WO2010089415A1

WO2010089415A1 - High impact resistance polyethylene

Info

Publication number: WO2010089415A1
Application number: PCT/EP2010/051604
Authority: WO
Inventors: Barbera Mandard; Leen De Groof; Elke Berges
Original assignee: Total Petrochemicals Research Feluy SA
Current assignee: Total Petrochemicals Research Feluy SA
Priority date: 2009-02-09
Filing date: 2010-02-09
Publication date: 2010-08-12
Anticipated expiration: 2011-08-09
Also published as: EP2216367A1

Abstract

The present invention relates to the use of a resin composition comprising from 5% to 100% by weight of a polyethylene having a density of from 0.947 to 0.970 g/c³ when measured according to ASTM D 1505 and a molecular weight distribution of less than 4 produced with a metallocene catalyst, and from 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed high density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof to produce films having improved impact resistance.

Description

High impact resistance polyethylene

The present invention relates to the use of a polyethylene composition having a good balance between rigidity and impact resistance.

Polyethylene is a thermoplastic commodity widely used in consumer products. Nowadays, the general public has become increasingly apprehensive of the impact man-made waste on the environment. For this, there is a growing demand on the market for producing thinner polyethylene articles.

Low density polyethylene offers good optical and impact properties. It can be processed at relatively low temperatures and pressures while maintaining a good melt strength. Low density polyethylene has however limited possibilities for downgauging due to a low draw ratio, and a low rigidity.

Linear-low-density polyethylene has good tear and impact properties; its rigidity however remains low and its processability is well below that of LDPE.

Wherever high rigidity is needed, low density polyethylene and linear low density polyethylene compositions will require overly thick structures. Especially for linear low density polyethylene, where its good impact and tear properties render its downgauging capability useful, the lack of rigidity may be a main drawback. High rigidity may be a requirement for the end product, it is very often a necessity for product handling.

Conventional high density polyethylene produced by polymerisation in the presence of Ziegler-Natta or chromium catalysts offers excellent rigidity but limited mechanical properties such as for example impact resistance. The density of the resin may be reduced to improve the mechanical properties but this results in reduced rigidity. For many applications, where high rigidity and impact resistance are desired, there is a need in the art to develop polyethylene resins having such a combination of properties. The need is particularly great in applications such as for example films because film producers can then provide thinner films without loss of properties (downgauging). This results in environment protection and cost reduction.

The technical article from Sukhadia et al. entitled "Blown film characterisation of metallocene resins made in the Philips slurry loop process", J. Plast.film sheeting, 14(1 ), 54-75, 1988 relates to the effects of density, molecular weight, slip/antiblock agents and film thickness on the processability, film property performance (impact and tear strengths) and clarity of blown films. This article discloses that when the density of the metallocene catalysed polyethylene increases, the dart impact of blown films made thereof decreases. This is well shown for blown films made from resins having a density between 0.900 and 0.940 g/cm³.

EP-A-0844277 discloses a homogeneous blend of a low density polyethylene and/or linear low density polyethylene with a metallocene catalysed medium density polyethylene. The blend has a good processability and is used to produce films, mainly blown films. Only examples of films produced by using a metallocene catalysed polyethylene having a density of 0.932 g/cm³ either in pure or in blend with low density polyethylene have been carried out.

EP-A-1225201 discloses the use of a homogeneous blend of a metallocene catalysed medium density polyethylene with low density polyethylene to produce blown films having good balanced shrink properties in machine direction and transverse direction with fast shrink speed and high shrink force at room temperature. Only examples of blown films produced by using a metallocene catalysed polyethylene having a density of 0.934 g/cm³ either in pure or in blend with low density polyethylene have been carried out. It is an object of the present invention to provide a polyethylene resin for producing films that exhibit a high impact resistance.

It is another object of the present invention to provide a polyethylene resin for producing films that exhibit a good rigidity.

It is another object of the present invention to provide a polyethylene resin for producing films that exhibit a good balance between rigidity and impact resistance.

At least one of the objects is achieved by the invention.

The term "film" as used herein is defined as an extremely thin continuous sheet: the upper limit for thickness is of about 250 microns (Hawley's Condensed Chemical Dictionary, Twelfth Edition, Rev. by R.J.Lewis, Van Nostrand Reinhold Co., New York).

The resin composition used in the present invention comprises from 5% to 100% by weight of a polyethylene resin produced with a metallocene catalyst, said polyethylene having a density of from 0.947 to 0.970 g/cm³ and a molecular weight distribution of less than 4, and from 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed high density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and ²mixtures thereof.

The present invention relates to the use of a resin composition comprising from 5% to 100% by weight of high density polyethylene having a density of from 0.947 to 0.970 g/cm³ when measured according to ASTM D 1505 and a molecular weight distribution of less than 4 produced with a metallocene catalyst having the general formula (I) R¹S(Cp)₂ MRn Xq (I)

wherein each Cp can independently be selected from substituted or non substituted cyclopentadienyl, indenyl or fluorenyl, the substituents on the cyclopentadienyl, indenyl and fluorenyl is a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring, R' is a substituted or unsubstituted C1 -C4 alkylidene radical, a dialkyl germanium, a dialkyl silicon, a diaryl silicon, a di-alkoxysilane, a diphenoxysilane, an alkyl phosphine or amine radical bridging two Cp such as defined hereabove, M is a group 4, 5 or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and s = 0 or 1 , n = 0-3, q = 0-3 and the sum of n and q will be equal to the valence of the transition metal, and 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed high density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof to produce a film having an impact resistance, measured according to ASTM D 1709-4 method A, greater than the impact resistance of a corresponding film of same thickness and produced under the same processing conditions made with the same composition, excepted that the polyethylene catalysed with the metallocene of general formula (I) has a density between 0.944 and 0.946 g/cm³, both metallocene catalysed polyethylenes having substantially the same melt index.

The % by weight of the high density polyethylene and of the other polyolefins such as disclosed is based on the total weight of the resin composition. The metallocene catalysed high density polyethylene as well as the other polyolefins as used in the present invention may also comprised standard additives such as fillers, antioxidants, anti-blocking agents, anti-static agents, anti-fog agents, slip additives, pigments, dyes, and the like. By same composition, it is meant that the corresponding film is made with a polyolefin, in the same percentage by weight, selected from the same group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed high density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof and with the same percentage by weight of a polyethylene produced with the same metallocene catalyst of general formula (I) excepted that this metallocene has a density between 0.944 and 0.946 g/cm³.

By substantially the same melt index, it is meant that the melt index between the two metallocene catalysed high density polyethylenes differ by at most 10% of the higher melt index value of the two.

According to the present invention, the metallocene catalysed polyethylene having a density of from 0.947 to 0.970 g/cm³ (mHDPE) has a melt index of from 0.1 to 10 when measured according to ASTM D 1238, conditions 190°C/2.16 kg.

According to the present invention, the very low density polyethylene (VLDPE) the linear low density polyethylene (LLDPE), the low density polyethylene (LDPE), the medium density polyethylene (MDPE), the Ziegler-Natta high density polyethylene (Zn-HDPE) or the chromium high density polyethylene (Cr-HDPE) have the following density ranges: below 0.900 g/cm³ for VLDPE; 0.900 to 0.935 g/cm³ for LDPE, 0.920 to 0.930 g/cm³ for LLDPE; 0.931 to 0.945 g/cm³ for MDPE; and 0.946 to 0.970 g/cm³ for ZN-HDPE or Cr-HDPE.

The mHDPE used in the present invention is produced with a metallocene having the general formula (I) R¹S(Cp)₂ MRn Xq

(I) wherein each Cp can independently be selected from substituted or non substituted cyclopentadienyl, indenyl or fluorenyl, the substituents on the cyclopentadienyl, indenyl and fluorenyl is a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring, R' is a substituted or unsubstituted C1 -C4 alkylidene radical, a dialkyl germanium, a dialkyl silicon, a diaryl silicon, a di-alkoxysilane, a diphenoxysilane, an alkyl phosphine or amine radical bridging two Cp such as defined hereabove, M is a group 4, 5 or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and s = 0 or 1 , n = 0-3, q = 0-3 and the sum of n and q will be equal to the valence of the transition metal.

Exemplary hydrocarbyl radicals are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like. Exemplary halogen atoms include chlorine, bromine, fluorine and iodine and of these halogen atoms, chlorine is preferred.

Exemplary hydrocarboxy radicals are methoxy, ethoxy, propoxy, butoxy, amyloxy and the like.

Preferably, R' is a substituted or unsubstituted C1 -C4 alkylidene radical. Exemplary of the alkylidene radicals are methylidene, ethylidene, propylidene, and isopropylidene. More preferably R' is ethylidene or isopropylidene.

Preferably, n=0, q=2, X=CI and s=1.

Preferably (Cp)2 is a bis indenyl, a bis tetrahydrogenated indenyl or a cyclopentadienyl fluorenyl. More preferably, (Cp)₂ is a is an unsubstituted bis tetrahydrogenated indenyl group.

Preferably, M is a group 4 transition metal such as titanium, zirconium or hafnium. More preferably, M is zirconium. Preferably, the metallocene catalyst used is a bridged bis (tetrahydro-indenyl) zirconium dichloride, more preferably an ethylene bis (4,5,6,7-tetrahydro-1- indenyl) zirconium dichloride.

The metallocene polyethylene having a density of from 0.947 to 0.970 g/cm³ (mHDPE) and the metallocene polyethylene having a density of from 0.944 to 0.946 g/cm³ are produced according to the same metallocene catalyst of formula (I).

The melt index of the metallocene polyethylene having a density of from 0.947 g/cm³ to 0.970 g/cm³ can be regulated by the amount of hydrogen injected in the reactor. The melt index (Ml₂) of the polyethylene ranges from 0.1 g/10 min to 100 g/10 min when measured according to ASTM D 1238, conditions 190°C/2.16 kg. The person skilled in the art is aware that the suitable melt index range of the polyethylene depends upon the respective method of forming an article. If used for films, the metallocene polyethylene of the present invention has a melt index in the range from 0.1 g/10 min to 10 g/10 min. For cast film extrusion, the preferred melt index range is from 2 g/10 min to 10 g/10 min, more preferably from 3 g/10 min to 8 g/10 min, yet more preferably from 4 g/10 min to 6 g/10 min. For blown film extrusion, the preferred melt index range is from 0.1 g/10 min to 2 g/10 min, more preferably from 0.3 to 1.2 g/10 min. If used for extrusion coating, the preferred melt index range from 4 to 25 g/10 min. If used for moulding applications, the metallocene polyethylene has a melt index in the range from 0.1 to 2. If used for injection applications, the metallocene polyethylene has a melt index in the range from 0.1 to 100 g/10 min. Prefrably, the metallocene polyethylene has a melt index in the range from 0.1 g/10 min to 10 g/10 min, more preferably from 0.3 to 4 g/10 min, yet more preferably from 0.5 to 2 g/10 min.

The mHDPE used in the present invention has a density of from 0.947 g/cm³ to 0.970 g/cm³. The density can be of from 0.947, 0.950, 0.955, 0.960 g/cm³ up to 0.962, 0.965 or 0.970 g/cm³. The density is measured at 23°C following the method described in ASTM D 1505. Preferably the density of the mHDPE is from 0.952 to 0.970 g/cm³, more preferably from 0.952 to 0.970 g/cm³, yet more preferably from 0.952 to 0.965 g/cm³.

The mHDPE can be a homopolymer or a copolymer of ethylene and at least one comonomer, said comonomer may be selected from the group consisting of propylene, 1-butene, 1 -hexene, 1 -octene and 4-methyl-1 -pentene, the preferred comonomer being 1 -butene, 1 -hexene, 1 -octene, the most preferable comonomer being 1-hexene.

The amount of comonomer is of from 0 to 12 wt% based on the weight of the polyethylene, more preferably it is of from 0 to 9 wt% and most preferably it is of from O to 7 wt%.

The mHDPE has a monomodal molecular weight distribution. The molecular weight distribution is defined by a parameter, known as the dispersion index (D), which is the ratio between the average molecular weight by weight (Mw) and the average molecular weight by number (Mn). The mHDPE of the present invention has a molecular weight distribution of less than 4, preferably between 2 a nd 3.5. The molecular weights are determined by gel permeation chromatography (GPC).

Preferably, the metallocene polyethylene having a density of from 0.947 to 0.970 g/cm³ (mHDPE) and the metallocene polyethylene having a density of from 0.944 to 0.946 g/cm³ have both a dispersion of less than 4, preferably between 2 and 3.5.

The mHDPE may also be characterised by a long chain branching structure. Preferably, the mHDPE resin used in the present invention has a long chain branching index, LCBI, such as defined by R.N. Shroff and H . Mavridis in Macromolecules, Vol.32, N° 25, pages 8454-8464 (1999) as the ratio of intrinsic viscosities of PE resins estimated by rheology to that determined via solution techniques:

wherein [η]_rheo and [η]_SOι are the intrinsic viscosities obtained respectively from rheology or via solution.

Thus, LCBI is zero for linear samples and is above zero for polyethylene containing long chain branching. A high level of LCB is encountered with LCBI above 0.8. Instead of determining intrinsic viscosity from the relative viscosity at 0.2 g/dl as explained in the above publication, intrinsic viscosity value is calculated here via solution (expressed in dl/g) in terms of weight average molecular weight Mw (expressed in Da) obtained by size exclusion chromatography (SEC) with equation

Zero shear viscosity η₀, expressed in Pa. s, is also related to the weight average molecular weight M_w, expressed in Da, by equation η_o = 4.4927 * 10^~16 (MJ^{3 8412}

This equation is derived with 50 linear PE samples, both metallocene and ZN PE, with Mw ranging from 30 to 700 kDa, dispersion index values from 2 to 25 and density from 0.87 to 0.965 g/cm³.

Zero shear viscosity is estimated by fitting with Carreau-Yasuda flow curve (η- W) at a temperature of 190⁰C, obtained by oscillatory shear rheology on ARES equipment (manufactured by TA Instruments) in the linear viscoelasticity domain. Circular frequency (W in rad/s) varies from 0.05-0.1 rad/s to 250-500 rad/s and the shear strain is typically 10 %. The intrinsic viscosity inferred from rheology can thus be expressed as

wherein parameters τ, bD and n are fitting parameters called respectively relaxation time, D breadth parameter and power-law parameter. The LCBI is thus rewritten as

The LCBI of the mHDPE used in the present invention is preferably at least 0.1. The polymerisation of the mHDPE can be carried out in gas, solution or slurry phase. Slurry polymerisation is preferred for the production of the mHDPE of the present invention. The diluent is preferably isobutane. The polymerisation temperature ranges from 20 to 125°C, preferably from 60 to 95°C and the pressure ranges from 0.1 to 6 MPa, preferably from 2 to 5 MPa, for a time ranging from 90 minutes to 120 minutes, preferably from 30 minutes to 90 minutes. The polymerisation can be carried out in several serially connected reactors.

The average molecular weight is controlled by adding hydrogen during polymerisation. The relative amounts of hydrogen and olefin introduced into the polymerisation reactor are from 0.01 to 10 mole percent hydrogen and from 99.99 to 90 mole percent olefin based on total hydrogen and olefin present, preferably from 0.02 to 0.4 mole percent hydrogen and from 99.98 to 99 mole percent olefin.

The metallocene-based catalytic system used to produce the m H DPE comprises a metallocene such as previously described, a support and an activating agent. The mHDPE may be used pure or in blend with VLDPE, LDPE, LLDPE, MDPE, ZN-HDPE, Cr-HDPE, EVA or mixtures thereof.

Preferably, the resin composition used in the present invention comprises from 20% to 100% by weight of mHDPE and from 0% to 80% by weight of VLDPE,

LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE, EVA and mixtures thereof, more preferably from 40% to 100% by weight of mHDPE and from 0% to 60% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE, EVA and mixtures thereof, yet more preferably from 50% to 100% by weight of mHDPE and from 0% to 50% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-

HDPE, EVA and mixtures thereof,

According to one embodiment, when used in blend, the resin composition of the invention comprises from 20% to 95% by weight of mHDPE and from 5% to 80% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE, EVA and mixtures thereof, preferably from 40% to 95% by weight of mHDPE and from 5% to 60% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr- HDPE, EVA and mixtures thereof, more preferably from 60% to 90% by weight of mHDPE and from 10% to 40% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-H DPE, Cr-H DPE, EVA and mixtures thereof. Resins compositions comprising from 60 to 90 % by weight of mHDPE and from 10 to 40% by weight of LDPE are for example particularly preferred.

According to another embodiment, when used in blend, the resin composition of the invention comprises from 5% to 90% by weight of mHDPE and from 10% to 95% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE, EVA and mixtures thereof, preferably from 5% to 50% by weight of mHDPE and from

50% to 95% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE,

EVA and mixtures thereof, more preferably from 20% to 50% by weight of mHDPE and from 50% to 80% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-

HDPE, Cr-HDPE, EVA and mixtures thereof. Resins compositions comprising from 20 to 30 % by weight of mHDPE and from 70 to 80% by weight of LDPE are for example particularly preferred.

Still according to another embodiment, when used in blend, the resin composition of the invention comprises from 5% to 45% by weight of mHDPE and from 55% to 95% by weight of VLDPE, LDPE, LLDPE MDPE, ZN-HDPE, Cr-HDPE, EVA and mixtures thereof.

LDPE, LLDPE, MDPE, ZN-HDPE, Cr-HDPE and mixtures thereof are preferably used in the resin composition, more preferably LDPE, LLDPE, MDPE and mixtures thereof are used, yet more preferably LDPE and LLDPE and mixtures thereof are used.

LDPE is generally produced in autoclave or tubular reactors at pressure above 120 MPa with the use of free-radical initiators. The manufacture of the LDPE and of the LLDPE is described for example in "Encyclopedia of Polymer Science and Engineering", second edition, volume 6, on pages 404 to 407 (LDPE) and pages 436 to 444 (LLDPE).

The ZN-HDPE and the Cr-HDPE may be a homopolymer or a copolymer of ethylene and at least one comonomer, said comonomer having from 3 to 10 carbon atoms such as for example 1 -butene, 1 -hexene and 1 -octene. In the LLDPE, LDPE and MDPE, the comonomer is also an alpha-olefin having from 3 to 10 carbon atoms, and may comprise for example 1 -butene, 4-methyl pentene, 1 -hexene, 1-octene. The LLDPE and MDPE can be produced by any suitable process, including metallocene catalysed process, Ziegler-Natta catalysed process or chrome catalysed process.

When the resin composition used in the present invention is a blend, the blend may be obtained by preliminary dry blend or by direct blend in the extruder.

The resin composition is particularly suitable for transformation into a film. The film may be a cast, a blown, a mono-oriented and a bi-ohented film. On one hand, it has been surprisingly found that films formed from the resin composition as previously described exhibit a greater impact resistance, measured according to ASTM D 1709-4 method A, than the impact resistance of a corresponding film of same thickness, produced under the same processing conditions and made with the same composition, excepted that the polyethylene catalysed with the metallocene of general formula (I) has a density between 0.944 and 0.946 g/cm³, both metallocene catalysed polyethylenes having substantially the same melt index. Preferably, the film produced has an impact resistance greater than 10 % compared to the impact resistance of the corresponding film. Preferably, the film produced has a MD tensile strength at yield when measured according to ASTM D 882-02 of at least 4% greater than that measured on the comparative corresponding film. Prferebly,the film produced has a MD tensile strength at yield when measured according to ASTM D 882-02 of at least 10% greater than that measured on the comparative corresponding film.

On the other hand, it has been surprisingly found that films formed from the resin composition as previously described exhibit, improved impact resistance compared to films, made from Ziegler-Natta or chromium catalysed polyethylene resins, at equivalent rigidity.

According to one embodiment, the film of the invention is a monolayer film.

According to another embodiment, the film of the invention is a multilayer film.

When used in multilayer films, the resin composition such as described in the present invention can be used in any layer of the film, or in more than one layer of the film, as desired. When more than one layer of the film is formed using the resin composition of the present invention, each such layer can be individually formulated, i.e. the layers formed can be the same or different in density, melt index, thickness and so on, depending upon the desired properties of the film. The other layer(s) can include resins made of for example, high-pressure polymerised low-density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polyethylene terephthalate, polypropylene, polyamide and ionomers. In multilayer structures, one or more layers can also be a tie layer or a gas barrier layer containing for example ethylene vinyl alcohol (EVOH). The multilayer structure may also include a laminate. Finally, the monolayer or multilayer films can be coated onto a substrate such as paper, metal and other materials capable of accepting a coating. Such coated structures are also within the scope of the invention.

The thickness of each layer of the film and of the overall film, is not particularly limited, but is determined according to the desired properties of the film. Typical film layers have a thickness of about 1 to 1000 μm, more typically about 2 to 100 μm, and typical films have an overall thickness of 2 to 200 μm, more typically 2 to 100 μm.

The films of the present invention may be formed by any number of well-known extrusion or coextrusion techniques. Any of the blown or chill roll techniques commonly used are suitable. For example, the composition can be extruded in a molten state through a flat die and then cooled to form a film. Alternatively, the composition can be extruded in a molten state through an annular die and then blown and cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Multi-layer films may be formed by methods well known in the art. The materials forming each layer may be coextruded through a coextrusion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted to the cast film or the blown film processes. Multi-layer films may also be formed by extrusion coating whereby a substrate material is contacted with the hot molten polymer as the polymer exits the die. Films according to the invention may be widely used for packaging applications, such as grocery sacks, shipping sacks, bags such as merchandise bags, trash bags. The films can also be applied more particularly in frozen food packaging.

The resin composition used in the present invention is also suitable for injection moulding and extrusion blow moulding applications. The articles made according to these processes can be mono- or multilayer, at least one of the layers comprising the resin composition of the invention.

The present invention further provides the use of a resin composition comprising from 5% to 100% by weight of high density polyethylene having a density of from 0.947 to 0.970 g/cm³ when measured according to ASTM D 1505 and a molecular weight distribution of less than 4 produced with a metallocene catalyst having the general formula (I) R¹S(Cp)₂ MRn Xq

(I) wherein each Cp can independently be selected from substituted or non substituted cyclopentadienyl, indenyl or fluorenyl, the substituents on the cyclopentadienyl, indenyl and fluorenyl is a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring, R' is a substituted or unsubstituted C1 -C4 alkylidene radical, a dialkyl germanium, a dialkyl silicon, a diaryl silicon, a di-alkoxysilane, a diphenoxysilane, an alkyl phosphine or amine radical bridging two Cp such as defined hereabove, M is a group 4, 5 or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and s = 0 or 1 , n = 0-3, q = 0-3, and 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed high density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof to produce films having an impact resistance, when measured according to ASTM D 1709-04 method A and /or ISO 7765-2, greater than the impact resistance of a corresponding film of same thickness and produced under the same processing conditions made with the same composition, characterised in that both films have substantially similar MD and/or TD tensile strength at yield when measured according to ASTM D 882- 02. Preferably, the film produced has an impact resistance of at least 10% greater than the impact resistance of the corresponding film. More preferably, the film produced has an impact resistance of at least 15% greater than the impact resistance of the corresponding film.

This improvement of the impact resistance has been observed when the film is either maintained at room temperature or is maintained at a temperature comprised in the range from 4°C to -60⁰C. The temperature can be of from 4°C, 0⁰C, -5°C, -10⁰C, -15°C, -18°C or -20⁰C up to -25°C, -30⁰C, -35°C, -40°C, -45°C, -50⁰C, -55°C or -60⁰C.

The films produced by using the resin composition such as previously described are particularly suitable as deep freeze packaging material, more particularly as deep freeze packaging material for food applications.

Examples

The advantages of the polyethylene resin of the present invention over those of conventional resins are shown in the following examples.

The tensile strength at yield of the blown and the cast films was determined according to ASTM D 882-02 in the machine direction (MD) and in the transverse direction (TD).

The impact resistance of the blown and of the cast films was determined by the free falling dart method either according to ASTM D 1709-04 (method A) at room temperature or according to ISO 7765-2 at room temperature (23°C) and at -30°C. In ISO 7765-2 method, the test has been done on a Fractovis Ceast equipment with a hammer having a diameter of 20 mm and a weight of 5.574 kg. The test speed was 4.43 m/s. For the test at -30⁰C, the equipement and the samples have been conditioned at -30⁰C respectively for 1 and 2 hours before testing. The samples exhibited a diameter of 40 mm. All the results are based upon an average of 5 samples. The force at peak (in Newton) that represents the maximum force that the film can bear before the beginning of the rupture is given as well as the total energy (in Joule) consumed during the rupture. The elongation of the film at the maximum force that the film can bear before the beginning of the rupture is also given and is identified herein as elongation before rupture (in mm).

Examples 1 -2

The metallocene polyethylene resins R1 and R2 prepared by using ethylene bis (4,5,6,7 tetrahydro-1-indenyl) zirconium dichlohde were used for producing monolayer blown films of 40 microns thickness identified hereafter respectively films F1 and F2. The catalyst was activated and supported. The properties of the resins are provided in table 1.

Table 1

The films were produced on a Macchi line with the following parameters: - BUR: 2.5

- Screw Speed: 80 rpm

- Die Gap: 1.4 mm

- Die diameter: 120 mm - Temperature: 200°C (feed zone) up to 215°C (die lip).

- Cooling temperature: 18°C Comparative examples 1 -2

Comparative monolayer blown films of 40 microns thickness were produced on the Macchi line under the same conditions as those described here-above by using:

A chromium catalysed high density polyethylene having a density of 0.958 g/cm³, a Ml₂ of 0.3 g/1 Omin, a dispersion index of 12.3, a LCBI of 0.4 (film F3),

A commercially available low density polyethylene produced by a high pressure polymerisation process sold by Total Petrochemicals having a density of 0.924 g/cm³, a Ml₂ of 0.8 g/1 Omin, a dispersion index of 5.4 (film F4).

The tensile strength at yield in both directions and the impact resistance of the films and comparative films determined according to ISO 7765-2 are summarised in table 2.

Table 2

Table 2 shows that the films F1 and F2 exhibit a better balance between rigidity and impact resistance when measured at 23°C as well as -30⁰C compared to that of the comparative films F3 and F4.

Figure 1 shows the falling weight curves represented by the force (in Newton) versus the time (in sec) at 23 and -30⁰C plotted for film F2 and comparative film F3. Said curves show a more ductile behaviour for film F2 than for comparative film F3. A ductile behaviour means that the film deforms for a substantial period of time before breaking.

Example 3

The mPE resin R2 was used for producing a monolayer blown film of 35 microns thickness (F5) on a Macchi line under the following parameters: - BUR: 2.1

- Screw Speed: 60 rpm

- Die Gap: 1.4 mm

- Die diameter: 120 mm

- Temperature: 195°C (feed zone) up to 230⁰C (die lip).

- Cooling temperature: between 20 and 24°C

Comparative example 3

A comparative monolayer blown film of 35 microns thickness was produced on the Macchi line under the same conditions as those described in the previous paragraph by using a Ziegler-Natta catalysed high density polyethylene having a density of 0.954 g/cm³, a Ml₂ of 0.8 g/1 Omin, a dispersion index of 5.1 , a LCBI of 0, identified hereinafter F6. The tensile strength at yield in both directions and the impact resistance of the films and comparative films determ ined according to ISO 7765-2 are summarised in table 3.

Table 3

Whereas films F5 and comparative film F6 have substantially the same rigidity, F5 shows a better impact resistance at 23°C and at -30⁰C compared to that of F6. Figure 2 shows the falling weight curves at 23 and -30⁰C plotted for film F5 and comparative film F6. Said curves show a more ductile behaviour for film F5 compared to that of F6.

Example 4 A metallocene polyethylene resin R3 prepared by using the activated and supported ethylene bis (4,5,6,7 tetrahydro-1 -indenyl) zirconium dichlohde and having a density of 0.960 g/cm³, a Ml₂ of 4.0 g/1 Omin and a dispersion index of 2.9 was used for producing a monolayer cast film of 20 microns thickness (F7). The films were extruded onto the MEAF equipment under the following conditions:

- Die gap: 250 μm

- Melt temperature: 260⁰C (temperature profile: 190°C-240°C-260°C- 260°C-260^oC-260^oC-260^oC-260^oC-260^oC-260°C)

- Chill roll temperature: 20⁰C - Throughput: +/- 6.3 kg/h

- Vacuum box at mid position

Comparative examples 4-5

Comparative monolayer cast films of 20 microns thickness were produced on the MEAF equipment under the same conditions as those described in the previous paragraph by using:

A Ziegler-Natta catalysed high density polyethylene having a density of 0.961 g/cm³, a Ml₂ of 2 g/1 Omin, a dispersion index of 5.7, a LCBI of 0 (film F8).

A commercially available low density polyethylene produced by a high pressure polymerisation process sold by Total Petrochemicals having a density of 0.924 g/cm³, a Ml₂ of 4 g/1 Omin, a dispersion index of 8 (film F9).

The tensile strength at yield in both directions and the impact resistance of the films and comparative films according to ISO 7762-2 are summarised in table 4.

Table 4

Film F7 exhibits a better balance between rigidity and impact performance at 23°C and at -30⁰C compared to films F8 and F9. Examples 5-6

The metallocene polyethylene resins R4 and R5 prepared by using the activated and supported ethylene bis (4,5,6,7 tetrahydro-1 -indenyl) zirconium dichlohde were used for producing monolayer blown film of 35 microns thickness identified hereafter respectively films F10 and F11. The catalyst was activated and supported. The properties of the resins are provided in table 5.

Table 5

The films were produced on a Macchi line with the parameters such as those already mentioned in example 3.

Comparative examples 6-8

Comparative monolayer blown films of 35 microns thickness were produced on the Macchi line under the same conditions as those already mentioned in exemple 3 by using:

A Ziegler-Natta catalysed polyethylene having a density of 0.951 g/cm³ and a Ml₂ of 0.95 g/1 Omin (film F12).

A Ziegler-Natta catalysed polyethylene having a density of 0.956 g/cm³ and a MI₂ of 0.6 g/10min (film F13).

A Ziegler-Natta catalysed polyethylene having a density of 0.961 g/cm³ and a MI₂ Of I g/1 Omin (film F14).

The tensile strength at yield and the impact resistance of the films and comparative films determined by the ASTM D 1709-04 (method A) are summarised in table 6 Table 6

One can see that at equivalent rigidity, the films of the present invention show higher dart impact values than films made of Ziegler-Natta catalysed polyethylene.

Examples 7-8

The metallocene polyethylene resins R4 and R5 were used for producing monolayer blown film of 40 microns thickness identified hereafter respectively films F15 and F16.

The films were produced on a Macchi line with the parameters such as those already mentioned in examples 1 -2.

Comparative examples 9-10

Comparative monolayer blown films of 40 microns thickness were produced on a Macchi line with the parameters such as those already mentioned in examples 1 -2 by using:

A chromium catalysed polyethylene having a density of 0.958 g/cm³ and a Ml₂ of 0.3 g/10min (film F17).

A Ziegler-Natta catalysed polyethylene having a density of 0.961 g/cm³ and a MI₂ Of 1 g/10min (film F18). The tensile strength at yield and the impact resistance of the films and comparative films determined by the ASTM D 1 709-04 (method A) are summarised in table 7

Table 7

One can see that at equivalent rigidity, the films of the present invention show higher dart impact values than films made of chromium catalysed polyethylene and Ziegler-Natta catalysed polyethylene.

Examples 9-16

In these examples, metallocene polyethylene resins R6 to R13 prepared by using ethylene bis (4,5,6,7 tetrahydro-1-indenyl) zirconium dichlohde were used for producing monolayer blown film of 40 microns thickness identified hereafter respectively films F19 to F26. The properties of the resins are provided in table 9. Resins R6, R7, R8, R9 and R10 are outside the scope of the invention.

Table 9

The films were produced on the Macchi line with the parameters such as already disclosed in examples 1 -2. The properties of the films are mentioned in table 10. The impact resistance of the films was determined by the ASTM D 1709-04 (method A).

Table 10

Table 10 shows that when the density of the resin increases, the dart impact of the film made thereof decreases. This is particularly the case for the resins having a density between 0.923 and 0.945 g/cm³. However, starting from 0.947 g/cm³, one can see that the impact resistance of the film increases when the density of the resin increases. This result was totally unexpected as it was known that when the density of the resin increases, the impact resistance of the film made thereof decreases.

Examples 17-18 and comparative examples 11 -15 In these examples and comparative examples; several polyethylene compositions were prepared by blending a linear low density polyethylene (R14) with a high density polyethylene for producing blown films. The resins used for producing the different polyethylene compositions are summarised in table 11.

Table 11

-: not measured The resin R15 was a metallocene polyethylene resins prepared by using ethylene bis (4,5,6,7 tetrahydro-1-indenyl) zirconium dichloride.

The resin R16 was a polyethylene resin produced with a chromium catalyst.

The resins R17and R18 were polyethylene resins produced with a Ziegler-Natta catalyst. These resins were used for producing the different polyethylene compositions as summarised in table 12. Each polyethylene composition was further used for producing monolayer blown film of 40 microns thickness identified hereafter respectively films F27 to F33 as mentioned in table 12.

The films were produced on the Macchi line under the following parameters:

- BUR: 2.5 - Screw Speed: 80 rpm - Die Gap: 1.56 mm

- Temperature: 190⁰C (feed zone) up to 230⁰C (die lip).

Table 12

The tensile strength at yield in the transverse direction and the impact resistance of the films and comparative films according to ISO 7762-2 and ASTM D 1709-04 (method A) are summarised in table 13.

Table 13

Examples 19-20 and comparative examples 16-20 In these examples and comparative examples; several polyethylene compositions were prepared by blending a low density polyethylene (R19) having a density of 0.924 g/cm³ and a melt index of 0.8 g/10 min with a high density polyethylene for producing blown films. The properties of the high density polyethylene resins used for producing the different polyethylene compositions are summarised in table 11. Each polyethylene composition was further used for producing monolayer blown film of 40 microns thickness identified hereafter respectively films F34 to F40 as mentioned in table 14.

The films were produced on the Macchi line under the following parameters: - BUR: 2.5

- Screw Speed: 60 rpm

- Die Gap: 1.56 mm

- Temperature: 190⁰C (feed zone) up to 230⁰C (die lip).

Table 14

The tensile strength at yield in both directions and the impact resistance of the films and comparative films according to ISO 7762-2 and ASTM D 1709-04 (method A) are summarized in table 15. Table 15

Claims

1. Use of a resin composition comprising from 5% to 100% by weight of high density polyethylene having a density of from 0.947 to 0.970 g/cm³ when measured according to ASTM D 1505 and a molecular weight distribution of less than 4, produced with a metallocene catalyst having the general formula (I)

R¹S(Cp)₂ MRn Xq (I)

wherein each Cp can independently be selected from substituted or non su bstituted cyclopentad ienyl , indenyl or fluorenyl , the substituents on the cyclopentadienyl, indenyl and fluorenyl is a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring, R' is a substituted or unsubstituted C1 -C4 alkylidene radical, a dialkyl germanium, a dialkyl silicon, a diaryl silicon, a di-alkoxysilane, a diphenoxysilane, an alkyl phosphine or amine radical bridging two Cp such as defined hereabove, M is a group 4, 5 or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and s = 0 or 1 , n = 0-3, q = 0-3 and the sum of n and q will be equal to the valence of the transition metal, and 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed h igh density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof to produce a film having an impact resistance, measured according to ASTM D 1709-4 method A, greater than the impact resistance of a corresponding film of same thickness and produced under the same processing conditions, made with the same composition, excepted that the polyethylene catalysed with the metallocene of general formula (I) has a density between 0.944 and 0.946 g/cm³, both metallocene catalysed polyethylenes having substantially the same melt index.

2. Use according to claim 1 wherein the metallocene polyethylene has a density of from 0.950 to 0.970 g/cm³.

3. Use according to claim 2 wherein the metallocene polyethylene has a density of from 0.952 to 0.970 g/cm³.

4. Use according to any of the preceding claims wherein the metallocene polyethylene has a melt index of from 0.1 to 10 when measured according to ASTM D 1238, conditions 190°C/2.16 kg.

5. Use according to any of the preceding claims wherein M is a group 4 transition metal.

6. Use according to any one of the preceding claims wherein n=0, q=2, X=CI₁ S=L

7. Use according to any one of the preceding claims wherein (Cp)2 is a bisindenyl, a bis tetrahydroindenyl or a cyclopentadienyl fluorenyl.

8. Use according to any one of the preceding claims wherein the metallocene catalyst is ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.

9. Use according to any one of the preceding claims wherein the film produced has an impact resistance greater than 5 % compared to the impact resistance of a corresponding film of same thickness and produced under the same processing conditions made with the same composition, excepted that the polyethylene catalysed with the metallocene of general formula (I) has a density of 0.945 g/cm³, both metallocene catalysed polyethylenes having substantially the same melt index.

10. Use according to claim 9 wherein the film produced has an impact resistance greater than 10 % compared to the impact resistance of the corresponding film.

11. Use according to claims 9 or 10 wherein the film produced has a MD tensile strength at yield when measured according to ASTM D 882- 02 of at least 4% greater than that measured on the corresponding film.

12. Use according to claim 11 wherein the film produced has a MD tensile strength of at least 10% greater than that measured on the corresponding film.

13. Use of a resin composition comprising from 5% to 100% by weight of high density polyethylene having a density of from 0.947 to 0.970 g/cm³ when measured according to ASTM D 1505 and a molecular weight distribution of less than 4 produced with a metallocene catalyst having the general formula (I) R¹S(Cp)₂ MRn Xq

(I) wherein each Cp can independently be selected from substituted or non su bstituted cyclopentad ienyl , indenyl or fluorenyl , the substituents on the cyclopentadienyl, indenyl and fluorenyl is a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms joined together to form a C4-C6 ring, R' is a substituted or unsubstituted C1 -C4 alkylidene radical, a dialkyl germanium, a dialkyl silicon, a diaryl silicon, a di-alkoxysilane, a diphenoxysilane, an alkyl phosphine or amine radical bridging two Cp such as defined hereabove, M is a group 4, 5 or 6 transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and s = 0 or 1 , n = 0-3, q = 0-3, and 0% to 95% by weight of a polyolefin selected from the group consisting of very low density polyethylene, low density polyethylene, l inear low density polyethylene, medium density polyethylene, Ziegler-Natta catalysed h igh density polyethylene, chromium catalysed high density polyethylene, ethylene vinyl acetate copolymers and mixtures thereof to produce films having an impact resistance, when measured according to ASTM D 1709-04 method A and /or ISO 7765-2, greater than the impact resistance of a corresponding film of same thickness and produced under the same processing conditions made with the same composition, characterised in that both films have substantially similar MD and/or TD tensile strength at yield when measured according to ASTM D 882-02.

14. Use according to claim 13 wherein the film produced has an impact resistance of at least 10% greater than the impact resistance of the corresponding film.

15. Use according to claim 14 wherein the film produced has an impact resistance of at least 15% greater than the impact resistance of the corresponding film.