WO2023227209A1 - Procédé de production d'un polyester - Google Patents

Procédé de production d'un polyester Download PDF

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Publication number
WO2023227209A1
WO2023227209A1 PCT/EP2022/064170 EP2022064170W WO2023227209A1 WO 2023227209 A1 WO2023227209 A1 WO 2023227209A1 EP 2022064170 W EP2022064170 W EP 2022064170W WO 2023227209 A1 WO2023227209 A1 WO 2023227209A1
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WO
WIPO (PCT)
Prior art keywords
polyester
starting material
phosphorous compound
polycondensation
composition
Prior art date
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PCT/EP2022/064170
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English (en)
Inventor
Jens-Peter Wiegner
Marion Nagel
Olaf Hempel
Original Assignee
Equipolymers Gmbh
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Publication date
Application filed by Equipolymers Gmbh filed Critical Equipolymers Gmbh
Priority to PCT/EP2022/064170 priority Critical patent/WO2023227209A1/fr
Publication of WO2023227209A1 publication Critical patent/WO2023227209A1/fr

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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
    • C08G63/78—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
    • 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
    • C08G63/80—Solid-state polycondensation

Definitions

  • the invention relates to a method for producing polyesters such as polyethylene terephthalate (PET) using a phosphorous compound as an additive.
  • PET polyethylene terephthalate
  • the invention further relates to the polyester composition obtained by this method.
  • PET Polyethylene terephthalate
  • the preforms are heated using quartz infrared heaters which have a maximum peak output at 1100 to 1200 nm. Since PET absorbs this wavelength poorly, additives are put into the PET to improve the absorption of this energy. These additives are typically carbon black, iron oxide or other inorganic materials, such as nitrides and carbides. These additives (I R additives) improve the heat absorption of the polymer, reducing the processing time and energy required forblow molding. Alternatively, reducing substances such as phosphorous acid are added to reduce the catalyst, e.g.
  • Phosphonic acids such as calciumdiethylbis[[[3,5-bis(1 ,1- dimethylethyl)-4-hydroxyphenyl]methyl]phosphonat] (also known under the trade name Irganox 1425), are not able to sufficiently reduce antimony (HI) to metallic antimony (0) due to the high molecular weight but low number of reducing groups. In the case of phosphorous acid, the antimony is reduced very quickly, so that the desired polycondensation rates are not achieved.
  • WO 2012/087600 discloses a glycol modified polyethylene terephthalate (GPET) with improved color, in particular a reduced yellowness.
  • the GPET is made by a polycondensation reaction using a chelating phosphorous compound, such as etidronic acid, in conjunction with a titanium compound catalyst. Since titanium is a base metal, the catalyst cannot be reduced by the phosphorous compound and is inhibited chemically instead, which leads to decreased rates of the melt phase polycondensation reaction when the additive is added to the catalyst system.
  • the present invention includes a method for producing a polyester comprising: providing a reaction composition comprising as starting material a polyacid and a polyol, or comprising as starting material a polyacid, a polyol, and a recycled polyester, or comprising as starting material a recycled polyester, or comprising as starting material a mixture of a monomer and an oligomer, preferably obtained from a recycled polyester; esterifying the starting material to produce a monomer and/or an oligomer, Wherein if the starting material comprises or is a mixture of a monomer and an oligomer the esterifying step can be shortened or omitted; polymerizing the monomer and/or the oligomer by way of polycondensation in the presence of a catalyst to form a polyester; wherein the polycondensation comprises a melt phase followed by a solid state phase; and wherein a phosphorous compound is timely added to the reaction composition so that the phosphorous compound is present at least during the solid state phase of the polyconden
  • the phosphorus compound may be selected from the group consisting of 1 ,2-ethylene diphosphonic acid, 1 ,2-butylene diphosphonic acid, P,P'-di(2-ethylhexyl) methanediphosphonic acid, P,P'-di(2-ethylhexyl) ethanediphosphonic acid, P,P'-di(2-ethylhexyl) butanediphosphonic acid, and 1- hydroxyethane 1 , 1 -diphosphonic acid (etidronic acid). Etidronic acid is particularly preferred.
  • the phosphorous compound as an infrared activating additive as described above has several advantages compared to other IR additives known in the prior art, such as carbon black.
  • the addition of the phosphorous compound according to the invention increases the ability of the polyester to absorb energy in the infrared light spectrum. Additionally, the color of the final product (e.g. PET bottle) is improved.
  • An “improved” color within the meaning of the present invention means that the darkening and yellowing effect in the final polymer products (e.g. PET bottle) is reduced compared to the yellowing and darkening effect of the final polymer products prepared by using state-of-the-art competitive IR-additve (e.g. carbon black, TIN).
  • state-of-the-art competitive IR-additve e.g. carbon black, TIN.
  • the addition of such phosphorous compounds may further lead to a reduced content of regenerated aldehydes during the processing.
  • the phosphorous compound for example the preferred etidronic acid, may be present in an amount in the range from 10 to 200 ppm, preferably in the range from 25 to 150 ppm, and more preferably in the range from 50 to 125 ppm, based on the weight of the polyester.
  • the polyester produced according to the invention may be selected from the group consisting of polyethylene terephthalates (PET), polyethylene furanoates (PEF), and polyethylene naphthalates (PEN).
  • PET polyethylene terephthalates
  • PET polyethylene furanoates
  • PEN polyethylene naphthalates
  • the polyester is a polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • PET polyethylene furanoate
  • PEN polyethylene naphthalate
  • the first one is an esterification reaction, in which a polyacid and a polyol are esterified to a monomer and/or an oligomer suitable for the polyester polycondensation reaction, such as bis(2-hydroxyethyl) terephthalate.
  • a polyacid within the meaning of the present invention is an organic compound containing more than one carboxyl groups (-COOH).
  • Suitable polyacids include terephthalic acid, isophthalic acid, cyclohexane dicarboxylic acid, naphthalene dicarboxylic acid, furane dicarboxylic acid; and long chain branching acids like trimesinic acid, trimellitic acid, and its anhydride.
  • PET the polyacid is terephthalic acid.
  • a polyol within the meaning of the present invention is an organic compound containing more than one hydroxyl (-OH) group.
  • Suitable polyols include ethylene glycol, diethylene glycol, cyclohexane dimethanol, 1 ,3-propanediol, 2,2- dimethylpropanediol, isosorbide; aromatic polyols such as resorcinol, hydroquinone; and long chain branching polyols such as trimethylolpropane and pentaerythritol.
  • the polyol is ethylene glycol.
  • the polyacid and the polyol are mixed to form a paste.
  • the reaction composition comprises the polyacid, the polyol and may comprise further ingredients, such as solvents, one or more IR- additives, one or more catalysts and/or other functional ingredients.
  • the phosphorous compound can either be added to the reaction composition prior to a paste being formed, or can be added to the formed paste, or can be added to the reaction composition during the esterification or can be added to the reaction composition during the melt phase of the polycondensation, or can be added before solid state polycondensation.
  • the phosphorous compound is added as a solution to the reaction composition.
  • the phosphorous-containing solution may comprise up to 20 % by weight, preferably 1 to 10 % by weight, and more preferably 3 to 8 % by weight, of the phosphorous compound according to the invention.
  • the phosphorous compound is added in form of an aqueous solution.
  • the esterification step can be carried out without any catalyst (autocatalysis). In some cases metal compounds can be added to catalyze the esterification reaction.
  • the esterification step may be conducted at a temperature of above 200°C, more preferably at a temperature of from 220°C to 270°C, and at a pressure of 1 to 10 bar (abs), preferably of 1 to 4 bar (abs).
  • Abs 1 to 10 bar
  • abs preferably of 1 to 4 bar
  • Acetaldehyde is a colorless, volatile substance with a fruity smell, which may cause an off-taste in bottled drinks, especially if nothing masks the aroma, e.g. in bottled water.
  • Acetaldehyde may be formed by degradation of PET during the various processing steps of the material due to high temperatures (PET decomposes above 300°C), high pressures and extruder speeds (excessive shear flow raises temperature) and tong barrel residence times. When acetaldehyde is produced, a part of it remains dissolved in the walls of a container and part of it migrates into the product stored inside, altering the taste and aroma.
  • the method of the present invention including the use of a phosphorous compound as described above may reduce the quantity of acetaldehyde.
  • the amount of acetaldehyde in the final polyester may be reduced by up to 30% by weight, preferably by up to 40% by weight, compared to polymers being prepared without the phosphorous compound.
  • the second step of the manufacturing of high molecular weight acyclic polyesters, such as polyethylene terephthalate (PET), is the polycondensation step, which is important for molecular weight build-up of the polyester.
  • the polycondensation reaction may include two phases, a melt phase and a solid state phase (SSP).
  • the melt phase of the polycondensation step is conducted at a temperature of from 240°C to 300°C, preferably from 250°C to 290°C, and more preferably from 260°C to 280°C, and at a reduced pressure from 5.0 to 0.1 mbar (abs), preferably from 3.0 to 0.5 mbar (abs), and more preferably from 2.0 to 1 .0 mbar (abs).
  • the SSP of the polycondensation step is conducted at a temperature from 190°C to 230°C and may be conducted either under nitrogen flow and an increased pressure from 1.0 to 5.0 bar (abs) or under reduced pressure from 3.0 to 0.1 mbar (abs).
  • the reaction product resulting from the melt phase polycondensation has almost no infrared activity.
  • the desired infrared activity resulting from the action of the phosphorous compound on antimony is observed after the SSP step of the polycondensation reaction.
  • the phosphorous compound is able to reduce a sufficient amount of the oxidized catalyst to the elemental form, such as antimony (III) to antimony (0), and thus, increases the infrared activity.
  • the rate of the polycondensation reaction in the melt phase step and in the SSP step can be increased or at least is not decreased by the phosphorous compound used in the method according to the invention as is observed by using prior art additives, such as phosphorous acid.
  • a catalyst is used to catalyze the polycondensation reaction and may also be used to catalyze the esterification reaction.
  • the catalysts for polycondensation or esterification reaction may be the same or different.
  • the catalyst may be a classic polycondensation catalyst as known in the prior art.
  • the catalyst may be selected from the group consisting of antimony acetate, antimony oxide, antimony glycolate and combinations thereof.
  • the catalyst may be an antimony (HI) containing compound.
  • the antimony (111) compounds used as catalysts have a high selectivity in polycondensation reactions. They additionally lead to an adequate reaction rate.
  • antimony (III) compounds used in the method of polycondensation reactions, the content of undesirable degradation products, such as acetaldehyde, is lower in the processed polyester compared to known titanium compounds.
  • antimony (III) compounds since these substances as heavy metal compounds are physiologically objectionable, the use of antimony (III) compounds as catalysts for polycondensation and/or esterification reactions is permissible only within defined limits. For this reason it is not possible to increase the reaction rate of the polycondensation reactions indefinitely by increasing the catalyst concentration.
  • Another cause for the economically unsatisfactory reaction rate is that the rate of the two reaction steps (melt phase and SSP) depends not only on the temperature, but also on the diffusion of volatile reaction products, such as ethylene glycol, water and acetaldehyde.
  • the antimony (III) catalyst may be present in an amount between 50 to 350 ppm by weight, preferably in an amount of 150 to 300 ppm by weight, most preferably in an amount of 200 to 300 ppm by weight, based on elemental antimony in the final polymer.
  • the catalyst may be added in the form of a powder, in which case it may be added to the reaction composition comprising the polyacid and the polyol before the esterification reaction starts or during the esterification reaction.
  • a catalyst-containing solution may be prepared comprising the catalyst and a suitable polyol such as ethylene glycol.
  • the catalyst-containing solution may be added to the reaction composition, being typically in form of a paste, or may be added directly to the esterification reaction, or may be added directly to the polycondensation reaction.
  • a recycled polyester can be used as a starting material in the esterification reaction to produce the monomer and/or the oligomer.
  • a part of the starting materials polyacid and polyol is substituted by the recycled polyester.
  • a "recycled polyester” is a polyester which has been used before, has been collected and cleaned and is provided as a raw material for further use.
  • a recycled polyester is preferably a recycled polyethylene terephthalates (recycled PET).
  • the recycled PET is provided in form of PET flakes.
  • the recycled polyester used as at least a part of the starting material will first depolymerize to form compounds selected from ester oligomers, ester monomers, polyols, polyacids, and mixtures thereof. Thereafter, these compounds take part as starting material in the esterification reaction to form new monomers and/or oligomers, and finally to form new polyester.
  • the esterification reaction is a dynamic combination of depolymerization reactions and esterification reactions which finally results in the formation of monomers and/or oligomers which then polycondensate to form a polyester.
  • the method may provide a food-grade PET.
  • the food-grade PET may comprise 10 to 100 % by weight, preferably 20 to 90 % by weight, more preferably 20 to 50 % by weight of recycled PET as starting material for the use in beverage botle production or in thermoforming applications, such as film packaging.
  • Another aspect of the invention includes a polyester composition produced by the method as described above.
  • the invention includes a polyester composition comprising a polyester, obtained through an esterification of a starting material, the starting material comprising a polyacid and a polyol, or comprising a polyacid, a polyol, and a recycled polyester, or comprising a recycled polyester, and a polymerization by way of polycondensation comprising a melt phase and a solid state phase in the presence of a catalyst; and a phosphorous compound, reaction products thereof, or mixtures thereof, represented by the structure wherein n is 1 , 2, 3, or 4 each R can be hydrogen or C1-C10-alkyl; and each R1 and R2 can be hydrogen, C1-C10-alkyl, hydroxyl, or aryl.
  • n may be 1 and each R may be a hydrogen.
  • the phosphorous compound may be selected from the group consisting of 1 ,2-ethylene diphosphonic acid, 1 ,2-butylene diphosphonic acid, P,P'-di(2-ethylhexyl) methanediphosphonic acid, P,P'-di(2-ethylhexyl) ethanediphosphonic acid, P,P'-di(2-ethylhexyl) butanediphosphonic acid, and 1- hydroxyethane 1 ,1 -diphosphonic acid (etidronic acid).
  • the etidronic acid is particularly preferred .
  • the polyester composition comprises in the range from 10 to 200 ppm, preferably in the range from 25 to 150 ppm, and more preferably in the range from 50 to 125 ppm of a phosphorous compound based on the weight of the polyester.
  • the etidronic acid is particularly preferred.
  • the polyester composition may be manufactured by using a catalyst as described above.
  • the polyester composition may be manufactured by using a catalyst, preferably antimony (III) compounds.
  • the polyester composition comprises acetaldehyde in an amount less than 10 ppm, or preferably less than 1 ppm based on the weight of the polyester composition.
  • the polyester composition comprises a polyester as manufactured by the method as described above.
  • the polyester may be selected from the group consisting of polyethylene terephthalates (PET), polyethylene furanoates (PEF), and polyethylene naphthalates (PEN).
  • the polyester composition comprises a polyethylene terephthalate (PET).
  • the polyester produced according to the invention can be amorphous or semicrystalline.
  • Various additional functional ingredients as known in the prior art may be added to the polyester composition.
  • the polyesters produced according to the invention can further comprise at least one chain extender, such as multifunctional and/or bifunctional isocyanates, multifunctional epoxides, including for example, epoxylated novolacs, and phenoxy resins.
  • the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.1 % by weight to about 10 % by weight, such as about 0.1 to about 5 % by weight, based on the total weight of the final polymer.
  • polyester compositions according to the invention may also comprise further additives in any amount, for example from 0.01 to 25% by weight based on the total weight of the overall polyester composition.
  • additives can be colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, UV stabilizer, fillers and impact modifiers.
  • the intrinsic viscosity (IV) may generally be used to classify polymers and helps to identify the applications that specific polymers can be used for.
  • polymers show unique properties. It is well-known tendency that the higher the molar mass of a polymer, the higher the viscosity of the corresponding polymer solution will be.
  • the IV is defined as the reduced specific viscosity in the limit of “infinite dilution” or zero concentration. Many different techniques for polymer characterization, such as the dilute solution viscosimetry, can be used to determine the IV of the polyester compositions according to this invention.
  • the IV range of fiber grade PET may be from 0.40 to 0.70 dl/g for textiles, and from 0.72 to 0.98 dl/g for technical tire cord.
  • the sheet grade PET for thermoforming grade may have an IV in the range from 0.70 to 1.00 dl/g, while the biaxially oriented PET film may have an IV from 0.60 to 0.70 dl/g.
  • the IV of PET for water bottles is from 0.70 to 0.78 dl/g and for carbonated soft drink grade PET from 0.78 to 0.85 dl/g.
  • the color values L*, a* and b* are averages of values measured on either polyester pellets or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate.
  • CIE International Commission on Illumination
  • L* represents the lightness coordinate
  • a* represents the red/green coordinate
  • b* represents the yellow/blue coordinate.
  • the addition of the prior art IR additives to PET causes a darkening of the material approximately 8 L* values compared to the non-IR-modified PET.
  • the phosphorous compound such as etidronic acid
  • the PET loses only approximately 5 to 6 L* values compared to the non-IR-modified PET.
  • polyesters compositions according to the present invention can be used to produce articles of manufacture, including but not limited to, injection molded parts, injection blow molded articles, injection stretch blow molded articles, extruded film, extruded sheet, extrusion blow molded articles, extrusion stretch blow molded articles, and fibers.
  • the present invention further includes the use of a phosphorous compound as an IR activating additive in the method according to the invention in order to obtain the polyester composition as described above.
  • the present invention includes the use of a phosphorous compound as an infrared active (IR) additive in a catalyzed polyester polycondensation reaction comprising a melt phase and a solid-state phase, wherein the phosphorous compound is represented by the structure wherein n is 1 , 2, 3, or 4; each R can be hydrogen or C1-C10-alkyl; and each R1 and R2 can be hydrogen, C1-C10-alkyl, hydroxyl, or aryl.
  • IR infrared active
  • the phosphorous compound described above can be advantageously used as an IR additive in a polyester polycondensation reaction which is catalyzed by an antimony (I I l)-containing compound.
  • PET was produced using conventional antimony(lll)-based catalyst by the following procedure:
  • Monoethylene glycol (MEG) (652 g), 0,15 g of an aqueous solution (25%) of tetramethyl-ammonium hydroxide (TMAH, used to inhibit formation of diethylene glycol) (26 ppm), 0.5 ppm Solvent Blue 104, 0.4 ppm Solvent Red 52 and 250 ppm antimony (added as 0.6543 g antimony glycolate) were fed into a paste mixer, which is a vessel used to mix the raw materials before being fed into a reactor. Etidronic acid was added as solution (5%) 25 to 75 ppm (0,72 - 2,16 g).
  • TMAH tetramethyl-ammonium hydroxide
  • Esterification The set points for reactor temperature and pressure for the esterification were approximately 290°C and 2.8 bar (absolute). The condensed ethylene glyco! (EG) and water (at the top of the reactor) was collected in a tank. During the esterification time the product temperature increases to 270°C. The esterification run lasts approximately 100 minutes.
  • EG condensed ethylene glyco!
  • water at the top of the reactor
  • the product temperature increased to 275°C.
  • the polycondensation was finished at a fixed value for the power consumption of the electric stirrer.
  • the highly viscous polyester was cooled in a water bath, and the thus formed strands were pelletized.
  • the SSP reactor was a fluidized bed reactor (pulse bed) from the Weber company.
  • the reactor had a batch capacity of 0.5 kg.
  • the PET pellets obtained from the melt phase polycondensation were treated in a hot nitrogen stream (60 Nm3/h) at approximately 2 bar. Crystallization and SSP were batch processes. The dew point of the nitrogen was -55°C.
  • reaction rate constants k for the melt phase polycondensation and for the SSP polycondensation were determined separately for the PET without any IR additive, for PET with 6 ppm carbon black (comparative example) and for PET with 25, 50, 75 and 100 ppm etidronic acid by weight of the final polymer. The results are shown in Table 1.
  • Table 1 Rate constants of the melt phase (kmeit) and SSP (kssp) of the polycondensation reaction, in % of the corresponding rate constant of the polymerization without an additive.
  • the color values L*, a* and b* are averages of values measured on either polyester pellets or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate.
  • CIE International Commission on Illumination
  • the samples were measured in their pellet form.
  • the cuvette was cleaned and filled to at least 85% of the maximum volume.
  • the sample was measured four times, while each measurement required new sample pellets.
  • the average value of all 4 measurements as well as the CIELab L*a*b* value was calculated using SPECTRA MAGIC software. The results are shown in Table 2.
  • Table 2 Results of PET obtained by polycondensation reaction according to the invention.
  • the results demonstrate that etidronic acid leads to reduced darkening of the final product resulting from the melt phase and from the SSP polycondensation reaction compared to carbon black.
  • the results further demonstrate that etidronic acid leads to reduced yellowing compared to PET without IR modification,
  • the color of the PET comprising recycled PET was better than the color obtained without the addition of etidronic acid. If the final product manufactured without etidronic acid were to be made IR-active by adding the appropriate additives, such as carbon black, this would cause a further drop in the L*- value of up to 6 units and thus be considerably darker than in the case of products manufactured with etidronic acid.
  • the PET obtained from the melt phase was prepared according to the following procedure. About 20 grams of PET material were ground in a ultra centrifugal mill by using liquid nitrogen. The resulting powder was dried at 125°C for maximum 2 minutes. A solvent (mixture of 50% o-dichlorobenzene and 50% phenol) was added to 250 mg of the dried powder in sufficient amount to result in a 0.5 g/dl concentration solution. The solution was heated at 125°C for 30 min in a closed glass vessel under continuous stirring, and then cooled to room temperature. The resulting cooled solution was placed into the AVSPro Viscosimeter equipped with a Micro-UBBELOHDEType No. 536 20 and thermostated to 25°C.
  • a solvent mixture of 50% o-dichlorobenzene and 50% phenol
  • the conversion from measured IV (BILLMEYER calculation) into the used Lighter - IV is based on a factor.
  • the acetaldehyde generation determination was as follows.
  • the PET was processed on an ES 200-50 injection molding machine (Engel Co.) with a 30 millimeter diameter screw and a length to diameter ratio of 20.
  • the drying was performed using a circulated air drying oven UT20 by Heraeus Instruments at 160°C for 6 hours.
  • the dried PET was then fed to the material hopper of the injection molding machine, to which a nitrogen curtain is applied.
  • the polymer was processed at a temperature from 270°C to 300°C.
  • the resulting melt is then injected into a cooled mold under pressure. More specifically, the following parameters were applied:
  • acetaldehyde content (AA) of the processed resins was determined according to the following method: At first, the various materials were ground with a 1 mm screen in a centrifugal mill by RETSCH Co. (ZMI) in the presence of liquid nitrogen. Approximately 0.1 g to 0.3 g of the ground material was put into a 22 ml sample bottle and sealed with a polytetrafluoroethylene seal. The sample bottles were heated under controlled temperature in a headspace oven (HS-40 XL headspace autosampler by Perkin Elmer) at 150°C for 90 minutes, and subsequently analyzed through gas chromatography (XL GC AutoSystem by Perkin Elmer) with an external standard. The calibration curve was prepared through complete evaporation of aqueous solutions of different AA content.
  • ZMI centrifugal mill by RETSCH Co.
  • Table 3 summarizes the intrinsic viscosity of the sample, the acetaldehyde contents (AA) and the increase of the temperature during IR heating compared to the PET without any IR additives. Table 3: Results of amorphous PET in tensile bars

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production de polyesters, tels que le polyéthylène téréphtalate (PET), à l'aide d'un catalyseur en combinaison avec un composé phosphoreux, tel qu'un acide alkyldiphosphonique, au lieu de noir de carbone pour améliorer l'activation infrarouge. L'invention concerne en outre une composition de polyester obtenue selon le procédé de l'invention et l'utilisation d'un composé phosphoreux spécifique en tant qu'additif dans une réaction de polycondensation de polyester catalysée.
PCT/EP2022/064170 2022-05-25 2022-05-25 Procédé de production d'un polyester WO2023227209A1 (fr)

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EP2287225A1 (fr) * 2009-08-20 2011-02-23 Saudi Basic Industries Corporation Procédé de fabrication de polyéthylène téréphthalate
US20120157619A1 (en) * 2010-12-20 2012-06-21 Eastman Chemical Company Color in Titanium Catalyzed Polyesters
CN104448262B (zh) * 2013-09-22 2018-05-29 东丽纤维研究所（中国）有限公司 一种聚酯组合物及其制造方法和用途

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