Patent Description:
The production of UHMW PE (ultrahigh molecular weight polyethylene) products (MW > <NUM><NUM><NUM>/mol) is very challenging and in practice extremely limited due to the bad operability of the processes. Adding UHMW PE material for compounding is not feasible due to too different character of the materials. The dispersion of the resulting resins is bad. It has been assumed dispersion requires broad molecular weight distributions of the carrier polypropylene polymer.

As far as PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition very little is known. <CIT> discloses polyolefin compositions comprising from <NUM> to <NUM>% by weight of a crystalline propylene polymer (A) having a MFR value equal to or lower than <NUM>/<NUM>. , and from <NUM> to <NUM>% by weight of a ultra high molecular weight polyethylene B) in form of particles having a mean particle size of from <NUM> to <NUM>. Component A) had a broad molecular weight distribution Mw/Mn of higher than <NUM>.

A different class of polyethylene compositions, i.e. the carrier polymer being not polypropylene but polyethylene, i.e. the compositions being a polyethylene has been described by <NPL>.

There was still the need for a pipe polypropylene composition resulting in good stiffness and pressure resistance. There was further the need for having a process allowing the mixing of polypropylene with ultra high molecular weight polyethylene.

The present invention is based on the finding that superior pipe properties can be achieved by a PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition having a melting temperature Tm in the range of <NUM> to <NUM> together with a relatively high content of units derived from <NUM>-hexene, and a xylene soluble content of less than <NUM> wt. It further has been surprisingly found that polymerization of propylene can be continued even in three reactors coupled in series and pure homo polyethylene polymer can be produced and blended in-situ.

The present invention provides a
PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition having.

The present invention further provides a
pipe comprising this PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition.

In a further aspect, the present invention further provides a process for the preparation of the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition according to the present invention, comprising the steps of.

In yet a further aspect the present invention concerns a PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as obtained by the inventive process as well as a pipe made from the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as obtained by the inventive process.

The present invention further concerns the use of a polypropylene composition having a melting temperature Tm in the range of <NUM> to <NUM> (DSC, ISO <NUM>, part <NUM>), and units derived from <NUM>-hexene in an amount of at least <NUM> wt. -%, for dispersing an UHMW-PE composition having a Mw of above <NUM> x <NUM><NUM> g/mol.

Ultra high molecular weight polyethylene denotes a polyethylene having a weight average molecular weight of more than <NUM><NUM><NUM>/mol.

Catalyst system denotes the combination of the actual catalyst and the cocatalyst(s).

Feeding no fresh catalyst system to the <NUM>nd and/or the <NUM>rd reactor (or any further reactor present) means that the catalyst system is introduced only into the first reactor.

It should be understood that the virgin catalyst system may be subjected to a prepolymerization possibly also in an external vessel. If so, the prepolymerized catalyst system must only be introduced into the first reactor but not into the second nor the third or any further reactor configured in the upstream direction.

The PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as described herein preferably has a melting temperature Tm in the range of <NUM> to <NUM>, more preferably <NUM> to <NUM>, even more preferably <NUM> to <NUM> and most preferably <NUM> to <NUM> all melting temperatures determined by DSC according to ISO <NUM>, part <NUM>.

The PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as described herein preferably has an MFR<NUM> of <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133), more preferably <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133), and most preferably <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133).

The PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as described herein preferably includes units derived from <NUM>-hexene in an amount of at least <NUM> wt. -%, more preferably at least <NUM> and most preferably at least <NUM> wt. Usually the content of units derived from <NUM>-hexene will not exceed <NUM> wt. -%:
The PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as described herein preferably has a xylene soluble content XS according to ISO16152 of less than <NUM> wt. -%, more preferably less than <NUM> wt. -% and most preferably less than <NUM> wt. -%, all weight percentages with respect to the total PP/UHMW-PE composition.

The present invention can allow higher <NUM>-hexene levels for a given melt flow rate compared with compositions not containing ultra high molecular weight polyethylene. This results in better impact. The UMHW polyethylene fraction also contributes to stiffness and pressure resistance of pipes made from the composition. It was further surprisingly found that the compositions produced had outstanding flowability. In addition to that, the inventive process also allows a higher total productivity via the use of three reactors. In yet a further aspect, the inventive process allows relatively high melt flow rates in the first and second reactor, which allows the use of higher hydrogen feeds also contributing to excellent productivity. Moreover, any remaining hexene residues may polymerize in the ultimate reactor, making product purging easier. In yet a further aspect, stable production and excellent operability were observed.

The PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition according to the present invention preferably has units derived from ethylene in an amount <NUM> to <NUM> wt. -%, preferably <NUM> to <NUM> wt. -%, all values with respect to the total PP/UHMW-PE composition.

As stated above the present invention also concerns a pipe comprising the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition of the present invention. All preferred ranges as disclosed for the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition shall also hold for the pipe according to the present invention comprising the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition.

The catalyst system as used in the present invention includes a catalyst component according to formula (I)
<CHM>
wherein.

The catalyst system further includes
(ii) a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst;.

The catalyst system of the invention can be used in non-supported form or in solid form. The catalyst system of the invention may be used as a homogeneous catalyst system or heterogeneous catalyst system.

The catalyst system of the invention in solid form, preferably in solid particulate form can be either supported on an external carrier material, like silica or alumina, or, in a particularly preferred embodiment, is free from an external carrier, however still being in solid form. For example, the solid catalyst system is obtainable by a process in which.

Particular complexes of the invention include:.

The catalysts have been described inter alia in <CIT>.

A particularly preferred catalyst is catalyst number <NUM>. The preparation of the complex has been described in <CIT> as E2.

For the avoidance of doubt, any narrower definition of a substituent offered above can be combined with any other broad or narrowed definition of any other substituent.

Throughout the disclosure above, where a narrower definition of a substituent is presented, that narrower definition is deemed disclosed in conjunction with all broader and narrower definitions of other substituents in the application.

The ligands required to form the complexes and hence catalysts/catalyst system of the invention can be synthesised by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials. For Example <CIT> discloses the necessary chemistry. Synthetic protocols can also generally be found in <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>. The examples section also provides the skilled person with sufficient direction.

To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.

According to the present invention a cocatalyst system comprising a boron containing cocatalyst as well as an aluminoxane cocatalyst is used in combination with the above defined complex.

The aluminoxane cocatalyst can be one of formula (X):
<CHM>
where n is usually from <NUM> to <NUM> and R has the meaning below.

Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR<NUM>, AlR<NUM>Y and Al<NUM>R<NUM>Y<NUM> where R can be, for example, C<NUM>-C<NUM> alkyl, preferably C<NUM>-C<NUM> alkyl, or C<NUM>-C<NUM>-cycloalkyl, C<NUM>-C<NUM>-arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C<NUM>-C<NUM> alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (X).

The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content.

According to the present invention the aluminoxane cocatalyst is used in combination with a boron containing cocatalyst.

Boron based cocatalysts of interest include those of formula (Z).

wherein Y independently is the same or can be different and is a hydrogen atom, an alkyl group of from <NUM> to about <NUM> carbon atoms, an aryl group of from <NUM> to about <NUM> carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from <NUM> to <NUM> carbon atoms in the alkyl radical and from <NUM>-<NUM> carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine. Preferred examples for Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl, <NUM>,<NUM>- difluorophenyl, pentachlorophenyl, pentafluorophenyl, <NUM>,<NUM>,<NUM>-trifluorophenyl and <NUM>,<NUM>- di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, triphenylborane, tris(<NUM>-fluorophenyl)borane, tris(<NUM>,<NUM>-difluorophenyl)borane, tris(<NUM>-fluoromethylphenyl)borane, tris(<NUM>,<NUM>,<NUM>-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(tolyl)borane, tris(<NUM>,<NUM>-dimethyl-phenyl)borane, tris(<NUM>,<NUM>-difluorophenyl)borane and/or tris (<NUM>,<NUM>,<NUM>-trifluorophenyl)borane.

Particular preference is given to tris(pentafluorophenyl)borane.

However it is preferred that borates are used, i.e. compounds containing a borate <NUM>+ ion. Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate and tetra phenyl borate. Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

Preferred ionic compounds which can be used according to the present invention include: triethylammoniumtetra(phenyl)borate,.

Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate,.

Suitable amounts of cocatalyst will be well known to the skilled man.

The molar ratio of boron to the metal ion of the metallocene may be in the range <NUM>:<NUM> to <NUM>:<NUM> mol/mol, preferably <NUM>:<NUM> to <NUM>:<NUM>, especially <NUM>:<NUM> to <NUM>:<NUM> mol/mol.

The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range <NUM>:<NUM> to <NUM>:<NUM> mol/mol, preferably <NUM>:<NUM> to <NUM>:<NUM>, and more preferably <NUM>:<NUM> to <NUM>:<NUM> mol/mol.

The catalyst of the invention can be used in supported or unsupported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina. The use of a silica support is preferred. The skilled man is aware of the procedures required to support a metallocene catalyst. Especially preferably the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in <CIT>), <CIT>) and <CIT>. The particle size is not critical but is preferably in the range <NUM> to <NUM>, more preferably <NUM> to <NUM>. The use of these supports is routine in the art.

In an alternative embodiment, no support is used at all. Such a catalyst system can be prepared in solution, for example in an aromatic solvent like toluene, by contacting the metallocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane previously dissolved in an aromatic solvent, or can be prepared by sequentially adding the dissolved catalyst components to the polymerization medium.

In one particularly preferred embodiment, no external carrier is used but the catalyst is still presented in solid particulate form. Thus, no external support material, such as inert organic or inorganic carrier, for example silica as described above is employed.

In order to provide the catalyst of the invention in solid form but without using an external carrier, it is preferred if a liquid/liquid emulsion system is used. The process involves forming dispersing catalyst components (i) and (ii) in a solvent, and solidifying said dispersed droplets to form solid particles.

In particular, the method involves preparing a solution of one or more catalyst components; dispersing said solution in an solvent to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase; immobilising the catalyst components in the dispersed droplets, in the absence of an external particulate porous support, to form solid particles comprising the said catalyst, and optionally recovering said particles.

This process enables manufacturing of active catalyst particles with improved morphology, e.g. with a predetermined spherical shape, surface properties and particle size and without using any added external porous support material, such as an inorganic oxide, e.g. silica. By the term "preparing a solution of one or more catalyst components" is meant that the catalyst forming compounds may be combined in one solution which is dispersed to the immiscible solvent, or, alternatively, at least two separate catalyst solutions for each part of the catalyst forming compounds may be prepared, which are then dispersed successively to the solvent.

In a preferred method for forming the catalyst at least two separate solutions for each or part of said catalyst may be prepared, which are then dispersed successively to the immiscible solvent.

More preferably, a solution of the complex comprising the transition metal compound and the cocatalyst is combined with the solvent to form an emulsion wherein that inert solvent forms the continuous liquid phase and the solution comprising the catalyst components forms the dispersed phase (discontinuous phase) in the form of dispersed droplets. The droplets are then solidified to form solid catalyst particles, and the solid particles are separated from the liquid and optionally washed and/or dried. The solvent forming the continuous phase may be immiscible to the catalyst solution at least at the conditions (e. temperatures) used during the dispersing step.

The term "immiscible with the catalyst solution" means that the solvent (continuous phase) is fully immiscible or partly immiscible i.e. not fully miscible with the dispersed phase solution.

Preferably said solvent is inert in relation to the compounds of the catalyst system to be produced. Full disclosure of the necessary process can be found in <CIT>.

The inert solvent must be chemically inert at least at the conditions (e.g. temperature) used during the dispersing step. Preferably, the solvent of said continuous phase does not contain dissolved therein any significant amounts of catalyst forming compounds. Thus, the solid particles of the catalyst are formed in the droplets from the compounds which originate from the dispersed phase (i.e. are provided to the emulsion in a solution dispersed into the continuous phase).

The terms "immobilisation" and "solidification" are used herein interchangeably for the same purpose, i.e. for forming free flowing solid catalyst particles in the absence of an external porous particulate carrier, such as silica. The solidification happens thus within the droplets. Said step can be effected in various ways as disclosed in said <CIT>. Preferably solidification is caused by an external stimulus to the emulsion system such as a temperature change to cause the solidification. Thus in said step the catalyst component (s) remain "fixed" within the formed solid particles. It is also possible that one or more of the catalyst components may take part in the solidification/immobilisation reaction.

Accordingly, solid, compositionally uniform particles having a predetermined particle size range can be obtained.

Furthermore, the particle size of the catalyst particles of the invention can be controlled by the size of the droplets in the solution, and spherical particles with a uniform particle size distribution can be obtained.

The process is also industrially advantageous, since it enables the preparation of the solid particles to be carried out as a one-pot procedure. Continuous or semicontinuous processes are also possible for producing the catalyst.

The inventive process for for the preparation of the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition as described herein , comprising the steps of a) introducing a stream of propylene and <NUM>-hexene to the a reactor, so that the ratio of the feed rate of <NUM>-hexene to the feed rate of propylene is from <NUM> to <NUM> mol/kmol; further introducing a stream of catalyst system to the first reactor, whereby the catalyst system includes the catalyst (i) and the cocatalyst system (ii) as described above. Preferably the ratio of the feed rate of <NUM>-hexene to the feed rate of propylene is from <NUM> to <NUM> mol/kmol and most preferably from <NUM> to <NUM> mol/kmol.

Usually a prepolymerization will precede the polymerization in the first reactor. Operation of a prepolymerization is known in the art. The prepolymerization usually takes place at <NUM> to <NUM>. Independent therefrom the pressure of the prepolymerization is preferably <NUM> to <NUM> kPa.

The catalyst system is preferably introduced into the prepolymerization reactor and transferred to the first reactor. According to the present invention it is particularly important not to introduce catalyst system to the second or third reactor. Thus, according to the present invention the stream from the prepolymerization should only enter the first reactor but should not directly enter the second or third reactor, i.e. without having passed the first reactor.

The first reactor is preferably a loop reactor.

In the first reactor propylene and <NUM>-hexene are polymerized in the presence of the catalyst system to produce a first intermediate. The product stream comprising the first intermediate from the first reactor is then transferred to a second reactor.

The second reactor is preferably a gas phase reactor.

In the second reactor propylene and <NUM>-hexene are polymerized in the presence of the first intermediate by feeding further propylene, <NUM>-hexene and hydrogen into the second reactor such that the molar ratio of the concentration of hydrogen to the concentration of propylene is in the range of <NUM> to <NUM> mol/kmol; and further the molar ratio of the concentration of <NUM>-hexene to the concentration of propylene is in the range of <NUM> to <NUM> mol/kmol.

Preferably the molar ratio of the concentration of hydrogen to the concentration of propylene is in the range of <NUM> to <NUM> mol/kmol; and further the molar ratio of the concentration of <NUM>-hexene to the concentration of propylene is in the range of <NUM> to <NUM> mol/kmol.

The polymerization in the second reactor yields a second intermediate which is withdrawn from the second reactor and transferred to a third reactor.

The third reactor preferably is a gas phase reactor.

In the third reactor ethylene, optionally together with some carry-over propylene and/or <NUM>-hexene, is polymerized in the presence of the second intermediate by introducing ethylene to yield the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition, whereby the molar ratio of the concentration of hydrogen to the concentration of ethylene is less than <NUM> mol / <NUM> x <NUM><NUM> mol. This means hydrogen is essentially absent.

Preferably the molar ratio of the concentration of hydrogen to the concentration of ethylene in the third reactor is less than <NUM> mol / <NUM> x <NUM><NUM> mol, more preferably less than <NUM> mol / <NUM> x <NUM><NUM> mol and most preferably less than <NUM> mol / <NUM> x <NUM><NUM> mol.

According to the process of the present invention, the first intermediate preferably has.

In a particularly preferred embodiment, the first intermediate preferably has.

In the process according to the present invention the second intermediate preferably has.

In a particularly preferred embodiment, the second intermediate preferably has.

units derived from <NUM>-hexene in an amount of at least <NUM> wt.

In a further aspect the amount of the first intermediate in the second intermediate preferably is from <NUM> to <NUM> % by weight. This value is also known as split.

In yet a further aspect, the amount of the second intermediate in the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition is from <NUM> to <NUM> % by weight, more preferably <NUM> to <NUM> % by weight and most preferably <NUM> to 97wt-%. Again, this value is commonly referred to as split.

In the process according to the present invention the ratio of the MFR<NUM>(second intermediate) to the MFR<NUM>(final PP/UHMW-PE composition) is preferably <NUM> to <NUM>.

As stated above, in the inventive process the first reactor is a loop reactor and/or the second reactor is a gas phase reactor and/or the third reactor is a gas phase reactor. Most preferably the first reactor is a loop reactor, and the second reactor is a gas phase reactor and the third reactor is a gas phase reactor.

Prepolymerization may take place in a prepolymerization vessel. A prepolymerization vessel is suitable a loop reactor. If a prepolymerization is carried out in a separate reactor, the catalyst system will be introduced into the first reactor in form of a prepolymer. However, it should be understood such prepolymer according to the present invention shall not be introduced into the second or third reactor.

In the following several particularly preferred embodiments are described.

In a first embodiment the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) has.

The MFR<NUM> of <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133) of the first embodiment is preferably <NUM> to <NUM>/<NUM>.

The XS according to ISO16152 of the first embodiment is less than <NUM> wt.

In a second embodiment the PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) has.

The MFR<NUM> of <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133) of the second embodiment is preferably <NUM> to <NUM>/<NUM>.

The melting temperature Tm of the second embodiment is preferably in the range of <NUM> to <NUM> (DSC, ISO <NUM>, part <NUM>).

The elementary analysis of a catalyst was performed by taking a solid sample of mass, M, cooling over dry ice. Samples were diluted up to a known volume, V, by dissolving in nitric acid (HNO<NUM>, <NUM> %, <NUM> % of V) and freshly deionised (DI) water (<NUM> % of V). The solution was then added to hydrofluoric acid (HF, <NUM> %, <NUM> % of V), diluted with DI water up to the final volume, V, and left to stabilise for two hours. The analysis was run at room temperature using a Thermo Elemental iCAP <NUM> Inductively Coupled Plasma - Optical Emmision Spectrometer (ICP-OES) which was calibrated using a blank (a solution of <NUM> % HNO<NUM>, <NUM> % HF in DI water), and <NUM> standards of <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm and <NUM> ppm of Al, with <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm, <NUM> ppm and <NUM> ppm of Hf and Zr in solutions of <NUM> % HNO3, <NUM> % HF in DI water.

Immediately before analysis the calibration is 'resloped' using the blank and <NUM> ppm Al, <NUM> ppm Hf, Zr standard, a quality control sample (<NUM> ppm Al, <NUM> ppm Hf, Zr in a solution of <NUM> % HNO3, <NUM> % HF in DI water) is run to confirm the reslope. The QC sample is also run after every 5th sample and at the end of a scheduled analysis set.

The content of hafnium was monitored using the <NUM> and <NUM> lines and the content for zirconium using <NUM> line. The content of aluminium was monitored via the <NUM> line, when Al concentration in ICP sample was between <NUM>-<NUM> ppm (calibrated only to <NUM> ppm) and via the <NUM> line for Al concentrations above <NUM> ppm.

The reported values are an average of three successive aliquots taken from the same sample and are related back to the original catalyst by inputting the original mass of sample and the dilution volume into the software.

In the case of analysing the elemental composition of prepolymerized catalysts, the polymeric portion is digested by ashing in such a way that the elements can be freely dissolved by the acids. The total content is calculated to correspond to the weight% for the prepolymerized catalyst.

Molecular weight averages (Mw, Mn), Molecular weight distribution (MWD) and its broadness, described by polydispersity index, PDI= Mw/Mn (wherein Mn is the number average molecular weight and Mw is the weight average molecular weight) were determined by Gel Permeation Chromatography (GPC) according to ISO <NUM>-<NUM>:<NUM> and ASTM D <NUM>-<NUM>.

A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with <NUM> x Olexis and 1x Olexis Guard columns from Polymer Laboratories and <NUM>,<NUM>,<NUM>-trichlorobenzene (TCB, stabilized with <NUM>/L <NUM>,<NUM>-Di tert butyl-<NUM>-methyl-phenol) as solvent at <NUM> and at a constant flow rate of <NUM>/min. <NUM>µL of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO <NUM>-<NUM>:<NUM>) with at least <NUM> narrow MWD polystyrene (PS) standards in the range of <NUM>,<NUM>/mol to <NUM><NUM>/mol. Mark Houwink constants for PS, PE and PP used are as described per ASTM D <NUM>-<NUM>. All samples were prepared by dissolving <NUM> - <NUM> of polymer in <NUM> (at <NUM>) of stabilized TCB (same as mobile phase) for <NUM> hours for PP or <NUM> hours for PE at max. <NUM> under continuous gentle shaking in the autosampler of the GPC instrument.

Quantitative nuclear-magnetic resonance (NMR) spectroscopy was further used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative <NUM>C{<NUM>H} NMR spectra were recorded in the solution-state using a Bruker Advance III <NUM> NMR spectrometer operating at <NUM> and <NUM> for <NUM>H and <NUM>C respectively. All spectra were recorded using a <NUM>C optimised <NUM> extended temperature probehead at <NUM> using nitrogen gas for all pneumatics. Approximately <NUM> of material was dissolved in <NUM> of <NUM>,<NUM>-tetrachloroethane-d<NUM> (TCE-d<NUM>) along with chromium-(III)-acetylacetonate (Cr(acac)<NUM>) resulting in a <NUM> solution of relaxation agent in solvent (<NPL>). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least <NUM> hour. Upon insertion into the magnet the tube was spun at <NUM>. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, <NUM> recycle delay and a bi-level WALTZ16 decoupling scheme (<NPL>; <NPL>). A total of <NUM> (<NUM>) transients were acquired per spectra.

Quantitative <NUM>C{<NUM>H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at <NUM> ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed <NPL>).

With characteristic signals corresponding to <NUM>,<NUM> erythro regio defects observed (as described in <NPL>, in <NPL>, and in <NPL>) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

The comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et al. This method was chosen for its robust nature and integration regions slightly adjusted to increase applicability to a wider range of comonomer contents.

Quantitative <NUM>C{<NUM>H} NMR spectra recorded in the molten-state using a Bruker Avance III <NUM> NMR spectrometer operating at <NUM> and <NUM> for <NUM>H and <NUM>C respectively. All spectra were recorded using a <NUM>C optimised <NUM> magic-angle spinning (MAS) probehead at <NUM> using nitrogen gas for all pneumatics. Approximately <NUM> of material was packed into a <NUM> outer diameter zirconia MAS rotor and spun at <NUM>. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification. Standard single-pulse excitation was employed utilising the NOE at short recycle delays of <NUM> (<NPL>. and the RS-HEPT decoupling scheme (<NPL>. A total of <NUM> (<NUM>) transients were acquired per spectra.

Quantitative <NUM>C{<NUM>H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at <NUM> ppm. Characteristic signals corresponding to the incorporation of <NUM>-hexene were observed and the comonomer content quantified in the following way.

The amount of <NUM>-hexene incorporated in PHP isolated sequences was quantified using the integral of the αB4 sites at <NUM> ppm accounting for the number of reporting sites per comonomer: <MAT>.

The amount of <NUM>-hexene incorporated in PHHP double consecutive sequences was quantified using the integral of the ααB4 site at <NUM> ppm accounting for the number of reporting sites per comonomer: <MAT>.

When double consecutive incorporation was observed the amount of <NUM>-hexene incorporated in PHP isolated sequences needed to be compensated due to the overlap of the signals αB4 and αB4B4 at <NUM> ppm: <MAT>.

The total <NUM>-hexene content was calculated based on the sum of isolated and consecutively incorporated <NUM>-hexene: <MAT>.

When no sites indicative of consecutive incorporation observed the total <NUM>-hexeen comonomer content was calculated solely on this quantity: <MAT>.

Characteristic signals indicative of regio <NUM>,<NUM>-erythro defects were observed ( <NPL>).

The presence of <NUM>,<NUM>-erythro regio defects was indicated by the presence of the Pαβ (21e8) and Pαγ (21e6) methyl sites at <NUM> and <NUM> ppm and confirmed by other characteristic signals.

The total amount of secondary (<NUM>,<NUM>-erythro) inserted propene was quantified based on the αα21e9 methylene site at <NUM> ppm: <MAT>.

The total amount of primary (<NUM>,<NUM>) inserted propene was quantified based on the main Sαα methylene sites at <NUM> ppm and compensating for the relative amount of <NUM>,<NUM>-erythro, αB4 and ααB4B4 methylene unit of propene not accounted for (note H and HH count number of hexene monomers per sequence not the number of sequences): <MAT>.

The total amount of propene was quantified as the sum of primary (<NUM>,<NUM>) and secondary (<NUM>,<NUM>-erythro) inserted propene: <MAT>.

The total mole fraction of <NUM>-hexene in the polymer was then calculated as: <MAT>.

The full integral equation for the mole fraction of <NUM>-hexene in the polymer was: <MAT>.

The total comonomer incorporation of <NUM>-hexene in mole percent was calculated from the mole fraction in the usual manner: <MAT>.

The total comonomer incorporation of <NUM>-hexene in weight percent was calculated from the mole fraction in the standard manner: <MAT>.

The melt flow rate (MFR) or melt index (MI) is measured according to ISO <NUM>. Where different loads can be used, the load is normally indicated as the subscript, for instance, MFR<NUM> which indicates <NUM> load. The temperature is selected according to ISO <NUM> for the specific polymer, for instance, <NUM> for polypropylene. Thus, for polypropylene MFR<NUM> is measured at <NUM> temperature and under <NUM> load.

DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):
measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on <NUM> to <NUM> samples. DSC is run according to ISO <NUM> / part <NUM> /method C2 in a heat / cool /heat cycle with a scan rate of <NUM>/min in the temperature range of -<NUM> to +<NUM>.

Crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while melting temperature and heat of fusion (Hf) are determined from the second heating step.

The xylene soluble (XS) fraction as defined and described in the present invention is determined in line with ISO <NUM> as follows: <NUM> of the polymer were dissolved in <NUM> p-xylene at <NUM> under agitation. After <NUM> minutes, the solution was allowed to cool for <NUM> minutes at ambient temperature and then allowed to settle for <NUM> minutes at <NUM> +/- <NUM>. The solution was filtered with filter paper into two <NUM> flasks. The solution from the first <NUM> vessel was evaporated in nitrogen flow and the residue dried under vacuum at <NUM> until constant weight is reached. The xylene soluble fraction (percent) can then be determined as follows:<MAT> mo = initial polymer amount (g); m = weight of residue (g); Vo = initial volume (ml); v = volume of analysed sample (ml).

The catalyst activity was calculated on the basis of following formula: <MAT> (h)).

Overall productivity was calculated as <MAT>.

For both the catalyst activity and the productivity the catalyst loading is either the grams of prepolymerized catalyst or the grams of metallocene present in that amount of prepolymerized catalyst.

The composition of the catalysts (before the off-line prepolymerization step) has been determined by ICP as described above. The metallocene content of the prepolymerized catalysts has been calculated from the ICP data as follows: <MAT> <MAT> <MAT> <MAT>.

Examples were carried out in pilot scale. A three reactor process set up was used, whereby the first reactor was a loop reactor and the second and third reactors were gas phase reactors.

The catalyst abbreviated "SSC" used in the inventive examples was prepared as described in detail in <CIT> (metallocene complex MC1 with methylaluminoxane (MAO) and borate (cocatalyst system) resulting in Catalyst <NUM> described in <CIT>) with the proviso that the surfactant was <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoro-<NUM>-(<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-heptafluoropropoxy)-<NUM>-propanol. The metallocene complex (MC1 in <CIT>) was prepared as described in <CIT> (metallocene E2 in <CIT>).

Comparative examples used a two reactor system. For comparative example <NUM><NUM> wt. -% of a LLDPE material produced with a single site catalyst was introduced in the pelletization.

Claim 1:
PP/UHMW-PE (Polypropylene-Ultrahigh-Molecular-Weight-Polyethylene) composition having
- a melting temperature Tm in the range of <NUM> to <NUM> (DSC, ISO <NUM>, Part <NUM>),
- an MFR<NUM> of <NUM> to <NUM>/<NUM> (<NUM>, <NUM>, ISO1133),
- units derived from <NUM>-hexene in an amount of at least <NUM> wt.-% up to <NUM> wt.-%, as determined according to the description
and
- units derived from ethylene in an amount of <NUM> to <NUM> wt.-%, as determined according to the description and
- a XS according to ISO16152 of less than <NUM> wt.-% all weight percentages with respect to the total PP/UHMW-PE composition.