EP3315640A1 - Fibre de gazon artificiel à partir d'un polyethylene renouvelable - Google Patents

Fibre de gazon artificiel à partir d'un polyethylene renouvelable Download PDF

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Publication number
EP3315640A1
EP3315640A1 EP16196633.8A EP16196633A EP3315640A1 EP 3315640 A1 EP3315640 A1 EP 3315640A1 EP 16196633 A EP16196633 A EP 16196633A EP 3315640 A1 EP3315640 A1 EP 3315640A1
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EP
European Patent Office
Prior art keywords
polymer
artificial turf
lldpe
weight
carbon source
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EP16196633.8A
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German (de)
English (en)
Inventor
Ulrich NEUHOFF
Stephan Sick
Ivo LOHR
Dirk Sander
Bernd Jansen
Stefan HALLY
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Polytex Sportbelage Produktions GmbH
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Polytex Sportbelage Produktions GmbH
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Priority to EP20159358.9A priority Critical patent/EP3741886A1/fr
Priority to EP16196633.8A priority patent/EP3315640A1/fr
Priority to PCT/EP2017/077118 priority patent/WO2018077850A1/fr
Publication of EP3315640A1 publication Critical patent/EP3315640A1/fr
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/08—Surfaces simulating grass ; Grass-grown sports grounds

Definitions

  • This invention relates to artificial turf, and more particularly to a sustainable artificial turf production method.
  • Artificial turf is a surface of synthetic fibers that is commonly made to look like natural grass. It is often used in arenas for sports that were originally or are normally played on natural grass. However, other applications are known as well, e.g. privately owned gardens and courtyards.
  • Artificial turf does not need to be irrigated or trimmed and has many other advantages regarding maintenance effort and other aspects. Irrigation can be difficult due to regional restrictions for water usage. In other climatic zones the regrowing of grass and re-formation of a closed grass cover is slow compared to the damaging of the natural grass surface by playing and/or exercising on the field. Artificial turf does not need sunlight and thus can be used at places where there is not enough sunlight to grow natural grass. To ensure that artificial turf replicates the playing qualities of good quality natural grass, artificial turf needs to be made of materials which will not increase the risk of injury to players and which are of adequate durability. Many fields are subjected to very high intensity use relating to player-to-surface interactions and ball-to-surface interaction.
  • the surface of the artificial turf fibers must be smooth enough to prevent injuries to the skin of the players when sliding on the surface, but at the same time must be (sufficiently embedded into the substructure to prevent the fibers from, e. g. being pulled out of the carrier if a strong tuft withdrawal force is applied.
  • the materials used for producing artificial turf must have highly specific properties regarding smoothness, brittleness, resistance to shear forces etc.
  • bioplastics Although meanwhile some few types of “bioplastics” exist on the market which are manufactured from renewable sources of biomass, the properties of these bioplastics are not suited for producing artificial turf with the desired properties.
  • Polymeric material for the preparation of artificial turf fibers is versatile.
  • Polyethylene has shown advantageous in comparison with other polymers.
  • linear polyethylene (LLDPE and HDPE) offers a wide range of physical material properties, covering the technical requirements of artificial turf fibers.
  • the density of linear polyethylene can be widely modified by co-monomers.
  • the molecular weight distribution can be controlled with catalysts and by polymerization process management.
  • Catalysts can be of the multi-site species or of the single-site species. Multi-site catalysts are also referred to as Ziegler, Ziegler-Natta or Phillips catalysts.
  • Single-site catalysts are also referred to as metallocene catalysts.
  • multi-site catalysts results in polymers with relatively broad molecular weight distributions and co-monomer distributions compared with single-site catalysts.
  • EP1378592 (Slootweg et al. ) suggests a blend for artificial turf fibers comprising a first polymer with a bimodal molecular weight distribution and a second polymer; the first polymer being a plastomer with very low density and the second polymer being HDPE.
  • WO2006066777 (Lambert et al. ) teaches the manufacture of fibers made from blends; one component having a density of 920 to 940 g/l and the other component having a density of 900 to 960 g/l with a difference in density of no more than 20 g/l.
  • WO2008113566 (Van Paridon et al. ) describe single-site metallocene LLDPE with densities of less than 980 g/l and unimodal or bimodal molecular weight distribution as suitable for fiber preparation.
  • WO2008098905 (Buriani et al. ) describe blends of HDPE and very low density PE, the HDPE having a density of 930 to 965 g/l and the VLDPE having a density of 868 g/l.
  • WO2011134897 (Perdomi et al. ) describe blends of a first component, being a plastomer with densities lower than 900 g/l and a second component, being LLDPE with densities in a range of 900 to 945 g/l.
  • WO2012005974 (Sandkuehler et al. ) describe a blend of three components; the first being a metallocene LLDPE with densities from 850 to 905; the second being a Ziegler-LLDPE with densities from 910 to 945 and the third being HDPE with densities of greater than 945 g/l.
  • the invention in a first aspect, relates to a method of manufacturing artificial turf fibers which consist at least partially of a polymer made from a renewable carbon source.
  • the method comprises creating a polymer mixture which comprises a first polymer and a second polymer.
  • the polymer mixture comprises the first polymer in an amount of at least 57% by weight of the polymer mixture.
  • a portion of at least 30 % by weight of the first polymer is made from the renewable carbon source.
  • the polymer mixture comprises the second polymer in an amount of at least 8 % by weight of the polymer mixture.
  • the second polymer is HDPE.
  • biobased PE for artificial turf production was hitherto technically not feasible: throughout the typical usage time of 5-15 years, an artificial turf sports field must withstand high mechanical wear, must resist UV-radiation, must withstand thermal cycling or thermal ageing, must resist interactions with the players, sports equipment, chemicals and various environmental impacts.
  • the fibers of an artificial turf are heavily exposed to mechanical stress like kicking, jumping, slipping, etc. and environmental impact like temperature changes, ozone, sunlight irradiation, etc. Therefore, the material of the fibers has to be chosen well in order to withstand that kind of stress for a long period, which means it should be rigid and chemically stable.
  • the material should be soft enough to inhibit skin abrasions and irritations when rubbing on the surface. Rigidity and softness are excluding properties. Rigid polymers are not soft and vice versa. That means the properties have to be balanced out thoroughly.
  • bio-based polymers While a huge variety of petrobased polymers exist allowing manufacturers to simply order a PE variant with the desired properties, the market for biobased polymers is still comparatively small and only a very limited number of bio-based polymers exists. Available bio-based polymers do not have the desired properties to suit for the production of artificial turf fibers without modification. That means, plastic converters have to develop polymer mixtures or blends to create a suitable material. Although the density of the bio-based LLDPE is in the same range as the petro-based comparator, they differ to some extent in their mechanical properties and wear resistance. In particular, properties like tensile strength and tear resistance of bio-based PE are not in the desired range. This would cause breakdown of the fibers at an early stage of usage when the fibers would be generated from pure bio-based polymers.
  • a specific amount of HDPE referred herein as the "second polymer”
  • a specific (and larger) amount of a PE manufactured at least partially from a renewable carbon source a polymer blend is provided which is suited for being used in artificial turf fiber production.
  • the resulting artificial turf comprising biobased-PE fibers has a long usable life, is durable, and keeps its playing and surface characteristics as well as appearance throughout its usage time.
  • polyethylene On a molecular scale the rigidity or the hardness of polyethylene correlates with the crystallinity and the softness correlates with the amorphousness. Crystalline and amorphous states are also excluding each other. The more crystalline something is the less amorphous it is. Polyethylene consists of material in both states, i. e. crystalline matter embedded in an amorphous phase. The resistance to tensile forces and shear forces may also depend on the branching pattern of the PE molecules, i.e., the number and length of the branches of a PE molecule.
  • LLDPE that is completely or largely made from a renewable carbon source, and HDPE, a polymer blend is provided whose rigidity, softness and resistance to tensile and shear forces is suitable for producing artificial turf fibers that are largely based on bio-PE.
  • Combining a first and a second PE type may be advantageous as the physicochemical properties of the fiber depend on the properties of two different polymers. With only one component the filaments might lack either tensile strength or wear resistance.
  • Embodiments of the invention may allow producing bio-PE based artificial turf fibers having the same or almost the same physical properties as the conventional petro-based fibers.
  • Embodiments of the invention may also allow the manufacturing of bio-fibers (artificial turf fiber comprising a significant portion, e.g. 20 % by weight, polymers derived from a renewable carbon source) and petrobased fibers on the same extruder lines and at the same draw ratios, relaxation and/or texturing equipment as used for processing the petrobased fibers.
  • Embodiments of the invention may also allow the same haul-off speeds, i. e. the mass output at the extruder die face without melt fraction of the bio-based fibers.
  • the renewable carbon source can be, for example, biomass.
  • the biomass can be, for example, sugarcane, sugar beet, wheat grain, organic household waste, plant waste products, industrial organic waste of any kind, and others.
  • the material for the generation of PE may also originate from other renewable, non-fossil carbon sources, e.g. CO 2 , which itself cannot be referred to as biomass.
  • CO 2 non-fossil carbon sources
  • renewable carbon source any kind of carbon source that is used for producing a material whose 14 C atom content is similar or basically identical to the 14 C content of biomass of recently living organisms is referred to as renewable carbon source.
  • Atmospheric CO 2 is the source of radioactive carbon C14.
  • Fossil (petro-based) carbon sources comprise a lower amount of radioactive C14 isotopes and thus can be discerned from bio-based carbon sources by performing an isotope analysis (radiocarbon dating). Roughly half of all 14 C atoms decay after 5700 years.
  • Suitable carbon sources for the bio-based polymer mixture may be a manufacturing process or any other natural or man-made material or process that can be used to produce a chemical substance.
  • the first polymer is a linear low density polyethylene (LLDPE).
  • LLDPE linear low density polyethylene
  • the first polymer or at least a part of the first polymer is not one of the typically used and conventionally manufactured 1-olefin co-monomer based LLDPEs.
  • LLDPE is derived from ethylene originating from crude oil or natural gas. It is a product of the petrochemical refinery process.
  • bio-based LLDPE is derived from biomass or another renewable carbon source.
  • the bio-based LLDPE can be derived from bio-based ethanol by converting the ethanol into bio-ethylene in a dehydration reaction.
  • ethanol dehydration for generating bio-ethylene from bio-ethanol see for example " Ethylene formation by catalytic dehydration of ethanol: industrial considerations", Denise Fan, Der-Jong Dai, and Ho-Shing Wu, Materials, 6, 101-115 (2013 ); or " Catalytic dehydration of bioethanol to ethylene over TiO2/ ⁇ -Al2O3 catalysts in microchannel reactors", G. Chen, S. Li, F. Jiao, and Q.
  • bio-PE The amount of ethanol needed to make one metric ton of bio-PE is roughly two metric tons, as dehydration takes a part of the weight in water from the sugar cane based ethanol.
  • An important environmental benefit of bio-PE is the sequestration of roughly 2,15 ton of CO 2 per ton of bio-PE produced, which comes from the CO 2 absorbed by the sugar cane while growing, minus the CO 2 emitted through the production process.
  • LLDPE with 1-octene as the co-monomer for the preparation of blends for artificial turf fibers resulting in better tear resistance when compared with 1-hexene or 1-butene LLDPE in the density range between 916 and 920 g/l.
  • bio-based ethylene molecules do not differ from petrochemical comparators, despite the fact that biomass was the origin, the co-monomers seem to determine the mechanical properties of LLDPE-fibers.
  • the process of manufacturing currently available bio-based LLDPEs significantly differs from the process used for generating petro-based LLDPE with 1-octene as co-monomer.
  • bio-LLDPE and petro-LLDPEs on the market significantly differ from each other.
  • the currently available bio-LLDPE types are not suitable for manufacturing artificial turf fibers.
  • Applicant has surprisingly observed that my mixing bio-LLDPE with bio- and/or petro-based HDPE in a defined ratio yields a polymer blend that has the desired material properties.
  • the portion of the first polymer that is made from the renewable carbon source is a Ziegler/Natta catalyzed, gas-phase polymerized LLDPE generated from mixtures of polymerization educts.
  • the polymerization educts comprise ethylene as the main monomer and a co-monomer.
  • the co-monomer is 1-butene and/or 1-hexene.
  • the co-monomer or co-monomer mixture used for generating the bio-LLDPE portion is basically free of 1-octene or higher molecular monomers.
  • the co-monomer is contained in the polymerization educt mixture in an amount of 12-14% by weight of the polymerization mixture.
  • the portion of the first polymer that is made from the renewable carbon source is a linear low density polyethylene LLDPE having a density of 0.916 to 0.920 g/ml and a melt flow rate of 2 to 4 g/10 min at 190 °C / 2.16 kg.
  • the renewable LLDPE available on the market significantly differs from petro-based LLDPE, because petro-based LLDPE can be generated in a co-polymerization reaction with octene (which may optionally further comprise a minor fraction of "smaller" co-monomers like butene or hexene).
  • octene which may optionally further comprise a minor fraction of "smaller" co-monomers like butene or hexene.
  • 1-octene-co-polymers available are all petro-based. Usually 1-octene co-polymers are produced in a solution polymerization process, whereas butene and hexene co-polymers are produced in gas-phase reactors.
  • bio-LLDPE (petro-based) co-monomers having only 4 or 6 rather than 8 or more carbon atoms.
  • the bio-LLDPE on the market today is largely generated from bio-ethylene in a co-polymerization process with 1-butene, optionally also 1-hexene, but basically without 1-octene or higher 1-olefines for increasing the fraction of "bio-based" carbon atoms in the product.
  • 1-butene or 1-hexene instead of 1-octene as a co-monomer for generating bio-LLDPE has a significant impact on the material properties of the resulting bio-LLDPE.
  • the bio-LLDPE is generated in a gas-phase process, whereby 1-butene and/or 1-hexene are used as co-monomers.
  • the gas-phase polymerization process is a "Spherilene"-process (LyondeIIBasell) which can be run with one reactor (Spherilene S) for unimodal polymers or in two reactors in series (Spherilene C) for unimodal or bimodal polymers.
  • Catalysts can be, for example, Ziegler-Natta catalysts like Avant Z (Ziegler) or Avant C (Phillips).
  • bio-based LLDPEs significantly differs from the process used for generating petro-based LLDPE with 1-octene as co-monomer, the physicochemical properties of bio-LLDPE also differ and are less suited for use in artificial turf fiber production.
  • bio-LLDPE differs from petrobased LLDPE in that a smaller weight fraction of co-monomers (1-butene, 1-hexene) is incorporated in the polymeric material compared to conventionally produced, petrobased 1-octene LLDPE. This is because said co-monomers are synthesized from bio-alcohol. They are synthesized from crude oil. Thus, even "bio"-LLDPE does not completely consist of carbon atoms derived from renewable sources as the co-monomers used in the co-polymerization are petrobased.
  • a bio-PE consists of renewable sources in 1-butene co-polymers and up to 84 wt% in 1-hexene co-polymers.
  • 1-butene consists of 4 carbon atoms while 1-hexen consists of 6 carbon atoms, this explains the difference in the "bio-content" of LLDPEs.
  • 1-butene instead of 1-octene results in a reduced length of the side chains. This has a negative impact on the stiffness.
  • a co-monomer for producing the bio-LLDPE may be advantageous as the plastification of polymeric materials, i.e. the flexibility of the polymer, is increased.
  • Polymerizing a co-monomer together with ethylene lowers the density of the resulting polymer.
  • every 1-olefin or ⁇ -olefin can act as a co-monomer in the polymerization process, but for the above mentioned reasons, typically only 1-butene or 1-hexene is in use for copolymerization of bio-LLDPE. As these molecules carry a double bond between two carbon atoms, it is possible to insert them instead of an ethylene molecule into the growing chain of the macromolecule which forms in the polymerization process.
  • a side chain on the main chain.1-butene includes 4 carbon atoms and generates an ethyl side chain, whereas two carbon atoms (the two with the double bond between carbon atoms 1 and 2) are incorporated into the main chain and another two carbon atoms extent outwardly of that main chain as a side chain.
  • the length of the side chain is 4 carbon atoms and it is 6 with octene.
  • the number and the length of the side chain branching determine the density of LLDPE and thereby other physicochemical properties.
  • the side chain branching is heterogeneous or homogeneous.
  • the distance from one branching point to another branching point is broadly distributed along the polymer main chain. The other way round, the branches are more evenly spaced in homogeneous branched LLDPEs.
  • the molecular architecture may greatly be influenced by the choice of the catalyst used in the polymerization process.
  • Ziegler catalysts also referred to as Ziegler-Natta catalysts or multi-site catalysts, yield in heterogeneously branched polymers
  • metallocene catalysts also referred to as single-site catalysts
  • yield in homogeneously branched polymers It has also been observed that with Ziegler catalysts the co-monomers are preferably incorporated into the short length main chains, while the longer main chains deplete of co-monomers.
  • LLDPE Low Density Polyethylene
  • bio-LLDPE has a different molecular architecture concerning the side chain branching pattern which has been often observed not to fulfill the requirements, and thus, alone is not suited for artificial turf production, it has been observed that by combining "standard bio-PE" with the second polymer, an artificial turf fiber having the desired properties can be produced, whereby the production process significantly reduces the depletion of petrol oil sources.
  • artificial turf production companies which typically do not operate refinery plants on their own) can order LLDPE being at least partially based on a renewable carbon source and combine it with HDPE for providing artificial grass fibers having the desired properties.
  • the bio-portion of the LLDPE polymer is prepared from ethylene that was generated from biomass used as the renewable carbon source.
  • the first polymer can be prepared from ethylene generated from bio-ethanol, whereby the bio-ethanol may be derived from biomass or another renewable carbon source. This may be advantageous as several well established procedures for generating bio-ethanol from various renewable organic sources are already known.
  • the first polymer does not completely consist of the bio-based LLDPE but rather comprises a further portion of LLDPE.
  • the further portion consists of LLDPE made from fossil fuels.
  • the further LLDPE portion is (a Ziegler/Natta catalyzed, solution polymerized LLDPE) generated from mixtures of polymerization educts.
  • the polymerization educts comprise ethylene as the (main) monomer and a co-monomer.
  • the co-monomer is 1-octene.
  • the co-monomer is contained in the polymerization polymer in an amount of less than 10 % by weight of the polymerization reaction mixture.
  • the further LLDPE portion consists of LLDPE made from fossil fuels and having a density of 0.930 to 0.940 g/ml and a melt flow rate of 2.5 to 5.5 g/10 min at 190 °C / 2.16 kg, and/or having a density of 0.915 to 0.919 g/ml and a melt flow rate of 2 to 4 g/10 min at 190 °C / 2.16 kg.
  • the second polymer is petro based HDPE, i.e., it is HDPE made of fossil fuels.
  • the second polymer is a Ziegler/Natta catalyzed, solution polymerized HDPE generated from mixtures of polymerization educts.
  • the polymerization educts comprise ethylene as the main monomer and a co-monomer.
  • the co-monomer is 1-octene.
  • the second polymer is petro-based HDPE has a density of at least 0,950 g/ml, in particular a density within 0.952 to 0.955 g/ml, and a melt flow rate of 3 to 5 g/10 min at 190 °C / 2.16 kg.
  • the second polymer is a Ziegler/Natta catalyzed, gas-phase polymerized HDPE generated from mixtures of polymerization educts.
  • the polymerization educts comprise ethylene as the main monomer and a co-monomer.
  • the co-monomer is 1-butene.
  • the second polymer is a HDPE having a density of 0.948 to 0.962 g/ml and a melt flow rate of 0.2 to 20 g/10 min at 190 °C / 2.16 kg.
  • a density of 0.948 to 0.959 g/ml and a melt flow rate of 4 to 5 g/10 min at 190 °C / 2.16 kg has been observed to be particularly advantageous.
  • the second polymer is a HDPE made from a renewable carbon source.
  • LLDPE/HDPE blends comprising at least a bio-LLDPE portion
  • the portion of the first polymer being made from the renewable carbon source is within a range of 57 % and 87 % by weight of the polymer mixture.
  • the amount of the second polymer being within a range of 8 % and 33 % by weight of the polymer mixture.
  • This blend may have the advantage that a high portion of the carbon atoms of the blend are derived from a renewable carbon source.
  • the polymer mixture comprises:
  • the whole LLDPE may consist of bio-LLDPE and the whole HDPE may consist of bio-HDPE or petro-HDPE.
  • This embodiment may have the advantage that only two different polymer types may need to be added in the polymer mixture (typically, a master batch is added in addition).
  • a simple formulation for the polymer mixture that can easily be prepared may be provided.
  • the polymer mixture comprises:
  • This embodiment may have the advantage that an even higher portion of the carbon atoms of the fiber are derived from a renewable carbon source.
  • the second polymer is a mixture of a first, bio-based HDPE and a second, petro-based HDPE. It has been observed that, although the physicochemical properties of bio- and petro- based HDPE differ from each other, also bio-based HDPE can be used - within the weight ranges described for embodiments of this invention - for producing artificial turf fibers having the desired properties.
  • the polymer mixture comprising 6-10% by weight of the polymer mixture and comprises 17-23% by weight of the second HDPE. It has been observed that this weight range of the bio-based and the petro-based HDPE provide for artificial turf fibers which are high in carbon derived from a renewable source and which at the same time have the desired physicochemical properties, in particular in respect to resilience, flexibility and resistance to mechanical stress.
  • the totality of the first polymer is made from the renewable carbon source.
  • the renewable carbon source there may be no need to add a further LLDPE polymer derived from fossil fuels.
  • the above mentioned polymer mixtures have been observed to provide for a polymer mixture that, after being molten and extruded for generating the artificial turf fiber from the extrusion product, provides PE fibers suitable for use as artificial turf fibers.
  • the method comprises generating an artificial turf by incorporating the artificial turf fibers into a carrier.
  • the first polymer is prepared from ethylene that was generated from the renewable carbon source.
  • the renewable carbon source is biomass.
  • the biomass can be sugar cane.
  • the method comprising selecting (i.e., choosing) the amount of the portion of the first polymer made from a renewable carbon source and optionally selecting (i.e., choosing) also the portion of the second polymer that is made from a renewable carbon source such that the resulting artificial turf fibers consist to at least 20 % of one or more polymers made from a renewable carbon source and/or such that the artificial turf to be generated from the fiber consists to at least 6% by its weight of one or more polymers made from a renewable carbon source.
  • the fraction of biobased carbon content can be determined via the amount of 14 C isotopes in a sample.
  • Embodiments of the artificial turf fiber may comprise a sufficiently high fraction of BCC to be awarded, one, two or even more "stars" according to the classification schema of VINCOTTE, Doc Ref OK20, 2013.
  • the bio-based carbon content of the generated artificial turf fiber may, for example, lie within a range of 7 and 86 % by weight of the polymer mixture.
  • the mixing may be performed in an extruder.
  • the polymer mixture is extruded into a monofilament.
  • One or more of the monofilaments are formed into one of the artificial turf fibers.
  • the method may comprise forming one or more of the monofilaments into one of the artificial turf fibers.
  • the polymer mixture is extruded directly into a monofilament. The method comprises quenching the monofilament, reheating the monofilament, and stretching the reheated monofilament to form the monofilament into an artificial turf fiber.
  • the polymer mixture is extruded into a tape.
  • the tape is sliced into stripes and one or more of the stripes are formed into one of the artificial turf fibers.
  • the stripes are quenched, reheated and stretched before they are formed into artificial turf fibers.
  • Extruding the polymer mixture and quenching, reheating and stretching the extrusion product may be advantageous as said aspects may affect the physical properties of the monofilament or PE stripe used for generating the artificial turf fiber.
  • the stretching may trigger the generation of crystalline portions which may increase the surface roughness of a fiber and help to mechanically fix the fiber in the carrier, in particular if a liquid backing (e.g. latex or polyurethane) is added on the backside of the carrier such that the liquid backing wets the lower portions of the fiber and firmly includes the fiber after the solidification of the backing.
  • reheating and stretching steps may be used to "fine-tune" the properties of the artificial turf fibers to the requirements of a specific end-product.
  • the backing can be, for example, latex or a polyurethane (PU) based backing.
  • the backing can be added as a liquid to the lower side of the carrier having incorporated the artificial turf fibers.
  • the liquid backing wets the carrier and the lower parts of the incorporated fibers. Upon solidification, the backing strongly fixes the fibers in the backing.
  • a cohesive layer is applied between the fibers and the backing.
  • the fibers are attached to the carrier or the backing by triggering a chemical reaction between the fibers and the carrier (or the backing).
  • one or more of the monofilaments or stretched stripes may be bundled into an artificial turf fiber.
  • the incorporation of the fibers into the carrier comprises:
  • the invention relates to an artificial turf fiber which consists at least partially of a polymer made from a renewable carbon source.
  • the fiber comprises:
  • the artificial turf fiber are generated from a renewable carbon source.
  • the artificial turf fiber is an extrusion product of a polymer mixture created according to a method of any one of the embodiments described herein.
  • the invention relates to an artificial turf fiber comprising the 14 C isotope in an amount indicating that 20 % by weight of the polymer of the artificial turf fiber is made from a renewable carbon source.
  • the invention relates to a piece of artificial turf.
  • the method comprises a carrier, e.g. a mesh made of natural or synthetic yarn, and a plurality of artificial turf fibers described above which are incorporated into the carrier.
  • the incorporation may be performed by tufting the fiber into the carrier.
  • the incorporation of the fibers into the carrier comprises knitting or weaving the artificial turf fibers into the carrier.
  • At least parts of the artificial turf fibers are embedded in a backing, e.g. by applying the backing in liquid form on the backside of the carrier comprising the tufted fibers.
  • the backing solidifies and mechanically fixes said portions of the fibers in the backing.
  • the backing may be made at least partially from a renewable carbon source.
  • Whether or not a polymer is biobased or petrobased or is a mixture of biobased and petrobased polymers can easily be determined via radiocarbon dating, e.g. according to the ASTM D6866 standard for determining the biobased content of solid, liquid, and gaseous samples.
  • the polymer mixture further comprises additives such as pigments, flame retardants, nucleating agents, or the like.
  • additives are typically added as ingredients of a "master batch", i.e., a portion of e.g. 10% by weight of the polymer mixture comprising the additives.
  • the polymer of the master batch is preferentially petro-based LLDPE, but may likewise be bio-LLDPE, petro-HDPE or bio-HDPE.
  • “Artificial turf” as used herein is a surface of synthetic fibers incorporated into a carrier, e.g. a woven textile or synthetic fabric. Artificial turf is commonly made to look like natural grass and is often used in arenas for sports that were originally or are normally played on grass.
  • the fibers may be tufted or otherwise fixed into the carrier and optionally a backing layer at the bottom side of the artificial turf.
  • the fibers are, for example, monofilamented or twisted yarns of thermoplastic materials, mostly polyethylene.
  • the carrier can be made, for example, of polypropylene.
  • the fibers are fixed with an adhesive to the carrier.
  • the adhesive can be, for example, a mixture of styrene-butadien-rubber (SBR) latices and fillers such as calcium carbonate.
  • the adhesive can be a polyurethane-based adhesive.
  • the infill may consist of sand, granules of recycled rubber or other synthetic granules or a mixture thereof.
  • artificial turfs can also be used as carpets placed onto a substructure of rubber granules acting as a shock damping layer.
  • the carpet structure is filled with sand and rubber granules in order to keep the structure in place so that the carpet does not slip and the fibers stay in an upright position.
  • the filling material is also referred to as infill or infill material.
  • the infill can be, for example, SBR-rubber or EPDM-rubber, both elastomeric materials in irregularly granulated form.
  • the SBR-rubber is commonly sourced from used tires.
  • a “polymer derived from renewable biomass”, “bioplastic” or “bio-based polymer” is a polymer that is derived from renewable biomass sources, e.g. renewable plant materials, such as vegetable fats and oils, corn starch, or microbiota. Biopolymers can be made from agricultural byproducts using microorganisms. This means that the chemicals used for generating the polymer, e.g. PE, do not any longer originate from petroleum oil, but from renewable resources, in particular plants and other organisms that sequestrate CO 2 from the (current, not cambric) atmosphere via photosynthesis and bind it in the form of biomass.
  • renewable biomass sources e.g. renewable plant materials, such as vegetable fats and oils, corn starch, or microbiota.
  • Biopolymers can be made from agricultural byproducts using microorganisms. This means that the chemicals used for generating the polymer, e.g. PE, do not any longer originate from petroleum oil, but from renewable resources, in particular plants and other organisms that sequestrate CO 2
  • Bio-LLDPE is also known as “renewable polyethylene”, “bio-polyethylene”, “green-PE” or “bio-PE”).
  • it is polyethylene made out of ethanol, which becomes ethylene after a dehydration process.
  • plastics such as fossil-fuel plastics (also called petro-based polymers) are derived from petroleum or natural gas. Production of such plastics tends to require more fossil fuels and to produce more greenhouse gases than the production of biobased polymers.
  • LDPE Low-density polyethylene
  • Embodiments of the invention are based on LDPE whose density range is within the above specified sub-range.
  • Linear low-density polyethylene as used herein is a substantially linear polymer (polyethylene), with significant numbers of short branches. LLDPE differs structurally from conventional LDPE because of the absence or reduced number of long chain branching. The linearity of LLDPE results from the different manufacturing processes of LLDPE and LDPE. In general, LLDPE is produced at lower temperatures and pressures by copolymerization of ethylene and alpha-olefins with the aid of a catalyst system.
  • High-density polyethylene is a PE having a density of greater or equal to 0.941 g/cm 3 .
  • HDPE has a low degree of branching. The mostly linear molecules pack together well, so intermolecular forces are stronger than in highly branched polymers.
  • HDPE can be produced by chromium/silica catalysts, Ziegler-Natta catalysts or metallocene catalysts; by choosing catalysts and reaction conditions, the smaller amount of branching that does occur can be controlled by adding alpha-olefins, acting as co-monomers. These catalysts prefer the formation of a transition state at the reacting ends of the growing polyethylene molecules. They cause new monomers to add to the ends of the molecules, rather than along the middle, causing the growth of a linear chain.
  • HDPE has high tensile strength.
  • a "co-monomer” as used herein is a polymerizable precursor to a copolymer aside from the principal monomer. In some cases, only small amounts of a comonomer are employed, in other cases substantial amounts of co-monomers are used. Furthermore, in some cases, the co-monomers are heterogeneously incorporated within the polymer chain, whereas in other cases, they are homogeneously incorporated. The distribution of co-monomers is referred to as the chemical composition distribution of a copolymer.
  • a "polymer mixture” as used herein is a mixture of polymers with different compositions, capable of being differentiated by their physicochemical properties, also referred to as blend after extrusion melting.
  • the melting process combines the individual and distinguishable components of the mixture homogeneously, such that a polymeric material is generated with specific capabilities.
  • Fig. 1 is a flow chart of a method for producing bio-PE based artificial turf 200.
  • a polymer mixture 300, 400 is created by mixing at least a first polymer 304; ⁇ 404; 406 ⁇ and a second polymer 302; 402.
  • the mixing may be performed in a separate container or directly in an extruder.
  • the first polymer e.g. a bio-LLDPE or a mixture of bio-LLDPE and petro-LLDPE, is added in an amount of at least 57% by weight of the polymer mixture and consists of polyethylene made from renewable biomass.
  • the second polymer e.g.
  • petro-HDPE or bio-HDPE or a mixture thereof is added in an amount of at least 8 % by weight of the polymer mixture.
  • additives may be added to the mixture, e.g. via a master-batch or as separate ingredients.
  • the polymer mixture is heated above the melting point of the polymers to form a liquid polymer mixture.
  • the polymer mixture is extruded, e.g. into monofilaments or a film.
  • the monofilaments or the film may be quenched, the film may be sliced into stripes, the monofilaments or stripes may be reheated and stretched and/or further processed for texturizing or curling the monofilaments or stripes.
  • the extrusion product is formed into artificial turf fibers, e.g. by bundling multiple monofilaments or stripes to a fiber.
  • the artificial turf fibers are incorporated into a carrier 204, e.g. by tufting or weaving the monofilaments into a woven fabric used as the carrier.
  • Fig. 2 depicts a piece of artificial turf 200 that faithfully reproduces natural grass.
  • a plurality of artificial turf fibers 202 having been generated from a polymer mixture comprising biobased PE and petrobased PE is incorporated into a carrier 204.
  • the fibers 202 can be tufted into the carrier 204 and be fixed at the bottom side of the carrier.
  • the largest fiber portions 208 extend upward from the carrier.
  • the carrier may be a mesh or a woven fabric made of synthetic or naturally occurring materials.
  • the carrier may be polypropylene.
  • a backing 206 may be applied on the backside of the carrier to improve the fixing of the fibers in the carrier.
  • a liquid PU or latex mass can be applied that wets the portions 210 of the fibers 202 extending to the lower side of the carrier. When the mass has solidified, it tightly fixes the fibers in the carrier.
  • adhesive substances which glue the fibers to the carrier can be applied.
  • the space above the carrier and between the upper portions 208 of the fibers can be filled with sand and rubber granules in order to keep the structure in place so that the artificial turf does not slip and the fibers stay in an upright position.
  • the production of a piece of artificial turf as depicted in Fig. 2 may comprise the following steps: 1. Extrusion of the polymer mixture into monofilaments (see Fig. 6 ); 2. Drawing and thermofixing of the filaments, e.g. by heating the portions of the fibers above or close to their melting temperature for a short period of time, e.g. some seconds; 3. Arranging multiple monofilaments such that they are aligned into bundles of monofilaments centered around a common axis; and optionally texturizing of the filaments. Texturizing means the transformation of the smooth and evenly stretched filaments into crimped and bent filaments. 4.
  • Tufting of the monofilaments or bundles of monofilaments as artificial turf fiber onto the fabric whereas tufting means the process of stitching the filaments or bundles through the fabric.
  • This forms loops 210 of filaments or filament bundles which are cut through at the outward ends of the loops. Thereby, bunches of fibers extending orthogonally away from the carrier layer are formed. 5. Fixing the fibers at the backside of the fabric with an adhesive.
  • Fig. 3 depicts a petrobased LDPE molecule 150, a petrobased LLDPE molecule 160 and a petrobased HDPE molecule 170.
  • HDPE high-ethylene
  • LLDPE low density polyethylene
  • HDPE and LLDPE are generated by different polymerization processes.
  • the PE macromolecules are more or less side-chain branched.
  • Side-chain branching means that the chain-like macromolecules comprise shorter or longer side branches extending from the main polymer chain.
  • the degree of crystallinity depends strongly on the extent of side-chain branching.
  • HDPE and LLDPE may be generated in the same process (swing reactor technique).
  • LLDPE is a substantially linear PE polymer with significant numbers of short branches, commonly made by copolymerization of ethylene with longer chain olefins.
  • LLDPE differs structurally from conventional LDPE because of the absence of long chain branching. It has turned out that petrobased LLDPE generated in a polymerization process that uses ethylene and a co-monomer is very much appropriate for an outbalanced ratio between softness and rigidity of artificial turf fibers. In LLDPE polymers, the ability of the macromolecules to crystallize is sterically hindered by the side chains introduced by the co-monomers.
  • LLDPE has higher tensile strength and higher impact and puncture resistance than does LDPE. It is very flexible and elongates under stress. It can be used to make thinner films, with better environmental stress cracking resistance. It has good resistance to chemicals. It has good electrical properties.
  • LLDPE low density polyethylene
  • LLDPE Upon applying and increasing a deformation force on a PE fiber, i.e., in case of an increasing deformation rate, LLDPE does not show an increase in viscosity because of the lack of long-chain branching in LLDPE allows the chains to slide by one another upon elongation without becoming entangled.
  • the rheological properties of LLDPE are summarized as "stiff in shear” and "soft in extension".
  • LLDPE linearity polymer results from the different manufacturing processes of LLDPE and LDPE.
  • LLDPE is produced at lower temperatures and pressures by copolymerization of ethylene (acting as monomer) and co-monomers such as higher alpha-olefins (e.g. 1-butene, 1-hexene, or 1-octene).
  • Polymerization of 1-olefins or ⁇ -olefins together with ethylene results in LLDPE polymers referred to as "PE co-polymers".
  • the copolymerization process produces a petrobased LLDPE polymer that has a narrower molecular weight distribution than petrobased LDPE and in combination with the linear structure, significantly different rheological properties.
  • the ethylene monomers form the main polymer chain.
  • a co-monomer is added to the main polymer chain, a side-chain branch is formed at that position of the chain.
  • the length, the number and the distribution of side-chain branches can be determined by the type and amount of co-monomer used in the co-polymerization process. Number, length and distribution (along the backbone of the macromolecules) of the co-monomers determine the degree of crystallinity and thereby the mechanical properties of the produced polymer.
  • LLDPE is prepared in a low pressure process (slurry/solution/gas-phase) by using metallocene transition metal catalysts, Ziegler/Natta-type catalysts or Phillips type of catalysts.
  • Ziegler and Phillips (multi-site) catalysts produce polymers with relatively broad molecular weight distributions and in case of co-polymers a relatively broad co-monomer distribution.
  • Metallocene (single site) catalysts produce polymers with narrow molecular weight distribution and homogeneous co-monomer distribution.
  • the actual polymerization process can be done either in slurry, solution phase or in gas phase reactors.
  • HDPE has less side branches than LDPE.
  • the degree of crystallinity can reach 80 %.
  • HDPE can be produced by chromium/silica Phillips catalysts, Ziegler-Natta catalysts or metallocene catalysts; by choosing catalysts, reaction conditions and co-monomer concentration, the small amount of branching that does occur can be controlled. These catalysts prefer the formation of a transition state at the reactive ends of the growing polyethylene molecules. They cause new monomers to add to the ends of the molecules, rather than along the middle, causing the growth of a linear chain. HDPE has high tensile strength.
  • LDPE demonstrates a dramatic rise in viscosity because of chain entanglement upon applying and increasing a deformation force on a PE fiber, i.e., in case of an increasing deformation rate.
  • LDPE is prepared in a high pressure process using a radical initiator. It is not created in a polymerization reaction using co-monomers.
  • the radical polymerization process used to make LDPE does not include a catalyst that "supervises" the radical sites on the growing PE chains.
  • biobased LLDPE types are available on the market.
  • a bio-based Ziegler/Natta catalyzed gas-phase polymerized LLDPE is available which is generated from mixture of polymerization educts comprising ethylene and 1-butene co-monomer or ethylene and 1-hexene co-monomer.
  • the polymerization reaction to generate the biobased LLDPE from said reaction mixture is performed in a Spherilene-process.
  • the resulting bio-based LLDPE polymer has a (presumably bimodal) molecular weight distribution and other physicochemical properties which differ significantly from that of the available petrobased LLDPE molecules which are generated in a solution based polymerization process.
  • a petro-based LLDPE sometimes used for producing artificial turf fibers is a Ziegler/Natta catalyzed solution polymerized LLDPE, whereby the mixture of polymerization educts comprise ethylene and 1-octene co-monomers in an amount of around 10 % by weight of the polymerization mixture.
  • polymer mixtures comprising a first polymer derived from a renewable polymer source and a second polymer typically derived from fossil fuels are described which are particularly suited for generating artificial turf fibers which are soft, flexible and at the same time sufficiently rigid.
  • Fig. 4 depicts a polymer mixture 300 according to one embodiment "A".
  • the polymer mixture essentially consists of a first polymer consisting of bio-LLDPE 304 and a second polymer consisting of petro-HDPE 304.
  • a portion of the first polymer may be added separately in the form of a bio-LLDPE-based master batch. All components of mixture A are added to an extruder, homogeneously mixed, and heated above their melt temperatures to form a homogeneous, liquid polymer mass.
  • the first polymer is a bio-LLDPE 304 having a density of 0,918 g/ml and a melt flow rate of 2 to 4 g/10 min.
  • the second polymer is a HDPE 302 having a density of 0,955 g/ml and a melt flow rate of 3 to 5 g/10 min. At least 57 % by weight of the polymer mixture, in this case: 75 %, consist of the first polymer, at least 8 %, in this case 25 %, by weight of the polymer mixture consist of the second polymer (petro-HDPE). In case the polymer mixture further comprises some additives (typically in the range of less than 5 % by weight of the polymer mixture), the fraction of the first and second polymers may be altered accordingly.
  • the liquid polymer mixture is extruded into a monofilament as depicted in Fig. 7 .
  • more than 70% of the PE fiber mass (which typically constitutes the largest portion of the mass of a piece of artificial turf) is made from renewable raw materials.
  • the polymer mixture has been observed to provide artificial turf fibers being both sufficiently flexible as well as sufficiently rigid for being used as artificial turf fibers.
  • Fig. 5 depicts a polymer mixture 400 according to another embodiment.
  • the polymer mixture comprises bio-LLDPE 404 having a density of 0.916 to 0.920 g/ml and a melt flow rate of 2 to 4 g/10 min at 190 °C / 2.16 kg.
  • the second polymer 402 is in fact a mixture of a petro-HDPE 408 having a density of 0,955 g/ml and a melt flow rate of 3 to 5 g/10 min and a bio-HDPE 406 having a density of 0.948 to 0.959 g/ml (e.g. 0,954 g/ml) and a melt flow rate of 4 to 5 g/10 min.
  • Both the LLDPE 404 and the HDPE 406 are made from renewable carbon source.
  • the LLDPE 404 may constitute 72 % of the weight of the polymer mixture
  • the bio-HDPE 406 may constitute 20 % of the weight of the polymer mixture
  • the petro-HDPE 408 may constitute 8% of the mixture.
  • more than 90% of the PE fiber mass is made from renewable raw materials.
  • bio-LLDPE and/or bio-HDPE By increasing the fraction of bio-LLDPE and/or bio-HDPE within the above specified ranges, up to 97 % by weight of the polymer mixture can be made of renewable "bio-PE” (the remaining 3% relating to petro-based HDPE and additives).
  • Fig. 6 depicts a polymer mixture 500 according to a further embodiment.
  • the second polymer 502 may be completely petrol based (as shown), completely bio-based or may be a mixture of bio- and petro-based HDPE.
  • the first polymer is a mixture of a bio-LLDPE having a density of 0,917 g/ml and a melt flow rate of 2 to 4 g/10 min and a petro-LLDPE 406 having a density of 0.915 to 0.919 g/ml and a melt flow rate of 2 to 4 g/10 min at 190 °C / 2.16 kg.
  • the weight fraction of the artificial turf fiber that is derived from a renewable carbon source may be chosen freely, e.g. 33 %.
  • Polymer mixtures 300, 400, 500 have all been observed to provide artificial turf fibers being both sufficiently flexible as well as sufficiently rigid for being used as artificial turf fibers. Based on said amounts and characteristics of the first and second polymers, 8 to 97 % by weight of the polymer mixture can be made of renewable "bio-PE".
  • the creation of the polymer mixture comprises mixing the first and the second polymer in an extruder. This may be advantageous as no additional container or process step for mixing the first and second polymers is necessary. Rather, both the first and the second polymer can be fed as polymer granules into the extruder. In the extruder, the polymer granules are mixed and heated to form a liquid polymer mass that is extruded to a plurality of holes in an extrusion plate.
  • compositions and type of polymers are not limiting the invention. Other types of polymers and different compositions may result in comparable blends and hence in filaments with comparable properties.
  • Two inventive blends and one comparative blend are prepared from commercially available polymers.
  • the blends are extruded and further processed into monofilaments.
  • the monofilaments are used for the fabrication of artificial turf surfaces.
  • the components for the blends are listed in the following table: Polymer type Co-monomer Density [kg/m 3 ] MI [g/10 min] Bio-LLDPE 1-hexene 918 2.7 Petro-HDPE 1-octene 955 4.0 Petro-LLDPE 1-octene 917 2.3
  • the nominal values for the melt flow rate are measured at 190 °C and 2.16 kg load.
  • Petro-LLDPE is used for the preparation of the master-batch.
  • the master-batch consists of the following main components:
  • the master-batch is prepared on a 40 D co-rotating twin screw extruder.
  • the specific proportions of polymers, pigments and additives are fed by gravimetric dosing into the hopper of the extruder, extruder-blended and pelletized.
  • the inventive blends 1 and 2 consist of a first polymer A, a second polymer B and master-batch.
  • the comparative blend consists of a first polymer C, a second polymer B and master-batch.
  • the components are extruder-blended in the course of the filament production.
  • the compositions of polymers and master-batch are given in the table below:
  • the fibers are produced by extrusion on an extruder.
  • the blend components i. e. the first polymer, the second polymer, the master-batch and the processing aid are fed via gravimetric dosing into the extruder.
  • the single-screw extruder is equipped with a melt pump, melt filtration and a circular die face with 165 spinnerets.
  • the temperature setting of the extruder is given in the next table.
  • zone 1 zone 2 zone 3-5 flange filtration zones melt pump 1 melt pump 2 dies °C 190 210 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230
  • the die face is located above a water-bath at a distance of 40 mm from the water surface.
  • the water temperature is kept within 30 ⁇ 0,5 °C.
  • the fibers are dried and heated on a first set of godets up to 80 °C.
  • the fibers are passed through a hot air oven to a next set of godets heated up to 90 °C.
  • the temperature of the first hot airheating zone is maintained at 90 °C.
  • the first and the second pair of godets run at differential speed, such that the fibers are stretched at a ratio between 1:5 and 1:6, preferably at a ratio of 1:5.6.
  • the fibers are annealed at temperatures of 115 °C and draw ratios of 0.9 and 0.97.
  • the fibers are cooled on godets to 20 °C.
  • the fibers are transferred to bobbin winders or texturizer units.
  • the properties of the filaments were determined by common test methods. Specimens of monofilaments from different polymer blends were sampled after production of the filaments. For the abrasion test the filaments were tufted onto a carrier fabric and the carpets were bed coated by applying SBR-latex to the backside of the carpet and passing through a hot-air oven at a temperature of 85 °C. Tufting, coating and drying were comparable for all samples with different filament composition.
  • Test Parameter Method Unit B1 B2 CB 1 Fibre thickness internal ⁇ m 108 111 115 2 Fibre width internal mm 1,265 1,354 1,382 3 Fibre weight EN 15330-1 dtex 1002 980 934 4 Shrinkage 5 min / 90 °C % 3 4 4 5 Curl 5 min / 85 °C no curl no curl no curl 6
  • the properties of artificial turf fibers made from inventive blends B1 and B2 are similar, sometimes even better than the comparative blend although a significant portion of bio-LLDPE was used for generating the fibers.
  • properties relating to resistance to artificial weathering, tensile strength, color change show that bio-based artificial turf fibers can be produced which fulfill the same quality criteria like conventional petro-based fibers.
  • no curling was observed also for the bio-based fibers, and the abrasion resistance is almost as high as that of the comparative blend.
  • the density is measured according to ASTM. The data were taken from the technical data sheets of the suppliers.
  • the density is measured according to ASTM. The data were taken from the technical data sheets of the suppliers.
  • Fiber dimensions relate to the cross section of the fibers.
  • the fibers are clamped and cut near the clamp. Length and thickness are determined under a microscope.
  • the weight (in dtex) is determined by weighing a sample of 10,000 meters in length.
  • the tests are carried out on a Zwick/Roell Z 1.0 tensile testing equipment. Tensile strength and elongation at break are taken from the stress/strain records.
  • Abrasion resistance was measured by Taber test according to EN 13672. 5000 Cycles with an H 18 rotatory abraser are done and the weight loss of the samples is measured.
  • the shrinkage of monofilaments and texturized yarn is measured by thermal treatment of 1 meter of a sample in a circulating air oven at 90 °C for 5 minutes. The length of the samples before and after thermal treatment is determined and calculated in % shrinkage.
  • the curl is measured by winding up approximately 1 meter of filament to a bundle, fixing one end with a strap and cutting the opposite end, such that a bunch forms. The bunch is heated at 85 °C for 5 minutes. The samples are visually assessed whether or not curling can be detected.
  • the bio-based carbon content is determined by 14 C radiocarbon method, according to ASTM D 6866.
  • 14 C is the unstable isotope of carbon. As long as living organisms are in exchange with the biosphere they digest carbon and with it 14 C-isotopes. As the 14 C-content is stationary in the atmosphere the amount of that isotope does not change in the biomass. In dead biomass the amount of 14 C begins to decrease by radioactive decay. The content of this isotope is depleting over time.
  • Fossil carbon material has a lower content of 14 C isotopes than younger carbon material. By that difference, the ratio between bio-based (younger) and petro-based (fossil) carbon can be measured with mass spectrometric isotope analysis.
  • Fig. 7 depicts the extrusion of a polymer mixture into a monofilament 606.
  • the polymer mixture can be a mixture 300, 400 as depicted, for example, in Figures 4 and 5 or according to any other embodiment described herein.
  • the heated, liquid polymer mixture contained in an extruder 604 wherein the first and second polymers are mixed is pressed through a hole 608 of an extrusion plate 602.
  • the extrusion product, in this case, a monofilament 606, is quenched in a quenching solution, e.g. a water bath having about 20°C to allow the monofilament to solidify.
  • the monofilament is reheated, e.g.
  • the monofilament may optionally be bundled with further monofilaments to form an artificial turf fiber.
  • the fiber is incorporated into a carrier material to form a piece of artificial turf as depicted in Fig. 2 .

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EP3604675B1 (fr) * 2018-07-30 2023-12-13 Polytex Sportbeläge Produktions-GmbH Fibres de gazon artificiel comprenant un déchet de polymère et un polymère compensatoire
EP3800284A1 (fr) * 2019-10-04 2021-04-07 Dow Global Technologies Llc Composition de filament
KR102143595B1 (ko) * 2020-02-06 2020-08-11 코오롱글로텍주식회사 인조잔디 파일사 및 이를 이용한 인조잔디 구조체
KR102222623B1 (ko) * 2020-08-07 2021-03-04 주식회사 주목씨지알 탄소 저감 및 미세먼지 포집이 용이한 인조잔디용 탄성 충진재 및 그 제조방법

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