in a bi-visDSM micro-extruder in the presence of 1% of carbonylbiscaprolactam (Allinco CBC).
- the extrusion was carried out on 12 g of polymer for 2 min at 300 ° C.
- the polymer has a solution viscosity of 85.5 mL / g.
- the esterification rate is estimated from the amount of distillate collected. Then, the pressure is reduced to 0.7 mbar in 90 minut.es according to a logarithmic ramp and the temperature brought to 285 ° C. These conditions of vacuum and temperature were maintained until a torque increase of 12.1 Nm compared to the initial torque. Finally, a polymer rod is poured through the bottom valve of the reactor, cooled in a tank of thermo-regulated water at 15 ° C and cut into granules of approximately 15 mg.
- the resin thus obtained had a reduced solution viscosity of 80, 1 mL / g ⁇ H NMR analysis of the polyester shows that the final polyester contains 8.5 mole% isosorbide with respect to all monomer units.
- the polymer has a glass transition temperature of 96 ° C, a melting temperature of 253 ° C with a melting enthalpy of 23.2 J / g.
- the clarity L * is 55.3.
- the polyester of Example 2 is used in a post-condensation step in the solid state.
- 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 230 ° C. and a nitrogen flow of 3.3 L / min.
- the polymer of ex 2 was extruded in a DSM bi-screw micro-extruder in the presence of 1% carbonylbiscaprolactam (Allinco CBC).
- the extrusion was carried out on 12 g of polymer for 2 min at 300 ° C.
- the polymer has a solution viscosity of 92.8 ml / g.
- the resin thus obtained had a reduced solution viscosity of 66.2 mL / g ⁇ H NMR analysis of the polyester shows that the final polyester contains 15.1 mole% isosorbide with respect to all monomer units.
- the polymer With regard to the thermal properties (recorded at the second heating), the polymer has a glass transition temperature of 109 ° C.
- the clarity L * is 51.5.
- the polyester of Example 3 is used in a post-condensation step in the solid state.
- the polymer is crystallized for 8:30 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 210 ° C. and a nitrogen flow of 3.3 l / min.
- the polymer of ex 2 was extruded in a DSM bi-screw micro-extruder in the presence of 1% carbonylbiscaprolactam (Allinco CBC).
- the extrusion was carried out on 12 g of polymer for 2 min at 300 ° C.
- the polymer has a solution viscosity of 85.4 mL / g.
- the resin thus obtained has a reduced solution viscosity of 16.4 ml / g under the conditions as defined in the present invention, that is to say a much lower viscosity than that of the polymer according to the invention.
- This polymer has insufficient properties to evaluate its mechanical properties.
- the resin thus obtained had a reduced solution viscosity of 58.8 mL / g ⁇ H NMR analysis of the polyester shows that the final polyester contains 8.7 mole% isosorbide with respect to all monomer units.
- the polymer With regard to the thermal properties (recorded at the second heating), the polymer has a glass transition temperature of 97 ° C.
- the clarity L * is 46.2.
- Comparative polyester 1 which is that described in application US 2012/0177854 A1, has a very low viscosity, compared with the polyester according to the invention of Example 1.
- polyesters according to the invention produced under the same conditions as the comparative polyester of the counterexample 2 (polyester further comprising a linear aliphatic diol) exhibit a lower coloration, as well as properties of impact resistance that are much greater.
- polyesters according to the invention have a high viscosity, or even a very high viscosity when performing a step of increasing the molecular weight by PCS or reactive extrusion.
- the semicrystalline polyesters whose molecular weight has been increased by PCS have a higher viscosity than polyesters whose molar mass has been increased by reactive extrusion.
- Polyesters of very high viscosity have excellent resistance to impact, at room temperature as well as cold.
- polyesters according to the invention have excellent mechanical properties, similar to Tritan TM performance copolyesters marketed by Eastman®. Their impact properties are even superior.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
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- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1554597A FR3036400B1 (fr) | 2015-05-22 | 2015-05-22 | Polyester de haute viscosite aux proprietes choc ameliorees |
PCT/FR2016/051208 WO2016189239A1 (fr) | 2015-05-22 | 2016-05-20 | Polyester de haute viscosité aux propriétés choc améliorées |
Publications (1)
Publication Number | Publication Date |
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EP3298064A1 true EP3298064A1 (fr) | 2018-03-28 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP16728066.8A Pending EP3298064A1 (fr) | 2015-05-22 | 2016-05-20 | Polyester de haute viscosité aux propriétés choc améliorées |
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Country | Link |
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US (1) | US11859046B2 (ja) |
EP (1) | EP3298064A1 (ja) |
JP (1) | JP6937247B2 (ja) |
KR (1) | KR20180011111A (ja) |
CN (1) | CN107636041A (ja) |
CA (1) | CA2986103C (ja) |
FR (1) | FR3036400B1 (ja) |
MX (1) | MX2017014990A (ja) |
WO (1) | WO2016189239A1 (ja) |
Families Citing this family (22)
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CN108473667A (zh) * | 2015-12-24 | 2018-08-31 | Sk化学株式会社 | 聚酯树脂、其制备方法以及由其形成的树脂模制物品 |
FR3052455B1 (fr) * | 2016-06-10 | 2018-06-29 | Roquette Freres | Polyester thermoplastique amorphe pour la fabrication de feuilles thermoformables |
FR3052454B1 (fr) * | 2016-06-10 | 2018-06-29 | Roquette Freres | Polyester thermoplastique amorphe pour la fabrication de corps creux |
FR3054244B1 (fr) * | 2016-07-22 | 2019-09-06 | Roquette Freres | Polyester thermoplastique semi-cristallin pour la fabrication de fibres |
FR3054551B1 (fr) * | 2016-07-29 | 2019-08-02 | Roquette Freres | Composition polymere comprenant un polyester thermoplastique |
FR3054891B1 (fr) * | 2016-08-05 | 2021-01-29 | Roquette Freres | Polyester thermoplastique amorphe pour la fabrication d'articles optiques |
FR3065958B1 (fr) * | 2017-05-05 | 2020-09-04 | Roquette Freres | Procede de fabrication d'un materiau composite |
FR3065957B1 (fr) * | 2017-05-05 | 2019-07-12 | Roquette Freres | Composite thermoplastique |
WO2018221944A1 (ko) * | 2017-05-31 | 2018-12-06 | 에스케이케미칼 주식회사 | 폴리에스테르 수지, 이의 제조 방법 및 이로부터 형성된 수지 성형품 |
KR102568694B1 (ko) * | 2017-06-22 | 2023-08-22 | 에스케이케미칼 주식회사 | 폴리에스테르 용기, 이의 제조 방법 |
KR102684863B1 (ko) | 2017-06-26 | 2024-07-15 | 에스케이케미칼 주식회사 | 폴리에스테르 필름 및 이의 제조 방법 |
EP3682048A4 (en) * | 2017-09-15 | 2021-09-01 | 3M Innovative Properties Company | FIBER FIBER WEB AND METHOD FOR IT |
FR3072094B1 (fr) | 2017-10-11 | 2020-09-04 | Roquette Freres | Polyester thermoplastique hautement incorpore en motif 1,4 : 3,6-dianhydro-l-iditol |
FR3078069B1 (fr) * | 2018-02-19 | 2020-09-04 | Roquette Freres | Polyester thermoplastique presentant une resistance amelioree au phenomene de fissuration |
FR3081871B1 (fr) * | 2018-05-31 | 2020-11-27 | Roquette Freres | Procede de cristallisation d'un polyester comprenant au moins un motif 1,4 : 3,6-dianhydrohexitol. |
FR3086662B1 (fr) * | 2018-10-01 | 2021-11-05 | Roquette Freres | Procede de cristallisation d'un polyester comprenant au moins un motif 1,4 : 3,6-dianhydrohexitol. |
FR3086663B1 (fr) | 2018-10-02 | 2020-11-13 | Roquette Freres | Procede de preparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephtalate) |
US20220315755A1 (en) * | 2019-06-28 | 2022-10-06 | Covestro Intellectual Property Gmbh & Co. Kg | Mineral-reinforced co-polyester blend |
FR3104179B1 (fr) | 2019-12-10 | 2022-09-09 | Roquette Freres | Fibre synthétique colorée |
US20230139077A1 (en) * | 2020-04-10 | 2023-05-04 | Poly-Med, Inc. | Methods and compositions comprising degradable polylactide polymer blends |
DE102021127425A1 (de) * | 2021-10-21 | 2023-04-27 | Fm Marketing Gmbh | Bruchstabiles elektrisches Handgerät, insbesondere Fernbedienung |
WO2024094616A1 (en) * | 2022-11-01 | 2024-05-10 | Avantium Knowledge Centre B.V. | Process for the production of a polyester (co)polymer |
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US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
US6140422A (en) * | 1998-04-23 | 2000-10-31 | E.I. Dupont De Nemours And Company | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
TWI224115B (en) * | 1999-12-27 | 2004-11-21 | Ind Tech Res Inst | Compositions based on high molecular weight polyesters and method for making the same |
US20030149226A1 (en) * | 2001-12-27 | 2003-08-07 | Conrad Neal Douglas | Methyltin catalysts for polyesterfication |
US6699545B2 (en) * | 2001-12-21 | 2004-03-02 | E. I. Du Pont De Nemours And Company | Method for increasing solid state polymerization rate of polyester polymers |
US6914120B2 (en) * | 2002-11-13 | 2005-07-05 | Eastman Chemical Company | Method for making isosorbide containing polyesters |
WO2006032022A1 (en) | 2004-09-14 | 2006-03-23 | E.I. Dupont De Nemours And Company | Processes for making low color poly(ethylene-co-isosorbide) terephthalate polymers |
AU2005318524B2 (en) * | 2004-12-24 | 2011-01-27 | Dsm Ip Assets B.V. | Composition suitable for a powder coating composition comprising at least one resin and at least one dispersant |
EP2402383A3 (en) | 2005-04-22 | 2015-05-13 | Mitsubishi Chemical Corporation | Biomass-resource-derived polyester and production process thereof |
US20090186973A1 (en) * | 2008-01-17 | 2009-07-23 | Dsm Ip Assets B.V. | Heat curable powder coating composition |
JP5586160B2 (ja) * | 2008-04-02 | 2014-09-10 | 関西ペイント株式会社 | 水性塗料組成物 |
FR2934272B1 (fr) | 2008-07-24 | 2013-08-16 | Roquette Freres | Procede de preparation de compositions a base de matiere amylacee et de polymere synthetique. |
NL2002382C2 (en) | 2008-12-30 | 2010-07-01 | Furanix Technologies Bv | A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers. |
US9034982B2 (en) * | 2009-08-12 | 2015-05-19 | Ashland Licensing And Intellectual Property, Llc | Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices |
KR20110028696A (ko) | 2009-09-14 | 2011-03-22 | 에스케이케미칼주식회사 | 아이소소바이드와 1,4-사이클로헥산디메탄올이 공중합된 폴리에스테르 수지 및 그 제조방법 |
EP2325229A1 (en) * | 2009-11-13 | 2011-05-25 | Cytec Surface Specialties, S.A. | Polyesters for coatings |
KR101639631B1 (ko) * | 2009-12-28 | 2016-07-14 | 에스케이케미칼주식회사 | 장식 물질을 포함하는 열가소성 성형제품 |
SG11201401745UA (en) | 2011-10-24 | 2014-09-26 | Furanix Technologies Bv | A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications |
JP2013237171A (ja) * | 2012-05-14 | 2013-11-28 | Mitsubishi Plastics Inc | 積層ポリエステルフィルム |
KR101969004B1 (ko) * | 2012-06-05 | 2019-04-15 | 에스케이케미칼 주식회사 | 폴리에스테르 수지 및 이의 제조 방법 |
WO2014100257A2 (en) * | 2012-12-20 | 2014-06-26 | Dow Global Technologies Llc | Fdca-based polyesters made with isosorbide |
-
2015
- 2015-05-22 FR FR1554597A patent/FR3036400B1/fr active Active
-
2016
- 2016-05-20 JP JP2017560667A patent/JP6937247B2/ja active Active
- 2016-05-20 EP EP16728066.8A patent/EP3298064A1/fr active Pending
- 2016-05-20 US US15/576,205 patent/US11859046B2/en active Active
- 2016-05-20 CA CA2986103A patent/CA2986103C/fr active Active
- 2016-05-20 MX MX2017014990A patent/MX2017014990A/es unknown
- 2016-05-20 WO PCT/FR2016/051208 patent/WO2016189239A1/fr active Application Filing
- 2016-05-20 KR KR1020177033479A patent/KR20180011111A/ko not_active IP Right Cessation
- 2016-05-20 CN CN201680029562.6A patent/CN107636041A/zh active Pending
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FR3036400B1 (fr) | 2019-04-26 |
US20180155493A1 (en) | 2018-06-07 |
US11859046B2 (en) | 2024-01-02 |
CA2986103A1 (fr) | 2016-12-01 |
KR20180011111A (ko) | 2018-01-31 |
WO2016189239A1 (fr) | 2016-12-01 |
MX2017014990A (es) | 2018-04-10 |
JP2018515666A (ja) | 2018-06-14 |
JP6937247B2 (ja) | 2021-09-22 |
CN107636041A (zh) | 2018-01-26 |
CA2986103C (fr) | 2024-05-28 |
FR3036400A1 (fr) | 2016-11-25 |
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