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WO2025099166A1 - Procédé de modification pour recyclats de polymères - Google Patents

Procédé de modification pour recyclats de polymères Download PDF

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Publication number
WO2025099166A1
WO2025099166A1 PCT/EP2024/081527 EP2024081527W WO2025099166A1 WO 2025099166 A1 WO2025099166 A1 WO 2025099166A1 EP 2024081527 W EP2024081527 W EP 2024081527W WO 2025099166 A1 WO2025099166 A1 WO 2025099166A1
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WO
WIPO (PCT)
Prior art keywords
polyolefin composition
post
consumer recycled
solvent
process according
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
PCT/EP2024/081527
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English (en)
Inventor
Andreas Albrecht
Joel FAWAZ
Noureddine AJELLAL
Lukas SOBCZAK
Mohammad AL-HAJ ALI
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Borealis GmbH
Original Assignee
Borealis GmbH
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Publication of WO2025099166A1 publication Critical patent/WO2025099166A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the present invention is directed to a process for modifying a post-consumer recycled polypropylene-based polyolefin composition.
  • the present invention is also directed to a modified polyolefin composition obtained by the process, as well as to an article comprising the modified polyolefin composition.
  • PCR post-consumer recycled
  • Polyolefins are the dominant plastic material in post-consumer recyclates.
  • modification methods for polyolefins from postconsumer recycled plastic materials should have high tolerance to the ratios of propylene polymers to ethylene polymers and should further be tolerant to the presence of non-polyolefin plastic materials and other contaminants present in the post-consumer recycled plastic materials.
  • recycled polyolefins several properties are important. These properties particularly relate to rheological and mechanical characteristics of the recycled polyolefins, which make them processible and applicable in the preparation of new articles.
  • modification methods of polyolefins resulting in polyolefins having these properties are important.
  • Rheology and mechanical characteristics of the recycled polyolefins may be modified by treating the recycled polyolefins with radicals and by a controlled introduction of long chain branching.
  • rheology can be modified by addition of peroxides and optional other agents.
  • European patent application EP3757152A1 discloses a process for providing a controlled rheology modified mixed-plastic-polyethylene blend having a melt flow rate of 0.1 to 0.45 g/10 min (ISO 1133, 2.16 kg load, 190 °C) from a waste stream, wherein a mixed-plastic- polyethylene reactant blend is melt-blended with peroxide.
  • VOC volatile organic compounds
  • FOG semi-volatile organic “fogging”
  • the objective of the present invention is to provide a process that addresses the above-described issues and to provide the respectively modified polyolefins.
  • the present invention provides a process for modifying a post-consumer recycled polyolefin composition comprising the steps of
  • A providing a post-consumer recycled polyolefin composition comprising, based on the total weight of the post-consumer recycled polyolefin composition, determined by FTIR spectroscopy, (a) at least 50 wt.-% of one or more propylene (co)polymer component(s) and
  • the present process enables modificiation of a post-consumer recycled polyolefin composition to provide a modified polyolefin composition, such as a modified polyolefin composition with a homogenized molecular weight which is observed by a narrowed molecular weight distribution (MWD) or by introduction of long- chain branching, as well as with low contents of volatile organic compounds (VOC) and semi-volatile organic “fogging” (FOG) compounds.
  • MWD molecular weight distribution
  • VOC volatile organic compounds
  • FOG semi-volatile organic “fogging”
  • the present invention also provides a modified polyolefin composition obtained by the process, as well as an article comprising the modified polyolefin composition.
  • Figure 1 shows the content of low-boiling compounds (LBS) for the inventive and comparative examples.
  • Figure 2 shows the content of high-boiling compounds (HBS) for the inventive and comparative examples.
  • Figure 3a shows the molecular weight distribution (MWD, expressed as dWZdlog(M)) for PCR1 and P2.
  • Fig 3b shows the radius of gyration (expressed as log Rg) along the molecular weight (log(M)) in relation to the prediction for a fully linear polymer.
  • Figure 4 shows the molecular weight distribution (MWD, expressed as dWZdlog(M)) for PCR2 and P5 or P6.
  • Figure 5 shows the correlation of the ethylene content of the crystalline fraction in respect to the ethylene content of the polymer for recycled and virgin polyolefins.
  • the present invention provides a process for modifying a post-consumer recycled polyolefin composition to obtain polyolefins characterized by a more homogeneous structure and, thus, improved rheological properties.
  • post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose.
  • virtual denotes the newly produced materials and/or objects prior to their first use, which have not already been recycled.
  • recycled such as used herein denotes materials reprocessed from “recycled waste”.
  • This process employs a post-consumer recycled (PCR) polyolefin composition with a high content of polypropylene and changes its structure, and thus, rheological properties.
  • the reaction with a radical initiator usually shifts the structure of the post-consumer recycled polyolefin composition towards lower molecular weight (Mw) and narrower molecular weight distribution (MWD). Accordingly, the melt flow rate is increased by this step.
  • Optional reaction with an unsaturated hydrocarbon compound concurrently to the reaction with a radical initiator introduces long chain branches into the postconsumer recycled polyolefin composition in a controlled manner. This may also have an impact on rheology by reducing the melt flow rate of the final product. Moreover, long-chain branching results in polyolefins with improved mechanical performance, like stiffness and toughness. After the final extraction step, the obtained polyolefins have lower levels of volatile and semi-volatile organic compounds. This facilitates handling of the composition in the production of new articles.
  • the modified polymers can be used in a greater variety of applications, in particular, where odor and taste are important issues.
  • Step (A) Provision of post-consumer recycled (PCR) polyolefin composition
  • step (A) of the process of the present invention a post-consumer recycled polyolefin composition is provided.
  • post-consumer recycled (PCR) polyolefin composition denotes a composition comprising polyolefins obtained from consumer waste.
  • post-consumer recycled polyolefin has already completed at least a first use cycle (or life cycle), i.e., having already served their first purpose.
  • Postconsumer recycled polyolefin is different from virgin polyolefin, i.e., a newly produced material, which has not already been recycled.
  • Post-consumer recycled polyolefin is also different from industrial waste, i.e., manufacturing scrap, which does normally not reach a consumer.
  • Virgin materials and used and/or recycled materials can easily be differentiated based on the absence or presence of contaminants such as limonene, fatty acids, paper and/or wood and other contaminants, or generally on their ash content.
  • Polyolefins e.g. polypropylene-pol- yethylene blends
  • non-polyolefin polymers such as polystyrene and/or polyamide.
  • the process of the present invention is suitable for the use of compositions comprising a wide range of propylene polymer to ethylene polymer ratios.
  • the postconsumer recycled polyolefin composition comprises, based on the total weight of the post-consumer recycled polyolefin composition, and determined by Fourier transform infrared (FTIR) spectroscopy,
  • the one or more ethylene (co)polymer component(s) may be present in the postconsumer recycled polyolefin composition in a content within the range of from 0 to 50 wt-%.
  • the one or more ethylene (co)polymer component(s) may be present in the post-consumer recycled polyolefin composition in a content of at least 1 wt.-% (i.e. , from 1 to 50 wt.-%), based on the total weight of the post-consumer recycled polyolefin composition, determined by FTIR spectroscopy.
  • the post-consumer recycled polyolefin composition may comprise a mixture (such as a polymer blend) of one or more propylene (co)polymer component(s) and one or more ethylene (co)polymer component(s).
  • the weight contents are determined from equivalent ratio from calibration by isotactic polypropylene (iPP) homopolymer and high density polyethylene (HDPE) using the herein described FTIR method.
  • the post-consumer recycled polyolefin composition comprises, based on the total weight of the post-consumer recycled polyolefin composition, determined by FTIR spectroscopy,
  • the (co)polymer components are preferably of high degree of crystallinity as defined below. However, less crystalline or non-crystalline copolymer components may additionally be present in the post-consumer recycled polyolefin composition.
  • the post-consumer recycled polyolefin composition comprises a crystalline fraction (CF), determined according to Crystex analysis described herein, in an amount in the range of from 75 to 98 wt.-%, based on the total weight of the post-consumer recycled polyolefin composition.
  • CF crystalline fraction
  • the less crystalline or noncrystalline copolymer components make up the majority of the soluble fraction (SF), determined according to Crystex analysis described herein, in an amount in the range of from 2 to 25 wt.-%, based on the total weight of the post-consumer recycled polyolefin composition.
  • the post-consumer recycled polyolefin composition may further comprise an ethylene content of the crystalline fraction (C2(CF)), determined according to FTIR during Crystex analysis described herein, in an amount in the range of from 3 to 60 wt.-%, preferably from 5 to 55 wt.-% and more preferably from 6 to 50 wt.-%, based on the total weight of the crystalline fraction of the post-consumer recycled polyolefin composition.
  • C2(CF) ethylene content of the crystalline fraction
  • the post-consumer recycled polyolefin composition may also comprise an ethylene content of the soluble fraction (C2(SF)), determined according to FTIR during Crystex analysis described herein, in an amount in the range of from 20 to 50 wt.-%, preferably from 23 to 47 wt.-% and more preferably from 25 to 45 wt.-%, based on the total weight of the soluble fraction of the post-consumer recycled polyolefin composition.
  • C2(SF) ethylene content of the soluble fraction
  • propylene (co)polymer component denotes a propylene homopolymer component and/or a propylene copolymer componentincluding blends thereof.
  • propylene homopolymer denotes a propylene polymer that consists of at least 99.0 wt.-%, preferably at least 99.5 wt.-%, more preferably at least 99.8 wt.-% of propylene monomer units, based on the total weight of the propylene polymer, determined by quantitative 13 C ⁇ 1 H ⁇ nuclear magnetic resonance (NMR) spectroscopy. In one embodiment, only propylene monomer units are detectable in the propylene homopolymer.
  • a propylene homopolymer may be present as isotactic, syndiotactic or atactic propylene homopolymer.
  • the propylene homopolymer has a high degree of crystallinity.
  • the propylene homopolymer is an isotactic propylene homopolymer, i.e. , a propylene homopolymer that has an isotacticity, at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences, of from 95 to 98 %, preferably from 95.5 to 98 % and more preferably from 96 to 97.5 %, determined by quantitative 13 C ⁇ 1 H ⁇ NMR spectroscopy.
  • propylene copolymer denotes a propylene polymer that generally comprises propylene monomer units and other comonomer units, preferably, ethylene comonomer units and/or one or more alpha-olefin(s) comonomer units having from 4 to 10 carbon atoms, most preferably ethylene comonomer units.
  • the content of the propylene monomer units in the propylene copolymer is at least 70 wt.-%, based on the total weight of the propylene copolymer, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy, or alternatively 70 mol- %, based on the total molar content of the propylene copolymer, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy.
  • the propylene copolymer is an isotactic propylene copolymer, i.e. , a propylene copolymer that has an isotacticity, at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences, of from 95 to 98 %, preferably from 95.5 to 98 % and more preferably from 96 to 97.5 %, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy.
  • isotactic propylene copolymer i.e. , a propylene copolymer that has an isotacticity, at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences, of from 95 to 98 %, preferably from 95.5 to 98 % and more preferably from 96 to 97.5 %, determined by quantitative 13 C ⁇
  • the at least one propylene (copolymer component(s) is an isotactic propylene homopolymer.
  • the at least one of propylene (copolymer components) is an isotactic propylene copolymer of propylene and comonomer(s) selected from ethylene and/or one or more alpha-olefin(s) having from 4 to 10 carbon atoms, preferably ethylene, wherein the copolymer preferably contains, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy, from 0.1 to 27 mol-%, more preferably from 0.1 to 20 mol-%, of comonomer(s).
  • ethylene copolymer component denotes an ethylene homopolymer component and an ethylene copolymer component as well as combinations, e.g. copolymers or blends, thereof.
  • ethylene homopolymer denotes an ethylene polymer that consists of at least 99.0 wt.-%, preferably at least 99.5 wt.-%, more preferably at least 99.8 wt.-% of ethylene monomer units, based on the total weight of the ethylene polymer, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy. In one embodiment, only ethylene monomer units are detectable in the ethylene homopolymer.
  • ethylene copolymer denotes an ethylene polymer that generally comprises ethylene monomer units and other comonomer units, preferably, one or more alpha-olefin(s) comonomer units having from 4 to 10 carbon atoms.
  • the content of the ethylene monomer units in the ethylene copolymer is at least 70 wt.-%, based on the total weight of the ethylene copolymer, determined by quantitative 13 C ⁇ 1 HJ-NMR spectroscopy, or alternatively 75 mol-%, based on the total molar content of the ethylene copolymer, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy.
  • the ethylene (co)polymer has a high degree of crystallinity of at least 40 %, determined by differential scanning calorimetry (DSC) and assuming a melting enthalpy of 293 J/g for fully crystalline ethylene polymer.
  • DSC differential scanning calorimetry
  • the at least one of ethylene (copolymer component(s) is an ethylene homopolymer having a degree of crystallinity, determined by differential scanning calorimetry (DSC) and assuming a melting enthalpy of 293 J/g for fully crystalline ethylene polymer, of 40 to 90 %.
  • the at least one of ethylene (copolymer component(s) is an ethylene copolymer of ethylene and comonomer(s) selected from one or more alpha-olefin(s) having from 4 to 10 carbon atoms, wherein the copolymer preferably contains, determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy, from 0.1 to 20 mol-%, more preferably from 0.1 to 15 mol-%, of comonomers), and having a degree of crystallinity, determined by differential scanning calorimetry (DSC) and assuming a melting enthalpy of 293 J/g for fully crystalline ethylene polymer, of 40 to 90 %.
  • DSC differential scanning calorimetry
  • the post-consumer recycled polyolefin composition comprises, from 0 to 1 wt% of non-polyolefin polymers, of the total weight of the post-consumer recycled polyolefin composition, determined by Fourier trans-form infrared (FTIR) spectroscopy. More preferably, polyamide (PA) and/or polystyrene (PS) polymer(s) is/are not detectable by FTIR spectroscopy in the post-consumer recycled polyolefin composition. Further preferably, PET and/or PVC is/are not determinable by FTIR spectroscopy in the post-consumer recycled polyolefin composition. Most preferably none of PA, PS, PET and PVC are detectable by FTIR spectroscopy in the post-consumer recycled polyolefin composition.
  • PA polyamide
  • PS polystyrene
  • PET and/or PVC is/are not determinable by FTIR spectroscopy in the post-consumer recycled
  • post-consumer recycled polyolefin composition used as starting material for the process of the present invention from virgin polyolefins.
  • the optional presence of contaminating compounds in the post-consumer recycled polyolefin composition may be considered as a distinguishing feature.
  • the post-consumer recycled polyolefin composition as used in the process of the present invention comprises, based on the total weight of the post-consumer recycled polyolefin composition, one or more of
  • the post-consumer recycled polyolefin composition comprises at least limonene in a content of at least 0.1 ppm.
  • the components a), b) and at least one of c) to f), preferably c), add up to 100 wt.-% of the post-consumer recycled polyolefin composition.
  • the post-consumer recycled polyolefin composition may also comprise a residual ash content, as determined according to the ISO 3451 -1 (1997) standard, of below 3.0 wt.-%, preferably in the range of from 0.5 to 2.7 wt.-% and more preferably 0.7 to 2.5 wt.-%.
  • the process of the present invention is tolerant to the cited components in the indicated amounts, and the modified polyolefin composition obtained by the process is of excellent quality for further reuse.
  • the post-consumer recycled polyolefin composition can additionally or alternatively be distinguished from virgin polyolefins by the ethylene content (C2(CF)) of the crystalline fraction (CF).
  • C2(CF) ethylene content
  • CF crystalline fraction
  • post-consumer recycled polyolefin composition with high contents of polypropylene can be determined in this way.
  • the post-consumer recycled polyolefin composition was prepared by use of a dissolution or extraction method and comprises highly pure polyolefin composition with only small amounts of contaminants, distinction from virgin polyolefins can still be made by this determination.
  • the ethylene content (C2(CF)) of the crystalline fraction (CF), determined by Crystex analysis described herein, is in the range of from [C2 - 3.4] to [C2 - 0.2] wt.-%, more preferably from [C2 - 3.0] to [C2 - 0.6] wt.-% and most preferably from [C2 - 2.4] to [C2 - 1 .2] wt.-%, of the total weight of the crystalline fraction of the post-consumer recycled polyolefin composition.
  • C2 represents here the value obtained for the ethylene content of the respective polymer in wt.- %, determined by Crystex analysis as described herein below.
  • the ethylene content (C2(CF)) of the crystalline fraction (CF) preferably is, [-3,4 + C2] ⁇ C2(CF) ⁇ [-0,2 + C2], more preferably [-3,0 + C2] ⁇ C2(CF) ⁇ [-0,6 + C2], and most preferably [-2,4 + C2] ⁇ C2(CF) ⁇ [-1 ,2 + C2] in wt.-%, based on the total weight of the crystalline fraction of the post-consumer recycled polyolefin composition.
  • the correlation of the ethylene content of the crystalline fraction in respect to the ethylene content of the polymer sample differs between recycled polyolefins (SbR) and virgin polyolefins.
  • Heco PP is an abbreviation for heterophasic propylene copolymer.
  • Homo PP is an abbreviation for propylene homopolymer.
  • RaHe Co PP is an abbreviation for random heterophasic propylene copolymer.
  • the post-consumer recycled polyolefin composition may have a melt flow rate MFR2 (1 ) (i.e., the starting melt flow rate in the beginning of the process), determined according to ISO 1 133 at 2.16 kg load, 230 °C, in the range of from 1.0 to 100 g/10 min, preferably from 2.0 to 80 g/10 min, more preferably from 3.0 to 60 g/10 min.
  • MFR2 (1 ) i.e., the starting melt flow rate in the beginning of the process
  • the melt flow rate is usually changed by the application of step (B) and optional step (C), as described below.
  • the post-consumer recycled polyolefin composition may generally be present in form of particles, which are not limited by their geometry, as long as they contain enough surface for reaction in steps (B) and (C).
  • the postconsumer recycled polyolefin composition is present in pellet form having a median thickness T50, determined by direct caliper measurement, in the range of from 0.5 to 5.0 mm, preferably in the range of from 0.8 to 3.5 mm.
  • the pellets preferably are cylindrical or lens-shaped having a median diameter D50, determined by optical analysis using a high-speed camera, in the range of from 2.0 to 5.0 mm, preferably in the range of from 2.5 to 4.5 mm.
  • the post-consumer recycled polyolefin composition as required by the present invention may be prepared from pre-compositions based on post-consumer re- cyclates with other contents or forms.
  • post-consumer polymeric waste may be treated by different mechanical (e.g. sorting) processes, washing or chemical (e.g. dissolving) processes, in order to provide the post-consumer recycled polyolefin composition to be used in the process of the present invention.
  • the post-consumer recycled polyolefin composition may be provided in the desired size and form by extrusion at 180 to 300 °C, preferably from 200 to 280 °C, in a single- or twin-screw extruder, preferably a co-rotating twin- screw extruder, followed by a suitable pelletization process, in which the pellet thickness and diameter are defined.
  • suitable pelletization processes include underwater pelletization, water-ring pelletization and strand pelletization, the latter comprising solidification of one or more melt strands in a water bath followed by cutting the strand into pellets. In all cases, the pellet diameter is defined by the die diameter and the pellet length by the cutting frequency used in pelletization.
  • step (A) provision of the post-consumer recycled polyolefin composition in step (A) means that this composition is made available.
  • the post-consumer recycled polyolefin composition may be provided by already placing the composition in a reactor, where the further components are added. However, the composition may also be added to a reactor concurrently to the addition of step (B).
  • the post-consumer recycled polyolefin composition of step (A) may be provided at a temperature of from -20 to 90 °C, such as from 15 to 90 °C, particularly from 15 to 25 °C.
  • the post-consumer recycled polyolefin composition of step (A) may be melted prior to step (B), for example at 180 to 300 °C, preferably from 200 to 280 °C.
  • step (B) of the process of the present invention a radical initiator is added to the post-consumer recycled polyolefin composition and, optionally, the components are mixed to form a mixture (1 ).
  • the radical initiator is added in an amount of from 0.01 to 1.50 wt.-%, more preferably from 0.02 to 1 .20 wt.-% and most preferably from 0.03 to 1.00 wt.-%, based on the total weight of the post-consumer recycled polyolefin composition.
  • the radical initiator may be selected from any radical initiator suitable for a visbreaking reaction in propylene polymers.
  • the radical initiator is a carbon-carbon free radical compound, an azo compound, a stable nitroxyl compound, a sterically hindered NO-acyl compound or a peroxy compound.
  • the peroxy compound is preferably selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester, peroxycarbonate, and combinations thereof.
  • the radical initiator is tert-butylperoxy isopropyl carbonate.
  • the radical initiator is preferably added to the post-consumer recycled polyolefin composition as a liquid. As most of the radical initiators are solid compounds, they may be dissolved in a liquid prior to addition.
  • the components are preferably mixed to form a mixture (1 ).
  • Mixing is preferably carried out by contacting the components for a time of at least 2 minutes, preferably a time in the range of from 5 to 30 min, more preferably from 8 to 25 min, in order to reach relatively homogeneous absorption of the radical initiator by the post-consumer recycled polyolefin composition.
  • step (B) is performed in a flow-through reactor, such as a horizontal mixer with paddle stirrer, preferably in a continuous mode.
  • the post-consumer recycled polyolefin and the radical initiator may be added in parallel streams into a flow-through reactor.
  • the flow- through reactor is a horizontal flow-through reactor, and the components may be transported through the reactor by means of transporting paddles. In this way, very efficient absorption of the radical initiator by the post-consumer recycled polyolefin is reached.
  • other reactors may be used, where, for example, the radical initiator is added to a reactor after the post-consumer recycled polyolefin composition has been placed therein.
  • Step (B) is preferably performed at a temperature in the range of from 20 to 90 °C, more preferably from 40 to 80 °C.
  • step (B) may be performed at a higher temperature in the range of for example from 180 to 300 °C, such as from 200 to 280 °C.
  • step (C) is applied or not
  • different temperatures for step (B) may be used. For example, if step (C) is not used, higher temperatures may be used for step (B).
  • step (C) where step (C) is subsequently used, it is essential that the process does not involve visbreaking, i.e. , subjecting any intermediate product to reaction with the radical initiator in the absence of the twofold unsaturated hydrocarbon compound.
  • step (C) is preferably performed subsequently to step (B).
  • steps (B) and (C) are carried out concurrently, by simultaneous addition of the radical initiator and the twofold unsaturated hydrocarbon compound (e.g., in a masterbatch). In these embodiments, only one mixture (mixture (2)) is formed.
  • the process of the present invention usually increases the melt flow rate of the post-consumer recycled polyolefin composition.
  • polypropylene chains in the post-consumer recycled polyolefin composition mainly break, leading to narrower molecular weight distribution (MWD) and increase of melt flow rate (MFR).
  • the modified polyolefin composition has a second melt flow rate MFR2 (B) (i.e., the melt flow rate of the final modified polyolefin composition after application of step (B) without step (C)), determined according to ISO 1133 at 2.16 kg load, 230 °C, in the range of from 20 to 300 g/10 min and more preferably from 30 to 270 g/10 min.
  • MFR2 B
  • the modified polyolefin composition which was prepared by the use of step (B) and without step (C) has a homogenized molecular weight, which is observed by a narrowed molecular weight distribution (MWD), determined according to the GPC method and expressed by the ratio between weight average molecular weight (Mw) and number average molecular weight (Mn).
  • Mw/Mn also called polydispersity
  • Figure 4 depicts a respective change of polydispersity.
  • Step (C) is an optional step of the process of the present invention.
  • step (C) if present - a twofold unsaturated hydrocarbon compound having the general formula (1 ) is added:
  • the twofold unsaturated hydrocarbon compound having the general formula (1 ) is added in an amount of from 0.05 to 0.50 wt.-%, more preferably from 0.08 to 0.45 wt.-% and most preferably from 0.10 to 0.40 wt.-%, based on the total weight of the post-consumer recycled polyolefin composition.
  • Formula (1 ) encompasses the formulas (1 a) and (1 b):
  • the twofold unsaturated hydrocarbon compound of formula (1 ) is 1 ,3-butadiene (i.e., R is absent in formula (1 )).
  • the residue R in the twofold unsaturated hydrocarbon compound of formula (1 ) is selected from the group consisting of methylene, ethylene, propylene, n-butylene, tert-butylene, n-pentylene, i-pentylene, tertpentylene, n-hexylene, tert-hexylene, i-hexylene, neo-hexylene and phenylene.
  • the twofold unsaturated hydrocarbon compound may be added in its natural aggregate state at the addition temperature.
  • the twofold unsaturated hydrocarbon compound is added in form of a gas.
  • Mixing of the components is performed in order to reach good absorption of the unsaturated hydrocarbon compound and the radical initiator by the post-consumer recycled polyolefin composition.
  • Mixing may be performed in any kind of reactor, preferably any reactor suitable for a solid-gas reaction.
  • Mixing time is preferably in the range of from 1 s to 30 min, more preferably from 2 s to 5 min.
  • the reactor is a vertical flow-through reactor, wherein the particles of the post-consumer recycled polyolefin composition are transported via gravity.
  • the unsaturated hydrocarbon compound is added to this reactor as a stream and mixing is performed during the fall motion of the postconsumer recycled polyolefin composition in the stream of the unsaturated hydrocarbon compound.
  • Step (C) is preferably performed at a temperature in the range of from 20 to 90 °C, more preferably from 40 to 80 °C.
  • step (C) the process of the present invention decreases the melt flow rate of the post-consumer recycled polyolefin composition.
  • MFR melt flow rate
  • the modified polyolefin composition has a third melt flow rate MFR2 (C) (i.e., the melt flow rate after application of steps (B) and (C) of the process), determined according to ISO 1 133 at 2.16 kg load, 230 °C, in the range of from 0.1 to 50 g/10 min, more preferably from 0.1 to 40 g/10 min and most preferably from 0.1 to 30 g/10 min.
  • MFR2 C
  • the third melt flow rate is only present if step (C) is used. In this case, the second melt flow rate does not exist.
  • the ratio of MFR2 (C) : MFR2 (1 ) is below 1.00 and more preferably below 0.90. It is further preferred that the ratio of MFR2 (C) : MFR2 (1 ) is in the range of from 0.01 to 0.95 and more preferably from 0.01 to 0.90.
  • the reduced melt flow rate makes the resultant modified polyolefin composition highly convenient in processing and suitable for reuse in a variety of polyolefin applications, requiring enhanced mechanical stability.
  • the modified polyolefin composition which was prepared by the use of step (B) and (C) has a homogenized molecular weight, which is reached by chain breaking in the reaction of the radical initiator and the controlled crosslinking by the unsaturated hydrocarbon compound.
  • the modified polyolefin composition is changed in its properties by the controlled introduction of long chain branching.
  • Excellent results in terms of processability and further application options are obtained for post-consumer recycled polyolefin compositions with different ratios of propylene polymers to ethylene polymers. This was unexpected as reaction with radical initiators leads to different mechanism of action in propylene polymers versus ethylene polymers. While visbreaking occurs in propylene polymers, ethylene polymers normally form highly crosslinked structures upon reaction with a radical initiator.
  • step (C) in the process of the present invention turns this problem into a possible advantage by combining the chain fracture in the propylene polymers with the branching and crosslinking reactions in ethylene polymers and involving some cross-polymer reactions leading to improved compatibility.
  • the molecular weight distribution of the modified polyolefin composition may be unamended when compared to the post-consumer recycled polyolefin composition, or may be changed.
  • the polydispersity determined according to the GPC method, is in the range of from 5 to 15, more preferably from 6 to 14 and most preferably from 7 to 13.
  • Figure 3a depicts polydispersities of treated and untreated post-consumer recycled polyolefin compositions.
  • Figure 3b indicates introduction of long-chain branching of treated postconsumer recycled polyolefin compositions.
  • Branched polypropylene shows higher melt strength with increasing shear applied on the polymer such as during melt extrusion. This property is well-known as strain hardening.
  • strain hardening In the Rheotens test, the strain hardening behavior of polymers is analyzed by Rheotens apparatus (product of Gdttfert, Siemensstr. 2, 74711 Buchen, Germany) in which a melt strand is elongated by drawing down with a defined acceleration. The haul-off force F in dependence of draw-down velocity v is recorded. The test procedure is performed at a temperature of 23 °C. Further details are given in the experimental part.
  • the modified polyolefin composition is preferably characterized by improved strength properties, indicated by at least one of the following parameters: a) an F30 melt strength, determined according to Rheotens method, ISO 16790:2005, in the range of from 3.5 to 30.0 cN, more preferably from 4.0 to 25.0 cN and most preferably from 4.5 to 22.0 cN; b) a V30 melt extensibility, determined according to Rheotens method, ISO 16790:2005, in the range of from 150 to 300 mm/s, more preferably from 155 to 290 mm/s and most preferably from 160 to 280 mm/s; c) an F30/MFR2 (C) value of at least 0.5 cN 10 min/g, and/or a value in the range of from 0.5 to 80.0 cN 10 min/g; d) a V30/MFR2 (C) value of at least 20 mm-600/g, more preferably 50 mm -600
  • Step (D) is performed subsequently to step (B) or, if step (C) is present, subsequently to step (C).
  • step (D) of the process of the present invention the mixture (1 ) or (2) comprising the post-consumer recycled polyolefin composition, the radical initiator and optionally the twofold unsaturated hydrocarbon compound is extruded.
  • Extrusion is preferably carried out at a temperature in the range of from 180 to 300 °C, preferably from 200 to 280 °C, to obtain an extruded polyolefin composition.
  • the post-consumer recycled polyolefin is generally melted.
  • Extrusion may be carried out in any conventional way known in the art.
  • extrusion is carried out in a continuous melt mixing device like a single screw extruder, a co-rotating twin screw extruder or a co-kneader.
  • the barrel temperature is preferably in the range of from 200 to 280 °C.
  • the screw speed of the melt mixing device preferably is adjusted to a range of from 100 to 750 rotations per minute (rpm).
  • the melt mixing device includes a feed zone, a kneading zone and a die zone and a specific temperature profile is maintained along the screw of the melt-mixing device, having an initial temperature T1 in the feed zone, a maximum temperature T2 in the kneading zone and a final temperature T3 in the die zone, all temperatures being defined as barrel temperatures.
  • Barrel temperature T 1 (in the feed zone) is preferably in the range of from 180 to 260 °C.
  • Barrel temperature T2 (in the kneading zone) preferably is in the range of from 180 to 300 °C.
  • Barrel temperature T3 (in the die zone) preferably is in the range of from 180 to 280 °C.
  • one part or the entire process of the present invention is performed as a continuous process under the use of the flow-through reactors described above, and with direct transport of the mixture (1 ) or (2) prepared in the step (B) or (C) into an extruder to prepare the extruded polyolefin composition.
  • the extruded polyolefin composition is preferably pelletized either in an underwater pelletizer or after solidification of one or more strands in a suitable pelletization process.
  • suitable pelletization processes include underwater pelletization, water-ring pelletization and strand pelletization, the latter comprising solidification of one or more melt strands in a water bath followed by cutting the strand into pellets.
  • Step (E) is performed subsequently to step (D). Between step (D) and step (E), an optional pelletization of the extruded polyolefin composition may be carried out.
  • step (E) the extruded polyolefin composition is contacted with a solvent.
  • Step (E) aims to reduce the content (in the extruded polyolefin composition) of volatile organic compounds (VOC) and/or semi-volatile organic compounds (FOG) via extraction thereof.
  • the solvent may be any solvent suitable to dissolve volatile (VOC) and/or semivolatile organic compounds (FOG) from the extruded polyolefin composition.
  • the solvent may be selected from the group consisting of n-alkanes having from 4 to 10 carbon atoms, cycloalkanes having from 4 to 10 carbon atoms, halogenated n-alkanes having from 4 to 10 carbon atoms, aldehydes having from 3 to 10 carbon atoms, ketones having from 3 to 10 carbon atoms and mixtures thereof.
  • the solvent may be selected from the group consisting of n-alkanes having from 4 to 10 carbon atoms, cycloalkanes having from 4 to 10 carbon atoms, aldehydes having from 3 to 10 carbon atoms, ketones having from 3 to 10 carbon atoms and mixtures thereof.
  • n-alkanes are n-butane, n-pentane, n-hexane, n-heptane, n-octane, n- nonane and n-decane and mixtures thereof, with n-hexane, n-heptane and n- octane being preferred. Very good dissolution of volatile and/or semi-volatile organic compounds was obtained with n-heptane.
  • cycloalkanes are cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and mixtures thereof, with cyclohexane, cycloheptane and cyclooctane being preferred
  • Particular halogenated n-alkanes are chlorinated n-alkanes, such as chlorinated n-butane, chlorinated n-pentane, chlorinated n-hexane, chlorinated n-heptane, chlorinated n-octane, chlorinated n-nonane and chlorinated n-decane and mixtures of thereof.
  • chlorinated n-alkanes such as chlorinated n-butane, chlorinated n-pentane, chlorinated n-hexane, chlorinated n-heptane, chlorinated n-octane, chlorinated n-nonane and chlorinated n-decane and mixtures of thereof.
  • aldehydes and ketones are acetone, methyl iso-butyl ketone or methyl ethyl ketone, with methyl ethyl ketone being preferred. Very good dissolution of volatile and/or semi-volatile organic compounds was obtained with methyl ethyl ketone.
  • the solvent is a solvent with a boiling point of less than 120 °C, preferably with a boiling point in the range of from 50 °C to less than 120 °C.
  • the solvent is selected from the group consisting of n-alkanes having from 4 to 10 carbon atoms, cycloalkanes having from 4 to 10 carbon atoms, ketones having from 3 to 10 carbon atoms, and any mixtures thereof.
  • the solvent is selected from the group consisting of n-alkanes having from 4 to 10 carbon atoms, cycloalkanes having from 4 to 10 carbon atoms, and any mixtures thereof.
  • the solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- decane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and methyl ethyl ketone, more preferably the solvent is n-hexane, n-heptane, n-octane, cyclohexane, cycloheptane, cyclooctane or any mixture thereof, most preferably the solvent is n-hexane, n-heptane, n-oc- tane or any mixture thereof.
  • the ratio (wt./wt.) of the extruded polyolefin composition to the solvent in step (E) is preferably in the range of from 1 :3 to 1 :20, more preferably from 3: 1 to 10: 1 and most preferably from 3:1 to 5: 1 , such as 4: 1 .
  • Step (E) is preferably performed at a temperature in the range of from 50 to 120 °C, more preferably from 70 to 110 °C and most preferably from 80 to 100 °C. In some embodiments, step (E) is performed by heating the contacted components under reflux.
  • Step (E) is preferably performed for a period of from 30 to 180 minutes, preferably from 60 to 150 minutes.
  • the residence time of the extruded polyolefin composition with the solvent is from 30 to 180 minutes, preferably from 60 to 150 minutes.
  • Step (E) may be performed in a broad range of pressures.
  • step (E) is performed in a pressure range of from 0.1 MPa abs. to 5.1 MPa abs., more preferably at atmospheric pressure (i.e., ca. 0.1 MPa abs.).
  • step (E) is performed at a temperature in the range of from 50 to 120 °C for a period of from 30 to 180 minutes and in a pressure range of from 0.1 MPa abs. to 5.1 MPa abs.
  • step (E) is carried out under agitation.
  • any reactor where agitation is possible can be used.
  • step (E) is carried out in a continuous stirred tank reactor.
  • a tubular reactor can be used.
  • the process of the present invention is performed as a continuous process under the use of the flow-through reactors described above, and with direct transport of the extruded polyolefin composition into the reactor of step (E).
  • step (F) that follows step (E), the solvent is removed to obtain the modified polyolefin composition.
  • Solvent removal can be carried out by a method known in the art for this application.
  • the solvent is removed by filtration.
  • solvent is removed by agitation under reduced pressure, i.e. , of less than 0.1 MPa abs., such as 1 ,000 to 10,000 Pa abs. Agitation under reduced pressure can be carried out for 1 to 24 hours, preferably for 10 to 15 hours.
  • filtration and/or agitation under reduced pressure are used for solvent removal.
  • the solvent is removed to obtain the modified polyolefin composition in a dry form.
  • a drying step is carried out subsequently to step (F).
  • step (F) By removal of the solvent in step (F), high amounts of volatile (VOC) and semivolatile organic compounds (FOG) are removed from the extruded polyolefin composition.
  • volatile volatile
  • FOG semivolatile organic compounds
  • the extraction steps (E) and (F) reduce the amount of these compounds by 50 % or more (when compared to the extruded polyolefin composition before step (E)).
  • Concurrently also other contaminants may be removed by the extraction steps.
  • polyethylene and polypropylene waxes and polystyrene may also be removed.
  • the process of the present invention reduces the content of low-boiling substances (LBS) by at least 60 %, preferably by at least 70 %, and/or the content of high-boiling substances (HBS) by at least 50 %, preferably by at least 60 %, the contents being determined as described herein below. More preferably, the content of LBS and HBS is reduced by the above-indicated percentage.
  • LBS low-boiling substances
  • HBS high-boiling substances
  • the modified polyolefin composition is obtained, which preferably has, determined as described herein below, i) a content of low-boiling substances (LBS) of less than 100 ppm, preferably less than 80 ppm and more preferably less than 60 ppm; and/or ii) a content of high-boiling substances (HBS) of less than 200 ppm, preferably less than 180 ppm and more preferably less than 160 ppm.
  • LBS low-boiling substances
  • HBS high-boiling substances
  • the process comprising steps of (A) to (F) - with step (C) being optional - may be combined with a solvent based recycling (SbR) process for the removal of further contaminants.
  • the modified polyolefin composition may be obtained with even higher purity (less amounts of contaminants).
  • SbR-processing a polymer will be initially dissolved in an appropriate solvent and following, either the solubility of the dissolved polymer will be decreased by the addition of a non-solvent (dissolution/precipitation) and/or a solidification of the polymer will be caused by the preferably complete separation of the solvent from the solidified polymer by thermal unit operations (evaporation, drying etc.).
  • WO2022/219091 and WO 2022/219092 discloses a_solvent based recycling process for recycling waste polymer material.
  • the process comprises the following steps: the steps of
  • step (E) optionally adding at least one polyolefin dissolving solvent, wherein the at least one polyolefin dissolving solvent may be the same or different from the solvent in step (E), preferably wherein the at least one polyolefin dissolving solvent has a boiling point at 1 bar of equal to or more than 70 °C, such as within the range of from 75 to 250 °C, particularly from 80 to 220 °C, more particularly from 80 and 180 °C (for example, one or more C4-C10 alkanes and/or C4-C10 cycloalkanes, for example cyclohexane, n-hexane, n-heptane and/or n-octane);
  • the process may be performed in an continuous manner where preferably the (first) solvent (used as extraction solvent) comprise one or more C4-C10 n-al- kanes and the at least one polyolefin dissolving solvent preferably comprises one or more C4-C10 n-alkanes, more preferably the (first) solvent (extraction solvent) is equivalent to the at least one polyolefin dissolving solvent, for example both being n-hexane or n-heptane or n-octane.
  • the (first) solvent used as extraction solvent
  • the at least one polyolefin dissolving solvent preferably comprises one or more C4-C10 n-alkanes
  • the (first) solvent (extraction solvent) is equivalent to the at least one polyolefin dissolving solvent, for example both being n-hexane or n-heptane or n-octane.
  • the process may contain further steps which are conventional to a solvent-based polyolefin recycling process.
  • the post-consumer recycled polyolefin composition process as provided in step (A) of the process as herein described may originate from a solvent-based polyolefin recycling process.
  • the process of the present invention may be characterized by the following further properties.
  • additives may be added to the mixture.
  • common additives for preparation processes of polyolefins such as modifiers, stabilizers, antistatic agents, lubricants, nucleating agents, foam nucleators, acid scavengers, UV stabilizers, slip agents and pigments, as well as fillers and reinforcement agents may be added.
  • the advantage of the post-consumer recycled polyolefin composition is that it usually contains additives from the preparation processes of virgin polymers and first-use articles, meaning that the further addition of additives may not be required at all. If, however, especially stabilizers like primary and secondary antioxidants have been consumed during the processing and usage phase, addition of stabilizers in suitable amounts is preferred.
  • the present invention is also directed to the modified polyolefin composition obtained by the process of the present invention in any of the above-described embodiments.
  • the modified polyolefin composition may be in any of these embodiments.
  • the modified polyolefin composition has a low content of volatile (VOC) and/or semi-volatile organic compounds (FOG).
  • VOC volatile
  • FOG semi-volatile organic compounds
  • the modified polyolefin composition is characterized by, determined as described herein below, i) a content of low-boiling substances (LBS) of less than 100 ppm, preferably less than 80 ppm and more preferably less than 60 ppm; and/or ii) a content of high-boiling substances (HBS) of less than 200 ppm, preferably less than 180 ppm and more preferably less than 160 ppm, more preferably both.
  • LBS low-boiling substances
  • HBS high-boiling substances
  • modified polyolefin compositions with less unwanted odor and/or taste.
  • the modified polyolefin compositions can find application where odor and taste are important. These compounds are sometimes connected with health issues. Thus, the elimination thereof is of health benefit for the user. Further, explosive atmospheres can be avoided which facilitates handling these polyolefin compositions.
  • the modified polyolefin composition is preferably characterized by a xylene hot insoluble (XHU) fraction, determined according to EN 579, in an amount in the range of from 0.0 to 3.5 wt.-%, more preferably from 0.1 to 3.0 wt.-% and most preferably from 0.1 to 2.5 wt.-%, based on the total weight of the modified polyolefin composition.
  • XHU xylene hot insoluble
  • the present invention is also directed to the use of an article comprising the modified polyolefin composition in any of the above-described embodiments and prepared by the process of the present invention.
  • the article is preferably a foamed article, a film or an extrusion coating.
  • the article is a foamed article, a film or an extrusion coating, and comprises more than 50 wt.-%, preferably more than 75 wt.-%, such as 90 wt.-%, of the modified polyolefin composition, based on the total weight of the article.
  • the article is a foamed article comprising more than 50 wt.-%, preferably more than 75 wt.-%, such as 90 wt.-%, of the modified polyolefin composition, based on the total weight of the foamed article, and the modified polyolefin composition has an MFR2, determined according to ISO 1 133 at 2.16 kg load, 230 °C, in the range of from 0.1 to 1.5 g/10 min.
  • the article is a film or an extrusion coating, preferably for substrates such as paper, metal, woven or non-woven textiles, comprising more than 50 wt.-%, preferably more than 75 wt.-%, such as 90 wt.-%, of the modified polyolefin composition, based on the total weight of the film or extrusion coating, respectively, and the modified polyolefin composition has an MFR2, determined according to ISO 1133 at 2.16 kg load, 230 °C, in the range of from 1.5 to 10.0 g/10 min.
  • the melt flow rate (MFR) was determined according to ISO 1 133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability and hence the processability of the polymer.
  • the MFR2 was determined at a temperature of 230 °C and under a load of 2.16 kg.
  • the test described herein follows ISO 16790:2005.
  • the strain hardening behavior was determined by the method as described in the article "Rheotens-Master- curves and Drawability of Polymer Melts", M. H. Wagner, Polymer Engineering and Science, Vol. 36, pages 925 to 935.
  • the strain hardening behavior of polymers was analyzed with a Rheotens apparatus (product of Gdttfert, Sie- mensstr.2, 7471 1 Buchen, Germany) in which a melt strand is elongated by drawing down with a defined acceleration.
  • the Rheotens experiment simulates industrial spinning and extrusion processes. In principle a melt is pressed or extruded through a round die and the resulting strand is hauled off. The stress on the extrudate is recorded as a function of melt properties and measuring parameters (especially the ratio between output and haul-off speed, practically a measure for the extension rate).
  • the gear pump was pre-adjusted to a strand extrusion rate of 5 mm/s, and the melt temperature was set to 200 °C.
  • the spinline length between die and Rhe- otens wheels was 80 mm.
  • the take-up speed of the Rheotens wheels was adjusted to the velocity of the extruded polymer strand (tensile force zero). Then the experiment was started by slowly increasing the take-up speed of the Rheotens wheels until the polymer filament breaks.
  • the acceleration of the wheels was small enough so that the tensile force was measured under quasi-steady conditions.
  • the acceleration of the melt strand drawn down is 120 mm/s 2 .
  • the Rheotens was operated in combination with the PC program EXTENS. This is a real-time data-acquisition program, which displays and stores the measured data of tensile force and drawdown speed.
  • the end points of the Rheotens curve (force versus pulley rotary speed) is taken as the F30 melt strength and drawability values.
  • SHF Strain hardening factor
  • the strain hardening factor is defined as wherein ii E + (t,s) is the uniaxial extensional viscosity; and n + LVE t> is three times the time dependent shear viscosity in the linear range of deformation.
  • the linear viscoelastic data (G’, G” (co)) is obtained by frequency sweep measurements undertaken at 180 °C on a Anton Paar MCR 300 coupled with 25 mm parallel plates.
  • the underlying calculation principles used for the determination of the discrete relaxation spectrum are described in Baumgartel M, Winter HH, “Determination of the discrete relaxation and retardation time spectra from dynamic mechanical data”, Rheol.Acta 28:51 1519 (1989).
  • IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of N Maxwell modes wherein g,and 2 ; are material parameters and G s the equilibrium modulus.
  • N used for determination of the discrete relaxation spectrum
  • N used for determination of the discrete relaxation spectrum
  • the equilibrium modulus G e was set at zero.
  • the non-linear fitting used to obtain 7 ⁇ (0 is performed on IRIS Rheo Hub 2008, using the Doi- Edwards model.
  • the uniaxial extensional viscosity is obtained from uniaxial extensional flow measurements, conducted on an Anton Paar MCR 501 coupled with the Sentmanat extensional fixture (SER-1 ).
  • the temperature for the uniaxial extensional flow measurements was set at 180 °C, applying extension (strain) rates ds/dt ranging from 0.3 s -1 to 10 s -1 and covering a range of Hencky strain
  • the strain hardening factor (SHF) was determined at 180 °C at a strain rate of 1 s’ 1 and a Hencky strain of 2.5. XHU fraction
  • the xylene hot insoluble (XHU) fraction was determined according to EN 579. About 2.0 g of the polymer (m P ) was weighted and put in a mesh of metal which was weighted, the total weight being represented by (m P+m ). The polymer in the mesh was extracted in a soxhlet apparatus with boiling xylene for 5 hours. The eluent was then replaced by fresh xylene and boiling was continued for another hour. Subsequently, the mesh was dried and weighted again (rnxHu+m).
  • the average pellet dimensions of the PCR polyolefin composition were determined by two methods applied for thickness and diameter respectively.
  • Median pellet thickness, T50 is calculated from manually measuring the thickness of 10 pellets with a standardized caliper.
  • Median pellet diameter, D50 is determined by optical measurement on pellets with a high-speed CCD camera, type PS25C of OCS GmbH, Germany.
  • NMR nuclear-magnetic resonance
  • TCE-c/2 7,2-tetrachloroethane-cfo
  • Standard single-pulse excitation was employed utilising the NOE and bilevel WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transients were acquired per spectra.
  • Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.
  • the tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001 ) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251 ).
  • the isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:
  • the comonomer fraction was quantified using the method of Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1 157) through integration of multiple signals across the whole spectral region in the 13 C ⁇ 1 H ⁇ spectra. This method was chosen for its robust nature and ability to account for the presence of regiodefects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents. For systems where only isolated ethylene in PPEPP sequences was observed the method of Wang et al. was modified to reduce the influence of non-zero integrals of sites that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to:
  • Molar mass averages (Mw and Mn) and polydispersity Mw/Mn, were determined by Gel Permeation Chromatography (GPC) according to ASTM D 6474-99 using the following formulas: where Ai and Mi are the chromatographic peak slice area and polyolefin molecular weight (MW). Mn is referred to as the number average molar mass, Mw is referred to as the weight average molar mass and Mz is referred to as the Z-average molar mass.
  • a PolymerChar GPC instrument equipped with infrared (IR) detector was used with 3 x Olexis and 1x Olexis Guard columns from Polymer Laboratories and 1 ,2,4-trichlorobenzene (TCB, stabilized with 250 mg/l 2,6-Di-tert-butyl-4-methyl- phenol) as solvent at 160 °C and at a constant flow rate of 1 ml/min. 200 pL of sample solution were injected per analysis.
  • the column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 1 1500 kg/mol.
  • PS narrow MWD polystyrene
  • the polymer sample was dissolved at a concentration of 1 mg/ml at 160°C for 150min in TCB. 200 pl of the polymer solution were injected per analysis.
  • the inter-detector volume between the different detectors, concentration (IR), LS and viscometer detector was achieved by analysing a narrow distributed PS standard having a molar mass of 30000 g/mol.
  • the normalisation of the different MALS angles was obtained with a narrow distributed PS standard having a molar mass of 30.000 g/mol.
  • the MALS detector was calibrated with certified PE standard, NIST1475a with a Mw of 54.000 g/mol using a dn/dc of 0.094 ml/mg at a laser wavelength (Ao) of 660 nm.
  • the laser wavelength (Ao) of 660 nm and a dn/dc of 0,094 ml/mg for the PP in TCB solution were used.
  • the crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160 °C, crystallization at 40 °C and re-dissolution in 1 ,2,4- trichlorobenzene at 160 °C.
  • Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an integrated infrared detector (IR4) and for the determination of the intrinsic viscosity (IV) an online 2-capillary viscometer is used.
  • the IR4 detector is a multiple wavelength detector measuring IR absorbance at two different bands (CH3 stretching vibration (centred at app. 2960 cm -1 ) and the CH stretching vibration (2700-3000 cm -1 ) that are serving for the determination of the concentration and the ethylene content in ethylene-propylene copolymers.
  • the IR4 detector is calibrated with series of 8 ethylene-propylene (EP) copolymers with known ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13 C-NMR) and each at various concentrations, in the range of 2 and 13 mg/ml.
  • EP ethylene-propylene
  • CH 3 /1000C a + b*Abs(CH) + c* Abs(CH 3 (Abs(CH 3 )/Abs(
  • the CH 3 /1000C is converted to the ethylene content in wt.-% using following relationship:
  • Wt.-% (ethylene in EP copolymers) 100 - CH 3 /1000TC * 0.3
  • the samples to be analyzed are weighed out in concentrations of 10 mg/ml to 20 mg/ml. To avoid injecting possible gels and/or polymers which do not dissolve in TCB at 160 °C, like PET and PA, the weighed out sample was packed into a stainless steel mesh MW 0.077/D 0.05 mm.
  • the sample is dissolved at 170 °C until complete dissolution is achieved, usually for 60 min, with constant stirring of 400 rpm. To avoid sample degradation, the polymer solution is blanketed with the N2 atmosphere during dissolution.
  • BHT 2,6-tert- butyl-4-methylphenol
  • a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at high temperature, determining the IV [dl/g] and the C2 [wt.-%] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are measured (wt.-% SF, wt.-% C2, IV). A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times.
  • the whole sample is measured at high temperature, determining the IV [dl/g] and the C2 [wt%] of the PP composition.
  • DSC Differential scanning calorimetry
  • the crystallinity was calculated from the melting enthalpy by assuming an Hm-value of 209 J/g for a fully crystalline polypropylene resp. 293 J/g for a fully crystalline polyethylene (see Brandrup, J., Immergut, E. H., Eds. Polymer Handbook, 3rd ed. Wiley, New York, 1989; Chapter 3).
  • the pressing process would be repeated three times to increase homogeneity by pressed and cutting the sample in the same conditions as described before.
  • Standard transmission FTIR spectroscope such as Bruker Vertex 70 FTIR spectrometer is used with the following set-up:
  • Borealis HC600TF as iPP
  • Borealis FB3450 as HDPE
  • RAMAPET N1 S Indorama Polymer
  • Ultramid® B36LN BASF
  • Styrolution PS 486N Ineos
  • HIPS High Impact Polystyrene
  • PVC Inovyn PVC 263B under powder form
  • Additional antioxidant such as Irgafos 168 (3000 ppm) is added to minimise the degradation.
  • the FTIR calibration principal is the same for all the components: the intensity of a specific FTIR band divided by the plate thickness is correlated to the amount of component determined by 1 H or 13C solution state NMR on the same plate.
  • Each specific FTIR absorption band is chosen due to its intensity increase with the amount of the component concentration and due to its isolation from the rest of the peaks, whatever the composition of the calibration standard and real samples.
  • a linear calibration (based on linearity of Beer-Lambert law) is constructed.
  • Ei is the absorbance intensity of the specific band related to the polymer component i (in a.u. absorbance unit). These specific bands are, 3300 cm -1 for PA, 1601 cm -1 for PS, 1410 cm -1 for PET, 615 cm’ 1 for PVC, 1167 cm’ 1 for iPP d is the thickness of the sample plate
  • a and Bi are two coefficients of correlation determined for each calibration curve
  • the amount of each component is determined by either 1 H or 13 C solution state NMR, as primary method (except for PA).
  • the NMR measurements are performed on the exact same FTIR plates used for the construction of the FTIR calibration curves.
  • Thermogravimetric Analysis (TGA) experiments were performed with a Perkin Elmer TGA 8000 in line with ISO 3451 -1 (1997). Approximately 10-20 mg of material was placed in a platinum pan. The temperature was equilibrated at 50 °C for 10 minutes, and afterwards raised to 950 °C under nitrogen at a heating rate of 20 °C/min. The weight loss between ca. 550 °C and 700 °C (WCO2) was assigned to CO2 evolving from CaCOs, and therefore the chalk content was evaluated as:
  • Ash content (Ash residue) - 56/44 x WCO2 - Web where Ash residue is the wt.-% measured at 900 °C in the first step conducted under nitrogen.
  • the ash content is estimated to be the same as the talc content for the investigated recyclates.
  • the metal amount was determined by X-ray fluorescence (XRF).
  • PCR polyolefin composition Amount of Paper and Wood
  • Paper and wood amounts were determined by conventional laboratory methods including milling, floatation, microscopy and Thermogravimetric Analysis (TGA).
  • Enrichment of the volatile fraction was carried out by headspace solid phase micro-extraction with a 2 cm stable flex 50/30 pm DVB/Car- boxen/PDMS fibre at 60 °C for 20 minutes. Desorption was carried out directly in the heated injection port of a GCMS system at 270 °C.
  • Carrier gas Helium 5.0, 31 cm/s linear velocity, constant flow
  • MS Single quadrupole, direct interface, 280 °C interface temperature Acquisition: SIM scan mode Scan parameter: 20-300 amu
  • PCR polyolefin composition Total free fatty acid content
  • Fatty acid quantification was carried out using headspace solid phase micro extraction (HS-SPME-GC-MS) by standard addition.
  • Carrier Helium 5.0, 40 cm/s linear velocity, constant flow
  • This method describes the semi-quantitative determination of organic compounds emitting from polyolefins. It is similar to the VDA 278 (October 2011 ) but includes specific adjustments.
  • the sample injection molded plaque, DIN-A5
  • injection molded plaque DIN-A5
  • an aliquot of 60 ⁇ 5 mg is prepared from the stored sample. Trimming the aliquot should aim for a maximum coherent area. It is not the aim to create the largest possible surface area by cutting the aliquot into smaller pieces.
  • the diameter of the sample injection tube should be used first. Length and thickness should be chosen accordingly, considering the specified aliquot weight. The aliquot is directly desorbed using heat and a flow of helium gas.
  • Volatile and semi-volatile organic compounds are extracted into the gas stream and cryo-focused prior to the injection into a gas chromatographic (GC) system for analysis.
  • the method comprises two extraction stages: In the analysis of low-boiling substances (LBS) the aliquot is desorbed at 90 °C for 30 min to determine volatile organic compounds in the boiling I elution range up to n-C25 (n-pentacosane).
  • LBS low-boiling substances
  • HBS high-boiling substances
  • Integration parameters for the LBS and HBS evaluation are chosen in such way that the “area reject” corresponds to the area of 1 pg/g (TE and HE, respectively). Thus, smaller peaks do not add to the semi-quantitative result.
  • the GC oven program is kept the same, no matter if a calibration run, an LBS run or an HBS run was performed. It starts at 50 °C (1 min hold), followed by a ramp of 10 °C/min and an end temperature of 320 °C (10 min hold).
  • an Agilent DB5 50 m x 250 pm x 0.25 pm (or comparable) is used.
  • the method requires a Thermal Desorption System TDS 3 (Gerstel) and a Cooled Injection System CIS 4 (Gerstel) as well as a GC system with a flame ionisation detector (FID) but does not involve a mass spectrometer. Instead of 280 °C the CIS end temperature is always set to 380 °C.
  • PCR1 to PCR4 Four post-consumer recycled polyolefin compositions, PCR1 to PCR4, were used to prepare polyolefin compositions (“P”, hereinafter also referred to as “polyolefins”) by compounding either with only a radical initiator or a radical initiator and butadiene, followed by extrusion.
  • P polyolefin compositions
  • Table 2 PCR1 was used to prepare P1 and P2; PCR2 was used to prepare P5 and P6; PCR3 was used to prepare P3; and PCR4 was used to prepare P4.
  • the so prepared polyolefins P1 , P2, P5 and P6 were contacted with solvents to prepare the inventive examples, while the comparative examples did not contain this extraction step.
  • the polyolefins P3 and P4 were used for measuring several physical properties.
  • PCR polyolefin compositions Properties of the PCR polyolefin compositions are indicated in Table 1 below. The wt% in Table 1 is based on the total weight of the PCR composition (unless specifically indicated otherwise in the respective method description). Table 1 : Properties of PCR polyolefin compositions.
  • PCR post-consumer recycled
  • the pellets were mixed with peroxide (POX) as the radical initiator (tert-butylperoxy isopropyl carbonate, %Trigonox BPIC C75, obtained by Nouryon) in a horizontal mixer with paddle stirrer at a temperature of 65 °C, maintaining an average residence time of about 20 minutes.
  • POX peroxide
  • %Trigonox BPIC C75 tert-butylperoxy isopropyl carbonate
  • This mixture was transferred under inert atmosphere to a Theyson TSK60 co-rotating twin screw extruder having a barrel diameter of 60 mm and an L/D-ratio of 48 equipped with a high intensity mixing screw having three kneading zones and a two-step degassing setup.
  • the screw speed was set at 200 or 220 rpm.
  • the resulting polymer melt was pelletized in a Gala AW6 underwater pelletizer with a die plate of 24 holes of 2.4 mm diameter.
  • the PCR polyolefin composition were dry-blended with the peroxide and directly subjected to the extrusion step in a Coperion ZSK18 co-rotating twin-screw extruder using an analogous temperature profile as in the TSK60 above.
  • the resulting melt was extruded through a die plate, and the two strands were solidified in a waterbath followed by strand pelletization.
  • Table 3 Parameters of the extruded polyolefin compositions.
  • a first set of 4 polyolefins was combined with n-heptane. 4 g of polyolefin was added to 200 ml heptane. The polymer solvent mixture was heated for 2 hours at 98.4°C (under reflux). The insoluble fraction was separated from the solvent by filtration and was dried under vacuum (20-30 mbar) using a vacuum oven at 90°C for 12 hours to reduce the solvent content.
  • a second set of 4 polyolefins was combined with methyl ethyl ketone. 4 g of polyolefin was added to 200 ml methyl ethyl ketone. The polymer solvent mixture was heated for 2 hours at 79.6°C (under reflux). The insoluble fraction was dried under vacuum (20-30 mbar) using a vacuum oven at 90°C for 12 hours to reduce the solvent content.
  • a third set of 4 polyolefins was treated by agitation at 90°C for 12 hours under vacuum (20-30 mbar) using a vacuum oven. These polyolefins resulted in comparative examples CE5 to CE8. A fourth set of 4 pololefins remained untreated and resulted in comparative examples CE1 to CE4.
  • LBS low-boiling substances
  • HBS high-boiling substances
  • LBS and HBS low and high-boiling compounds
  • VOC volatile organic compounds
  • FOG semi-volatile organic compounds
  • Table 5 Physical properties of the extruded polyolefin compositions.

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Abstract

La présente invention concerne un procédé de modification d'une composition de polyoléfine à base de polypropylène recyclée après consommation. La présente invention concerne également une composition de polyoléfine modifiée obtenue par le procédé, ainsi qu'un article comprenant la composition de polyoléfine modifiée.
PCT/EP2024/081527 2023-11-08 2024-11-07 Procédé de modification pour recyclats de polymères Pending WO2025099166A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103030882A (zh) * 2012-12-04 2013-04-10 合肥杰事杰新材料股份有限公司 一种用于制备汽车保险杠的再生材料及其制备方法
EP3757152A1 (fr) 2019-06-28 2020-12-30 Borealis AG Mélange de polyéthylène - plastique modifié et à rhéologie contrôlée
WO2022090105A1 (fr) * 2020-10-28 2022-05-05 Basell Poliolefine Italia S.R.L. Compositions de polyoléfines obtenues à partir de polyoléfine recyclées
WO2022219091A1 (fr) 2021-04-15 2022-10-20 Borealis Ag Procédé de recyclage à base de solvant de polyoléfines
WO2022219092A2 (fr) 2021-04-15 2022-10-20 Borealis Ag Procédé de recyclage d'une polyoléfine

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Publication number Priority date Publication date Assignee Title
CN103030882A (zh) * 2012-12-04 2013-04-10 合肥杰事杰新材料股份有限公司 一种用于制备汽车保险杠的再生材料及其制备方法
EP3757152A1 (fr) 2019-06-28 2020-12-30 Borealis AG Mélange de polyéthylène - plastique modifié et à rhéologie contrôlée
WO2022090105A1 (fr) * 2020-10-28 2022-05-05 Basell Poliolefine Italia S.R.L. Compositions de polyoléfines obtenues à partir de polyoléfine recyclées
WO2022219091A1 (fr) 2021-04-15 2022-10-20 Borealis Ag Procédé de recyclage à base de solvant de polyoléfines
WO2022219092A2 (fr) 2021-04-15 2022-10-20 Borealis Ag Procédé de recyclage d'une polyoléfine

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