EP4121267A1 - Procédé de préparation d'une matière de départ pet convenant pour la mise en oeuvre d'un procédé d'extrusion-soufflage et corps creux réalisé au moyen du procédé d'extrusion-soufflage - Google Patents

Procédé de préparation d'une matière de départ pet convenant pour la mise en oeuvre d'un procédé d'extrusion-soufflage et corps creux réalisé au moyen du procédé d'extrusion-soufflage

Info

Publication number
EP4121267A1
EP4121267A1 EP21712776.0A EP21712776A EP4121267A1 EP 4121267 A1 EP4121267 A1 EP 4121267A1 EP 21712776 A EP21712776 A EP 21712776A EP 4121267 A1 EP4121267 A1 EP 4121267A1
Authority
EP
European Patent Office
Prior art keywords
pet
viscosity
chain
hollow body
melt
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
Application number
EP21712776.0A
Other languages
German (de)
English (en)
Inventor
Robert Siegl
Andreas Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alpla Werke Alwin Lehner GmbH and Co KG
Original Assignee
Alpla Werke Alwin Lehner GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alpla Werke Alwin Lehner GmbH and Co KG filed Critical Alpla Werke Alwin Lehner GmbH and Co KG
Publication of EP4121267A1 publication Critical patent/EP4121267A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0015—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C08G63/89—Recovery of the polymer
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B2017/001—Pretreating the materials before recovery
    • B29B2017/0015—Washing, rinsing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B2017/001—Pretreating the materials before recovery
    • B29B2017/0021—Dividing in large parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0203—Separating plastics from plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0268—Separation of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/042—Mixing disintegrated particles or powders with other materials, e.g. with virgin materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for producing a polyester starting material suitable for use in an extrusion blow molding process for producing a hollow body made of plastic, in particular a plastic bottle, according to the preamble of claim 1, and a hollow body produced by extrusion blow molding according to the preamble of claim 29.
  • extrusion blow molding can only be used if the PET molding compound has the necessary melt strength, i.e. the plastic tube has a shape and consistency when the blow mold halves are closed, which leads to a hollow body when the blow mold halves are closed that meets the specified specifications.
  • the melt strength of the PET material, which is used for the stretch blow molding process, in which the containers are formed from a preform produced in an injection molding process, does not meet the requirements for extrusion blow molding, since its intrinsic viscosity is too low and at Use in extrusion blow molding leads to said inadmissible lengths of the plastic tubing.
  • the PET material must be modified accordingly for extrusion blow molding.
  • PET molding compounds are used for extrusion blow molding, which are known under abbreviations such as PET X (extrudable), PET G (glycol modified) and PET B (branched). Terms such as EPET or E-PET (especially in the USA) or EBM PET are also used.
  • PET X extrudable
  • PET G glycocol modified
  • PET B branched
  • Terms such as EPET or E-PET (especially in the USA) or EBM PET are also used.
  • PET materials specially developed for extrusion blow molding the quantity of which is produced is low and therefore has a correspondingly high price.
  • the PET hollow bodies produced with these PET molding compounds can be easily fed into the recycling stream. However, these hollow bodies cannot be blown with the standard recycling material on the market, as this standard recycling material has the usual viscosity of the most common bottled goods, but EBM requires a higher viscosity.
  • Standard PET types are linear PET types (not branched) with a low copolymer content of less than 5% by weight and an intrinsic viscosity (IV) between 0.72 and 0.86 dl / g (according to ASTM D 4603) .
  • the PET which is mainly used today for the production of bottles in a stretch blow molding process, is a PET with an intrinsic viscosity (IV) between 0.72 and 0.86 dl / g measured according to ASTM D4603.
  • the material typically reduces viscosity between 0.01 and 0.09 dl / g.
  • extrusion blow molding In contrast to the stretch blow molding process that is most commonly used for the production of PET bottles, extrusion blow molding (EBM) requires viscosities between 0.9 and 1.4 dl / g. This means that the material produced in the standard PET recycling process and also the usual regenerates cannot be used for the EBM process
  • the viscosity of the standard PET recycling stream is much too low to contain 20 percent by weight. or to be able to add more recycled PET material to an EBM process.
  • EP2747981B1 and EP2807082B1 describe that PET for ISBM (typical virgin material has an intrinsic viscosity IV between 0.72 and 0.86 dl / g) for use in an EBM process via solid phase polycondensation to an IV of 0.96 to 1.4 dl / g can be brought.
  • WO2018127431 (A1) discloses a method to raise material from the standard PET recycling stream to the desired viscosity by means of a longer dwell time in the SSP reactor.
  • a longer residence time in the SSP reactor also has decisive disadvantages: The longer one throttles Dwell time, the output capacity of the recycling plant, depending on the target viscosity by 2 to 8 times.
  • the longer residence time in the SSP reactor leads to more yellowing of the material.
  • chain extenders An alternative way to increase the molecular mass of PET is to use so-called chain extenders.
  • the chain extension of rPET by using the chain extender pyromellitic dianhydride (PMDA) by means of reactive extrusion is known in the prior art.
  • Reactive extrusion means that the rPET in the melt reacts directly with the PMDA during the dwell time in the extruder and is immediately used in a forming or primary forming process.
  • EP0748346B1 discloses a process for increasing the molecular weight of polyesters, in which a mixture of a polyester and a tetracarboxylic dianhydride and a sterically hindered hydroxyphenylalkylphosphonic acid ester, for example, Irganox ® 1425 (BASF), in the case of crystalline polyesters above the melting point or in the case of amorphous polyesters on the Glass transition temperature is heated.
  • a tetracarboxylic dianhydride and a sterically hindered hydroxyphenylalkylphosphonic acid ester for example, Irganox ® 1425 (BASF)
  • a polyol, a polyfunctional epoxy compound, a polyamine, polyaziridine, polyisocyanate, polyoxazoline or a polyfunctional thioalcohol can be used as component b.
  • the molecular weight can be greatly increased in short reaction times. It was found that the addition of polyfunctional components does not result in crosslinked polycondensates, but rather that the polyfunctional compounds are essentially built into the chain and lead to chain extensions and / or branches.
  • temperatures are proposed which are preferably in the range between the melting temperature and a temperature about 50 ° C. above the melting temperature. In the case of amorphous polyesters, the reaction takes place in the range between 50 ° C and 150 ° C above the respective glass transition temperature.
  • Typical EBM PET types that are used today to manufacture bottles in an EBM process are, for example, Indorama Polyclear 5507 and PETKO PET 160-X.
  • Typical EBM PET types usually have the narrow molecular weight distribution typical of polycondensates without significant long chain branching and thus result in a low melt elasticity. This manifests itself in low elastic restoring forces when exiting the nozzle gap, which results in a slight swelling of the diameter and thickness of the hose.
  • This has the disadvantage that the free-hanging hose in extrusion blow molding changes much more quickly than the materials normally used in extrusion blow molding, such as HDPE or PP, and therefore has a significantly narrower process window.
  • the object of the present invention is to provide a material for extrusion blow molding, in particular of PET bottles, which preferably originates primarily from rPET, which is obtained from the collection of post-consumer PET articles, in particular PET bottles.
  • rPET which is obtained from the collection of post-consumer PET articles, in particular PET bottles.
  • the material be compatible with the PET recycling stream and be partially crystalline.
  • Another aim is for the material to have a high melt stiffness and therefore be particularly suitable for extrusion blow molding.
  • Another goal is that as few additives as possible are added for the production of the material in order not to significantly impair the purity of the PET recycling stream.
  • Another goal is that the production of the material is significantly faster than the pure condensation of rPET in a solid-phase polycondensation.
  • the material should be low-gel and deliver bottles with few specks when used.
  • viscosity is understood to mean the intrinsic viscosity (IV) measured according to the ASTM 4603-03 standard.
  • pure PET is understood to mean that PET has been sorted within the framework of today's technological possibilities, so that the weight percentage of non-varietal plastic is less than 2%, preferably less than 1% and particularly preferably less than 0.5%.
  • rPET is used here as a short name for recycled post-consumer PET.
  • EBM-PET is understood to mean PET (including PET copolymers) which is suitable for use in an EBM process, i.e. has an IV between 0.87 dl / g and 1.4 dl / g.
  • the object is achieved in a method according to the preamble of claim 1 in that the intrinsic viscosity of the extruded granulate is further increased by a subsequent heat treatment in a solid-state post-condensation (solid state polycondensation, SSP).
  • solid state polycondensation solid state polycondensation
  • the viscosity can again be increased significantly by means of a solid-phase post-condensation.
  • SSP solid state polycondensation
  • the chain mobility is reduced in the amorphous zones and even greatly reduced in the crystallites, which should lead to a greatly reduced reactivity, especially in the crystalline areas.
  • the chain mobility is already lower, since the SSP operates below the melting temperature and significantly above it in reactive extrusion.
  • the Arrhenius approach for reaction rates shows that an increase in temperature by 10K results in approximately a doubling of the reaction rate. Accordingly, the person skilled in the art could not expect that, given the restricted mobility of the molecules, a further, substantial condensation could take place.
  • the solid-phase post-condensation is preferably carried out at temperatures ⁇ 225 ° C. This has the advantage that the granulate is spared and yellowed less than at even higher temperatures, which in an SSP process for PET is typically 225 ° C or higher (cf. EP 1054031, [108]).
  • the viscosity increase in process step f) is preferably higher than that in process step d). This increase in viscosity in process step f) is surprising to the person skilled in the art, since the PET in process step f) is not present as a melt, but rather as granules.
  • the residence time of the granules in the SSP reactor is less than 20 hours, preferably less than 15 hours and particularly preferably less than 12 hours.
  • the relatively short dwell time can not only shorten the manufacturing process, but also prevents the granulate from yellowing, which occurs if the dwell times are too long.
  • the post-consumer PET material used in method step a) has a viscosity between 0.65 and 0.84 dl / g.
  • the starting material therefore has a low viscosity and can nevertheless be converted by the inventive method into a material with a corresponding viscosity that can be used for an EBM process.
  • the method advantageously enables the viscosity of the material used to be increased by 0.05 to 0.2 dl / g as a result of the reactive extrusion.
  • the viscosity is increased by a further 0.1 to 0.6 dl / g, preferably by 0.15 to 0.55 dl / g and particularly preferably by 0.3 to 0.55 dl with the aid of the solid phase post-condensation / g raised.
  • the viscosity of the PET starting material can therefore be increased in an SSP reactor and in a reactive extrusion.
  • the temperature during extrusion and the amount of chain extender are chosen so that the extruded material has an intrinsic viscosity (IV) greater than 0.75 dl / g, in particular between 0.75 and 0.9 dl / g and preferably between 0.8 and has 0.9 dl / g.
  • IV intrinsic viscosity
  • a polyfunctional anhydride i.e. a molecule with two or more anhydride groups, is advantageously used as the chain extender.
  • tetracarboxylic acid dianhydrides are used as chain extenders.
  • pyromellitic dianhydride is used as the chain extender.
  • one of the chain extenders mentioned below is used: bisoxazolines, bisepoxides, diisocyanates, polyepoxides, compounds containing several glycidyl groups, maleic anhydride, phthalic anhydride, triphenyl phosphates, lactamyl phosphites, cyclo-phosphazene, polyacyllactam, and bis-2 -Oxazolines, bis-5,6-dihydro-4h-l, 3-oxazines, diisocyanates, trimethyl 1,2,4-benzenetricarboxylate (trimethyl trimellitate, TMT), carbonyl bis (1-caprolactam).
  • TMT trimellitate
  • Polyols and polycarboxylic acids are advantageously used as chain branches.
  • Compounds with more than two hydroxyl groups are advantageously used as chain branches.
  • the polyols used are advantageously glycerol, pentaerythritol or a combination of both compounds.
  • between 0.05% by weight and 1.0% by weight of chain extender is added to the rPET.
  • the extruded melt is filtered before granulation.
  • a further chain build-up preferably takes place after the filter in order to avoid excessively high melt pressure.
  • the extruded melt is pressed through a perforated filter with a hole size between 30 miti and 300 miti and preferably between approximately 50 miti and 100 miti.
  • the melt has sufficient purity and cloudiness and impurities can be prevented in the end product of a hollow body.
  • an acid scavenger is added to the PET material prior to extrusion.
  • Acid scavengers prevent the acid-catalyzed chain cleavage (hydrolysis) of PET in the melt.
  • calcium stearate, zinc stearate, zinc oxide or hydrotalcite or a combination of the aforementioned acid scavengers is used as the acid scavenger.
  • the material is degassed during extrusion.
  • the degassing allows the viscosity of the material to be increased by a further 0.01 to 0.1 dl / g.
  • the rPET material obtained in method step f) is fed to the EBM system, and a chain extender is added to the EBM system.
  • This increases the viscosity through reactive extrusion.
  • the fine adjustment of the required viscosity can therefore be carried out on the blow molding machine.
  • the extruded tube for the production of smaller bottles requires a lower viscosity, since lower tensile forces arise from the force of gravity.
  • the melt is divided into thin layers or strands in the extruder. This massively increases the surface of the material.
  • the extrusion takes place in a vacuum or in a protective gas atmosphere, in particular under nitrogen. This increases the viscosity by 0.1 to 0.5 dl / g. This form of extrusion is particularly efficient when the surface of the melt is enlarged by dividing it into layers and strands.
  • a tube or a plurality of tubes is extruded, blown into one or more hollow bodies and then cut off. According to a further embodiment of the invention, a tube or a plurality of tubes is extruded, cut off and then blown into one or more hollow bodies.
  • the strength of the hose is advantageously increased by active cooling by 5 to 50 ° C.
  • the hose is advantageously cooled by expanding the hose, coming into contact with another medium, by blowing nozzles, aerosols or other forms of heat dissipation, in particular by means of heat pipes.
  • untreated PET (virgin material or rPET) with an IV (intrinsic viscosity) of 0.6 to 0.95 dl / g in a mass fraction of 0 to 50% is added to the PET in order to adjust the melt strength specifically for the article
  • IV intrinsic viscosity
  • Another aspect of the invention relates to a hollow body, in particular a bottle, made of at least partially recycled PET.
  • the hollow body is characterized in that the PET starting material for producing the hollow body is between 30% by weight. and 100% by weight.
  • the hollow body can advantageously be obtained from a method as described above.
  • the recycled PET is produced from recycled post-consumer PET (“Bottle Grade PET Post-consumer Recycling Flake”) with a viscosity between 0.65 and 0.84 dl / g by condensation.
  • the PET starting material of the finished hollow body advantageously has a shear viscosity at 275 ° C. and 50 s 1 of less than 3000 Pa * s, in particular between 1000 and 2500 Pa * s.
  • the PET starting material for producing the hollow body has an extensional viscosity (at 275 ° C, 50s-1) of at least 5500 Pa * s at 275 ° C when producing hollow bodies with a volume between 100 ml and approximately 500 ml and more than 7000 Pa * s for hollow bodies with a volume of more than 500 ml and preferably more than 600 ml, and in particular between 7000 Pa * s and 14000 Pa * s.
  • Exemplary tetracarboxylic dianhydrides that can be used as chain extenders are pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 1,1,2,2-ethanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, diphenylsulphonic dianhydride (2,5-tetracarboxylic acid, 5- 3-furanyl) -3-methyl-3 cyclohexane-1,2-dicarboxylic acid dianhydride, bis (S, 4-dicarboxylic acid phenyl) ether dianhydride, bis (3,4-dicarboxylic acid phenyl) thioether dianhydride, 2 , 2-bis- (3,4-dicarboxylic acid phenyl) -hexafluoropropane dianhydride, 2,3,6,7-naphthalene-tetracarboxylic acid dianhydr
  • the melt rheological characterization was carried out according to ISO 11443: 2014. Samples are dried in vacuo at 120 ° C. for 12 hours. A Göttfert Rheograph 75 with a 2x15mm test channel was used for testing. The 10/1 and 0 / lmm capillaries were used. The test temperature was 275 ° C. A Bagley correction and a Rabinowitsch-Weissenberg correction were carried out. Both the shear and the extensional viscosity were determined. The extensional viscosity was determined using the Cogswell method (first description by Cogswell 1972) from the inlet pressure losses by means of WinRheo II software (Göttfert material testing machines GmbH, Buchen, Germany).
  • Example 1 A commercially available virgin PET product for injection molding (IV 0.8 dl / g) was left in an SSP reactor at 215 ° C. for a period of 17 hours. When tested on an EBM system, the material exhibited relatively poor melt stiffness. A cosmetic bottle with a height of approx. 20 cm and a volume of approx. 400 ml was difficult to shape.
  • a commercially available rPET granulate consisting of "post-consumer” waste was procured and left in the SSP reactor at 210 ° C. for 15 hours.
  • the material is suitable for the production of the cosmetic bottle described above.
  • a commercially available rPET granulate consisting of "post-consumer” waste was procured and left in the SSP reactor at 215 ° C. for 22 hours.
  • the material is suitable for the production of the cosmetic bottle described above.
  • Examples 7 and 8 show that by using the PMDA under "milder" reaction conditions (lower process temperature, significantly shorter residence time) it is possible to work in the SSP and even higher extensional viscosities can be achieved than without the use of PMDA at the significantly longer residence times and process temperatures in Examples 5 and 6.
  • the comparison of Examples 1 and 5 or 6 shows that rPET can basically have faster reaction kinetics than vPET (virgin material). However, the behavior of rPET can also fluctuate, depending on the composition of the incoming goods flow.
  • examples 1 and 7 show an almost identical IV of 1.193 dl / g, respectively. l, 194dl / g. The same applies to the shear viscosities of 1669 Pa * s and 1657 Pa * s at 275 ° C and 50s 1 . At the same time, however, the two materials show massive differences the extensional viscosity of 5331 Pa * s or 13192 Pa * s at 275 ° C and 50 s 1 .
  • One of the weaknesses of the IV is actually that relatively small amounts of sample are used for the determination in relation to melt rheological methods. In the case of materials that are definitely inclined to inhomogeneities (which can certainly be recycled materials), this can lead to strongly scattering IV measured values or generally to a low accuracy of the determination.
  • the rPET treated according to the invention showed an unusual behavior characterized by a high melt elasticity or extensional viscosity, as described with reference to the above examples, and a high tendency to swell.
  • the high extensional viscosity in relation to the low shear viscosity is an indication of a rather elastic nature of the rPET treated according to the invention.
  • these materials show, in contrast to the materials from Examples 1 to 5 (materials with more plastic behavior), a much lower tendency to adhere to metallic surfaces. Without these elastic restoring forces, the melting behavior towards metallic surfaces would be dominated by the wetting behavior (surface tension).
  • FIG. 1 shows the subjective "EBM rating” against the extensional viscosity according to Cogswell (EtaCo) at 275 ° C. and 50 s 1.
  • the "EBM rating” results as follows: Examples 1 and 2 which caused difficulties were rated 0 (unsuitable) and 1 (difficulties with small bottle format), respectively. Materials that could be processed without problems for the above-mentioned cosmetic bottle were rated 3. Materials that would be suitable for bottles with 1L net capacity or slightly larger (up to 5L) were rated 4. In order to be able to take into account the even higher observed, subjective melt strength on the EBM system compared to class 4, class 5 was also introduced. It can be seen from Fig.
  • the extensional viscosity defines a limit curve that a part resembles a parabola. It is not known whether this limit curve conforms to an asymptote, as no data are available for this. This is currently not relevant for the intended use of the materials. But the limit curve shows with clarity that an extensional viscosity of approximately min. 5500 Pa * s at 275 ° C and 50 s 1 of the PET must be to make it suitable for extrusion blow molding of small hollow bodies, ie those with a volume of between 100 ml and 500 ml are suitable, whereas for larger hollow bodies, ie for hollow bodies with a volume greater than 500 ml, at least 6500 Pa * s are required.
  • post-consumer PET bottles are sorted, washed, cut and contaminants such as metal, paper and other contaminants are removed.
  • the cut PET flakes are dried.
  • conditions can already be created in which the PET builds up molecular weight. (e.g. Vacurema process from EREMA Engineering Recycling Maschinen und Anlagen Ges.m.b.H., Ansfelden, Austria).
  • a chain extender and / or a chain branch is added to the PET, and a reactive extrusion of the flakes is carried out, preferably under vacuum.
  • the PET is rapidly condensed during extrusion, i.e. the mean molecular weight of the rPET increases.
  • it can also take place in a protective gas atmosphere.
  • the rPET with the addition of the chain extender resp. of the chain branch additionally 0.01 to 1.0 wt .-%, preferably 0.05 to 0.8 wt .-% of an acid scavenger such as calcium stearate,
  • Zinc stearate, zinc oxide or hydrotalcite or a combination of these acid scavengers are added and the flakes are then extruded.
  • the acid scavenger can prevent or at least reduce the acid-catalyzed chain cleavage (hydrolysis) of PET in the melt.
  • stabilizing phosphorus compounds can be added to the rPET in the form of an acid (e.g.
  • H3P04 or an acid ester in the range of 0 to 50ppm can be added.
  • melt is filtered (optional) and granulated.
  • the granulate is placed in an SSP reactor and raised to a viscosity of over 0.9 dl / g.
  • the material can be dried on the extrusion blow molding machine, the viscosity being increased again at the appropriate temperature.
  • the material can be mixed again with a chain extender and raised to a viscosity that is useful for the EBM process.
  • the chain extender can be added before or at the same time as the extrusion.
  • the material is preferably transferred directly from the SSP reactor to the EBM system. If, on the other hand, the material is filled into big bags or storage containers after the SSP process, for example, because it cannot be further processed directly, then the residual moisture is preferably set to below 50ppm, preferably below 30ppm (typically preferably by drying immediately before processing on the EBM- System).
  • the extrusion blow molding process produces so-called slugs that are separated from the final bottle and preferably fed back into the process by comminuting them to flakes, the regrind PET, and subjecting them to post-condensation in the SSP reactor or dryer.
  • a chain extender can optionally be added to the regrind PET to increase condensation.
  • untreated PET (virgin material (vPET) or rPET) with an IV of 0.6 to 0.95 dl / g in a mass fraction of 0 to 50%
  • vPET vangin material
  • rPET rPET
  • IV 0.6 to 0.95 dl / g in a mass fraction of 0 to 50%
  • process step d there is a degassing zone in the extruder (process step d) which builds up the PET by 0.01 to 0.10 dl / g during extrusion.
  • the melt is divided into thin layers or strands in the extruder, which massively increases the surface area of the material and makes it more accessible to melt polymerization (condensation).
  • the intrinsic viscosity can be built up by 0.10 to 0.50 in the melt.
  • This process step preferably takes place under vacuum or a protective gas atmosphere, e.g. under nitrogen.
  • a tube is extruded and blown into a flea body and cut.
  • the remaining slugs above and below the bottle are removed.
  • the strength of the extruded hose can be increased by cooling the hose by 5 to 50 ° C.
  • the cooling is carried out either through expansion of the hose, through contact with another medium, through air nozzles, through aerosols or other forms of heat dissipation, in particular by means of fleat pipes. Due to the evaporation of a medium, fleat pipes lead to a very uniform cooling with temperature differences of less than 1 ° C.
  • the subject matter of the invention is a method which converts a “bottle grade PET post-consumer recycling flake”, ie a recycled post-consumer PET, with a viscosity of 0.65 to 0.84 dl / g to an EBM bottle with 0.90 up to 1.5 dl / g with the help of extrusion processes, solid state polycondensation processes and a blowing process.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé qui permet de réaliser, à partir de copeaux de recyclage post-consommation de PET type bouteille, c'est-à-dire à partir d'un PET post-consommation recyclé ayant une viscosité de 0,65 à 0,84 dl/g, une bouteille EBM de 0,90 à 1,5 dl/g à l'aide de processus d'extrusion, de processus de polycondensation à l'état solide et d'un processus de soufflage.
EP21712776.0A 2020-03-16 2021-03-15 Procédé de préparation d'une matière de départ pet convenant pour la mise en oeuvre d'un procédé d'extrusion-soufflage et corps creux réalisé au moyen du procédé d'extrusion-soufflage Pending EP4121267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH00304/20A CH717234A1 (de) 2020-03-16 2020-03-16 Verfahren zur Herstellung eines zur Verwendung in einem Extrusionsblasverfahren geeigneten PET-Ausgangsmaterials und daraus hergestellter Hohlkörper.
PCT/EP2021/056527 WO2021185757A1 (fr) 2020-03-16 2021-03-15 Procédé de préparation d'une matière de départ pet convenant pour la mise en œuvre d'un procédé d'extrusion-soufflage et corps creux réalisé au moyen du procédé d'extrusion-soufflage

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EP4121267A1 true EP4121267A1 (fr) 2023-01-25

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US (1) US20230182365A1 (fr)
EP (1) EP4121267A1 (fr)
CN (1) CN115298007A (fr)
CH (1) CH717234A1 (fr)
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WO (1) WO2021185757A1 (fr)

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CH719694A1 (de) * 2022-05-13 2023-11-30 Alpla Werke Alwin Lehner Gmbh & Co Kg Verfahren zum Recycling von Polyester-Behältern.

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161579A (en) * 1978-04-10 1979-07-17 Celanese Corporation Extrusion grade polyethylene terephthalate
EP0422282B1 (fr) * 1989-10-13 1995-04-05 Phobos N.V. Procédé de préparation en continu de résines de polyester à poids moléculaire élevé
TW460525B (en) 1994-02-28 2001-10-21 Ciba Sc Holding Ag A process for increasing the molecular weight of polyesters with a tetracarboxylic acid dianhydride and a sterically hindered hydroxy-phenylalkylphonic acid ester or half-ester
DE19710098A1 (de) * 1997-03-12 1998-09-17 Paul Stehning Gmbh Verfahren zur Erzeugung von PET-Recyclat aus Flakes, sowie nach dem Verfahren erzeugtes PET-Produkt
DE50011006D1 (de) 1999-05-21 2005-09-29 Ciba Sc Holding Ag Molekulargewichtsaufbau und Modifizierung von Polykondensaten
AUPQ294699A0 (en) * 1999-09-17 1999-10-14 Visy Plastics Pty Ltd Process for preparing food contact grade polyethylene terephthalate resin from waste pet containers
JP2014527924A (ja) 2011-08-25 2014-10-23 プラスチパック パッケージング，インコーポレイテッド 押出成形されたｐｅｔパリソン、容器、および方法
MX361085B (es) 2012-01-25 2018-11-27 Plastipak Packaging Inc Preforma, recipiente y método de pet extruido.
WO2014162238A2 (fr) * 2013-03-31 2014-10-09 Jain Pranay Procédé de recyclage d'un film de polyester métallisé
CH713339A1 (de) * 2017-01-03 2018-07-13 Alpla Werke Alwin Lehner Gmbh & Co Kg PET-Regranulat mit hoher intrinsischer Viskosität und Verfahren zu dessen Herstellung.

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WO2021185757A1 (fr) 2021-09-23
MX2022010719A (es) 2022-10-07
CH717234A1 (de) 2021-09-30
CN115298007A (zh) 2022-11-04
US20230182365A1 (en) 2023-06-15

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