EP2129818B1 - Fibre, bandes ou filaments comportant une composition de polyéthylène - Google Patents

Fibre, bandes ou filaments comportant une composition de polyéthylène Download PDF

Info

Publication number
EP2129818B1
EP2129818B1 EP08734667.2A EP08734667A EP2129818B1 EP 2129818 B1 EP2129818 B1 EP 2129818B1 EP 08734667 A EP08734667 A EP 08734667A EP 2129818 B1 EP2129818 B1 EP 2129818B1
Authority
EP
European Patent Office
Prior art keywords
mpe
fibre
molecular weight
fibres
carpet
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.)
Revoked
Application number
EP08734667.2A
Other languages
German (de)
English (en)
Other versions
EP2129818A2 (fr
Inventor
Henk Van Paridon
Bert Broeders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borealis Technology Oy
Original Assignee
Borealis Technology Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39415112&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2129818(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to EP08734667.2A priority Critical patent/EP2129818B1/fr
Publication of EP2129818A2 publication Critical patent/EP2129818A2/fr
Application granted granted Critical
Publication of EP2129818B1 publication Critical patent/EP2129818B1/fr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent

Definitions

  • This invention relates to carpets and sports surfaces comprising fibres, tapes and filaments comprising a polyethylene (PE) composition, and to a preparation method thereof.
  • PE polyethylene
  • Polyethylene materials used for fibre, tape and filament products have conventionally been unimodal and produced using Ziegler Natta (znPE) or Chromium catalyst (CrPE). Typically they also have high density, e.g. above 945 kg/m 3 .
  • WO2006053709 describes a multimodal polyethylene for drawn tapes, fibres and filaments having a density of at least 940 kg/m 3 .
  • Such polymers are stated to provide similar or improved properties, such as tenacity, to fibres compared to unimodal polyethylene products in the same density level.
  • fibres need to withstand heavy mechanical stress and wear.
  • it would sometimes also be beneficial that the fibre material is soft, but at the same time has good mechanical properties.
  • a soft fibre material would be desirable, optionally together with good UV (ultra violet) light stability. The above properties would be advantageous for fibres in order to maintain a constant performance and/or appearance in the longer term.
  • Polypropylene based fibres have been used in prior art for many demanding applications, such as in sport surfaces.
  • An example is described in JP 11-269811 which relates to lawns comprising fibres which are made from a mixed composition of an HDPE and a linear PE.
  • prior art fibres may have insufficient softness and UV-stability.
  • abrasion wear resistance of prior art polyethylene e.g. unimodal polyethylene, fibres is usually not sufficient to maintain a constant performance for long periods.
  • the invention provides a process for producing carpets or sports surfaces of the invention.
  • fibres, tapes or filaments comprising an mPE composition have an excellent resilience property and/or tenacity properties which makes said mPE very suitable i.a. for various technical, household, interior and sports applications, wherein one or both of said mechanical properties are desired.
  • fibres, tapes or filaments comprising an mPE composition as defined below have advantageous tensile properties expressed as a balance between tenacity and elongation at break. Said resilience property and property balance between tenacity and elongation are further described below and the determination method thereof is defined below under Determination Methods.
  • the present invention provides a carpet or sports surface comprising:
  • the invention provides a carpet or sports surface comprising fibres, tapes or filaments comprising a linear low density polyethylene composition obtainable by polymerisation of ethylene using a single site catalyst (mPE), wherein said mPE composition has a density of more than 905 to less than 940 kg/m 3 , and an MFR 2 of 5 g/10min or less when measured according to ISO 1133 at 190°C at load of 2.16 kg which is unimodal with respect to molecular weight distribution.
  • mPE single site catalyst
  • fibres, tapes or filaments used in this application for fibers, tapes and filaments of the invention is shortly abbreviated as “Fibre” and it covers and means all conventional forms known, producible and used in the field of fibres.
  • mPE and mLLDPE as defined later below used in this invention mean a linear polyethylene which is produced using a single site catalyst in relative low pressure polymerisation process e.g. in conventional reactor(s) designed for polymerisations using coordination catalysts such as Ziegler Natta, Chromium or single site catalyst. It is thus different from low density polyethylene (LDPE) produced in a high pressure polymerisation in a tubular or an autoclave reactor using typically a free radical initiator.
  • LDPE low density polyethylene
  • the present invention covers two equal alternative embodiments (A) and (B).
  • said Fibre of the invention comprises a mPE composition having a density as defined above, wherein said mPE is unimodal with respect to molecular weight distribution.
  • Said unimodal mPE present in the Fibre of the invention can be a homopolymer or copolymer of ethylene.
  • the Fibre of embodiment (A) has inter alia (i.a.) excellent tensile properties, more preferably an advantageous balance between tenacity and elongation properties, when measured as defined below under Determination Methods.
  • Fibre (A) preferably has a very good resilience property. The property balance of Fibre of embodiment (A) makes it very suitable for technical, household, interior and sports applications, particularly for technical applications.
  • said Fibre of the invention comprises mPE having a density as defined above, wherein said mPE is multimodal with respect to molecular weight distribution, and comprises at least (i) a lower weight average molecular weight (LMW) ethylene homopolymer or copolymer component, and (ii) a higher weight average molecular weight (HMW) ethylene homopolymer or copolymer component.
  • LMW lower weight average molecular weight
  • HMW higher weight average molecular weight
  • the Fibre of embodiment (B) has an advantageous resilience property.
  • said Fibre of embodiment (B) has also very feasible tensile properties, more preferably a feasible balance between tenacity and elongation properties, when measured as defined below under Determination Methods.
  • the property balance of Fibre of embodiment (B) makes it very suitable for technical, household, interior and sports applications.
  • Said Fibre of embodiment (A) and/or (B) may further have i.a. one or more the following properties: advantageous wear resistance which is also known as abrasion resistance and/or UV stability.
  • said Fibre of the present invention comprises a linear low density polyethylene composition obtainable by polymerisation of ethylene using a single site catalyst (mLLDPE), wherein said mLLDPE composition has a density of more than 905 kg/m 3 to less than 940 kg/m 3 .
  • mLLDPE single site catalyst
  • the low density of mLLDPE results in softer Fibres which, surprisingly, have at the same time also an excellent resilience property. Accordingly, the resilience property can be maintained together with gained softness property.
  • the property balance thus obtained is very interesting in many application areas including technical and sports applications.
  • said mLLDPE composition present in the Fibre of the invention is unimodal with respect to the molecular weight distribution.
  • Fibre of embodiment (a) preferably has the properties given above under embodiment (A) and has additionally very feasible softness making it suitable for various end applications indicated above including technical and sports fibre applications.
  • said mLLDPE composition present in the Fibre of the invention is multimodal with respect to molecular weight distribution, and comprises at least (i) a lower weight average molecular weight (LMW) ethylene homopolymer or copolymer component, and (ii) a higher weight average molecular weight (HMW) ethylene homopolymer or copolymer component.
  • LMW lower weight average molecular weight
  • HMW higher weight average molecular weight
  • at least one of said LMW and HMW components is a copolymer of ethylene with at least one comonomer.
  • the multimodality of the mLLDPE of embodiment (b) contributes also to highly feasible processing properties during the preparation of Fibres.
  • Fibre of embodiment (b) has preferably the properties given above under embodiment (B) and has additionally very feasible softness making it suitable for various end applications indicated above including technical and sports fibre applications, such as sports applications wherein softness is an advantage such as in artificial grass materials.
  • a polyethylene composition having a density of more than 905 kg/m 3 to less than 940 kg/m 3 may sometimes be defined in the polymer literature as covering i.a. a medium density polyethylene (MDPE) composition and a linear low density ethylene (LLDPE) composition.
  • MDPE medium density polyethylene
  • LLDPE linear low density ethylene
  • mLLDPE composition a polyethylene with a density of more than 905 kg/m 3 to less than 940 kg/m 3
  • mLLDPE composition or “mLLDPE” and it naturally covers polyethylenes within the density range of "MDPE”.
  • the terms such as "mLLDPE”, "metallocene based LLDPE”, or “single site based LLDPE” mean that the polyethylene is obtainable by a single site catalyst.
  • Fibres are attached by any conventional fixing means to a typically flat base or carrier element so that at least one of the fibre ends is freely protruding from the base element. Fibres may also be fixed to the base element from their centre part leaving the Fibre ends with a certain length free and “freely moving". The length of the free “Fibre ends” can vary depending on the desired end application, as well known in the art.
  • mPE or mLLDPE composition present in said Fibres can be further tailored and optimised in relation to one or more of the additional preferable properties as listed e.g. above, depending on the end use application wherein the Fibre is intended.
  • mLLDPE is used herein to define mPE compositions having a density of more than 905 kg/m 3 to less than 940 kg/m 3 .
  • An mPE or mLLDPE composition present in said Fibre as defined above or below may be polymerised by any conventional single site, including metallocene and non-metallocene, catalysts (referred herein as mPE or mLLDPE).
  • said mPE or mLLDPE is unimodal with respect to molecular weight distribution.
  • said mPE or mLLDPE is multimodal with respect to molecular weight distribution. Unimodal and multimodal mPE or mLLDPE, respectively, both are thus preferable.
  • unimodal is meant that the molecular weight profile of the polymer comprises a single peak and is produced by one reactor and one catalyst.
  • multimodal means herein, unless otherwise stated, multimodality with respect to molecular weight distribution and includes also bimodal polymer.
  • a polyethylene e.g. mPE or mLLDPE composition, comprising at least two polyethylene fractions, which have been produced under different polymerization conditions resulting in different (weight average) molecular weights and molecular weight distributions for the fractions, is referred to as "multimodal".
  • multi relates to the number of different polymer fractions present in the polymer.
  • multimodal polymer includes so called “bimodal" polymer consisting of two fractions.
  • the appearance of the graph of the polymer weight fraction as a function of its molecular weight, of a multimodal polymer will show two or more maxima or is typically distinctly broadened in comparison with the curves for the individual fractions.
  • the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
  • the individual curves from these fractions form typically together a broadened molecular weight distribution curve for the total resulting polymer product.
  • the multimodal mLLDPE usable in the present invention comprises a lower weight average molecular weight (LMW) component and a higher weight average molecular weight (HMW) component.
  • LMW lower weight average molecular weight
  • HMW weight average molecular weight
  • Said LMW component has a lower molecular weight than the HMW component.
  • the multimodal mPE or mLLDPE comprises at least (i) a lower weight average molecular weight (LMW) ethylene homopolymer or copolymer component, and (ii) a higher weight average molecular weight (HMW) ethylene homopolymer or copolymer component.
  • LMW lower weight average molecular weight
  • HMW higher weight average molecular weight
  • at least one of said LMW and HMW components is a copolymer of ethylene with at least one comonomer. It is preferred that at least said HMW component is an ethylene copolymer.
  • said LMW is the preferably the homopolymer.
  • said multimodal mPE or mLLDPE may comprise further polymer components, e.g. three components being a trimodal mPE or mLLDPE.
  • multimodal mPE or mLLDPE may also comprise e.g. up to 10 % by weight of a well known polyethylene prepolymer which is obtainable from a prepolymerisation step as well known in the art, e.g. as described in WO9618662 .
  • the prepolymer component is comprised in one of LMW and HMW components, preferably LMW component, as defined above.
  • said multimodal mPE or mLLDPE is bimodal mPE or mLLDPE, respectively, comprising said LMW and HMW components and optionally a prepolymerised fraction as defined above.
  • the single site based nature of mPE as defined in claim 1 provides the unexpected effect of the invention, i.e. resilience.
  • the density also provides a further unexpected effect to the Fibres, i.e. balance between softness and mechanical properties.
  • the other properties of said mPE or mLLDPE can further contribute to the excellent properties of the invention and may be varied within the scope of the invention depending on the desired end use application. Accordingly, the below given preferable property ranges are applicable to uni- or multimodal mPE and mLLDPE, unless otherwise stated below.
  • the mLLDPE composition useful for Fibre has a density of more than 905 kg/m 3 to less than 940 kg/m 3 .
  • the density is 938 kg/m 3 or less, more preferably a density of 935 kg/m 3 or less.
  • the lower density limit of said mPE or mLLDPE is more than 905 kg/m 3 , e.g. 910 kg/m 3 .
  • "softer" Fibre even densities of 930 kg/m 3 or below, or even 925 kg/m 3 or less, are highly feasible.
  • Said mPE suitable for the formation of the Fibre of the invention may be a homopolymer or copolymer of ethylene.
  • Said mLLDPE suitable for Fibre is typically a copolymer.
  • the term "ethylene copolymer” or “LLDPE copolymer” as used herein encompasses polymers comprising repeat units deriving from ethylene and at least one other C3-20 alpha olefin comonomer.
  • mPE or mLLDPE copolymer may be formed from ethylene along with at least one C3-12 alpha-olefin comonomer, e.g. 1-butene, 1-hexene or 1-octene.
  • mPE or mLLDPE is a binary copolymer, i.e. the polymer contains ethylene and one comonomer, or a terpolymer, i.e. the polymer contains ethylene and two or three comonomers.
  • mPE or mLLDPE comprises an ethylene hexene copolymer, ethylene octene copolymer or ethylene butene copolymer.
  • the amount of comonomer present in mPE or mLLDPE is at least 0.25 mol-%, preferably at least 0.5 mol-%, such as preferably 0.5 to 12 mol%, e.g. 2 to 10 mol-% relative to ethylene.
  • a comonomer range of 4 to 8 mol-% may be desired.
  • comonomer contents present in mPE or mLLDPE may be 1.5 to 10 wt%, especially 2 to 8 wt% relative to ethylene.
  • any copolymeric HMW component preferably at least 0.5 mol-%, e.g. at least 1-mol%, such as up to 10 mol-%, of repeat units are derived from said comonomer.
  • Said mPE or mLLDPE as defned above or below has a MFR 2 of 5 g/10 min or less, when measured according to ISO 1133 at 190°C at load of 2.16 kg.
  • the MFR 2 is typically more than 0.2 g/10 min, preferably 0.5 to 6.0, e.g. 0.7 to 4.0 g/10min.
  • Said mPE or mLLDPE suitable for Fibre preferably has a weight average molecular weight (Mw) of 100,000 to 250,000, e.g. 110,000 to 160,000.
  • Unimodal mPE or mLLDPE useful for Fibre preferably posses a narrow molecular weight distribution MWD expressed as Mw/Mn.
  • Said Mw/Mn value of unimodal mPE or mLLDPE is typically less than 30, preferably less than 10, more preferably 2 to 4.
  • the upper limit of Mw/Mn is not critical and may be e.g. less than 40.
  • Mw/Mn is preferably in the range of 3 to 30, more preferably of 3 to 10, and depending on the end application may even be in the range of 4 to 8.
  • Said LMW component of multimodal mPE or mLLDPE suitable for Fibre preferably has a MFR 2 of at least 50 g/10 min, preferably below 500 g/10 min, e.g. up to 400 g/10 min, such as between 100 to 400 g/10 min.
  • the weight average molecular weight (Mw) of the LMW component is preferably in the range of 15,000 to 50,000, e.g. of 20,000 to 40,000.
  • the density of LMW component of said multimodal mPE or mLLDPE may range from 930 to 980 kg/m 3 , e.g. 930 to 970 kg/m 3 , more preferably 935 to 960 kg/m 3 in case of a LMW copolymer component, and 940 to 980 kg/m 3 , especially 960 to 975 kg/m 3 in case of a LMW homopolymer component.
  • the LMW component of said multimodal mPE or mLLDPE may form from 30 to 70 wt%, e.g. 40 to 60% by weight of the multimodal LLDPE with the HMW component forming 70 to 30 wt%, e.g. 40 to 60% by weight.
  • said HMW component forms 50 wt% or more of the multimodal mPE or mLLDPE as defined above or below.
  • the HMW component of said multimodal mPE or mLLDPE has a lower MFR 2 and a lower density than the LMW component.
  • the HMW component of said mPE or mLLDPE has preferably an MFR 2 of less than 1 g/10 min, preferably less than 0.5 g/10 min, especially less than 0.2 g/10min.
  • the density of the HMW component may be above 900 kg/m 3 , preferably a density of 910 to 930, e.g. up to 925 kg/m 3 .
  • the Mw of the higher molecular weight component may range from 100,000 to 1,000,000, preferably 250,000 to 500,000.
  • the mPE composition to contain both components (A) and (B).
  • the mPE or mLLDPE suitable as a Fibre material of the invention can be any conventional, e.g. commercially available, polymer composition.
  • Useful mPE or mLLDPE polymers are available from, without limiting to these, i.a. from Borealis e.g. under trademark BoreceneTM FMXXX, such as BoreceneTM FM5220, BoreceneTM FM5340 etc.
  • suitable mPE or mLLDPE polymer compositions can be produced in a known manner according to or analogously to conventional polymerisation processes, including solution, slurry and gas phase processes, described in the literature of polymer chemistry.
  • Unimodal mPE or mLLDPE useful in the present invention is preferably prepared using a single stage polymerisation, e.g. solution, slurry or gas phase polymerisation, preferably a slurry polymerisation in slurry tank or, more preferably, in loop reactor in a manner well known in the art.
  • said unimodal mPE or mLLDPE can be produced e.g. in a single stage loop polymerisation process according to the principles given below for the polymerisation of low molecular weight fraction in a loop reactor of a multistage process, naturally with the exception that the process conditions (e.g. hydrogen and comonomer feed) are adjusted to provide the properties of the final unimodal polymer.
  • Multimodal (e.g. bimodal) mPE or mLLDPE useful in the present invention is obtained by in-situ blending in a multistage polymerisation process during the preparation process of the polymer components.
  • the multimodal mPE or mLLDPE polymers when used, are obtainable by in-situ blending in a multistage, i.e. two or more stage, polymerization process including solution, slurry and gas phase process, in any order.
  • Suitable multimodal mPE or mLLDPE is preferably produced in at least two-stage polymerization using the same single site catalyst.
  • two slurry reactors or two gas phase reactors, or any combinations thereof, in any order can be employed.
  • the multimodal mPE or mLLDPE is made using a slurry polymerization in a loop reactor followed by a gas phase polymerization in a gas phase reactor.
  • a loop reactor - gas phase reactor system is well known as Borealis technology, i.e. as a BORSTAR ® reactor system.
  • Any multimodal mPE or mLLDPE present in the Fibre of the invention is thus preferably formed in a two stage process comprising a first slurry loop polymerisation followed by gas phase polymerisation.
  • Such multistage process is disclosed e.g. in EP517868 .
  • the reaction temperature will generally be in the range 60 to 110°C, e.g. 85-110°C
  • the reactor pressure will generally be in the range 5 to 80 bar, e.g. 50-65 bar
  • the residence time will generally be in the range 0.3 to 5 hours, e.g. 0.5 to 2 hours.
  • the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100°C.
  • polymerization may if desired be effected under supercritical conditions.
  • Slurry polymerisation may also be carried out in bulk where the reaction medium is formed from the monomer being polymerised.
  • the reaction temperature used will generally be in the range 60 to 115°C, e.g. 70 to 110°C
  • the reactor pressure will generally be in the range 10 to 25 bar
  • the residence time will generally be 1 to 8 hours.
  • the gas used will commonly be a non-reactive gas such as nitrogen or low boiling point hydrocarbons such as propane together with monomer, e.g. ethylene.
  • a chain-transfer agent preferably hydrogen
  • at least 100 to preferably at least 200, and up to 1500, preferably up to 800 moles of H 2 /kmoles of ethylene are added to the loop reactor, when the LMW fraction is produced in this reactor, and 0 to 60 or 0 to 50 moles of H 2 /kmoles of ethylene, and, again depending on the desired end application, in certain embodiments even up to 100, or up to 500 moles of H 2 /kmoles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.
  • the LMW polymer fraction is produced in a continuously operating loop reactor where ethylene is polymerised in the presence of a polymerization catalyst as stated above and a chain transfer agent such as hydrogen.
  • the diluent is typically an inert aliphatic hydrocarbon, preferably isobutane or propane.
  • the reaction product is then transferred, preferably to continuously operating gas phase reactor.
  • the HMW component can then be formed in a gas phase reactor using preferably the same catalyst.
  • a prepolymerisation step may precede the actual polymerisation process.
  • the density, MFR 2 etc of the HMW component can be calculated using Kim McAuley's equations.
  • both density and MFR 2 can be found using K. K. McAuley and J. F. McGregor: On-line Inference of Polymer Properties in an Industrial Polyethylene Reactor, AIChE Journal, June 1991, Vol. 37, No, 6, pages 825-835 .
  • the density is calculated from McAuley's equation 37, where final density and density after the first reactor is known.
  • MFR 2 is calculated from McAuley's equation 25, where final MFR 2 and MFR 2 after the first reactor is calculated.
  • the unimodal or multimodal mPE or mLLDPE, as defined above or below, useful in the present invention may be made using any conventional single site catalysts, including metallocenes and non-metallocenes as well known in the field.
  • the choice of an individual catalyst used to make mLLDPE is not critical.
  • Catalyst and “catalyst system” are used herein interchangeably for a system comprising the single site compound, e.g. metallocene complex which is referred herein as "procatalyst" as well, and one or more cocatalyst(s), as well known in the field.
  • the catalyst may be supported on an external carrier or be non-supported.
  • the catalyst may be in solid or liquid state.
  • said catalyst is one comprising a metal coordinated by one or more ⁇ -bonding ligands.
  • ⁇ -bonded metals are typically transition metals of Group 3 to 10, e.g. Zr, Hf or Ti, especially Zr or Hf.
  • the ⁇ -bonding ligand is typically an ⁇ 5 -cyclic ligand, i.e. a homo or heterocyclic cyclopentadienyl group optionally with fused or pendant substituents.
  • Such single site, preferably metallocene, procatalysts have been widely described in the scientific and patent literature for about twenty years. Procatalyst refers herein to said transition metal complex.
  • the metallocene procatalyst may have a formula II: (Cp) m R n MX q (II) wherein:
  • each Y is independently selected from C6-C20-aryl, NR" 2 , -SiR" 3 or -OSiR" 3 .
  • X as -CH 2 -Y is benzyl.
  • Each X other than -CH 2 -Y is independently halogen, C1-C20-alkyl, C1-C20-alkoxy, C6-C20-aryl, C7-C20-arylalkenyl or -NR" 2 as defined above, e.g. -N(C1-C20-alkyl) 2 .
  • each X is halogen or -CH 2 -Y
  • each Y is independently as defined above.
  • Cp is preferably cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, optionally substituted as defined above.
  • each Cp independently bears 1, 2, 3 or 4 substituents as defined above, preferably 1, 2 or 3, such as 1 or 2 substituents, which are preferably selected from C1-C20-alkyl, C6-C20-aryl, C7-C20-arylalkyl (wherein the aryl ring alone or as a part of a further moiety may further be substituted as indicated above), -OSiR" 3 , wherein R" is as indicated above, preferably C1-C20-alkyl.
  • R" is other than hydrogen.
  • a specific subgroup includes the well known metallocenes of Zr, Hf and Ti with two ⁇ -5-ligands which may be bridged or unbridged cyclopentadienyl ligands optionally substituted with e.g. siloxy, or alkyl (e.g. C1-6-alkyl) as defined above, or with two unbridged or bridged indenyl ligands optionally substituted in any of the ring moieties with e.g. siloxy or alkyl as defined above, e.g. at 2-, 3-, 4- and/or 7-positions.
  • Preferred bridges are ethylene or -SiMe 2 .
  • the preparation of the metallocenes can be carried out according or analogously to the methods known from the literature and is within skills of a person skilled in the field.
  • examples of compounds wherein the metal atom bears a -NR" 2 ligand see i.a. in WO-A-9856831 and WO-A-0034341 .
  • examples of compounds wherein the metal atom bears a -NR" 2 ligand see i.a. in WO-A-9856831 and WO-A-0034341 .
  • EP-A-260 130 WO-A-9728170 , WO-A-9846616 , WO-A-9849208 , WO-A-9912981 , WO-A-9919335 , WO-A-9856831 , WO-A-00/34341 , EP-A-423 101 and EP-A-537 130 .
  • the metal bears a Cp group as defined above and additionally a ⁇ 1 or ⁇ 2 ligand, wherein said ligands may or may not be bridged to each other.
  • a Cp group as defined above and additionally a ⁇ 1 or ⁇ 2 ligand, wherein said ligands may or may not be bridged to each other.
  • Such compounds are described e.g. in WO-A-9613529 .
  • metallocenes include those of formula (I) Cp' 2 HfX' 2 wherein each X' is halogen, C 1-6 alkyl, benzyl or hydrogen; Cp' is a cyclopentadienyl or indenyl group optionally substituted by a C 1-10 hydrocarbyl group or groups and being optionally bridged, e.g. via an ethylene or dimethylsilyl link.
  • Bis (n-butylcyclopentadienyl) hafnium dichloride and Bis (n-butylcyclopentadienyl) hafnium dibenzyl are particularly preferred.
  • Metallocene procatalysts are generally used as part of a catalyst system which also includes a cocatalyst or catalyst activator, for example, an aluminoxane (e.g. methylaluminoxane (MAO), hexaisobutylaluminoxane and tetraisobutylaluminoxane) or a boron compound (e.g. a fluoroboron compound such as triphenylpentafluoroboron or triphentylcarbenium tetraphenylpentafluoroborate ((C 6 H 5 ) 3 B+B-(C 6 F 5 ) 4 )).
  • aluminoxane e.g. methylaluminoxane (MAO), hexaisobutylaluminoxane and tetraisobutylaluminoxane
  • a boron compound e.g. a fluoroboron compound such as
  • the procatalyst, procatalyst/cocatalyst mixture or a procatalyst/cocatalyst reaction product may be used in unsupported form or it may be precipitated and used as such.
  • One feasible way for producing the catalyst system is based on the emulsion technology, wherein no external support is used, but the solid catalyst is formed from by solidification of catalyst droplets dispersed in a continuous phase. The solidification method and further feasible metallocenes are described e.g. in WO03/051934 .
  • Useful activators are, among others, aluminium alkyls and aluminium alkoxy compounds.
  • Especially preferred activators are aluminium alkyls, in particular aluminium trialkyls, such as trimethyl aluminium, triethyl aluminium and triisobutyl aluminium.
  • the molar ratio of the aluminium in the activator to the transition metal in the transition metal complex is from 1 to 500 mol/mol, preferably from 2 to 100 mol/mol and in particular from 5 to 50 mol/mol.
  • Suitable combinations of transition metal complex and activator are disclosed among others, in the examples of WO 95/35323 .
  • Any catalytically active catalyst system including the procatalyst, e.g. metallocene complex, is referred herein as single site or metallocene catalyst (system).
  • the obtained reaction product of said mPE polymerisation process is typically pelletised in well known manner and the pellets of mPE are then used for Fibre formation.
  • the obtained reaction product of said mLLDPE polymerisation process is typically pelletised in well known manner and the pellets of mLLDPE are then used for Fibre formation.
  • the Fibres of the invention may contain other polymer than mPE, as well.
  • the Fibre consists of mLLDPE, preferably unimodal or multimodal mLLDPE, of the invention.
  • the Fibre consists of a mPE, preferably unimodal or multimodal mPE, of the invention
  • the used term "consists of” means herein only that no other polymer components are present in the Fibres, but naturally said Fibres of such embodiment may comprise conventional fibre additives such as antioxidants, UV stabilisers, colour masterbatches, acid scavengers, nucleating agents, anti-blocking agents, slip agents etc. as well as polymer processing agent (PPA).
  • PPA polymer processing agent
  • the fibres can preferably be produced via a film extrusion process, such as cast film or blown film process, via film slitting to produce i.a. tapes, or via a direct extrusion process to produce filaments, preferably monofilaments.
  • a film extrusion process such as cast film or blown film process
  • film slitting to produce i.a. tapes
  • a direct extrusion process to produce filaments, preferably monofilaments.
  • Fibres of the invention comprise a mixture of mPE together with other polymer components
  • the different polymer components are typically intimately mixed prior to extrusion as is well known in the art.
  • said mPE or mLLDPE polymer product can be extruded into fibres, tapes or filaments, preferably monofilaments, using known filament extrusion process.
  • One useful process for producing the Fibres of invention is described in "Fiber Technology” Hans A.Krässig, Jürgen Lenz, Herman F. Mark; ISBN: 0-8247-7097-8.
  • said mPE or mLLDPE composition may be extruded into a film which is subsequently cut into fibres and tapes in a known manner. Both preparation methods are conventional and generally known in the production of fibres, tapes and filaments.
  • the film may be prepared by any conventional film formation process including extrusion procedures, such as cast film or blown film extrusion, lamination processes or any combination thereof.
  • the film may be mono or multilayer film, e.g. coextruded multilayer film.
  • the film layers may comprise the same or different polymer composition, whereby at least one layer comprises said mPE or mLLDPE of the invention.
  • all layers of a multilayer film comprise, more preferably consist of, the same mPE or mLLDPE composition.
  • the film is formed by blown film extrusion and in case of multilayered film structure by blown film coextrusion processes.
  • said mPE or mLLDPE composition may be blown (co)extruded at a temperature in the range 160°C to 240°C, and cooled by blowing gas (generally air) at a temperature of 10 to 50°C to provide a frost line height of 1 or 2 to 8 times the diameter of the die.
  • the blow up ratio should generally be less than 6, e.g. less than 4, more preferably between 1.0 to 1.5, and even more preferably 1.0 to 1.2.
  • the film may be (co)extruded to form first a bubble which is then collapsed and cooled, if necessary, and the obtained tubular film is cut to fibres.
  • the (co)extruded bubble may be collapsed and split into two film laminates. The formed film is then cut to Fibres.
  • Fibres can be cut from a cast film that is produced by procedures well known in the field.
  • Fibres are in stretched, i.e. oriented, form.
  • Fibres are stretched uniaxially, more preferably in the machine direction (MD). Accordingly, in the first direct filament formation alternative, said Fibres can be stretched to a desired draw ratio after extrusion to filaments.
  • MD machine direction
  • Fibre preparation alternative wherein a film is first formed and cut to Fibres, said film can be stretched before cutting to stretched Fibres, e.g. tapes, or the film is first cut e.g. to tapes and then the formed tapes are stretched to form final Fibres.
  • the Film is first cut e.g. to tapes which are then stretched to a desired draw ratio to form final Fibres.
  • Lenzing process for stretching a film prior to cutting into tapes
  • Iso process for cutting a film into tapes and stretching the formed tapes.
  • stretched Fibres are provided which are preferably in stretched, i.e. oriented, form, preferably in uniaxially oriented form.
  • Heat may typically be applied during the stretching, e.g. during in line stretching.
  • the stretching ratio can be determined e.g. by the speed ratio of the godet rolls before and after the heating means in a manner known in the art.
  • the stretch and heat setting ratio's can be optimised and adapted depending on the demands of the end application.
  • heating means e.g. oven or hot plate can be used.
  • the Fibre preparation process preferably comprises a step of stretching extruded filaments, of stretching fibres/tapes cut from a film, or of stretching film prior to cutting into fibres/tapes, whereby the stretching is preferably effected in the machine direction (MD) in a draw ratio of at least 1:3.
  • MD machine direction
  • a preferable Fibre preparation process thus comprises a step of extruding said mPE or mLLDPE into
  • extruded fibres, fibres/tapes cut from a film or a film prior to cutting into fibres/tapes is/are stretched 3 to 10 times its/their original length in the MD.
  • the expressions "stretching 3 times its/their original length” and “drawn down to 3 times its/their original length” mean the same and can also be expressed as a "stretch ratio of at least 1:3" and, respectively, “draw ratio of at least 1:3", wherein "1" represents the original length of the film and "3" denotes that it has been stretched/drawn down to 3 times that original length.
  • Preferred films of the invention are stretched in a draw ratio of at least 1:4, more preferably in the range of 1:5 to 1:8, e.g. in a draw ratio of between 1:5 and 1:7.
  • An effect of stretching, i.e. drawing, is that the thickness of the film is similarly reduced.
  • a draw ratio of at least 1:3 means preferably that also the thickness of the film is at least three times less than the original thickness.
  • the Fibres can then be further processed to form a carpet or sports surface.
  • the Fibre can be in a form of a fibre, tape or filament comprising a unimodal or multimodal mPE or a unimodal or multimodal mLLDPE, preferably a unimodal or multimodal mLLDPE, copolymer as defined above.
  • the Fibre forms part of the invention.
  • said Fibre consists of a unimodal or multimodal mPE or a unimodal or multimodal mLLDPE copolymer, preferably a unimodal or multimodal mLLDPE copolymer, as defined above or in the claims below.
  • the Fibre of the invention does not have a hollow core, rather it is solid across its cross section.
  • the fibres of the invention should not be hollow.
  • Fibre thus naturally covers fibres, tapes and filaments of any shape and size. The dimensions thereof depend on the end application area, as well known in the art. Filaments are preferably monofilaments.
  • Fibre is in stretched form as defined above.
  • such tape of the invention may typically have a width of at least 0.5 mm, preferably of at least 1 mm.
  • the upper limit of a tape width is not critical and can be e.g. up to 10 mm, preferably up to 6 mm.
  • the thickness of a tape of the invention may be e.g. at least 5 ⁇ m, preferably at least 10 ⁇ m.
  • the upper limit of a tape thickness is not limited and can be e.g. up to 80 ⁇ m, preferably up to 50 ⁇ m, in some end applications preferably up to 20 ⁇ m.
  • the dimensions thereof typically correspond to the size range, i.e. dimensions, given above for a tape form.
  • the width ranges and other dimensions given above apply both to Fibres in stretched form and Fibres in non-stretched form.
  • Fibres are in stretched form and may have the width and other dimensions as defined above.
  • Fibres have an excellent resilience property and/or a very feasible balance between tenacity and elongation.
  • Fibres may also be "soft" Fibres comprising mLLDPE as defined above.
  • Fibres may have additionally one or more of the following properties: good UV-stability and/or wear resistance.
  • the application area of Fibres is not limited and it has unexpectedly found that the Fibres and the "soft" Fibres of the invention exhibiting good resilience property are very feasible for many mechanically demanding applications as well.
  • the Fibres show good tensile properties expressed as a balance between tenacity and elongation at break, when measured using tensile tests according to ISO 2062 (year 1993) as defined below under Determination Methods.
  • the samples used for the tensile determinations were prepared as described under Sample Preparation.
  • Fibre of the invention comprises an mPE or mLLDPE as defined above or in claims which mPE or mLLDPE has a tenacity of at least 0.33 N/tex and residual elongation at break of at least 16 %, preferably a tenacity of at least 0.35 N/tex and residual elongation at break of at least 16 %, e.g. when measured according to ISO 2062 (year 1993) using a tape sample consisting of said mPE or mLLDPE and drawn to 6 times it original length.
  • said Fibre comprises a mPE or mLLDPE as defined above or in claims which mPE or mLLDPE has a density of at least 930 kg/m 3 and a tenacity of at least 0.33 N/tex and residual elongation at break of at least 30 %, preferably of at least 35 %, e.g. when measured according to ISO 2062 (year 1993) using a tape sample consisting of said mPE or mLLDPE and drawn to 6 times it original length. Said method is described below under Determination Methods. The tape sample was prepared as described below under Fibre Sample Preparation.
  • Fibre of the invention when drawn to 6 times to its original length has a tenacity of at least 0.33 N/tex, preferably 0.35 N/tex, and residual elongation at break of at least 16 %.
  • Fibre of the invention when drawn to 6 times to its original length has a tenacity of at least 0.33 N/tex and residual elongation at break of at least 30 %, preferably a tenacity of at least 0.33 N/tex and residual elongation at break of at least 35 %, e.g. when measured according to ISO 2062 (year 1993) as defined below.
  • the Fibres are used to prepare carpets or sports surfaces.
  • the Fibres of the invention can be sufficiently soft and have good wear resistance, i.e. they are resistant to abrasion.
  • Fibre Sample Preparation the properties of Fibre of the invention given above in the description and below in claims are not limited to the Fibre Sample used in the determinations, but apply generally to the Fibre of the invention as defined in claims and/or in preferred embodiments.
  • the Fibre Sample defined herein is merely for meeting the sufficiency/reproducibility of the invention.
  • Density of the materials is measured according to ISO 1183:1987 (E), method D, with isopropanol-water as gradient liquid.
  • the cooling rate of the plaques when crystallising the samples was 15 C/min. Conditioning time was 16 hours.
  • MFR 2 , MFR 5 and MFR 21 measured according to ISO 1133 at 190°C at loads of 2.16, 5.0, and 21.6 kg respectively.
  • a Waters 150CV plus instrument, equipped with refractive index detector and online viscosimeter was used with 3 x HT6E styragel columns from Waters (styrene-divinylbenzene) and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 140 °C and at a constant flow rate of 1 mL/min. 500 ⁇ L of sample solution were injected per analysis.
  • the column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 15 narrow MWD polystyrene (PS) standards in the range of 1.0 kg/mol to 12 000 kg/mol.
  • Melting temperature and crystallization temperature, Tm and Tcr, both were measured according to ISO 11357-1 on Perkin Elmer DSC-7 differential scanning calorimetry. Heating curves were taken from -10°C to 200°C at 10°C/min. Hold for 10 min at 200°C. Cooling curves were taken from 200°C to -10°C at 10°C per min. Melting and crystallization temperatures were taken as the peaks of endotherms and exotherms. The degree of crystallinity was calculated by comparison with heat of fusion of a perfectly crystalline polyethylene, i.e. 290 J/g.
  • Comonomer content (mol% ) was determined based on Fourier transform infrared spectroscopy (FTIR) determination calibrated with C13-NMR.
  • FTIR Fourier transform infrared spectroscopy
  • Tenacity and elongation at break were determined by tensile tests. Tensile tests were performed on an Instron apparatus according to the ISO 2062 (year 1993) Norm with the following measuring settings: Clamping length 250 mm Drawing speed 250 mm/s Number of measurements 20 Tensile strength at break Elongation at break
  • the tapes were tufted onto a plastic carrier.
  • the carrier was a plate with a thickness of 1 cm and contained holes of 1mm through which the tapes could be tufted.
  • the tuft was fixated by clamping a second plate to the bottom of the carrier plate.
  • Fibre samples were tape samples which were prepared by using a state of the art pilot cast film stretch tape line.
  • the extruder was equipped with a metering pump to ensure a constant output.
  • the water quenching tank, godets and oven used were Riefenh Reifen components.
  • the temperature profile of the extruder used was 225 °C, 230°C and 235 °C.
  • the die was kept at 235 °C.
  • Film die had a 0.1 mm gap width.
  • a 75 micron primary film was extruded into a water quench (30 °C) water bath.
  • the take of speed off the first godet roll was kept at 10 m/min.
  • Fibre sample series tape samples were drawn 5 times their original length (draw ratio of 1:5) and 2.
  • Fibre sample series tape samples were drawn 6 times their original length (draw ratio of 1:6), unless otherwise stated.
  • Example 1 Polymerisation of mLLDPE1 of the invention
  • the polymerisation was carried out in a continuously operated pilot polymerisation process.
  • the reaction product obtained from prepolymerisation step was fed to the actual loop reactor having a volume 500 dm 3 and ethylene, hydrogen, 1-butene as comonomer and propane as diluent were fed in amounts that the ethylene concentration in the liquid phase of the loop reactor was 6,5 mol-%.
  • the other amounts and ratios of the feeds are given in table 1 below.
  • the loop reactor was operated at 85°C temperature and 60 bar pressure.
  • the formed polymer (LMW component) had a melt index MFR 2 of 110 g/10 min at 26 kg/h.
  • the slurry was intermittently withdrawn from the reactor by using a settling leg and directed to a flash tank operated at a temperature of about 50°C and a pressure of about 300 kPa (3 bar).
  • the powder containing a small amount of residual hydrocarbons, was transferred into a gas phase reactor operated at 80°C temperature and 20 bar pressure.
  • a gas phase reactor operated at 80°C temperature and 20 bar pressure.
  • additional ethylene nitrogen as inert gas as well as 1-butene and 1-hexene as comonomers in such amounts that the ethylene concentration in the circulating gas was 50 mol-%.
  • the ratio of hydrogen to ethylene, the ratio of comonomers to ethylene and the polymer production rate are given in the below table 1.
  • the production rate was 28 kg/h.
  • the production split between the loop and gas phase reactors was thus 50/50 wt-%.
  • the polymer collected from the gas phase reactor was stabilised by adding to the powder 1500ppm Irganox B215.
  • the stabilised polymer was then extruded and pelletised under nitrogen atmosphere with CIM90P extruder, manufactured by Japan Steel Works.
  • the melt temperature was 214 °C
  • throughput 221 kg/h and the specific energy input (SEI) was 260 kWh/kg.
  • Density and MFR 2 of the final polymer are given in the below table.
  • Table 1 Polymerisation conditions and the product properties of the obtained products of example 1
  • Polymerization conditions Unit Ex 1 mLLDPE1 Prepolymerisation temperature °C 60 pressure kPa (bar) 6300 (63) Catalyst feed g/h 33 C2 feed kg/h 1,5 C4 feed g/h 58 Loop reactor C2 concentration mol-% 6,5 H2/C2 ratio mol/kmol 0,56 C4/C2 ratio mol/kmol 107
  • Polymerization conditions Unit Ex 1 mLLDPE1 C6/C2 ratio mol/kmol - MFR 2 g/10 min. 110 Density kg/m3 938 Prod.
  • Example 2 mLLPE2 of invention: A unimodal ethylene hexene copolymer was produced using a bis(n-butylcyclopentadienyl) hafnium dibenzyl catalyst in a slurry loop reactor having a volume 500 dm 3 at the polymerization conditions given below.
  • the obtained unimodal mLLDPE polymer had a density of 922 kg/m 3 and MFR 2 of 1.3 g/10min.
  • mLLDPE3 of invention A unimodal ethylene hexene copolymer was produced using a bis(n-butylcyclopentadienyl) hafnium dibenzyl catalyst in a slurry loop reactor having a volume 500 dm 3 at the polymerization conditions given below.
  • Pressure 4200 kPa (42 bar)
  • C2 amount in flash gas 5 wt% C6/C2 in flash gas: 67 mol/kmol
  • Temperature 90°C
  • Catalyst feed 15 g/h Residence time: 40 to 60 minutes Production rate: 30 kg/h
  • the resulting unimodal mLLDPE polymer had a MFR 2 of 1.3 g/10min and a density of 934 kg/m 3 .
  • Test Fibre samples of the invention comprising the mLLDPE polymer material of the invention and the comparative test fibre samples were produced according to the procedure defined under "Fibre Sample Preparation” and tested for mechanical properties listed in Table 1 below and are further illustrated in figures 1 and 2 .
  • Resilience test Resilience was determined as described above under Determination Methods. For all other materials tape samples with a draw ratio of 1:6 was used, except for mLLDPE1 of invention, for which the draw ratio was 1:5. A load of 0.22 N/mm 2 was applied to the tufted sample for 24 hrs. Thickness of the samples (pool thickness) was measured after removal of the applied pressured and after 1 and 24 h recuperation times and compared with the thickness before the test. The results are given in figure 1 . As can be seen from the results all mLLDPE examples mLLDPE1, mLLDPE2 and mLLDPE3 have clearly better results than the reference materials.
  • Tensile tests The balance between tenacity and elongation was determined for two series of tape samples, i.e. for sample series stretched 5 times their original length and for sample series stretched 6 times their original length.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Claims (13)

  1. Tapis ou revêtement de sport comprenant :
    (A) une fibre, un ruban ou un filament comprenant une composition de polyéthylène linéaire de faible densité susceptible d'être obtenue par polymérisation d'éthylène en utilisant un catalyseur à site unique (mPE), dans lequel ladite composition de mPE présente une densité supérieure à 905 et inférieure à 940 kg/m3, et une valeur de MFR2 de 5 g/10 min ou moins mesurée selon la norme ISO 1133 à 190 °C à une charge de 2,16 kg ; et dans lequel ladite composition de mPE est produite in-situ selon un procédé de polymérisation multi-étapes et est multimodale en termes de distribution des poids moléculaires, et comprend au moins
    (i) un composant copolymère ou homopolymère d'éthylène à bas poids moléculaire moyen (BPM), et
    (ii) un composant copolymère ou homopolymère d'éthylène à haut poids moléculaire moyen (HPM) ; et
    (B) un stabilisateur d'UV.
  2. Tapis ou revêtement de sport selon la revendication 1, dans lequel ladite composition de mPE présente une densité de 938 kg/m3 ou moins.
  3. Tapis ou revêtement de sport selon la revendication 2, dans lequel ladite composition de mPE présente une densité de 935 kg/m3 ou moins.
  4. Tapis ou revêtement de sport selon les revendications 1 à 3, dans lequel ladite composition de mPE est multimodale en termes de distribution des poids moléculaires et comprend au moins (i) un composant copolymère ou homopolymère d'éthylène à bas poids moléculaire moyen (BPM), et (ii) un composant copolymère ou homopolymère d'éthylène à haut poids moléculaire moyen (HPM), dans lequel ladite composition de mPE multimodale présente une distribution des poids moléculaires DPM (Mw/Mn) inférieure à 40.
  5. Tapis ou revêtement de sport selon les revendications 1 à 4, dans lequel au moins l'un desdits composants BPM et HPM est un copolymère d'éthylène avec au moins un comonomère.
  6. Tapis ou revêtement de sport selon les revendications 1 à 5, dans lequel ladite composition de mPE multimodale présente une distribution des poids moléculaires comprise entre 10 et 30.
  7. Tapis ou revêtement de sport selon les revendications 1 à 6, dans lequel ladite fibre, ledit ruban ou filament est sous forme étirée.
  8. Tapis ou revêtement de sport selon les revendications 1 à 7, dans lequel ladite fibre, ledit ruban ou filament présente un rapport d'étirage d'au moins 3 fois sa longueur initiale (1:3).
  9. Tapis ou revêtement de sport selon la revendication 8, dans lequel ladite fibre, ledit ruban ou filament présente un rapport d'étirage compris entre 1:5 et 1:8.
  10. Procédé de production d'un tapis ou d'un revêtement de sport tel que défini dans les revendications 1 à 9, comprenant une polymérisation de monomères d'éthylène en présence de comonomères et d'un système de catalyseur à site unique, de préférence un système de catalyseur de métallocène, dans un procédé multi-étapes pour produire un mPE multimodal tel que défini à la revendication 1,
    - une transformation du mPE obtenu sous la forme de fibre, de ruban ou de filament ; et
    - une transformation de ladite fibre, dudit ruban ou filament en ledit tapis ou revêtement de sport.
  11. Procédé selon la revendication 10, dans lequel l'étape de transformation de mPE en fibre, ruban ou filament comprend une étape d'extrusion pour façonner ledit mPE en
    - une fibre, ruban ou filament qui est optionnellement étiré au moins 3 fois de sa longueur initiale, ou
    - une pellicule qui est optionnellement étirée d'au moins 3 fois sa longueur initiale et est ensuite coupée en fibres, filaments ou rubans, ou ladite pellicule est coupée en fibres, filaments ou rubans qui sont optionnellement étirés d'au moins 3 fois leur longueur initiale.
  12. Tapis ou revêtement de sport comprenant des fibres, rubans ou filaments comprenant une composition de polyéthylène linéaire de faible densité susceptible d'être obtenue par polymérisation d'éthylène en utilisant un catalyseur à site unique (mPE), dans lequel ladite composition de mPE présente une densité supérieure à 905 et inférieure à 940 kg/m3, et une valeur de MFR2 de 5 g/10 min ou moins mesurée selon la norme ISO 1133 à 190 °C à une charge de 2,16 kg qui est unimodale en termes de distribution des poids moléculaires.
  13. Tapis ou revêtement de sport selon la revendication 12, dans lequel ladite composition de mPE est unimodale en termes de distribution des poids moléculaires et présente une DPM (Mw/Mn) inférieure à 10, de préférence comprise entre 2 et 4.
EP08734667.2A 2007-03-22 2008-03-19 Fibre, bandes ou filaments comportant une composition de polyéthylène Revoked EP2129818B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08734667.2A EP2129818B1 (fr) 2007-03-22 2008-03-19 Fibre, bandes ou filaments comportant une composition de polyéthylène

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07005907A EP1972704A1 (fr) 2007-03-22 2007-03-22 Fibre, bandes ou filaments comportant une composition de polyéthylène
PCT/EP2008/002189 WO2008113566A2 (fr) 2007-03-22 2008-03-19 Fibres, rubans ou filaments comprenant une composition de polyéthylène
EP08734667.2A EP2129818B1 (fr) 2007-03-22 2008-03-19 Fibre, bandes ou filaments comportant une composition de polyéthylène

Publications (2)

Publication Number Publication Date
EP2129818A2 EP2129818A2 (fr) 2009-12-09
EP2129818B1 true EP2129818B1 (fr) 2017-06-21

Family

ID=39415112

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07005907A Withdrawn EP1972704A1 (fr) 2007-03-22 2007-03-22 Fibre, bandes ou filaments comportant une composition de polyéthylène
EP08734667.2A Revoked EP2129818B1 (fr) 2007-03-22 2008-03-19 Fibre, bandes ou filaments comportant une composition de polyéthylène

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07005907A Withdrawn EP1972704A1 (fr) 2007-03-22 2007-03-22 Fibre, bandes ou filaments comportant une composition de polyéthylène

Country Status (4)

Country Link
EP (2) EP1972704A1 (fr)
CN (1) CN101663425B (fr)
DK (1) DK2129818T3 (fr)
WO (1) WO2008113566A2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012004422A1 (fr) 2010-07-06 2012-01-12 Dow Global Technologies Llc Mélanges de polymères d'éthylène et articles orientés à résistance améliorée à la contraction
US20130273268A1 (en) 2010-09-23 2013-10-17 Total Research & Technology Feluy Artificial grass
CN103282563A (zh) 2010-10-29 2013-09-04 陶氏环球技术有限责任公司 基于聚乙烯的取向的单丝和条带以及制备它们的方法
US9044297B2 (en) * 2011-03-17 2015-06-02 Technologies Holdings Corp. System and method for estrus detection using real-time location
US20140242304A1 (en) 2011-10-24 2014-08-28 Peter Sandkuehler Artificial turf yarn
CN103088445A (zh) * 2013-03-04 2013-05-08 北京石油化工学院 茂金属基低密度聚乙烯亚微米纤维的制备方法
CN104562283B (zh) * 2014-12-29 2016-05-11 中国水产科学研究院东海水产研究所 南极磷虾网纲用纤维的制备方法
WO2018002196A1 (fr) * 2016-07-01 2018-01-04 Total Research & Technology Feluy Composition de polyéthylène pour fil de gazon artificiel
CN106320140A (zh) * 2016-07-29 2017-01-11 宁波绿菱新材料科技有限公司 人造草坪
CN106192496B (zh) * 2016-08-13 2019-09-03 浙江东一海洋集团有限公司 渔用纲索专用绳材及其制备工艺和用于拖网上空纲的应用
EP3741886A1 (fr) 2016-10-31 2020-11-25 Polytex Sportbeläge Produktions-GmbH Fibre de gazon artificiel à partir d'une biomasse renouvelable
CN114990719B (zh) * 2022-06-10 2023-06-20 湖北工业大学 一种用于人造草坪的纤维丝及其制备方法
CN116005282A (zh) * 2023-03-07 2023-04-25 东华大学 一种均一连续的微纳米纤维超临界纺丝方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269811A (ja) * 1998-03-23 1999-10-05 Diatex Co Ltd 人工芝生
US6316549B1 (en) * 1991-10-15 2001-11-13 The Dow Chemical Company Ethylene polymer fiber made from ethylene polymer blends
JP2004238774A (ja) 2003-02-10 2004-08-26 Japan Polypropylene Corp 柔軟ヤーン及びそれからなる人工芝
EP1469104A1 (fr) 2003-04-16 2004-10-20 ATOFINA Research Société Anonyme Polyéthylène pour fibres obtenu avec un catalyseur métallocène
EP1672020A1 (fr) 2004-12-20 2006-06-21 Innovene Manufacturing Belgium NV Composition à base de polyéthylène pour gazon artificiel
WO2006066777A1 (fr) 2004-12-20 2006-06-29 Ineos Manufacturing Belgium Nv Composition de polyethylene destinee a du gazon artificiel
WO2006113983A1 (fr) * 2005-04-28 2006-11-02 Nova Chemicals (International) S.A. Resines de polyethylene a double reacteur pour emballage electronique: films, bandes, sacs et pochettes
JP2007016367A (ja) 2005-07-11 2007-01-25 Hagihara Industries Inc 人工芝パイル糸及びそれを用いた人工芝生
WO2007082817A1 (fr) 2006-01-19 2007-07-26 Basell Polyolefine Gmbh Composition de polyéthylène pour produits sous forme de bandelettes étirées
EP2137344B1 (fr) * 2007-03-22 2011-07-20 Borealis Technology Oy Fibres, rubans ou filaments comprenant une composition de polyéthylène multimodal

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674342A (en) * 1991-10-15 1997-10-07 The Dow Chemical Company High drawdown extrusion composition and process
US5322728A (en) * 1992-11-24 1994-06-21 Exxon Chemical Patents, Inc. Fibers of polyolefin polymers
IL133922A (en) * 1999-02-01 2005-03-20 Ciba Sc Holding Ag Compositions comprising polyolefins produced by polymerization over a metallocene catalyst and a stabilizer mixture and a method for stabilizing said polyolefins
EP1709117B1 (fr) * 2004-01-26 2009-10-28 The Procter and Gamble Company Fibres et non-tisses comprenant des assemblages de polyethylene et des melanges

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6316549B1 (en) * 1991-10-15 2001-11-13 The Dow Chemical Company Ethylene polymer fiber made from ethylene polymer blends
JPH11269811A (ja) * 1998-03-23 1999-10-05 Diatex Co Ltd 人工芝生
JP2004238774A (ja) 2003-02-10 2004-08-26 Japan Polypropylene Corp 柔軟ヤーン及びそれからなる人工芝
EP1469104A1 (fr) 2003-04-16 2004-10-20 ATOFINA Research Société Anonyme Polyéthylène pour fibres obtenu avec un catalyseur métallocène
EP1672020A1 (fr) 2004-12-20 2006-06-21 Innovene Manufacturing Belgium NV Composition à base de polyéthylène pour gazon artificiel
WO2006066777A1 (fr) 2004-12-20 2006-06-29 Ineos Manufacturing Belgium Nv Composition de polyethylene destinee a du gazon artificiel
WO2006113983A1 (fr) * 2005-04-28 2006-11-02 Nova Chemicals (International) S.A. Resines de polyethylene a double reacteur pour emballage electronique: films, bandes, sacs et pochettes
JP2007016367A (ja) 2005-07-11 2007-01-25 Hagihara Industries Inc 人工芝パイル糸及びそれを用いた人工芝生
WO2007082817A1 (fr) 2006-01-19 2007-07-26 Basell Polyolefine Gmbh Composition de polyéthylène pour produits sous forme de bandelettes étirées
EP2137344B1 (fr) * 2007-03-22 2011-07-20 Borealis Technology Oy Fibres, rubans ou filaments comprenant une composition de polyéthylène multimodal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Plastics - Methods for determining the density and relative density of non-cellular plastics", INTERNATIONAL STANDARDS (ISO 1183), 15 July 1987 (1987-07-15), pages 1 - 12, XP055477456

Also Published As

Publication number Publication date
WO2008113566A3 (fr) 2009-03-12
CN101663425B (zh) 2013-06-12
CN101663425A (zh) 2010-03-03
WO2008113566A2 (fr) 2008-09-25
EP2129818A2 (fr) 2009-12-09
DK2129818T3 (en) 2017-08-14
EP1972704A1 (fr) 2008-09-24

Similar Documents

Publication Publication Date Title
EP2129818B1 (fr) Fibre, bandes ou filaments comportant une composition de polyéthylène
EP2106421B2 (fr) Compositions de polyethylene multimodal
CA2839965C (fr) Polyethylene obtenu par catalyse par un metallocene
US8821995B2 (en) Fiber, tapes, monofilaments based on ethylene copolymers with alfa-olefins
EP2118158B1 (fr) Polymère
EP2137344B2 (fr) Fibres, rubans ou filaments comprenant une composition de polyéthylène multimodal
CN100434575C (zh) 纤维应用的茂金属生成的聚乙烯
EP3390523A1 (fr) Composition de polyéthylène pour fil de gazon artificiel
US20200149193A1 (en) Polyethylene Fabric, and Backing and Artificial Turf Made Therefrom
EP2321369A1 (fr) Pellicule épaisse de polyéthylène et procédé de synthèse de polyéthylène

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091019

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20120206

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20170125

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 903028

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008050777

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20170811

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170922

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170921

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 903028

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170921

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171021

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602008050777

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: TOTAL RESEARCH & TECHNOLOGY FELUY

Effective date: 20180315

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180319

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080319

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170621

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: TOTALENERGIES ONE TECH BELGIUM

Effective date: 20180315

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220321

Year of fee payment: 15

Ref country code: DK

Payment date: 20220323

Year of fee payment: 15

Ref country code: DE

Payment date: 20220322

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20220321

Year of fee payment: 15

Ref country code: FR

Payment date: 20220322

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 602008050777

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 602008050777

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

27W Patent revoked

Effective date: 20221118

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20221118

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC