WO2021123655A1 - Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d'incorporation dudit motif améliorés - Google Patents
Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d'incorporation dudit motif améliorés Download PDFInfo
- Publication number
- WO2021123655A1 WO2021123655A1 PCT/FR2020/052520 FR2020052520W WO2021123655A1 WO 2021123655 A1 WO2021123655 A1 WO 2021123655A1 FR 2020052520 W FR2020052520 W FR 2020052520W WO 2021123655 A1 WO2021123655 A1 WO 2021123655A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- catalyst
- acid
- reactor
- mixture
- Prior art date
Links
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
- C08G63/66—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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0843—Cobalt
Definitions
- the present invention relates to a polyester manufacturing process comprising at least one unit 1, 4: 3,6-dianhydrohexitol, using a catalytic system to reduce the coloring of the polyester thus formed and d 'increase the rate of incorporation of said unit into the polyester.
- a subject of the invention is also a polyester composition comprising said catalytic system.
- plastics have become essential for the mass production of objects. Indeed, due to their thermoplastic nature, all kinds of objects can be manufactured at high speed from these plastics.
- PET polyethylene terephthalate
- PET polyethylene glycol and terephthalic acid units
- PET can be a transparent polymer and thus be useful in the manufacture of objects with important optical properties. It can also be opaque and white in the case where this polymer is semi-crystalline, if the crystallinity and the size of the crystallites are important. It is therefore necessary in both cases for the PET to exhibit the lowest possible coloration.
- the term "monomeric units" means units included in the polyester which can be obtained after polymerization of a monomer.
- ethylene glycol and terephthalic acid units included in the PET they can either be obtained by reaction of esterification of ethylene glycol and of terephthalic acid, or by a reaction of trans-esterification of ethylene glycol and of terephthalic acid. ester of terephthalic acid.
- polyesters from short-term renewable biological resources has become an ecological and economic imperative, in the face of exhaustion and the rise in the prices of fossil resources such as petroleum.
- One of the major concerns today in the field of polyesters is therefore to provide polyesters of natural origin (biobased). This is particularly true for polyesters comprising aliphatic diol and aromatic acid units.
- groups such as Danone or Coca-Cola today market beverage bottles in partially biobased PET, this PET being made from biobased ethylene glycol.
- a drawback of this PET is that it is only partially biobased, since terephthalic acid is itself generally derived from fossil resources.
- PETg glycol modified PETs
- CHDM cyclohexanedimethanol
- modified PETs have also been developed by introducing into the polyester units 1, 4: 3,6-dianhydrohexitol, in particular isosorbide (PEIT). These modified polyesters exhibit higher glass transition temperatures than unmodified PETs or gPETs 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.
- PEITs can exhibit a generally significant coloration, generally greater than those of PETg or PET, and this even when the amounts of isosorbide used in the manufacture of the polyester are very weak.
- the Applicant has been able to observe by carrying out studies on polymerization catalysts for the manufacture of polyesters containing units 1, 4: 3,6- dianhydrohexitol, that the polyesters obtained from these processes are not fully satisfactory, especially in terms of coloring.
- This coloring can be either very yellow as is the case when using exclusively a germanium-based polycondensation catalyst, or gray when using a catalytic system comprising germanium-based and cobalt-based catalysts. .
- polyesters comprising 1, 4: 3,6-dianhydrohexitols units
- rate of incorporation of these units is not always high.
- a high level of incorporation of 1, 4: 3,6-dianhydrohexitol units is however desirable in order to achieve sufficient thermal and mechanical performance for various applications such as for example in the packaging sector.
- the binding unit then undergoes a polycondensation step by mixing with a prepolymer.
- the prepolymer can be chosen from poly (alkylene terephthalate), preferably with poly (1, 3-propylene terephthalate).
- a preferred polymer is poly (ethylene-co-isosorbide isophthalate).
- Document US6818730 describes a process for the production of polyester comprising isosorbide, said process making it possible to obtain a high level of incorporation of isosorbide in the final polyester.
- the process describes the fusion of a first polyester incorporating isosorbide with a second polyester for a sufficient time to allow a transesterification reaction to thereby obtain a copolymer.
- the first polyester consists essentially of an isosorbide unit and a dicarboxylic acid unit while the second polyester consists essentially of a dicarboxylic acid unit and a diol unit other than isosorbide.
- a method for obtaining PEIT showing an improved incorporation rate of isosorbide of up to 30% is proposed by document WO2019 / 004679. According to the examples of this same document, when a germanium oxide GeC> 2 is used, said rate is around 10%.
- the subject of the invention is thus a process for manufacturing a polyester containing at least one 1,4: 3,6-dianhydrohexitol unit comprising at least:
- a step of introducing into a reactor monomers comprising at least one monomer (A) which is a diacid or a diester and at least one monomer (B) which is a 1, 4: 3,6-dianhydrohexitol;
- a step of introducing into the reactor a catalytic system comprising either a catalyst comprising the element germanium and a catalyst comprising the element tin, either a catalyst comprising the elements germanium and tin or a mixture of these catalysts;
- Catalytic systems combining a germanium-based catalyst with an aluminum-based catalyst or combining a tin-based catalyst with an aluminum-based catalyst have already been described for the manufacture of PEU type polyesters in application WO 2016/066956.
- this application are compared the colors of a polyester obtained from a catalyst based on germanium with a polyester obtained from a catalytic system comprising a catalyst based on germanium and aluminum or with a polyester obtained from from a catalytic system comprising a catalyst based on tin and aluminum. If the coloring of the polyester is reduced, they still show a weak yellow coloring.
- Such a catalytic system does not appear to have a significant impact on the rate of incorporation of the unit 1, 4: 3,6-dianhydrohexitol.
- the polyester recovered at the end of the process according to the invention has both a lower coloration than that of a polyester obtained from a similar process which differs in the catalytic system used and a higher level of incorporation of the unit 1, 4: 3,6-dianhydrohexitol.
- polyester composition comprising:
- a catalytic system comprising either a catalyst comprising the element germanium and a catalyst comprising the element tin, or a catalyst comprising the elements germanium and tin or a mixture of these catalysts.
- an article comprising the polyester composition according to the second aspect.
- a catalytic system comprising a catalyst comprising the element germanium and a catalyst comprising the element tin, of a catalyst comprising the elements germanium and tin or of a mixture of these catalysts to reduce the coloring of a polyester containing at least one unit 1, 4: 3,6-dianhydrohexitol.
- the invention relates to a method of manufacturing a polyester containing at least one unit 1, 4: 3,6-dianhydrohexitol.
- This method comprises a step of introducing monomers into a reactor.
- the monomers introduced into the reactor comprise at least one monomer (A) which is a diacid or a diester and at least one monomer (B) which is a 1,4: 3,6-dianhydrohexitol.
- diacid or diester is meant according to the invention a dicarboxylic acid or diester of carboxylic acid.
- the monomer (A) is a diacid or a mixture of diacids.
- the diacid can be an aromatic diacid, an aliphatic diacid or a mixture of these diacids.
- the diacid is aromatic. It can be chosen from terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, furanedicarboxylic acid, and a mixture of these diacids. .
- the aromatic acid is terephthalic acid.
- the monomer (A) can also be an aliphatic diacid or a mixture of these diacids.
- the aliphatic diacid can be a saturated or unsaturated aliphatic diacid.
- the saturated aliphatic diacid can be linear, branched or cyclic.
- the linear saturated aliphatic diacid can be chosen from among succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and their mixtures.
- the linear saturated aliphatic diacid is chosen from succinic acid, adipic acid and their mixture, most preferably succinic acid.
- saturated cyclic aliphatic diacid mention may be made of 1,4 cyclohexanedioic acid.
- the monomer (A) can also be an unsaturated aliphatic diacid such as fumaric acid or maleic acid or itaconic acid or a mixture of these diacids.
- the diester is preferably a methyl and / or ethyl diester.
- the diester can be chosen from the diesters of the diacids mentioned above.
- the diester is an aromatic diacid diester, preferably a diester of terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid. , furanedicarboxylic acid, or a mixture of these diesters, most preferably a terephthalic acid diester.
- the monomer (B) is a 1, 4: 3,6-dianhydrohexitol.
- the 1, 4: 3,6-dianhydrohexitols have the drawback of causing the coloring of the polyester when using the monomers and the manufacturing processes conventionally used for their manufacture.
- the 1,4: 3,6-dianhydrohexitol can be isosorbide, isomannide, isoidide, or a mixture thereof, preferably isosorbide.
- Isosorbide, isomannide and isoidide can be obtained by dehydration of sorbitol, mannitol and iditol, respectively.
- isosorbide it is marketed by the Applicant under the brand name POLYSORB® ® P.
- the monomers introduced into the reactor further comprise a diol (C), other than 1, 4: 3,6-dianhydrohexitols.
- the diol (C) can be:
- an aliphatic diol in particular a linear aliphatic diol (C1), a cycloaliphatic diol (C2), a branched aliphatic diol (C3) or;
- the diol (C1) is advantageously chosen from ethylene glycol, 1, 3-propanediol,
- the diol (C2) can be cyclobutanediol, for example tetramethylcyclobutanediol, bis-hydroxymethyl tricyclodecane or cyclohexanedimethanol, in particular 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol or 1, 3-cyclohexanedimethanol or a mixture of these diols or isomers of these diols. Indeed, these diols can be in cis or trans configuration. When different isomers exist for the same monomer, unless explicitly specified, when this monomer is referred to, it may be an isomer of this monomer or a mixture of isomers.
- the diol (C3) can for its part be 2-methyl-1, 3-propanediol, 2,2,4-trimethyl-
- the diol (C) is advantageously chosen from aliphatic diols, preferably chosen from ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6- hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 4- cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and mixtures of these diols, very preferably ethylene glycol, 1,4-butanediol,
- the diol (C) is introduced into the reactor, the monomer (A) is terephthalic acid, the monomer (B) is isosorbide and the monomer (C) is ethylene glycol.
- the diol (C) is introduced into the reactor, the monomer (A) is terephthalic acid, the monomer (B) is isosorbide and the diol (C) is a mixture ethylene glycol and 1,4-cyclohexanedimethanol.
- the molar percentage of monomers (A) relative to the total number of moles of monomers (A), (B) and where appropriate (C) ranges from 25 to 50%, preferably from 33 to 49% , most preferably from 40 to 48%.
- the molar percentage of (B), relative to the total number of moles of monomers (B) and (C), ranges from 1 to 60%, preferably from 2 to 55%, most preferably from 5 to 50%.
- the monomers (B) and (C) can be introduced into the reactor in the form of an aqueous solution. Monomers other than monomers (A), (B) and optionally (C), called “additional monomers” can also be added.
- hydroxy acid monomers carrying a hydroxide function and a carboxylic acid function.
- the hydroxy acid can be glycolic acid, lactic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxyvaleric acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, hydroxymethylfurancarboxylic acid, hydroxybenzoic acid or a mixture of these hydroxy acids.
- Mention may also be made, as additional monomer which can be used, of dilactones such as glycolide or lactide.
- the amount of hydroxy acid monomers is, relative to the total sum of the monomers, less than 10 mol%.
- the monomers introduced into the reactor can be free from hydroxy acid monomers.
- the additional monomers can also include chain-extending monomers, which for their part are generally introduced into the reactor before or during the formation of the polyester produced during the polymerization step, or even before a second step called "step". of post-polymerization "consisting in reacting the polyester formed during the polymerization step with the chain extender monomer.
- This post-polymerization step can in particular be a step of reactive extrusion of the chain-extending monomer with the polyester recovered after the polymerization step.
- chain-extending monomers means a monomer comprising two functions other than the hydroxyl, carboxylic acid and carboxylic acid ester functions, and capable of reacting with these same functions.
- the functions can be isocyanate, isocyanurate, lactam, lactone, carbonate, epoxy, oxazoline and imide functions, said functions possibly being identical or different.
- - diisocyanates preferably methylenediphenyl-diisocyanate (MDI), isophorone-diisocyanate (IPDI), dicyclohexylmethane-diisocyanate (H12MDI), toluene-diisocyanate (TDI), naphthalene-Nethyl-diisocyanate (IPDI), -diisocyanate (HMDI) or lysine-diisocyanate (LDI), aliphatic diisocyanate with a molar mass of 600 g / mol obtained from fatty diacid dimers (DDI®1410 Diisocyanate),
- dialkylcarbonates in particular dialkylcarbonates of dianhydrohexitols, and in particular isosorbide dialkylcarbonates,
- dicarbamoylcaprolactams preferably 1,1 '-carbonyl-bis-caprolactam, dicarbamoylcaprolactones,
- heterocyclic compounds preferably bis-oxazolines, bis-oxazolin-5-ones and bis-azalactones,
- the amount of chain-extending monomers is, relative to the total sum of the monomers introduced, less than 10 mol%.
- the monomers introduced into the reactor can be free of chain-extending monomer.
- the additional monomers can also be polyfunctional monomers.
- polyfunctional monomers denotes a monomer capable of reacting with the hydroxide and / or carboxylic acid and / or carboxylic acid ester functions and whose functionality is greater than 2.
- the polyfunctional monomers can be introduced into the reactor before l. the polymerization or post-polymerization step as described above (the polyfunctional monomer then replacing the chain-extending monomer), preferably before the polymerization step.
- branching agents can be hydroxide, carboxylic acid, anhydride, isocyanate, isocyanurate, caprolactam, caprolactone, carbonate, epoxy, oxazoline and imide functions, said functions possibly being identical or different, preferably carboxylic acid, hydroxide, epoxide or isocyanate, most preferably carboxylic acid or hydroxide.
- the functionality of these branching agents can be 3 to 6, preferably 3 to 4.
- branching agents conventionally used, mention may be made of: malic acid, citric or isocitric acid, tartaric acid, trimesic acid, tricarballylic acid, cyclopentane tetracarboxylic acid, trimellitic anhydride, pyromellitic mono or dianhydride, glycerol, pentaerythritol, dipentaerythritol, monoanhydrosorbitol, monoanhydromannitol, epoxidized oils, dihydroxystearic acid, trimethylolpropane, ethers of these polyols such as for example glycerol propoxylate (marketed under the name Voranol 450 by Dow Chemical), polymers having side epoxy functions, triisocyanates, tetraisocyanates as well as the respective homopolymers of existing di-, tri- and tetraisocyanates, polyanhydrides, alkoxysilanes, preferably tetraethoxys
- the amount of polyfunctional monomers is, relative to the total sum of the monomers, less than 10 mol%.
- the monomers introduced into the reactor can be free from polyfunctional monomers.
- the molar amount of additional monomer is less than 20%, preferably less than 10%, or even less than 5%.
- the monomers introduced into the reactor can be free from additional monomers.
- the method according to the invention also comprises a step of introducing into the reactor a catalytic system comprising:
- the catalyst comprising the element germanium
- it can be chosen from the following compounds: salts of aliphatic carboxylic acids such as formate, acetate, propionate, butyrate, oxalate, acrylate, methacrylate, salts of aromatic carboxylic acids such as benzoate, salts of halogenated carboxylic acids such as trichloroacetate, trifluoroacetate, hydroxycarbonate salts such as lactate, citrate, oxalate, mineral salts such as carbonate, sulfate, nitrate, phosphate, phosphonate, phosphinate, hydrogensulfate, hydrogencarbonate, hydrogenphosphate, sulfite, thiosulfate, hydrochloride, hydrobromide, chloride, chlorate, bromide, bromate, organosulfonates such as 1-propane sulfonate, 1-pentane sulfonate, naphthalene
- the catalyst comprising the element tin can be chosen from the following compounds: salts of aliphatic carboxylic acids such as formate, acetate, propionate, butyrate, oxalate, acrylate, methacrylate, octoate, salts of aromatic carboxylic acids such as benzoate, salts of halogenated carboxylic acids such as trichloroacetate, trifluoroacetate, hydroxycarbonate salts such as lactate, citrate, oxalate, mineral salts such as carbonate, sulfate, nitrate, phosphate, phosphonate, phosphinate, hydrogensulfate, hydrogencarbonate, hydrogenphosphate , sulfite, thiosulfate, hydrochloride, hydrobromide, chloride, chlorate, bromide, bromate, organosulfonates such as 1 -propane sulfonate, 1-pentane sulfonate, naphthalene
- the catalytic system comprises a catalyst comprising the elements germanium and tin, for example comprises a mixed oxide of germanium and tin.
- the catalytic system comprises a mixture of the catalysts described in the two preceding variants.
- the catalytic system can be chosen so that the elementary molar ratio Ge: Sn ranges from 1: 1 to 5: 1, advantageously from 1.5: 1 to 5: 1, advantageously from 2: 1 to 5 : 1, preferably 1: 1 to 3: 1, advantageously from 1, 5: 1 to 3: 1, advantageously from 2: 1 to 3: 1, preferably from 1: 1 to 2.5: 1, advantageously from 1.5: 1 to 2.5: 1, preferably from 1.75: 1 to 2.5: 1.
- the elemental molar ratio is around 2: 1. It is specified that this elementary ratio only takes into consideration the metals included in the catalytic system.
- the resin obtained is transparent when such an elemental molar ratio is around 2: 1, with an elemental molar ratio ranging from 2: 1 to 5: 1, the resin obtained has a slight yellow coloration.
- the catalysts can be chosen and present in amounts such that the elementary molar ratio Ge: Sn is that described above.
- the catalyst comprising the element germanium and tin is chosen such that the elementary molar ratio Ge: Sn is that described above.
- the amount of the germanium element in the catalytic system varies from 50 to 300 ppm, preferably from 180 to 220 ppm.
- the amount of the tin element in the catalytic system varies from 10 to 200 ppm, preferably from 50 to 150 ppm, and, more preferably still, from 75 to 125 ppm.
- a catalytic system of a catalytic system comprising a catalyst comprising the germanium element and a catalyst comprising the tin element.
- the total mass quantity of metal included in the catalytic system introduced into the reactor, relative to the total mass quantity of polymer obtained ranges from 50 to 500 ppm.
- the catalytic system can be introduced into the reactor before or during the polymerization step, preferably before the polymerization step. It can be introduced by different stages of introduction, for example by introducing different catalysts at different times. Preferably, when the catalytic system comprises different catalysts, they are introduced simultaneously into the reactor, most preferably simultaneously and before the polymerization step.
- the catalyst (s) can be used as such or in the form of solution (s), in particular aqueous or alcoholic solution, preferably in the form of a solution in a monomer such as ethylene glycol, in which is (are) diluted (s) ) or dispersed (s) the catalyst (s).
- the use of a compound comprising the element cobalt makes it possible in particular to obtain polyester compositions exhibiting an improved b * coloring.
- salts of aliphatic carboxylic acids such as formate, acetate, propionate, butyrate, oxalate, acrylate, methacrylate
- salts of aromatic carboxylic acids such as benzoate
- salts of halogenated carboxylic acids such as trichloroacetate, trifluoroacetate, hydroxycarbonate salts such as lactate, citrate, oxalate
- mineral salts such as carbonate, sulphate, nitrate, phosphate, phosphonate, phosphinate, hydrogen sulphate, hydrogen carbonate, hydrogenphosphate, sulphite, thiosulphate, hydrochloride, hydrobromide, thiosulphate, hydrochloride, hydrobromide, chlorate, bromide, bromate, organosulphonates such as 1 -propane sulphonate, 1-pentane sulphonate
- the method according to the invention also comprises a step of polymerizing the monomers to form the polyester.
- this polymerization step is carried out by the molten route, that is to say by maintaining the reaction medium in the molten state in the reactor, in the absence of solvent.
- This polymerization step can be carried out by supplying heat and heat.
- This polymerization step can also be carried out under vacuum.
- the step of polymerization of the monomers comprises:
- the reaction medium can be stirred by any type of agitator conventionally used for the synthesis of polyesters.
- the stirring speed can be kept constant during the polymerization step or the stirring speed can be reduced during the reaction, as the viscosity of the polyester increases.
- the first stage can be carried out at atmospheric pressure or under pressure, generally at a pressure ranging from 1.1 to 10 bar.
- the oligomers formed during the first stage generally have a number-average molar mass of less than 5000 g / mol, often less than 4000 g / mol. They generally have a viscosity index of less than 20ml_ / g.
- the monitoring of this first stage can be done by controlling the evolution of the quantity of distillates extracted from the reactor.
- the second stage of the polymerization step it is carried out under vacuum, preferably at a pressure less than 10 mbar, most preferably less than 1 mbar.
- the polymerization reaction can be monitored by monitoring the change in the amount of torque measured on the stirrer or by any other system making it possible to evaluate the viscosity of the molten reaction medium.
- the catalytic system comprising the catalyst (s) described above, is introduced into the reactor before the first stage of the polymerization stage.
- the method comprises a step of deoxygenating the reactor carried out prior to the step of polymerization of the monomers, and in particular before the first step of forming the oligomers, advantageously by placing the reactor under an atmosphere of an inert gas such as than nitrogen.
- This deoxygenation step is generally carried out at low temperature, that is to say often at a temperature below 100 ° C.
- This can be done by carrying out at least once a sequence of a vacuum stage, for example between 100 and 700 mbar in the reactor followed by a stage of introducing an inert gas into the reactor, for example between 1 , 2 and 2 bars.
- This vacuum-introduction cycle of inert gas can be done for example 3 to 5 times.
- this vacuum-nitrogen cycle is carried out at a temperature between 60 and 80 ° C. so that the reactants, and in particular the monomers (B), are completely melted.
- This deoxygenation step has the advantage of further improving the coloring properties of the polyester obtained at the end of the process.
- additives called “polymerization additives” can also be introduced into the reactor before the polymerization step.
- Antioxidants can be primary and / or secondary antioxidants.
- the primary antioxidant can be a sterically hindered phenol such as the compounds Hostanox® 0 3, Hostanox® 0 10, Hostanox® 0 16, Ultranox® 210, Ultranox®276, Dovernox® 10, Dovernox® 76, Dovernox® 3114, Irganox® 1010, Irganox® 1076 or a phosphonate such as Irgamod® 195.
- the secondary antioxidant may be trivalent phosphorus compounds such as Ultranox® 626, Doverphos® S-9228, Hostanox® P-EPQ, or Irgafos 168.
- a polymerization additive into the reactor at least one compound capable of limiting side etherification reactions, such as sodium acetate, tetramethylammonium hydroxide, or tetraethylammonium hydroxide.
- the method according to the invention also comprises a step of recovering a polyester composition comprising the polyester and the catalytic system.
- This composition can be recovered by extracting it from the reactor as a rod of molten polymer. After cooling, this rod can be transformed into granules using conventional granulation techniques.
- the polyester obtained at the end of the polycondensation step can, after cooling, be semi-crystalline or amorphous.
- the method according to the invention can also comprise, after the step of recovering the polyester composition, a step of polycondensation in the solid state (PCS).
- PCS solid state
- a subject of the invention is also the polyester composition, obtainable according to the process of the invention, in which the polyester contains at least one unit 1, 4: 3,6-dianhydrohexitol, the composition comprising furthermore a catalytic system comprising either a catalyst comprising the element germanium and a catalyst comprising the element tin, or a catalyst comprising the elements germanium and tin or a mixture of these catalysts.
- the catalytic system included in the polyester composition is identical to that described above for the process according to the invention.
- the metals included in the catalytic system can exhibit an elementary molar ratio Ge: Sn which ranges from 1: 1 to 5: 1, advantageously from 1.5: 1 to 3: 1 , preferably from 1.75: 1 to 2.5: 1.
- the amounts of catalyst in the polyester composition are also close but may be slightly less than those introduced into the reactor, due to the possible loss by entrainment of catalyst described above. However, these losses can be considered to be relatively low.
- the total quantity by weight of metal included in the catalytic system of the polyester composition, relative to the total quantity by weight of polyester, generally ranges from 30 to 500 ppm.
- the metal amounts of the catalysts included in the polyester can be determined by elemental analysis.
- the term "monomeric units" means units included in the polyester which can be obtained after polymerization of a monomer.
- the ethylene glycol and terephthalic acid units included in a PET they can either be obtained by reaction of esterification of ethylene glycol and of terephthalic acid, or by a reaction of transesterification of ethylene glycol and terephthalic acid ester.
- the polyester included in the composition according to the invention can comprise, relative to all the units of diols (B) and, where appropriate (C) of the polyester, from 0.1 to 100% of units 1, 4 : 3,6-dianhydrohexitol (100% is the case where no monomer (C) is used during the process), advantageously from 1 to 60%, preferably from 2 to 550%, most preferably from 5 to 50%.
- the polyester included in the composition comprises, relative to the sum of the monomeric units:
- the polyester included in the composition comprises, relative to the sum of the monomeric units:
- the number of diacid units and the number of diol units are generally substantially identical.
- the ratio of diol units / diacid units included in the polyester can range from 1.15 / 1 to 0.85 / 1, often from 1.08 / 1 to 0.92 / 1.
- the amounts in different units in the polyester can be determined by 1 H NMR.
- the polyester composition has a clarity L * greater than 45, preferably greater than 55.
- the clarity L * can reach or even exceed 65.
- the polyester composition has a b * coloration of between -10 and 10, preferably between -6 and 6. This parameter makes it possible to quantify the coloration ranging from blue (if b * is negative) to yellow ( if b * is positive).
- the parameters L * and b * can be determined using a spectrophotometer, using the CIE Lab model.
- the polyester composition may have a relative viscosity greater than 35 ml / g, preferably greater than 50 ml / g.
- the viscosity index can be determined according to the method described in the examples section.
- the number-average molar mass of the polyester included in the polyester composition according to the invention can range from 5,000 to 50,000 g / mol.
- the molar mass of the polyester can be determined by conventional methods, such as for example by size exclusion chromatography (SEC) in a mixture of chloroform and 1, 1, 1, 3,3,3-Hexafluoro- 2-propanol in a volume ratio 98/2. Signal detection can then be performed by a differential refractometer calibrated with polymethyl methacrylate standards.
- SEC size exclusion chromatography
- the glass transition temperature of the polyester is greater than or equal to 80 ° C.
- the glass transition temperature of polyester can be measured by conventional methods, in particular using differential scanning calorimetry. (DSC) using a heating rate of 10K / min.
- DSC differential scanning calorimetry
- the polyester has a glass transition temperature ranging from 80 to IQO' ⁇ , preferably from 100 to 170 ° C, more preferably from 105 to 160 ⁇ €.
- the invention also relates to a composition
- a composition comprising the polyester according to the invention and at least one additive or at least one additional polymer or at least a mixture thereof.
- the polyester composition according to the invention can comprise the polymerization additives optionally used during the process. It can also include other additives and / or additional polymers which are generally added during a subsequent thermomechanical mixing step.
- fillers or fibers of organic or inorganic nature 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 unstructured granular starch.
- These fillers or fibers can improve hardness, stiffness or permeability to water or gases.
- the composition can comprise from 0.1 to 75% by weight of fillers 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 can also include opacifying agents, dyes and pigments. They can be chosen from cobalt acetate and the following compounds: HS-325 Sandoplast® RED BB (which is a compound carrying an azo function also known under the name Solvent Red 195), HS-510 Sandoplast® Blue 2B which is an anthraquinone, Polysynthren® Blue R, and Clariant® RSB Violet.
- the composition may also comprise, as an additive, a process agent, or Processing aid, for reducing the pressure in the processing tool.
- a process agent for reducing the pressure in the processing tool.
- a mold release agent to reduce adhesion to polyester forming materials can also be used.
- These agents can be selected from fatty acid esters and amides, metal salts, soaps, paraffins or hydrocarbon waxes. Specific examples of these agents are zinc stearate, calcium stearate, stearate aluminum, stearamid, erucamide, behenamid, beeswax or candelilla.
- composition according to the invention may also comprise other additives such as stabilizers, for example light stabilizers, UV stabilizers and heat stabilizers, thinners, flame retardants and agents. antistatic agents.
- stabilizers for example light stabilizers, UV stabilizers and heat stabilizers, thinners, flame retardants and agents. antistatic agents.
- the composition may further comprise an additional polymer, different from the polyester according to the invention.
- This polymer can 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, acrylic copolymers.
- poly (ether-imides) polyphenylene oxide such as poly (2,6-dimethylphenylene) oxide, polysulfate of phenylene, poly (ester-carbonates), polycarbonates, polysulfones, polysulfone ethers, polyether ketone and mixtures of these polymers.
- composition can 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 polymers and copolymers of ethylene or propylene, core-shell copolymers or copolymers. to block.
- a polymer making it possible to improve the impact properties of the polymer, in particular functional polyolefins such as functionalized polymers and copolymers of ethylene or propylene, core-shell copolymers or copolymers. to block.
- composition according to the invention can 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 which may or may not be modified physically or chemically.
- Starch can be used in destructured or plasticized form.
- the plasticizer can be water or a polyol, in particular glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol or even urea.
- the composition according to the invention can be manufactured by conventional methods of processing thermoplastics. These conventional methods comprise at least one step of mixing the polymers in the molten or softened state and a step of recovering the composition. This process can be carried out in internal mixers with blades or rotors, external mixers, single-screw, twin-screw extruders. co-rotating or counter-rotating. However, it is preferred to produce this mixture by extrusion, in particular using a co-rotating extruder.
- the mixing of the constituents of the composition can be done under an inert atmosphere.
- the various constituents of the composition can be introduced using introduction hoppers located along the extruder.
- the invention also relates to an article comprising the polyester or the composition according to the invention.
- This article can be of any type and be obtained using conventional processing techniques.
- These may, for example, be fibers or yarns useful for the textile industry or other industries. These fibers or threads can be woven to form fabrics or even nonwovens.
- the article according to the invention can also be a film, a sheet. These films or sheets can be manufactured by calendering techniques, flat film extrusion (in English "cast film”), blown sheath extrusion.
- the article according to the invention can also be a container for transporting gases, liquids and / and solids.
- These can be baby bottles, gourds, bottles, for example bottles of carbonated or non-carbonated water, bottles of juice, bottles of soda, water bottles, bottles of alcoholic beverages, flasks, for example of medicine bottles, cosmetic product bottles, dishes, for example for ready meals, microwave dishes or even 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, optical fibers, films for LCD screens. (in English “Liquid Crystal Display”, or “liquid crystal display” in French) or windows. These optical articles have the advantage of being able to be placed close to sources of light and therefore of heat, while retaining excellent dimensional stability and good resistance to light.
- the articles can 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 co-extrusion step in the case where the materials of the different layers are brought into contact in the molten state.
- tube co-extrusion profile co-extrusion
- bottle flask or reservoir co-extrusion blow molding
- hollow body blowing co-extrusion inflation co-extrusion also called sheath blowing (“film blowing”) and flat co-extrusion (“cast coextrusion”).
- film blowing sheath blowing
- cast coextrusion flat co-extrusion
- They can also be manufactured according to a process comprising a step of applying a layer of polyester in the molten state on a layer based on an organic polymer, on a metal or on an adhesive composition in the solid state. This step can be carried out by pressing, by overmolding, lamination or rolling (in English "lamination”), extrusion-rolling, coating (in English “coating”), extrusion-coating or coating.
- the invention also relates to the use of the catalyst system described above in a polymerization process to reduce the coloring of a polyester containing at least one unit 1, 4: 3,6-dianhydrohexitol.
- the reduced viscosity in solution is evaluated using an Ubbelohlde capillary viscometer at 35 ° C in orthochlorophenol after dissolving the polymer at 130 ° C with stirring. For these measurements, the concentration of polymer introduced is 5 g / L.
- the color of the polymer was measured on the granules using a Konica Minolta CM-2300d spectrophotometer.
- the thermal properties of the polyesters were measured by differential scanning calorimetry (DSC): The sample is first of all heated under a nitrogen atmosphere in an open crucible from 10 to 280 q C (10 ° C.min. -1), cooled to 10 ° C (10 ° C.min-1) then warmed to 320 ° C under the same conditions as the first step. Glass transition temperatures were taken at the mid-point of the second heating. The possible melting temperatures are determined on the endothermic peak (start of the peak (in English, "onset”)) at the first heating. Likewise, the enthalpy of fusion (area under the curve) is determined on the first heating. For the illustrative examples presented below, the following reagents were used.
- Germanium dioxide > 99.99%) from Sigma Aldrich
- ADK PEP-8 Anti-oxidant
- the resin thus obtained exhibits an isosorbide incorporation rate relative to the total amount of diols of 31.8 mol%.
- the polymerization (condensation) time is 198 minutes.
- the viscosity index is 41 mL / g.
- the glass transition temperature Tg, for its part, has a value of 113 ° C.
- Table 1 shows the summary of the tests for the manufacture of poly (ethylene-co-isosorbide) terephthalate and the results relating to the viscosity and to the color.
- Example 2 is also very remarkable with polymers having a molar isosorbide incorporation rate close to 40%, colorless and having a higher viscosity index than that of comparative example CEx4.
- the comparative test CEx4 the catalytic system of which comprises only germanium, leads to polymers also having a weak coloration, but having a much lower viscosity index than the examples according to the invention Ex 1 and Ex 3.
- a polymer with a viscosity index as low as that obtained in the comparative test CEx4 does not make it possible to be transformable.
- the example according to the invention Ex3 is remarkable because it combines good physical properties (viscosity index) and good coloring (pale yellow).
- the CEx6 test corresponds to Example 4 of international patent application WO2016 / 066956. It shows that the use of germanium in combination with a metal other than tin, in this case aluminum * does not result in a colorless polymer either, but rather a polymer with a weak coloration.
- the resins according to the invention exhibit reduced coloring, even transparent, and an incorporation rate.
- molar isosorbide much larger than the polymers obtained in the presence of other known catalytic systems presented in the context of the present disclosure, while retaining a good ability to be transformable.
- FIG. 1 shows a graph illustrating the variation of the engine torque as a function of the polycondensation time during the synthesis of a PEU in the presence of different catalytic systems.
- This graph clearly demonstrates the catalytic activity improved by the addition of tin in opposition to germanium alone.
- the polymerization reaction is monitored by monitoring the change in the amount of torque measured on the stirrer.
- the catalytic activity is reflected on the graph by the increase in engine torque as a function of the polycondensation time.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022536904A JP2023506882A (ja) | 2019-12-20 | 2020-12-17 | 少なくとも1つの1,4:3,6-ジアンヒドロヘキシトールユニットを含有するポリエステルの、着色が低減され該ユニット組み込み率が改善された製造方法 |
EP20845786.1A EP4077471A1 (fr) | 2019-12-20 | 2020-12-17 | Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d'incorporation dudit motif améliorés |
US17/757,413 US20230013441A1 (en) | 2019-12-20 | 2020-12-17 | Method for manufacturing a polyester containing at least one 1,4:3,6-dianhydrohexitol unit with reduced colouring and improved rates of incorporation of the unit(s) |
KR1020227024773A KR20220119096A (ko) | 2019-12-20 | 2020-12-17 | 착색이 감소되고 단위(들)의 혼입율이 향상된 적어도 하나의 1,4:3,6-디안하이드로헥시톨 단위를 포함하는 폴리에스테르를 제조하는 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1915172A FR3105232B1 (fr) | 2019-12-20 | 2019-12-20 | Procédé de fabrication d’un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d’incorporation dudit motif améliorés |
FRFR1915172 | 2019-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021123655A1 true WO2021123655A1 (fr) | 2021-06-24 |
Family
ID=70008773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2020/052520 WO2021123655A1 (fr) | 2019-12-20 | 2020-12-17 | Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d'incorporation dudit motif améliorés |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230013441A1 (fr) |
EP (1) | EP4077471A1 (fr) |
JP (1) | JP2023506882A (fr) |
KR (1) | KR20220119096A (fr) |
FR (1) | FR3105232B1 (fr) |
WO (1) | WO2021123655A1 (fr) |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6737481B1 (en) | 2002-12-19 | 2004-05-18 | E. I. Du Pont De Nemours And Company | Ester-modified dicarboxylate polymers |
US6818730B2 (en) | 2002-04-26 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Process to produce polyesters which incorporate isosorbide |
US20060173154A1 (en) | 2004-09-14 | 2006-08-03 | Charbonneau Larry F | Process for making low color poly(ethylene-co-isosorbide) terephthalate polymer |
WO2010010282A1 (fr) | 2008-07-24 | 2010-01-28 | Roquette Freres | Procede de preparation de compositions a base de composant amylace et de polymere synthetique |
WO2013034743A1 (fr) | 2011-09-08 | 2013-03-14 | Societe Anonyme Des Eaux Minerales D'evian Et En Abrege "S.A.E.M.E" | Procédé pour la production d'un polymère de type pet d'origine biologique |
WO2013183873A1 (fr) | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Résine polyester et procédé de production de cette dernière |
WO2013183874A1 (fr) | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Résine polyester et procédé de production de cette dernière |
WO2016066956A1 (fr) | 2014-10-29 | 2016-05-06 | Roquette Freres | Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3, 6-dianhydrohexitol à coloration améliorée |
WO2018101320A1 (fr) | 2016-11-30 | 2018-06-07 | 株式会社クラレ | Polyester, procédé de production de polyester, article moulé comprenant un polyester |
WO2018202918A1 (fr) * | 2017-05-05 | 2018-11-08 | Roquette Freres | Procede de fabrication d'un materiau composite |
KR20180131436A (ko) | 2017-05-31 | 2018-12-10 | 에스케이케미칼 주식회사 | 폴리에스테르 수지, 이의 제조 방법 및 이로부터 형성된 수지 성형품 |
US20180362707A1 (en) | 2015-12-02 | 2018-12-20 | Roquette Freres | Aromatic thermoplastic copolyesters comprising 1,4:3,6-dianhydrohexitol and various cyclic diols |
WO2019004679A1 (fr) | 2017-06-26 | 2019-01-03 | 에스케이케미칼 주식회사 | Film polyester et son procédé de fabrication |
-
2019
- 2019-12-20 FR FR1915172A patent/FR3105232B1/fr active Active
-
2020
- 2020-12-17 JP JP2022536904A patent/JP2023506882A/ja active Pending
- 2020-12-17 US US17/757,413 patent/US20230013441A1/en active Pending
- 2020-12-17 EP EP20845786.1A patent/EP4077471A1/fr active Pending
- 2020-12-17 WO PCT/FR2020/052520 patent/WO2021123655A1/fr unknown
- 2020-12-17 KR KR1020227024773A patent/KR20220119096A/ko active Search and Examination
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6818730B2 (en) | 2002-04-26 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Process to produce polyesters which incorporate isosorbide |
US6737481B1 (en) | 2002-12-19 | 2004-05-18 | E. I. Du Pont De Nemours And Company | Ester-modified dicarboxylate polymers |
US20060173154A1 (en) | 2004-09-14 | 2006-08-03 | Charbonneau Larry F | Process for making low color poly(ethylene-co-isosorbide) terephthalate polymer |
WO2010010282A1 (fr) | 2008-07-24 | 2010-01-28 | Roquette Freres | Procede de preparation de compositions a base de composant amylace et de polymere synthetique |
WO2013034743A1 (fr) | 2011-09-08 | 2013-03-14 | Societe Anonyme Des Eaux Minerales D'evian Et En Abrege "S.A.E.M.E" | Procédé pour la production d'un polymère de type pet d'origine biologique |
WO2013183874A1 (fr) | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Résine polyester et procédé de production de cette dernière |
WO2013183873A1 (fr) | 2012-06-05 | 2013-12-12 | 에스케이케미칼주식회사 | Résine polyester et procédé de production de cette dernière |
WO2016066956A1 (fr) | 2014-10-29 | 2016-05-06 | Roquette Freres | Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3, 6-dianhydrohexitol à coloration améliorée |
US20170335055A1 (en) | 2014-10-29 | 2017-11-23 | Roquette Freres | Method for producing a polyester containing at least one 1,4:3,6-dianhydrohexitol unit with improved colouring |
US20180362707A1 (en) | 2015-12-02 | 2018-12-20 | Roquette Freres | Aromatic thermoplastic copolyesters comprising 1,4:3,6-dianhydrohexitol and various cyclic diols |
WO2018101320A1 (fr) | 2016-11-30 | 2018-06-07 | 株式会社クラレ | Polyester, procédé de production de polyester, article moulé comprenant un polyester |
WO2018202918A1 (fr) * | 2017-05-05 | 2018-11-08 | Roquette Freres | Procede de fabrication d'un materiau composite |
KR20180131436A (ko) | 2017-05-31 | 2018-12-10 | 에스케이케미칼 주식회사 | 폴리에스테르 수지, 이의 제조 방법 및 이로부터 형성된 수지 성형품 |
WO2019004679A1 (fr) | 2017-06-26 | 2019-01-03 | 에스케이케미칼 주식회사 | Film polyester et son procédé de fabrication |
Non-Patent Citations (1)
Title |
---|
W. J. YOON ET AL.: "Synthesis and Characteristics of a Biobased High-Tg Terpolyester of Isosorbide, Ethylene Glycol, and 1,4-Cyclohexane Dimethanol: Effect of Ethylene Glycol as a Chain Linker on Polymerization", MACROMOLECULES, vol. 46, 2013, pages 7219 - 7231, XP055422933, DOI: 10.1021/ma4015092 |
Also Published As
Publication number | Publication date |
---|---|
FR3105232B1 (fr) | 2021-12-24 |
EP4077471A1 (fr) | 2022-10-26 |
JP2023506882A (ja) | 2023-02-20 |
FR3105232A1 (fr) | 2021-06-25 |
US20230013441A1 (en) | 2023-01-19 |
KR20220119096A (ko) | 2022-08-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2965900C (fr) | Procede de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol a coloration amelioree | |
CA2986103C (fr) | Polyester de haute viscosite aux proprietes choc ameliorees | |
EP3143068B1 (fr) | Polyesters aromatiques thermoplastiques comprenant des motifs tétrahydrofuranediméthanol et acide furanedicarboxylique | |
WO2015142181A1 (fr) | Polyesters comprenant des motifs 2,5-furannedicarboxylate et des motifs diol saturé ayant une température élevée de transition vitreuse | |
WO2017093684A1 (fr) | Copolyesters thermoplastiques comprenant du 1,4 : 3,6-dianhydrohexitol et divers diacides aromatiques | |
WO2015170049A1 (fr) | Polyesters aromatiques thermoplastiques comprenant des motifs tétrahydrofuranediméthanol | |
WO2021123655A1 (fr) | Procédé de fabrication d'un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d'incorporation dudit motif améliorés | |
EP3694903B1 (fr) | Polyester thermoplastique hautement incorpore en motif 1,4 : 3,6-dianhydro-l-iditol | |
WO2020070445A1 (fr) | Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate) | |
EP3755736A1 (fr) | Polyester thermoplastique présentant une résistance améliorée au phénomène de fissuration |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20845786 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022536904 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20227024773 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020845786 Country of ref document: EP Effective date: 20220720 |