WO2014180989A1

WO2014180989A1 - Hdpe

Info

Publication number: WO2014180989A1
Application number: PCT/EP2014/059579
Authority: WO
Inventors: Andrey Buryak; Christian Rein; Luc Monnissen; Geir Kristian Johnsen; Joy Cheng
Original assignee: Borealis Ag; Abu Dhabi Polymers Company Limited (Borouge) L.L.C.
Priority date: 2013-05-09
Filing date: 2014-05-09
Publication date: 2014-11-13
Also published as: EP2994506B2; AU2014264567A1; CN105408412B; RU2674695C2; RU2015149952A; US9441062B2; ES2636850T3; CL2015003240A1; PL2994506T3; EP2994506B1; EP2994506A1; US20160083488A1; RU2015149952A3; PH12015502552B1; PE20160102A1; BR112015028045B1; MA38644A1; AP2015008887A0; TN2015000489A1; CN105408412A

Abstract

A multimodal polyethylene polymer having an MFR₂ of 0.05 to 10.0 g/10min, a density of 940 kg/m³ or more, a tensile modulus of 900 MPa or more wherein Formula (I).

Description

HDPE

The present invention relates to a polyethylene polymer for injection moulded articles, in particular for the manufacture of caps and closures. The present invention also relates to a process for the production of said polymer, an injection moulded article comprising said polymer and to the use of said polymer for the production of an injection moulded article such as a cap or closure. The

polyethylene of the invent ion is a mult imodal high density polyethylene with a particular molecular weight distribution enabling the formation of injection moulded articles with advantageous properties in terms of stress crack resistance and tensile modulus and in terms of art icle aspect (appearance ).

Background Injection moulding may be used to make a wide variety of articles including articles having relatively complex shapes and a range of sizes. Injection moulding is, for instance, suited to the manufacture of articles used as caps and closures for food and drink applications, such as for bottles containing carbonated or non-carbonated drinks, or for non-food applications like containers for cosmetics and

pharmaceut icals.

Injection moulding is a moulding process in which a polymer is melted and then filled into a mould by injection. During initial injection, high pressure is used and the polymer melt is compressed. Thus, upon injection into the mould the polymer melt initially expands or "relaxes" to fill the mould. The mould, however, is at a lower temperature than the polymer melt, and therefore as the polymer melt cools, shrinkage tends to occur. To compensate for this effect, back pressure is applied. Thereafter the polymer melt is cooled further to enable the moulded article to be removed from the mould without causing deformation.

An important property of an injection moulded article is its stress crack resistance. It will be appreciated that the injection moulded articles of the invention should not exhibit brittle failure and should therefore possess a high stress crack resistance. An increase in stress cracking resistance is however, generally associated with decreases i n tensile strength, e.g. in tensile modulus. It will also be appreciated that inject ion moulded articles are preferably stiff. This decrease in tensile modulus is particularly marked for HDPE. The present inventors sought new HDPEs, developed in particular for the cap and closure market, which posses improved stress cracking resistance and high tensile modulus. To add to the challenge however, these improvements must not be at the expense of processability of the polymer or the appearance of any article formed. Processabil ity must be maintained or even improv ed to meet customer needs. In jection mou lded articles arc produced rapidly and any reduction in processabi lity can increase cycle times and hence reduce process efficiency.

The present inventors have found that if HDPEs possess a certain relat ionship of molecular weight properties at melt flow rates appropriate for inject ion moulding, high stress crack resistance and tensi le strength can be achieved. I n particular, the present inv ent ion describes a multimodal H DPE polymer with tailored molecular weight that results in improved FNC'T without reduction in tensile modul us. Our FNCT is clearly improved over a select ion of comparable commercial polymer grades. I n addit ion, caps or closures produced using this polymer have better aspect, speci fical ly in terms of lower high-tips and less angcl- hair.

When a cap or closure is formed in the inject ion moulding process, there is normally a small defect at the point of in jection on top of the cap. This defect is a slight ly raised portion on the top of the cap and is cal led a high tip. Wh i lst it is difficult to observe wit h the naked eye, the h igh tip can usual ly be felt on the top of most caps and closures. The polymers of the present inv ent ion allow this h igh tip to be m inim ised in size.

We attach hereto as figures 1 and 2, pictures of a high tip ( figure 2) which is generally unacceptably extended, and a low "high tip" (typically one that is less than 0.5 mm in height - figure 1) which is the target in the industry.

Moreover, when the injection moulding process is complete, a further problem which can occur is the format ion of angel hair. Angel hair is fibre like strands of polymer that form on the top of the cap at the in jection point as the cap is mov ed away from the inject ion mou lding nozzle in the conti nuous inject ion moulding process. If the injection moulding process and the polymer used is not ideally suited to the injection moulding process, the polymer melt can stretch to form these fibre l ike hairs. The polymers of the inv ent ion also m inimise formation of such hair. Figure 3 shows the format ion of angel hair on a cap. Angel hairs can hav e serious consequences for further manipulation of the cap, e.g. print ing thereon and upon its appearance.

The inv ent ion relies on the use of polymers which have particular mo lecular weight distribut ion through a comparison on their Mz, Mn and Mw values. The present inv entors have found that a particular relationship of Mz, Mw and Mn gives rise to polymers with advantageous properties. In particular therefore, the ratio of Mz/Mw must be low compared to the ratio of Mw. Mn. The relat ionship in claim 1 defines polymers that have a less pronounced high molecular weight tail. This does not prev ent the polymers possessing a relatively broad molecular weight distribution Mw/Mn however.

Without wishing to be lim ited by theory, it may be that the problem of angel hair is exacerabated by the presence of high molecular weight chains within the polymer. I t may be that because the polymers of the invention have a less pronounced high molecular weight tail that the polymers offer benefits in terms of minimising angel hair. Also, the inv entors suggest that high levels of Mz/Mw may result i n the format ion of larger "high tips" on caps Our polymers may therefore enable the format ion of lower "high tip".

For avoidance of doubt, these high tips are so small that cutting them off is impractical. Also, caps are produced rapidly in high numbers and the cost of even attempt ing a cutting process on a plurality of caps would be prohibitive.

The advantageous properties of the H DPE of the inv ent ion can also be achieved without loss of processability. Again, the relationship between the high Mw and low Mw chains within the polymer of the invent ion means that the processability of the polymers of the invent ion is excellent.

In EP-A- 1940942, HDPE compositions are described primarily for blow moulding appl icat ions. The compositions comprise a blend of unimodal H DPE and a high Mw un imodal polymer to thus form a bi modal composit ion. The polymers do not satisfy the ratio in claim 1 however. The present inventors have compared the polymer of the invention to a broad range of commercial injection moulding grades of comparable tensi le modulus to show that the relationship in claim 1 is not one which can be found in commercial polymers and is one which yields the advantageous properties highlighted above.

Summary of Invention

Viewed from one aspect the invention prov ides a mult imodal polyethylene polymer having an M FR₂ of 0.05 to 10.0 g 10m in, a density of 940 kg m ³ or more, a tensile modulus of 900 MPa or more and wherein

Preferably, the mult imodal po lyethylene polymer comprises a lower molecular weight homopolymer component and a h igher molecular weight copolymer component, e.g. with a C3- 12 alpha olefin comonomer.

Thus, viewed from another aspect the invention provides a multimodal polyethylene polymer having a lower mo lecular weight homopolymer component and a higher mo lecular weight copolymer component, e.g. with a C3- 12 alpha olefin comonomer and having an MFR₂ of 0.05 to 10.0 g 10min, a density of 940 kg m³ or more, a tensi le modulus of 900 MPa or more and wherein

The polymer of the invent ion has a large Mw/Mn ratio and small Mz/Mw ratio. This molecular distribution structure results in injection moulded articles, and in particular caps and closures, which have a good aspect (e.g. lower high-tip and less angel-hair).

Viewed from another aspect the invention provides a multimodal polyethylene polymer hav ing an M FR₂ of 0.05 to 10.0 g 10m in, a density of 940 kg/m³ or more, a tensi le modulus of 900 MPa or more, wherein and wherein

Preferably, said multimodal polyethylene polymer comprises a lower molecular weight homopolymcr component and a higher molecular weight copolymer component, e.g. with a C3-12 alpha olefin comonomer.

Thus, viewed from another aspect the invention provides a multimodal polyethylene polymer having a lower molecular weight homopolymer component and a higher mo lecular weight copolymer component, e.g. with a C3- 12 alpha olefin comonomer and hav ing an MFR₂ of 0.05 to 10.0 g 10m in, a density of 940 kg m³ or more, a tensile modulus of 900 MPa or more, wherein and wherein

V iew ed from another aspect the i nv ent ion prov ides an inject ion or

compression moulded article, such as a cap or closure comprising a polymer as herein before defined. Such caps or closures may w eight from 1 to 10 g. Moreover, caps or closures of the invention may possess a high tip of less than 0.5 mm in height, such as less than 0.25 mm in height.

View ed from another aspect the invent ion prov ides the use of the polymer as hereinbefore defined in the manufacture of a injection moulded or compression article, such as a cap or closure.

Viewed from another aspect the inv ent ion provides a process for the preparation of a polyethylene as herein before defined comprising: polymerising ethylene and optionally at least one C3- 10 alpha olefin comonomer so as to form a lower molecular weight component (A); and

subsequently

polymerising ethylene and optionally at least one C3- 10 alpha olefin comonomer in the presence of component (A) so as to form a higher molecular weight component (B). The invention further comprises compression or injection moulding the product of said process to form an article. Preferably, the mult imodal polyethylene polymer made in this process comprises a lower mo lecular weight homopolymer component and a h igher molecular weight copolymer component, e.g. with a C3- 12 alpha olefin comonomer.

Definitions

The term Mz refers to the Z average mo lecular weight of the polymer. The Mz is measured by establ ish thermodynamic equil ibrium where molecules distribute according to mo lecular size. Mz is more sensitive than the other averages to the largest molecules present in the sample and hence the val ues we report in the present invent ion represent polymers with a less pronounced high molecular weight tai l.. Detailed Description of Invention i t has been found that the h igh density polyethylene polymer according to the invent ion provides an improved material for compression or especially inject ion moulding, in particular for cap and closure applications, which combines very good mechanical properties e.g. in terms of FNCT and tensile modulus w ith excel lent processability and aspect, e.g. in terms of high tip and angel hair. Whi lst problems of angel hair and h igh tips are not so critical w hen a cap is compression moulded, the improv ements which we observe in terms of FNCT and tensile modulus are important in compression mou lded caps.

The polymer of the invent ion is a mult imodal high density ethylene polymer and may be an ethylene homopolymer or an ethylene copolymer. By ethylene copolymer is meant a polymer the majority by weight of wh ich derives from ethylene monomer units. The comonomer contribution preferably is up to 10% by mo I. more preferably up to 5 % by mo 1. Ideally however there are very low lev els of comonomer present in the polymers of the present invent ion such as 0. 1 to 2 mol%, e.g. 0. 1 to 1 mol%.

The other copolymerisable monomer or monomers are preferably C3-20, especially C3- 10, alpha olefin co monomers, particu larly singly or mult iply ethylenically unsaturated comonomers, in particular C3- 10-alpha olefins such as propene, but- 1 -cue, hex- 1 -ene, oct- l -ene, and 4-methyl-pent- 1 -enc. The use of hexene and butene is particularly preferred. Ideal ly there is only one comonomer present.

I t is preferred if the polymer of the invent ion is a copolymer and therefore comprises ethylene and at least one comonomer. Ideally that comonomer is 1 - butene.

The polymer of the inv ent ion is mult i modal and therefore comprises at least two components. The polymer of the inv ention preferably comprises

(A) a lower molecular weight first ethylene homo- or copolymer component, and

(B) a higher molecular weight second ethylene homo- or copolymer component.

I t is generally preferred i f the higher molecular weight component has an Mw of at least 5000 more than the lower molecular weight component, such as at least 10,000 more.

The HDPE of the inv ent ion is mult imodal. Usually, a polyethylene composit ion comprising at least two polyethylene fractions, which have been produced under different polymerisation conditions resulting in different (weight average) molecular weights and mo lecular weight distribut ions for the fractions, is referred to as "multimodal". Accordingly, in this sense the compositions of the inv ent ion arc mu lt imodal polyethylenes. The prefix "multi" relates to the number of di fferent polymer fract ions the composition is consist i ng of. Thus, for example, a composition consisting of two fractions only is called "bimodal".

The form of the molecular weight distribution curve, i.e. the appearance of the graph of the polymer weight fract ion as funct ion of its mo lecular weight, of such a multimodal polyethylene will show two or more maxima or at least be distinctly broadened in comparison with the curves for the individual fractions. For example, if a polymer is produced in a sequential multistage process, utilising reactors coupled in series and using different conditions in each reactor, the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight. When the molecular weight distribution curve of such a polymer is recorded, the individual curves from these fractions are superimposed into the molecular weight distribution curve for the total resulting polymer product, usually yielding a curve with two or more dist inct max ima.

The polymer of the inv ent ion preferably has an MFR₂ of 5 g 1 0 m in or less, preferably 4.5 g/lOmin or less, such as 3.5 g/lOmin or less, more preferably 2.8 g 10m in or less, especial ly 2 g 1 0m in or less, most especial ly 1 .5 g 1 0m in or less, such as 1.1 g 10m in or less, more especially 1.0 g/ 10m in or less. The polymer preferably has a m inimum M FR > of 0. 1 g l Omin, such as 0.3 g/^'10 min.

The polymer of the invent ion preferably has an MFR21 of 20 to 100 g/10 m in, such as 25 to 90 g/ l Omin, more preferably 30 to 80 g/lOmin, most preferably 30 to 60 g/lOmin.

The polymer of the invent ion preferably has an MFR₅ of 0.5 to 20 g l Omin, such as 0.8 to 1 5 g 10m in, preferably 1 to 10 g 10m in.

The density of the polymer preferably is 940 kg m ^' or more. The polymers of the invent ion are therefore high density polyethylene*, HDPE. More preferably, the polymer has a density of 945 kg/m³ or more, still more preferably is 950 kg/m³ or more, still more preferably is 952 kg/m³ or more, and most preferably is 954 kg/m³ or more.

Furthermore, the density of the polymer preferably is 970 kg/m³ or lower, and more preferably is 965 kg/m³ or lower. An ideal density range is 950 to 960 kg/m³.

Preferably, the polymer of the invention has a tensile modulus of at least 900 kPa, more preferably at least 910 kPa.

The polymer preferably has an env ironmental stress crack resistance measured as FNCT of 30 h or more, more preferably 40 h or more, more preferably of 50 h or more. l n particular, the polymers of the invention possess both a tensile modulus of at least 900 MPa and a FNCT of 50h or more.

It will be appreciated that the molecular weight and molecular distribution of the polymers of the invent ion is important. The polyethylene polymer preferably has a molecular weight distribution Mw/Mn, being the ratio of the weight average molecular weight Mw and the number average molecular weight Mn, of 10 or more, more preferably of 1 2 or more, still more preferably of 14 or more.

The polymer preferably has an Mw/Mn of 30 or below, more preferably of 25 or below.

The weight average molecular weight Mw of the polymer preferably is at least 50 kD, more preferably at least 80 kD, and most preferably at least 100 kD.

Furthermore, the Mw of the composition preferably is at most 300 kD, more preferably 275 kD.

The Mz/Mw ratio is preferably no more than 8.0, more preferably no more than 7.0. especially no more than 6.5. The Mz/Mw ratio is preferably at least 3.0, more preferably at least 3.5. The actual value of Mz is preferably in the range of 400k D to 700kD, such as 450 kD to 600 kD.

The value of Mw²/MnMz is preferably at least 2.8, such as at least 2.9, especially at least 3.0. This value preferably does not exceed 5.0.

The value of 0.29(Mw/Mn) + 0.8 is preferably between 4.25 and 6.25 mean ing the Mz/Mw v alue should be less than that.

It is particularly, preferred if Mz/Mw is at least 0.25 less, more preferably 0.5 less, especially 0.75 less, most preferably 1.0 less than the value of 0.29Mw/Mn + 0.8.

In another embodiment the value of the equation is preferably

( 1 .05 Mz)/Mw < (0.29Mw/Mn) + 0.8 (1.1 Mz)/Mw < (0.29Mw/Mn) + 0.8

( 1 . 1 5 Mz)/Mw < (0.29Mw/Mn) + 0.8; or even (1.2 Mz l ^'Mw < (0.29Mw/Mn) + 0.8

These equations emphasize therefore that the difference between the Mz/Mw value and (0.29Mw/^'Mn) + 0.8 is significant.

These molecular weight relationships in claim 1 define a high density polyethylene with a larger concentration of higher content of low molecular chains and a lower content of higher molecular weight chains. Whilst this affects the Mz value, the Mw/Mn value is independent. This weighting of the mo lecular weight distribution occurs results in the advantageous properties which we observe in the present application.

As noted above, the polymers of the invention preferably comprise a lower molecular weight component (A) and a higher molecular weight component (B). The weight ratio of fraction (A) to fraction (B) in the composit ion is in the range 30:70 to 70:30, more preferably 35:65 to 65:35, most preferably 40:60 to 60:40. In some embodiments the ratio may be 45 to 55 wt% of fraction (A) and 55 to 45 wt% fraction (B), such as 45 to 52 wt% ef fraction (A) and 55 to 48 wt% fract ion (B). I t has been found however that the best results are obtained when the HMW component is present at the same prcecntage or even predominates, e.g. 50 to 54 wt% of the HMW component (B) and 50 to 46 wt% fraction (A).

Fract ions (A) and (B) may both be ethylene copolymers or ethylene homopolymers, although preferably at least one of the fract ions is an ethylene copolymer. Preferably, the polymer comprises an ethylene homopolymer and an ethylene copolymer component.

Where one of the components is an ethylene homopolymer, this is preferably the component with the lower weight average molecular weight (Mw), i.e. fract ion (A). An ideal polymer is therefore a lower mo lecular weight homopolymer component (A) with a higher mo lecular weight component (B), ideal ly an ethylene butene higher molecular weight component.

The lower molecular weight fract ion (A) preferably has an M FR > of 10 g 10m in or higher, more preferably of 50 g 10m in or higher, and most preferably 100 g/ 1 0m in or higher. Furthermore, fraction (A) preferably, has an M FR i of 1000 g/10 min. or lower, preferably 800 g/10 min or lower, and most preferably 600 g/lOmin or lower.

The weight average molecular weight Mw of fract ion (A) preferably is 10 kD or higher, more preferably is 20 kD or higher. The Mw of fraction (A)

preferably is 90 kD or lower, more preferably 80 kD or lower, and most preferably is 70 kD or lower.

Preferably, fract ion (A) is an ethylene homo- or copolymer with a density of at least 965 kg/m³.

Most preferably, fract ion (A) is an ethylene liomopolymer. If fraction (A) is a copolymer, the comonomer is preferably 1 -butcne. The comonomer content of fraction (A), if it is a copolymer, is preferably very low, such as less than 0.2 mol%, preferably less than 0. 1 mol%, especially less than 0.05 mol%. A further preferred option therefore, is for fraction (A) to be a liomopolymer or a copolymer with a very low comonomer content, such as less than 0.2 mol%, preferably less than 0. 1 moi%, especially less than 0.05 mol%. The higher Mw fraction (B) is then preferably a copolymer.

The higher molecular weight fract ion (B) preferably has an Mw of 60 k D or h igher, more preferably of 1 00 kD or higher. Furthermore, fract ion (B) preferably has an Mw of 500 kD or lower, more preferably of 400 kD or lower.

Preferably, fract ion (B) is an ethylene homo- or copolymer with a density o f less than 965 kg/m³ .

Most preferably, fraction (B) is a copolymer. Preferred ethylene copolymers employ alpha-olefins (e.g. C3- 12 a!pha-olefins ) as co monomers. Examples of suitable alpha-olefins include but- 1 -cue, hex- 1 -cue and oct- l -ene. But- 1 -cue is an especial ly preferred comonomer.

Where herein features of fractions (A) and/or (B) of the composit ion of the present invention are given, these values are generally valid for the cases in which they can be direct ly measured on the respective fraction, e.g. when the fraction is separately produced or produced in the first stage of a multistage process. However, the composit ion may also be and preferably is produced in a mu lt istage process wherein e.g. fractions (A) and (B) are produced in subsequent stages. In such a case, the properties of the fractions produced in the second step (or further steps) of the mult istage process can cither be inferred from polymers, which are separately produced in a single stage by applying identical polymerisat ion condit ions ( e.g. ident ical temperature, partial pressures of the reactants di luents, suspension medium, reaction time) with regard to the stage of the multistage process in which the fraction is produced, and by using a catalyst on which no previously produced polymer is present. Alternat ively, the properties of the fractions produced in a higher stage of the mu lt istage process may also be calculated, e.g. in accordance wit h B. Hagstrom, Conference on Polymer Processing ( The Polymer Processing Society), Extended Abstracts and Final Programme, Gothenburg, August 19 to 21, 1997, 4: 13.

Thus, although not directly measurable on the multistage process products, the properties of the fractions produced in higher stages of such a multistage process can be determined by applying either or both of the abov e methods. The sk illed person will be able to select the appropriate method.

A mult imodal (e.g. bi modal ) polyethylene as hereinbefore described may be produced by mechan ical blending two or more polyethylenes ( e.g. monomodal polyethylenes ) hav ing di fferently centred maxima in their molecular weight distribut ions. The monomodal polyethylenes required for blending may be avai lable commercial ly or may be prepared using any convent ional procedure know n to the sk illed man in the art. Each of the polyethylenes used in a blend and/or the final polymer composit ion may have the properties hereinbefore described for the lower molecular weight component, higher mo lecular w eight component and the composit ion, respectively.

The process of the invent ion preferably involves

polymerising ethylene and optionally at least one C3- 10 alpha olefin comonomer so as to form a lower molecular weight component (A); and

subsequent ly

polymerising ethylene and optional ly at least one C3- 10 alpha olefin comonomer in the presence of component (A) so as to form a higher molecular weight component (B).

I t is preferred if at least one component is produced in a gas-phase reaction.

Further preferred, one of the fractions (A) and (B) of the polyethylene composit ion, preferably fraction (A), is produced in a slurry reaction, preferably in a loop reactor, and one of the fractions (A) and (B), preferably fraction (B), is produced in a gas-phase reaction.

Preferably, the mult imodal polyethylene composit ion may be produced by polymerisation using conditions which create a multimodal (e.g. bimodal) polymer product, e.g. using a catalyst system or mixture with two or more different catalyt ic sites, each site obtained from its own catalytic site precursor, or using a two or more stage, i.e. multistage, polymerisation process with different process conditions in the different stages or zones (e.g. different temperatures, pressures, polymerisation media, hydrogen partial pressures, etc).

Preferably, the mult imodal (e.g. bimodal ) composition is produced by a mult istage ethylene polymerisat ion, e.g. using a series of reactors, with optional comonomer addit ion preferably in only the reactor(s) used for production of the higher/highest molecular weight components ) or di ffering comonomcrs used in each stage. A multistage process is defined to be a polymerisation process in which a polymer comprising two or more fract ions is produced by producing each or at least two polymer fraction(s) in a separate reaction stage, usually with different reaction condit ions in each stage, in the presence of the react ion product of the previous stage which comprises a polymerisation catalyst. The polymerisation reactions used in each stage may involve convent ional ethylene homopolymerisat ion or copolymerisation reactions, e.g. gas-phase, slurry phase, liquid phase

polymerisations, using conv entional reactors, e.g. loop reactors, gas phase reactors, batch reactors etc. (see for example W097/44371 and W096/18662).

Polymer compositions produced in a multistage process are also designated as "in-situ" blends.

Accordi ngly, it is preferred that fract ions (A) and (B) of the polyethylene composition are produced in different stages of a multistage process.

Preferably, the multistage process comprises at least one gas phase stage in which, preferably, fraction (B) is produced.

Further preferred, fraction (B) is produced in a subsequent stage in the presence of fract ion (A) which has been produced in a previous stage.

i t is previously known to produce mu lt imodal, in particular bimodal, olefin polymers, such as multimodal polyethylene, in a multistage process comprising two or more reactors connected in series. As instance of this prior art, ment ion may be made of EP 517 868, which is hereby incorporated by way of reference in its entirety, including all its preferred embodiments as described therein, as a preferred multistage process for the production of the polyethylene composition according to the invention.

Preferably, the main polymerisation stages of the multistage process for producing the composition according to the invention are such as described in EP 517 868, i.e. the production of fractions (A) and (B) is carried out as a combination of slurry polymerisat ion for fract ion (A ) gas-phase polymerisation for fract ion (B). The slurry polymerisat ion is preferably performed in a so-called loop reactor.

Further preferred, the slurry polymerisation stage precedes the gas phase stage.

Optional ly and advantageously, the main polymerisation stages may be preceded by a prcpolymerisat ion, in which case up to 20 % by weight, preferably 1 to 10 % by weight, more preferably 1 to 5 % by weight, of the total composit ion is produced. The prepolymer is preferably an ethylene homopolymcr ( H igh Density PE). At the prcpolymerisat ion. preferably al l o f the catalyst is charged into a loop reactor and the prcpolymerisat ion is performed as a slurry po lymerisat ion. Such a prcpolymerisat ion leads to less fine particles being produced in the follow ing reactors and to a more homogeneous product being obtained in the end.

The polymerisat ion catalysts include coordinat ion catalysts of a transit ion metal, such as Ziegler-Natta (ZN), metal locenes, non-metallocenes, Cr-catalysts etc. The catalyst may be supported, e.g. with convent ional supports including sil ica, A l- containing supports and magnesium dichloride based supports. Preferably the catalyst is a ZN catalyst, more preferably the catalyst is sil ica supported ZN catalyst,.

The Ziegler-Natta catalyst further preferably comprises a group 4 (group numbering according to new IUPAC system) metal compound, preferably titanium, magnesium dichloride and aluminium.

The catalyst may be commercial ly avai lable or be produced in accordance or analogously to the l iterature. For the preparation of the preferable catalyst usable in the inv ention reference is made to WO2004055068 and WO2004055069 of Boreal is. EP 0 688 794 and EP 0 810 235. The content of these documents in its ent ircty is incorporated herein by reference, in particular concerning the general and all preferred embodiments of the catalysts described therein as well as the methods for the production of the catalysts. Particularly preferred Ziegler-Natta catalysts arc described in EP O 810 235.

The resulting end product consists of an intimate mixture of the polymers from the two or more reactors, the different molecular-weight-distribution curves of these polymers together forming a molecular- weight-distribution curve having a broad maximum or two or more maxima, i.e. the end product is a bimodal or multimodal polymer mixture.

It is preferred that the base resin, i.e. the entirety of all polymeric constituents, of the composition according to the invention is a bimodal polyethylene mixture consist ing of fract ions (A) and (B), optionally further comprising a small prepolymerisat ion fraction in the amount as described above. I t is also preferred that this bimodal polymer mixture has been produced by polymerisation as described above under different polymerisation conditions in two or more polymerisation reactors connected in series. Owing to the flexibility with respect to reaction conditions thus obtained, it is most preferred that the

polymerisation is carried out in a loop reactor/a gas-phase reactor combination.

Preferably, the polymerisat ion condit ions in the preferred two-stage method are so chosen that the comparat ively low-mo lecular polymer having no content of comonomer is produced in one stage, preferably the first stage, owing to a high content of chain-transfer agent ( hydrogen gas), whereas the high-mo lecular polymer having a content of comonomer is produced in another stage, preferably the second stage. The order of these stages may, however, be rev ersed.

I n the preferred embodiment of the polymerisation in a loop reactor followed by a gas-phase reactor, the polymerisat ion temperature in the loop reactor preferably is 85 to 1 15 °C, more preferably is 90 to 105 °C, and most preferably is 92 to 100 °C, and the temperature in the gas-phase reactor preferably is 70 to 105 °C, more preferably is 75 to 100°C, and most preferably is 82 to 97°C.

A chain-transfer agent, preferably hydrogen, is added as required to the reactors, and preferably 100 to 800 mo les of 112 kmoles of ethylene are added to the reactor, when the LMW fract ion is produced in this reactor, and 50 to 500 moles of H 2 kmoles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.

I n the production of the composition of the present inv ention, preferably a compounding step is applied, wherein the composition of the base resin, i.e. the blend, which is typical ly obtained as a base resin powder from the reactor, is extruded in an extruder and then pcl lct iscd to polymer pellets in a manner known in the art.

The polyethylene composition may also contain minor quantities of additives such as pigments, nucleating agents, antistatic agents, fillers, antioxidants, etc., general ly in amounts of up to 10 % by weight, preferably up to 5 % by weight .

Optional ly, addit iv es or other polymer components can be added to the composition during the compounding step in the amount as described above.

Preferably, the composition of the invention obtained from the reactor is compounded in the extruder together with additives in a manner known in the art.

The polyethylene po lymer of the invent ion may also be combined with other polymer components such as other polymers of the inv ention, with other H DPEs or with other polymers such as LLDPE or LDPE. However articles of the invention such as caps and closures are preferably at least 90 wt% of the polymer of the inv ent ion, such as at least 95 wt%. I n one embodiment, the articles consist essentially of the polymer of the invention. The term consists essentially of means that the polymer of the invent ion is the only "non addit iv e" polyolefm present. It will be appreciated however that such a polymer may contain standard polymer addit ives some of wh ich might be supported on a polyolefm (a so cal led masterbatch as is well known in the art). The term consists essentially of does not exclude the presence of such a supported addit iv e.

Applications

Still further, the present invention relates to an injection or compression moulded art icle, preferably a cap or closure, comprising a polyethylene composit ion as described above and to the use of such a polyethylene composition for the production of an injection or compression moulded article, preferably a cap or closure. Preferably, injection moulded articles are made.

Injection moulding of the composition hereinbefore described may be carried out using any convent ional inject ion moulding equipment. A typical inject ion moulding process may be carried out a temperature of 190 to 275°C.

Still further, the present invention relates to a compression moulded article, preferably a caps or closure article, comprising a polyethylene polymer as described above and to the use of such a polyethylene polymer for the production of a compression moulded article, preferably a cap or closure.

Preferably, the composit ion of the invent ion is used for the production of a caps or closure article.

As noted above, the caps and closures of the present invention are advantageous not only because of their high FNCT and tensile modulus properties, but also because they minimise the formation of angel hair and high tips. It is thus preferred if any injection moulding process does not result in the fomiation of angel hair.

It is also preferred if caps comprising the polymer of invention have a high tip of less than 0.5 mm in height, such as 250 microns or less, in height, e.g. 200 microns or less such as 100 microns or less. Ideally, the high tip is so small that the human being cannot feel it on top of the cap or closure.

The caps and closures of the invention are of conventional size, designed therefore for bottles and the like. They are approximately 2 to 8 cm in outer diameter (measured across the solid top of the cap) depending on the bottle and provided with a screw. Cap height might be 0.8 to 3 cm.

Caps and closure may be prov ided with tear strips from which the cap detaches on first opening as is well known in the art. Caps may also be provided with liners.

I t will be appreciated that any parameter ment ioned above is measured according to the detailed test given below. In any parameter where a narrower and broader embodiment are disclosed, those embodi ments are disclosed in connect ion with the narrower and broader embodiments of other parameters. Tlic invention will now be described with reference to the following non l imit ing examples and figures.

Figure 1 shows a cap with an acceptable small tip. Figure 2 shows a cap with "h igh tip". Figure 3 shows the presence of angel hair on a cap.

Figure 4 shows the relationship between Mz/Mw and Mw/Mn plotting the line of the equation of the invention.

Figure 5 shows FNCT vs tensile modulus of the polymers of the invention and those of the prior art. Test Methods:

Melt Flow Rate

The melt flow rate (MFR) is determined according to ISO 1 133 and is indicated in g/10 m in. The MFR is an indicat ion of the melt viscosity of the polymer. The MFR is determined at 190°C for PE. The load under which the melt flow rate is determined is usually indicated as a subscript, for instance M FR > is measured under 2.16 kg load (condit ion D), MFR_? is measured under 5 kg load (condition T) or MFR21 is measured under 21 .6 kg load (condition G). The quantity FRR (flow rate ratio) is an indication of molecular weight distribution and denotes the ratio of flow rates at different loads. Thus, FRR21/2 denotes the value of MFR21_./MFR2.

Density

Density of the polymer was measured according to I SO 1 183 / 1872-2B.

For the purpose of this invention the density of the blend can be calculated from the densities of the components according to:

where pb is the density of the blend,

w; is the weight fraction of component "i" in the blend and p, is the density of the component "i".

Quant ification of microstructure by NMR spectroscopy Quantitative nuclear- magnetic resonance (NM R ) spectroscopy was used to quantify the comonomer content of the polymers.

Quant itative ¹³C {¹H} NMR spectra recorded in the molten-state using a Bruker Advance I I I 500 NMR spectrometer operating at 500.13 and 125.76 MHz for ¹ I I and ^!3C respectively. All spectra were recorded using a ¹³C optimised 7 mm magic-angle spinning (MAS) probehcad at 150°C using nitrogen gas for al l pneumat ics. Approximately 200 mg of material was packed into a 7 mm outer diameter zircon ia MAS rotor and spun at 4 k Hz. Standard single-pulse excitat ion was employed ut ilis ing the transient NOB at short recycle delays of 3s {poliard04, klimke06} and the RS-H EPT decoupl ing scheme {fillip05, griffin07} . A total of 1024 (lk) transients were acquired per spectrum. This setup was chosen due its high sensitivity towards low comonomer contents.

Quant itativ e NMR spectra were processed, integrated and quantitative properties determined using custom spectral analysis automation programs. All chemical shifts are internally referenced to the bulk methylene signal (δ+) at 30.00 ppm {randall89} .

Characteristic signals corresponding to the incorporation of 1-butene were observed (randall89) and all contents calculated with respect to ail other monomers present in the polymer.

Characteristic signals resulting from isolated 1 -butene incorporation i.e. EEBEE comonomer sequences, were observed. Isolated 1 -butene incorporation was quantified using the integral of the signal at 39.84 ppm assigned to the *B2 sites, accounting for the number of reporting sites per comonomer:

B = I*B2

With no other signals indicativ e of other comonomer sequences, i.e.

consecutive comonomer incorporation, observed the total 1 -butene comonomer content was calculated based solely on the amount of isolated 1 -butene sequences:

The relative content of ethylene was quantified using the integral of the bulk methylene (δ+) signals at 30.00 ppm:

The total ethylene comonomer content was calculated based the bulk methylene signals and accounting for ethylene units present in other observed comonomer sequences or end-groups:

The total mole fraction of 1-butene in the polymer was then calculated as:

The total comonomer incorporation of 1-butene in mole percent was calculated from the mole fraction in the usual manner:

The total comonomer incorporation of 1 -butene i n weight percent was calculated from the mole fraction in the standard manner:

klimke06

Klimke, K., Parkinson, M, Piel, C, Kaminsky, W., Spiess, H.W., Wilhelm, M, Macromol. Chem.

Phys. 2006;207:382.

pollard04

Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C, Kaminsky, W., Macromolecules 2004;37:813.

filip05

Filip, X., Tripon, C, Filip, C, J. Mag. Resn. 2005, 176, 239

griffm07

Griffin, J.M., Tripon, C, Samoson, A., Filip, C, and Brown, S.P., Mag. Res. in Chem. 2007 45, SI, S198

randall89

J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

Molecular weight

Molecular weight averages, molecular weight distribution ( Mn, Mw,Mz MWD) Molecular weight averages (Mz, Mw and Mn ), Molecular weight distribut ion (MWD) and its broadness, described by poiydispersity 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 16014- 1 :2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474- 12 using the following formulas:

For a constant elut ion volume interval AVj, where Aj, and M, are the

chromatographic peak slice area and polyolefin molecular weight (MW), respectively associated with the elution volume, Vi, where N is equal to the number of data points obtained from the chromatogram between the integration limits.

A high temperature GPC instrument, equipped with either infrared (IR) detector ( I R4 or I R5 from PolymerChar ( Valencia, Spain ) or differential refractometer (RI) from Agilent Technologies, equipped with 3 x Agilent-P Lgel Olexis and lx Agilent- PL gel Olexis Guard columns was used. As the solvent and mobile phase 1 ,2,4- triclilorobenzenc (TCB ) stabi l ized with 250 mg/^'L 2,6-Di tert butyl-4-methyl-plienol ) was used. The chromatographic system was operated at 160 °C and at a constant flow rate of 1 mL/min. 200 μ L of sample solut ion was i njected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PoiymerChar GPC-I R control software.

The column set was calibrated using universal calibration (according to ISO 16014- 2:2003) with 19 narrow MWD polystyrene (PS) standards in the range of 0,5 kg/mol to 1 1 500 kg/mol. The PS standards were dissolved at room temperature over several hours. The conversion of the polystyrene peak molecular weight to poi vole fin molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants:

A third order polynomial fit was used to fit the calibration data.

All samples were prepared in the concentration range of 0,5 - I mg ml and dissolved at 160 °C for 2.5 hours for PP or 3 hours for PE under continuous gentle shaking.

Spiral Flow

Spiral Test is carried out using an Engei ES330/65 cc90 injection molding apparatus with a spiral mould and pressure of 1 000 bar;

screw diameter: 35 mm

max. piston displacement: 150 cm³

tool form: oval form; provided by Axxicon; thickness 2 mm. breadth: 5 mm temperature in pre-chamber and die: 220° C.

temperature i n zone 2/zone 3/zone 4 zone 5: 220° C/230° C/225° C./200°C. injection cycle: injection time including holding: 15 s

cooling time: 1 5 s

inject ion pressure: Follows from the predetermined length of the testing material.

dwell pressure=injection pressure screw speed: 30 rpm

system pressure: 160 bar

metering path: Metering stroke should be set so the screw stops 20 mm before final position by end of the holding pressure,

tool temperature: 40° C.

The spiral flow length can be determined immediately after the inject ion operation.

Tensile properties

Tensile properties were measured on injection moulded samples according to ISO 527-2, Specimen type M ult ipurpose bar 1 A , 4 mm thick. Tensile modulus was measured at a speed of 1 mm min. Sample preparation was done acc I SO 1872-2

Environmental Stress Crack Resistance

Environmental Stress Crack Resistance (ESCR) may be measured according to the ful l notch creep test method (FNCT) according to ISO/DIS 1 6770 at 50°C with a notch depth of 1 mm and specimen dimensions 6 mm x 6 mm x 90 mm. The solvent used was 2 wt% Arcopal N 1 10 in deionized water. Compression moulded samples were employed ( I SO 1872-2), cooling rate at compression mou lding: 1 5 K min. Time to fai lure (tj) was measured at 4 different stress levels (σ) between 5-7 MPa. A plot of log(t/) vs. log(a) was fitted with a straight line and a equation of the form log(tf) = A log(a) +B. FNCT value at 6 MPa stress is then calculated based on l inear interpolat ion using the equat ion.

Environmental Stress Crack Resistance

Environmental stress crack resistance (ESCR) was determined according to ASTM 1693, condit ion B at 50° C. and using 10% Igcpal co-630.

Experimental

Synthesis of the polymers of the invention:

Catalyst preparation Complex preparation:

87 kg of toluene was added into the reactor. Then 45.5 kg Bomag A in heptane was also added in the reactor. 161 kg 99.8 % 2-cthyl- l -hexanoi was then introduced into the reactor at a flow rate of 24-40 kg/h. The molar ratio between BOMAG-A and 2- ethyl- 1 -hexanoi was 1 : 1.83.

Solid catalyst component preparation:

275 kg silica ( ES747JR of Crossfie!d, hav ing average particle size of 20 mm ) activated at 600 °C in nitrogen was charged into a catalyst preparation reactor. Then, 41 1 kg 20 % EADC (2.0 mmo l g silica) di luted in 555 l itres pentane was added into the reactor at ambient temperature during one hour. The temperature was then increased to 35 °C while st irring the treated silica for one hour. The sil ica was dried at 50 °C for 8.5 hours. Then 655 kg of the complex prepared as described above (2 mmo l Mg/g silica) was added at 23 °C during ten minutes. 86 kg pentane was added into the reactor at 22 °C during ten m inutes. The slurry was st irred for 8 hours at 50 °C. Final ly, 52 kg TiCU was added during 0.5 hours at 45 °C. The slurry was st irred at 40 °C for five hours. The catalyst was then dried by purging w ith nitrogen.

The polymers of the invention were prepared as outlined in table 1 in a Borstar process using the catalyst above and TEA L cocatalyst:

Table 1

Table 2

Table 3

Table 4

Table 5

Tensile FNCT (6.0 modulus M Pa/50 °C)

0.29(Mw/Mn) +

MPa hours

Sample 0.8 Mz/Mw (Mw)²/(Mn Mz)

Ex 1 5.52 5.5 3.0 916 56.8

Ex 2 5.69 4.7 3.6 957.6 51.9

Ex 3 5. 1 1 4.5 3.3 972.6 52.3

Ex 4 5.04 4.5 3.2 955.6 36.8

Ex 5 4.57 4.3 3.0 931.8 35.4

Ex 6 5.69 4. 1 4.2 937 109.6 Injection moulding of the screw caps:

Injection moulding of the screw caps (type: PE PC01881 short neck) was done on an Engel speed 180, melt temperature ~ 225°C, injection speed: reiativ 180 mm/s, absoiut 173 cmVs; injection time 0,35 s, back pressure 1 bar. The mould was equipped with a hot runner system, mould-temperature: 10 °C.

Cap properties are reported in table 6.

Table 6

The polymers of the invention have been compared to a wide range of commercially avai lable caps closures grades sold by various manufacturers.

Table 7

Tablc 8

It can be seen that all grades tested fail to satisfy the equation forming pat of c laim 1. The polymers of the invention therefore possess a higher FNCT without loss of tensile modulus.

Claims

1 . A multimodal polyethylene polymer having an M FR of 0.05 to 10.0 g/lOmin, a density of 940 kg m³ or more, a tensi le modulus of 900 M Pa or more and wherein

2. A mult imodal polyethylene polymer as claimed in claim 1 wherein

3. A mult imodal polyethylene polymer as claimed in any precedi ng claim having M FR > 0. 1 to 2 g l Omin.

4. A mult imodal polyet liylene polymer as claimed in any preceding claim having a lower mo lecular weight component and a higher molecular weight copolymer component wherein said lower molecular weight component is a homopolymer or a copolymer with a comonomer content of less than 0.2 mol%, preferably less than 0. 1 mol%, especial ly less than 0.05 mol%.

5. A mult imodal polyethylene polymer as claimed in any preceding claim. having a lower molecular weight (LMW) homopolymer component and a h igher molecular weight (HMW) ethylene copolymer component, preferably wherein said HMW copolymer component comprises at least one C3- 12 alpha olefin, preferably but-1 - ene, hex-1 -ene and oct-1 -ene but-1 -ene, hex-1 -ene and oct-1 -ene

6. A mult imodal polyethylene polymer as claimed in any preceding claim having 48 to 55 wt% of a HMW component (B) and 52 to 45 wt% LMW component (A).

7. A mult imodal polyethylene polymer as claimed in any preceding claim having 0. 1 to 1 mol% comonomer.

8. A multimodal polyethylene polymer as claimed in any preceding claim wherein said polymer is a copolymer with the comonomer 1 -butene.

9. A multimodal polyethylene polymer as claimed in any preceding claim having FNCT more than 50 h.

10. A multimodal polyethylene polymer as claimed in any preceding claim having tensile modulus 910 MPa or more.

1 1. A mult imodal polyethylene polymer as claimed in any precedi ng claim having a density of 950 to 960 kg/m³.

12. A mult imodal polyet hylene polymer as claimed in any preceding clai m wherein Mz is in the range of 400kD to 700k D, such as 450 kD to 600 kD.

13. An injection or compression moulded article, such as a cap or closure, comprisi ng a polymer as claimed in claim 1 to 1 2.

14. An art icle as claimed i n claim 13 being a cap having a high tip of less than 0.5 mm or having no high tip at all.

15. Use of the polymer as claimed in any one of claims 1 to 1 2 in the manufacture of a injection or compression moulded article, such as a cap or closure.

16. A process for the preparation of a polyethylene as claimed in claims 1 to 12 comprising;

subsequent ly

polymerising ethylene and optionally at least one C3- 10 alpha olefin comonomer in the presence of component (A) so as to form a higher molecular weight component (B).