(19)
(11)EP 3 149 060 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
25.03.2020 Bulletin 2020/13

(21)Application number: 15719697.3

(22)Date of filing:  28.04.2015
(51)Int. Cl.: 
C08L 23/16  (2006.01)
C08L 23/08  (2006.01)
C08F 2/00  (2006.01)
C08L 23/06  (2006.01)
C08F 210/02  (2006.01)
(86)International application number:
PCT/EP2015/059245
(87)International publication number:
WO 2015/180919 (03.12.2015 Gazette  2015/48)

(54)

ETHYLENE POLYMER COMPOSITION AND USE THEREOF IN POLYOLEFIN COMPOSITIONS

ETHYLENPOLYMERZUSAMMENSETZUNG UND VERWENDUNG DAVON IN POLYOLEFINZUSAMMENSETZUNGEN

COMPOSITION DE POLYMÈRE D'ÉTHYLÈNE ET LEUR UTILISATION DANS DES COMPOSITIONS DE POLYOLÉFINE


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

(30)Priority: 28.05.2014 EP 14170318

(43)Date of publication of application:
05.04.2017 Bulletin 2017/14

(73)Proprietor: Basell Polyolefine GmbH
50389 Wesseling (DE)

(72)Inventors:
  • CAVALIERI, Claudio
    I-44122 Ferrara (IT)
  • GRAZZI, Michele
    I-44122 Ferrara (IT)
  • PANTALEONI, Roberto
    I-44122 Ferrara (IT)

(74)Representative: LyondellBasell 
c/o Basell Poliolefine Italia Intellectual Property P.le Donegani 12
44122 Ferrara
44122 Ferrara (IT)


(56)References cited: : 
WO-A1-2006/125720
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] The present disclosure relates to an ethylene polymer composition and to its use as additive, in particular as impact modifier, for polyolefin compositions.

    BACKGROUND OF THE INVENTION



    [0002] Impact modifiers, consisting of or comprising a prevailingly amorphous olefin copolymer, are often added in polyolefin compositions to enhance the impact resistance.

    [0003] It would be also desirable to make it possible to modify other valuable properties of polyolefin compositions, including optical properties, while enhancing impact resistance.

    [0004] In answer to such need, it has now been found that by properly balancing the total fusion enthalpy with the hydrocarbon-solubility of specific polymer components, it is possible to obtain an ethylene polymer composition particularly suited for preparing final polyolefin compositions having an excellent set of properties.

    [0005] In particular, the ethylene polymer composition of the present invention allows to obtain polyolefin compositions having an unusually favorable balance of impact resistance at low temperatures, optical properties (high gloss) and reduced shrinkage on cooling.

    SUMMARY OF THE INVENTION



    [0006] Thus the present invention provides an ethylene polymer composition having a fusion enthalpy ΔHfus, measured by Differential Scanning Calorimetry with a heating rate of 20°C per minute, of 60 J/g or more, preferably of 70 J/g or more, and comprising, all per cent amounts being by weight:
    1. A) 25-55%, preferably 30-45%, of an ethylene polymer containing 10% or less, preferably 8% or less, more preferably 5% or less, referred to the weight of A), of a fraction XSA soluble in xylene at 25°C;
    2. B) 45-75%, preferably 55-70%, of a copolymer of ethylene and propylene containing from 45% to 70%, preferably from 50% to 70%, of ethylene and 60% or more, preferably 65% or more, in particular 70% or more, of a fraction XSB soluble in xylene at 25°C, both ethylene and XSB amounts being referred to the weight of B);
    wherein the amounts of A) and B) are referred to the total weight of A) + B).

    DETAILED DESCRIPTION OF THE INVENTION



    [0007] In general, the term "copolymer" is meant to include also polymers containing more than one kind of comonomers, such as terpolymers.

    [0008] The upper limit of ΔHfus for the ethylene polymer composition of the invention is preferably of 90 J/g.

    [0009] Such upper limit applies to all the lower limits specified above.

    [0010] The ethylene polymer A) is preferably an ethylene homopolymer (i) or a copolymer (ii) of ethylene with one or more comonomers selected from olefins having formula CH2=CHR wherein R is an alkyl radical, linear or branched, having from 1 to 10 carbon atoms, or a mixture of (i) and (ii).

    [0011] Specific examples of said olefins are propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1.

    [0012] Preferably the ethylene polymer A) has a density of from 0.930 to 0.960 g/cm3, more preferably from 0.935 to 0.955 g/cm3, most preferably from 0.940 to 0.955 g/cm3, determined according to ISO 1183 at 23°C.

    [0013] The component B) in the ethylene polymer composition of the present invention is an ethylene copolymer which is more soluble in xylene, thus less crystalline than component A).

    [0014] The upper limit of XSB content in component B) is preferably of 90% by weight.

    [0015] Such upper limit applies to all the lower limits specified above.

    [0016] Preferably the intrinsic viscosity [η] of the XSB fraction is of 2 dl/g or more, in particular from 2 to 3.5 dl/g.

    [0017] The ethylene polymer composition of the present invention preferably has a melting peak at a temperature Tm of 120°C or higher, in particular from 120°C to 130°C, measured by Differential Scanning Calorimetry with a heating rate of 20°C per minute.

    [0018] The melt flow rate (MFR) of the ethylene polymer composition is preferably from 0.3 to 5 g/10 min., more preferably from 0.5 to 3 g/10 min., determined according to ISO 1133 at 230°C with a load of 2.16 kg.

    [0019] Moreover, the ethylene polymer composition of the present invention can have at least one of the following additional features:
    • a MFR value of the ethylene polymer A), determined according to ISO 1133 at 230°C with a load of 2.16 kg, of from 1 to 15 g/10 min.;
    • glass transition temperature (Tg), measured on the blend of A) + B), of equal to or higher than - 50 °C, in particular from -35 to -50 °C;
    • Tg of component B) of equal to or higher than -50 °C, in particular from -35 to -50 °C;
    • an ethylene content, determined on the total amount of A) + B), of 65% - 85% by weight, preferably of 65 - 80% by weight;
    • an amount of total fraction XSTOT soluble in xylene at 25°C, determined by extraction carried out on the total amount of A) + B), of 35% - 60% by weight, preferably of 40 - 60% by weight;
    • an intrinsic viscosity [η] of the XSTOT fraction of 1.8 dl/g or more, in particular from 1.8 to 3.0 dl/g;
    • an ethylene content of the the XSTOT fraction of 45% - 60% by weight;
    • a flexural modulus value from 90 to 200 MPa.


    [0020] All the said [η] values are measured in tetrahydronaphthalene at 135 °C.

    [0021] It is to be considered that in the composition of the present invention, the Tg of B) substantially determines the Tg of the blend of A) + B), so that, when the Tg value measured on the blend of A) + B) is of -48 °C or higher, the Tg of B) has still to be equal to or higher than -50 °C.

    [0022] While no necessary limitation is known to exist in principle on the kind of polymerization process and catalysts to be used, it has been found that the ethylene polymer composition of the present invention can be prepared by a sequential polymerization, comprising at least two sequential steps, wherein components A) and B) are prepared in separate subsequent steps, operating in each step, except the first step, in the presence of the polymer formed and the catalyst used in the preceding step. The catalyst is added only in the first step, however its activity is such that it is still active for all the subsequent steps.

    [0023] The polymerization, which can be continuous or batch, is carried out following known techniques and operating in liquid phase, in the presence or not of inert diluent, or in gas phase, or by mixed liquid-gas techniques. It is preferable to carry out the polymerization in gas phase.

    [0024] Reaction time, pressure and temperature relative to the polymerization steps are not critical, however it is best if the temperature is from 50 to 100 °C. The pressure can be atmospheric or higher.

    [0025] The regulation of the molecular weight is carried out by using known regulators, hydrogen in particular.

    [0026] The said polymerizations are preferably carried out in the presence of a Ziegler-Natta catalyst. Typically a Ziegler-Natta catalyst comprises the product of the reaction of an organometallic compound of group 1, 2 or 13 of the Periodic Table of elements with a transition metal compound of groups 4 to 10 of the Periodic Table of Elements (new notation). In particular, the transition metal compound can be selected among compounds of Ti, V, Zr, Cr and Hf and is preferably supported on MgCl2.

    [0027] Particularly preferred catalysts comprise the product of the reaction of said organometallic compound of group 1, 2 or 13 of the Periodic Table of elements, with a solid catalyst component comprising a Ti compound and an electron donor compound supported on MgCl2.

    [0028] Preferred organometallic compounds are the aluminum alkyl compounds.

    [0029] Thus in a preferred embodiment, the ethylene polymer composition of the present invention is obtainable by using a Ziegler-Natta polymerization catalyst, more preferably a Ziegler-Natta catalyst supported on MgCl2, even more preferably a Ziegler-Natta catalyst comprising the product of reaction of:
    1. 1) a solid catalyst component comprising a Ti compound and an electron donor (internal electron-donor) supported on MgCl2;
    2. 2) an aluminum alkyl compound (cocatalyst); and, optionally,
    3. 3) an electron-donor compound (external electron-donor).


    [0030] The solid catalyst component (1) contains as electron-donor a compound generally selected among the ethers, ketones, lactones, compounds containing N, P and/or S atoms, and mono- and dicarboxylic acid esters.

    [0031] Catalysts having the above mentioned characteristics are well known in the patent literature; particularly advantageous are the catalysts described in US patent 4,399,054 and European patent 45977.

    [0032] Particularly suited among the said electron-donor compounds are phthalic acid esters, preferably diisobutyl phthalate, and succinic acid esters.

    [0033] Suitable succinic acid esters are represented by the formula (I):

    wherein the radicals R1 and R2, equal to or different from each other, are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; the radicals R3 to R6 equal to or different from each other, are hydrogen or a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms, and the radicals R3 to R6 which are joined to the same carbon atom can be linked together to form a cycle.

    [0034] R1 and R2 are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particularly preferred are the compounds in which R1 and R2 are selected from primary alkyls and in particular branched primary alkyls. Examples of suitable R1 and R2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl.

    [0035] One of the preferred groups of compounds described by the formula (I) is that in which R3 to R5 are hydrogen and R6 is a branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10 carbon atoms. Another preferred group of compounds within those of formula (I) is that in which at least two radicals from R3 to R6 are different from hydrogen and are selected from C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms. Particularly preferred are the compounds in which the two radicals different from hydrogen are linked to the same carbon atom. Furthermore, also the compounds in which at least two radicals different from hydrogen are linked to different carbon atoms, that is R3 and R5 or R4 and R6 are particularly preferred.

    [0036] Other electron-donors particularly suited are the 1,3-diethers, as illustrated in published European patent applications EP-A-361 493 and 728769.

    [0037] As cocatalysts (2), one preferably uses the trialkyl aluminum compounds, such as Al-triethyl, Al-triisobutyl and Al-tri-n-butyl.

    [0038] The electron-donor compounds (3) that can be used as external electron-donors (added to the Al-alkyl compound) comprise the aromatic acid esters (such as alkylic benzoates), heterocyclic compounds (such as the 2,2,6,6-tetramethylpiperidine and the 2,6-diisopropylpiperidine), and in particular silicon compounds containing at least one Si-OR bond (where R is a hydrocarbon radical).

    [0039] Examples of the said silicon compounds are those of formula R1aR2bSi(OR3)c, where a and b are integer numbers from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R1, R2 and R3 are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.

    [0040] Useful examples of silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si (OCH3)2, (phenyl)2Si(OCH3)2 and (cyclopentyl)2Si(OCH3)2.

    [0041] The previously said 1,3- diethers are also suitable to be used as external donors. In the case that the internal donor is one of the said 1,3-diethers, the external donor can be omitted.

    [0042] The catalysts may be precontacted with small quantities of olefin (prepolymerization), maintaining the catalyst in supension in a hydrocarbon solvent, and polymerizing at temperatures from room to 60 °C, thus producing a quantity of polymer from 0.5 to 3 times the weight of the catalyst.

    [0043] The operation can also take place in liquid monomer, producing, in this case, a quantity of polymer up to 1000 times the weight of the catalyst.

    [0044] The ethylene polymer composition of the present invention can also contain additives commonly employed in the art, such as antioxidants, light stabilizers, heat stabilizers, colorants and fillers.

    [0045] As previously said, the ethylene polymer composition of the present invention can be advantageously compounded with additional polyolefins, in particular propylene polymers such as propylene homopolymers, random copolymers, and thermoplastic elastomeric polyolefin compositions. Accordingly, a second embodiment of the invention relates to a polyolefin composition containing the above-defined ethylene polymer composition. Preferably, the said polyolefin composition comprises at least 50% by weight, typically from 50% to 85% by weight, of one or more additional polyolefins, thus 50% or less, typically from 15% to 50% by weight, of the ethylene polymer composition according to the present invention, all per cent amounts being referred to the total weight of the ethylene polymer composition and of the additional polyolefin or polyolefins.

    [0046] Practical examples of the said additional polyolefins are the following polymers:
    1. 1) crystalline propylene homopolymers, in particular isotactic or mainly isotactic homopolymers;
    2. 2) crystalline propylene copolymers with ethylene and/or a C4-C10 α-olefin, wherein the total comonomer content ranges from 0.05 to 20% by weight with respect to the weight of the copolymer, and wherein preferred C4-C10 α-olefins are 1-butene; 1-hexene; 4-methyl-1-pentene and 1-octene;
    3. 3) crystalline ethylene homopolymers and copolymers with propylene and/or a C4-C10 α-olefin, such as HDPE;
    4. 4) thermoplastic elastomeric compositions comprising one or more of propylene homopolymers and/or the copolymers of item 2) and an elastomeric moiety comprising one or more copolymers of ethylene with propylene and/or C4-C10 α-olefins, optionally containing minor quantities of a diene, such as butadiene, 1,4-hexadiene, 1,5-hexadiene and ethylidene-1-norbornene, wherein the diene content is typically from 1 to 10% by weight, typically prepared according to known methods by mixing the components in the molten state or by sequential polymerization, and generally containing the said elastomeric moiety in quantities from 5 to 80% by weight.


    [0047] The polyolefin composition may be manufactured by mixing the ethylene polymer composition and the additional polyolefin(s) together, extruding the mixture, and pelletizing the resulting composition using known techniques and apparatus.

    [0048] The polyolefin composition may also contain conventional additives such as mineral fillers, colorants and stabilizers. Mineral fillers that can be included in the composition include talc, CaCO3, silica, such as wollastonite (CaSiO3), clays, diatomaceaous earth, titanium oxide and zeolites. Typically the mineral filler is in particle form having an average diameter ranging from 0.1 to 5 micrometers.

    [0049] The present invention also provides final articles, in particular injection moulded articles, such as finished parts for the automotive industry, made of or comprising the said polyolefin composition.

    EXAMPLES



    [0050] The practice and advantages of the various embodiments, compositions and methods as provided herein are disclosed below in the following examples. These Examples are illustrative only, and are not intended to limit the scope of the invention in any manner whatsoever.

    [0051] The following analytical methods are used to characterize the polymer compositions.

    Melting temperature (ISO 11357-3)



    [0052] Determined by differential scanning calorimetry (DSC). A sample weighting 6 ± 1 mg is heated to 200 ± 1° C at a rate of 20 °C/min and kept at 200 ± 1° C for 2 minutes in nitrogen stream and is thereafter cooled at a rate of 20° C/min to 40 ± 2° C, thereby kept at this temperature for 2 min to crystallise the sample. Then, the sample is again melted at a temperature rise rate of 20° C/min up to 200° C ± 1. The melting scan is recorded, a thermogram is obtained, and, from this, temperatures corresponding to peaks are read. The temperature corresponding to the most intense melting peak recorded during the second fusion is taken as the melting temperature. The fusion enthalpy ΔHfus is measured on said most intense melting peak. Obviously, if only one peak is detected, both melting temperature and ΔHfus are provided by (i.e. measured on) such peak. To determine fusion enthalpy ΔHfus, construct the base-line by connecting the two closest points at which the melting endotherm peak deviate from the baseline. The heat of fusion (ΔHfus) is then calculated by integrating the area between DSC heat flow recorded signal and constructed baseline.

    Xylene soluble fraction



    [0053] 2.5 g of polymer and 250 cm3 of o-xylene are introduced in a glass flask equipped with a refrigerator and a magnetical stirrer. The temperature is raised in 30 minutes from room temperature up to the boiling point of the solvent (135°C). The so obtained clear solution is then kept under reflux and stirring for further 30 minutes. The closed flask is then kept in a thermostatic water bath at 25 °C for 30 minutes as well so that the crystallization of the insoluble (XI) part of the sample takes place. The so formed solid is filtered on quick filtering paper. 100 cm3 of the filtered liquid is poured in a previously weighed aluminum container which is heated on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container is then kept in an oven at 80 °C under vacuum to dryness and then weighed after constant weight is obtained.

    [0054] Thus one calculates the percent by weight of polymer soluble and insoluble in xylene at 25 °C.

    Melt Flow Rate



    [0055] Measured according to ISO 1133 at 230°C with a load of 2.16 kg, unless otherwise specified.

    [η] intrinsic viscosity



    [0056] The sample is dissolved in tetrahydronaphthalene at 135 °C and then is poured into the capillary viscometer. The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows temperature control with a circulating thermostated liquid. The downward passage of the meniscus is timed by a photoelectric device.

    [0057] The passage of the meniscus in front of the upper lamp starts the counter which has a quartz crystal oscillator. The meniscus stops the counter as it passes the lower lamp and the efflux time is registered: this is converted into a value of intrinsic viscosity through Huggins' equation (Huggins, M.L., J. Am. Chem. Soc., 1942, 64, 2716) provided that the flow time of the pure solvent is known at the same experimental conditions (same viscometer and same temperature). One single polymer solution is used to determine [η].

    Ethylene or Propylene content determined via I.R. Spectroscopy



    [0058] The NIR (6000-5500 cm-1) spectrum of as pressed film of the polymer is recorded in absorbance vs. wavenumbers (cm-1). The following measurements are used to calculate the ethylene content:
    1. a) Height of the absorption band due to CH2 group, with maximum at 5669 cm-1, omitting area beneath a baseline drawn between the 6000-5500 cm-1.
    2. b) Height of the shoulder at 5891 cm-1 due to CH3 group, omitting area beneath a baseline drawn between the 6000-5500 cm-1.


    [0059] The ratio D5891 /D5669 is calibrated by analysing copolymers of known compositions, determined by NMR spectroscopy.

    [0060] The following measurements are used to calculate the propylene content:
    1. a) Area (ANIR) of the combination absorption bands between 4482 and 3950 cm-1 which is used for spectrometric normalization of film thickness.
    2. b) Area (A971) of the absorption band due to propylene sequences in the range 986-952 cm-1, omitting area beneath a baseline drawn between the endpoints.


    [0061] The ratio A971 / ANIR is calibrated by analysing copolymers of known compositions, determined by NMR spectroscopy.

    Tg determination via DMTA (Dynamic Mechanical Thermal Analysis)



    [0062] Molded specimen of 20 mm x 5 mm x 1 mm are fixed to the DMTA machine for tensile stress. The frequency of the sinusoidal oscillation is fixed at 1 Hz. The DMTA translate the elastic response of the specimen starting from -100°C (glassy state) to 130°C (softening point). In this way it is possible to plot the elastic response versus temperature. The elastic modulus in DMTA for a viscoelastic material is defined as the ratio between stress and strain also defined as complex modulus E*=E'+iE". The DMTA can split the two components E' and E" by their resonance and it is possible to plot E' (elastic component), E" (loss modulus) and E"/E' = tan δ (damping factor) vs temperature. The glass transition temperature Tg is assumed to be the temperature at the maximum of the curve tan = (δ) E"/E' vs temperature.

    Flexural Modulus*: ISO 178, measured 24 hours after moulding.

    Tensile strength at yield*: ISO 527, measured 24 hours after moulding.

    Tensile strength at break*: ISO 527, measured 24 hours after moulding.

    Elongation at break and at yield*: ISO 527, measured 24 hours after moulding.

    Notched IZOD impact test*: ISO 180/1A



    [0063] The IZOD values are measured at 23 °C, -20 °C and -30 °C, 24 hours after moulding.

    [0064] Note: *Test specimens prepared by injection moulding according to ISO 1873-2: 1989.

    Gloss at 60°



    [0065] A ISO D1 plaque of 1 mm is moulded in an injection moulding machine "NB 60" (where 60 stands for 60 tons of clamping force) in accordance with the following parameters.
    • Melt temperature = 260°C,
    • Mold temperature = 40°C,
    • Injection speed = 100 mm/sec,
    • Holding time = 10 sec,
    • Screw rotation = 120 rpm


    [0066] Injection and Holding pressures are properly set-up in order to assure a complete filling of the mold thus avoiding flashes.

    [0067] Alternatively an injection moulding machine "NB VE70" (where 70 stands for 70 tons of clamping force) can also be used.

    [0068] Gloss @ 60° is measured on the plaque according to ASTM D 2457.

    Longitudinal and transversal thermal shrinkage



    [0069] A plaque of 100 x 200 x 2.5 mm is moulded in an injection moulding machine "SANDRETTO serie 7 190" (where 190 stands for 190 tons of clamping force).

    [0070] The injection conditions are:
    • melt temperature = 250°C;
    • mould temperature = 40°C;
    • injection time = 8 seconds;
    • holding time = 22 seconds;
    • screw diameter = 55 mm.


    [0071] The plaque is measured 24 hours after moulding, through callipers, and the shrinkage is given by:



    wherein 200 is the length (in mm) of the plaque along the flow direction, measured immediately after moulding;

    100 is the length (in mm) of the plaque crosswise the flow direction, measured immediately after moulding;

    the read_value is the plaque length in the relevant direction.


    Example 1


    Preparation of the ethylene polymer composition



    [0072] The solid catalyst component used in polymerization is a Ziegler-Natta catalyst component supported on magnesium chloride, containing titanium and diisobutylphthalate as internal donor, prepared as follows.

    [0073] An initial amount of microspheroidal MgCl2·2.8C2H5OH was prepared according to the method described in Example 2 of USP 4,399,054 but operating at 3,000 rpm instead of 10,000. The so obtained adduct was then subject to thermal dealcoholation at increasing temperatures from 30 to 130°C operating in nitrogen current until the molar alcohol content per mol of Mg is 1.16.

    [0074] Into a 1000 mL four-necked round flask, purged with nitrogen, 500 mL of TiCl4 were introduced at 0°C. While stirring, 30 grams of the microspheroidal MgCl2·1.16C2H5OH adduct (prepared as described above) were added. The temperature was raised to 120°C and kept at this value for 60 minutes. During the temperature increase, an amount of diisobutylphthalate was added such as to have a Mg/ diisobutylphthalate molar ratio of 18. After the mentioned 60 minutes, the stirring was stopped, the liquid siphoned off and the treatment with TiCl4 was repeated at 100°C for 1 hour in the presence of an amount of diisobutylphthalate such as to have a Mg/ diisobutylphthalate molar ratio of 27. After that time the stirring was stopped, the liquid siphoned off and the treatment with TiCl4 was repeated at 100°C for 30 min. After sedimentation and siphoning at 85°C the solid was washed six times with anhydrous hexane (6 x 100 ml) at 60 °C.

    CATALYST SYSTEM AND PREPOLYMERIZATION TREATMENT



    [0075] Before introducing it into the polymerization reactors, the solid catalyst component described above is contacted at 30 °C for 9 minutes with aluminum triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS), in a TEAL/DCPMS weight ratio equal to about 15 and in such quantity that the TEAL/solid catalyst component weight ratio be equal to 4.

    [0076] The catalyst system is then subjected to prepolymerization by maintaining it in suspension in liquid propylene at 50 °C for about 75 minutes before introducing it into the first polymerization reactor.

    POLYMERIZATION



    [0077] The polymerization is carried out in continuous in a series of two gas-phase reactors equipped with devices to transfer the product from the first reactor to the second one.

    [0078] Into the first gas phase polymerization reactor an ethylene/propylene copolymer (component A)) is produced by feeding in a continuous and constant flow the prepolymerized catalyst system, hydrogen (used as molecular weight regulator), ethylene and propylene in the gas state.

    [0079] The ethylene polymer coming from the first reactor is discharged in a continuous flow and, after having been purged of unreacted monomers, is introduced, in a continuous flow, into the second gas phase reactor, together with quantitatively constant flows of hydrogen, ethylene and propylene in the gas state.

    [0080] In the second reactor a second ethylene/propylene copolymer (component B)) is produced. Polymerization conditions, molar ratio of the reactants and composition of the copolymers obtained are shown in Table I.

    [0081] The polymer particles exiting the second reactor, which constitute the not stabilized ethylene polymer composition according to the present invention, are subjected to a steam treatment to remove the reactive monomers and volatile substances, and then dried.

    [0082] Then the polymer particles are mixed with a usual stabilizing additive composition in a twin screw extruder Berstorff ZE 25 (length/diameter ratio of screws: 33) and extruded under nitrogen atmosphere in the following conditions:
    Rotation speed: 250 rpm;
    Extruder output: 15 kg/hour;
    Melt temperature: 280-290 °C.
    The stabilizing additive composition is made of the following components:
    • 0.1% by weight of Irganox® 1010;
    • 0.1% by weight of Irgafos® 168;
    • 0.04% by weight of DHT-4A (hydrotalcite).


    [0083] The said Irganox® 1010 is 2,2-bis[3-[,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropoxy]methyl]-1,3-propanediyl-3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene-propanoate, while Irgafos® 168 is tris(2,4-di-tert.-butylphenyl)phosphite.

    [0084] The per cent amounts are referred to the total weight of the polymer and stabilizing additive composition.

    [0085] The characteristics relating to the polymer composition, reported in Table II, are obtained from measurements carried out on the so extruded polymer, which constitutes the stabilized ethylene polymer composition according to the exemplary embodiments disclosed herein.

    Preparation of a blend of the stabilized ethylene polymer composition with propylene polymer



    [0086] The stabilized ethylene polymer composition prepared as described above (hereinafter called SEP) is blended by extrusion under the previously described conditions with a heterophasic polypropylene composition (HPP) and the other additives hereinafter described, in the proportions reported below and in Table III. The properties of the so obtained final composition are reported in Table III.

    Added components



    [0087] 
    1. 1 HPP: heterophasic polypropylene composition having MFR of 16.5 g/10 min., made of 70% by weight of propylene homopolymer with isotactic index of 98% (fraction insoluble in xylene at 25°C, determined as described above) and 30% by weight of an ethylene/propylene copolymer containing 49% by weight of ethylene;
    2. 2 talc HTP Ultra 5C: fine talc powder comprising about 98% by weight of particles having particle size of less than 5 µm;
    3. 3 carbon black master-batch having total MFR of about 0.6 g/10 min. (measured according to ISO 1133 at 230°C / 5 kg load) and made of 40% by weight of carbon black and 60% of a copolymer of propylene with 8% by weight of ethylene, having MFR of about 45 g/10 min.;
    4. 4 Irganox® B 215 (made of about 34% by weight of Irganox® 1010 and 66% of Irgafos® 168);


    [0088] The added amounts of components 1 to 4 are the following (percent by weight with respect to the total weight):
    ComponentAmount
    1 51.5%
    2 12%
    3 1.3%
    4 0.2%

    Comparative Example 1C



    [0089] A comparative polyethylene composition is prepared with the same catalyst and polymerization process as in Example 1 and is then extruded with the same stabilizing additive composition and with the same extrusion conditions as in Example 1. The specific polymerization conditions and the resulting polymer properties are reported in Table I and Table II.

    [0090] The stabilized composition is used in the preparation of a blend with the same added components in the same amounts as in Example 1.

    [0091] The properties of the so obtained final composition are reported in Table III.
    Table I
    Example No. 11C
    1st Reactor (component A))   
    Temperature °C 70 70
    Pressure barg 20 20
    H2/C2- mol. 0.59 0.37
    C3-/(C3- + C2-) mol. 0.15 0.12
    Split wt% 40 40
    Xylene soluble (XSA) wt% 2.4 4.3
    MFR of A) g/10 min. 5.7 14
    Density of A) g/cm3 0.943 0.940
    C3- content of A) wt% 3.2 2.8
    2nd Reactor (component B))   
    Temperature °C 65 65
    Pressure barg 20 20
    H2/C2- mol. 0.10 0.13
    C2-/(C2- + C3-) mol. 0.41 0.68
    Split wt% 60 60
    C2- content of B) wt% 60 80
    Xylene soluble of B) (XSB) wt% 73 36
    Intrinsic Viscosity of XSB dl/g 2.2 2.3
    Tg of A) + B) °C -45 -46
    Notes: C3- = propylene; C2- = ethylene; split = amount of polymer produced in the concerned reactor.
    Table II
    Example No. 11C
    ΔHfus J/g 78.8 100.1
    Tm °C 125 123.9
    MFR g/10 min. 1.15 0.56
    Xylene soluble (XSTOT) wt% 44.5 23.1
    Intrinsic Viscosity of XSTOT dl/g 2.17 2.6
    C2- content of XSTOT wt% 53 70
    Total C2- content wt% 73.6* 84.9
    Total C3- content wt% 26.4 15.1*
    Flexural Modulus MPa 120 260
    Notes: C3- = propylene; C2- = ethylene; * Calculated values.
    Table III
    Example No. 11C
    SEP of EXAMPLE 11C
    SEP amount wt% 35 35
    MFR g/10 min. 5.3 4.2
    Flexural Modulus MPa 810 960
    Tensile Strength at Yield MPa 12.2 14.6
    Elongation at Yield % 14.0 12.8
    Tensile strength at break MPa 12.7 16.9
    Elongation at break % 570 460
    Gloss at 60° 57 29
    Longitudinal shrinkage % 0.29 0.4
    Transversal shrinkage % 0.52 0.63
    IZOD Impact Str. at 23° C KJ/m2 61.7 64.7
    IZOD Impact Str. at -20° KJ/m2 73.2 58.6
    IZOD Impact Str. at -30° KJ/m2 67.7 35.7



    Claims

    1. An ethylene polymer composition having a fusion enthalpy ΔHfus, measured by Differential Scanning Calorimetry with a heating rate of 20°C per minute, of 60 J/g or more and comprising, all per cent amounts being by weight:

    A) 25-55% of an ethylene polymer containing 10% or less, referred to the weight of A), of a fraction XSA soluble in xylene at 25°C;

    B) 45-75% of a copolymer of ethylene and propylene containing from 45% to 70% of ethylene and 60% or more of a fraction XSB soluble in xylene at 25°C, both ethylene and XSB amounts being referred to the weight of B);

    wherein the amounts of A) and B) are referred to the total weight of A) + B).
     
    2. The ethylene polymer composition of claim 1, wherein the ethylene polymer A) is an ethylene homopolymer (i) or a copolymer (ii) of ethylene with one or more comonomers selected from olefins having formula CH2=CHR wherein R is an alkyl radical, linear or branched, having from 1 to 10 carbon atoms, or a mixture of (i) and (ii).
     
    3. The ethylene polymer composition of claim 1, wherein the ethylene polymer A) has a density of from 0.930 to 0.960 g/cm3, determined according to ISO 1183 at 23°C.
     
    4. The ethylene polymer composition of claim 1, showing a melting peak at a temperature Tm of 120°C or higher, measured by Differential Scanning Calorimetry with a heating rate of 20°C per minute.
     
    5. The ethylene polymer composition of claim 1, wherein the intrinsic viscosity [η] of the XSB fraction is of 2 dl/g or more.
     
    6. The ethylene polymer composition of claim 1, having a MFR value of from 0.3 to 5 g/10 min., determined according to ISO 1133 at 230°C with a load of 2.16 kg.
     
    7. The ethylene polymer composition of claim 1, having a flexural modulus value from 90 to 200 MPa, measured according to ISO 178 on test specimens prepared by injection moulding according to ISO 1873-2: 1989, 24 hours after moulding.
     
    8. Polymerization process for preparing the ethylene polymer composition of claim 1, comprising at least two sequential stages, wherein components A) and B) are prepared in separate subsequent stages, operating in each stage, except the first stage, in the presence of the polymer formed and the catalyst used in the preceding stage.
     
    9. A polyolefin composition comprising the ethylene polymer composition of claim 1 and at least 50% by weight, referred to the total weight of the polyolefin composition, of one or more additional polyolefins.
     
    10. The polyolefin composition of claim 9, wherein the additional polyolefin or polyolefins are selected from propylene homoploymers and copolymers.
     
    11. Formed articles comprising the polyolefin composition of claims 9 and 10.
     
    12. Formed articles according to claim 11, in form of injection moulded articles.
     


    Ansprüche

    1. Ethylenpolymerzusammensetzung mit einer Schmelzenthalpie ΔHSchmelz, gemessen mittels Differentialscanningkalorimetrie mit einer Heizrate von 20 °C pro Minute, von 60 J/g oder mehr, und welche folgendes umfasst, wobei sich alle prozentualen Mengen auf das Gewicht beziehen:

    A) 25 bis 55 % eines Ethylenpolymers, das 10 % oder weniger, bezogen auf das Gewicht von A), von einer Fraktion XSA enthält, die in Xylol bei 25 °C löslich ist;

    B) 45 bis 75 % eines Copolymers von Ethylen und Propylen, das 45 % bis 70 % Ethylen und 60 % oder mehr von einer Fraktion XSB enthält, die in Xylol bei 25 °C löslich ist, wobei sich die Mengen von sowohl Ethylen als auch XSB auf das Gewicht von B) beziehen;

    wobei sich die Mengen von A) und B) auf das Gesamtgewicht von A) + B) beziehen.
     
    2. Ethylenpolymerzusammensetzung nach Anspruch 1, wobei das Ethylenpolymer A) ein Ethylenhomopolymer (i) oder ein Copolymer (ii) von Ethylen mit einem oder mehreren Comonomeren ausgewählt aus Olefinen mit der Formel CH2=CHR, wobei R ein linearer oder verzweigter Alkylrest mit 1 bis 10 Kohlenstoffatome ist, oder eine Mischung von (i) und (ii) ist.
     
    3. Ethylenpolymerzusammensetzung nach Anspruch 1, wobei das Ethylenpolymer A) eine Dichte von 0,930 bis 0,960 g/cm3 aufweist, bestimmt gemäß ISO 1183 bei 23 °C.
     
    4. Ethylenpolymerzusammensetzung nach Anspruch 1, die einen Schmelzpeak bei einer Temperatur Tm von 120 °C oder höher, gemessen mittels Differentialscanningkalorimetrie, mit einer Heizrate von 20°C pro Minute zeigt.
     
    5. Ethylenpolymerzusammensetzung nach Anspruch 1, wobei die Grenzviskosität [η] der Fraktion XSB 2 dl/g oder mehr beträgt.
     
    6. Ethylenpolymerzusammensetzung nach Anspruch 1 mit einem MFR-Wert von 0,3 bis 5 g/10 min., bestimmt gemäß ISO 1133 bei 230 °C unter einer Last von 2,16 kg.
     
    7. Ethylenpolymerzusammensetzung nach Anspruch 1 mit einem Biegemodulwert von 90 bis 200 MPa, gemessen gemäß ISO 178 an Testprüfkörpern, die durch Spritzguss hergestellt sind, gemäß ISO 1873-2: 1989, 24 Stunden nach dem Formen.
     
    8. Polymerisationsverfahren zur Herstellung der Ethylenpolymerzusammensetzung nach Anspruch 1, umfassend mindestens zwei aufeinander folgende Stufen, wobei Komponenten A) und B) in separaten Folgestufen hergestellt werden, wobei in jeder Stufe außer der ersten Stufe in Gegenwart des in der vorhergehenden Stufe gebildeten Polymers und verwendeten Katalysators gearbeitet wird.
     
    9. Polyolefinzusammensetzung, umfassend die Ethylenpolymerzusammensetzung nach Anspruch 1 und mindestens 50 Gew.%, bezogen auf das Gesamtgewicht der Polyolefinzusammensetzung, von einem oder mehreren zusätzlichen Polyolefinen.
     
    10. Polyolefinzusammensetzung nach Anspruch 9, wobei das zusätzliche Polyolefin oder die zusätzlichen Polyolefine ausgewählt sind aus Propylenhomopolymeren und -copolymeren.
     
    11. Formartikel, welche die Polyolefinzusammensetzung der Ansprüche 9 und 10 umfassen.
     
    12. Formartikel nach Anspruch 11 in Form von spritzgegossenen Artikeln.
     


    Revendications

    1. Composition de polymère d'éthylène présentant une enthalpie de fusion ΔHfus, mesurée par calorimétrie différentielle à balayage à une vitesse de chauffage de 20°C par minute, de 60 J/g ou plus et comprenant, toutes les quantités en pourcentage étant en poids :

    A) 25 à 55% d'un polymère d'éthylène contenant 10% ou moins, par rapport au poids de A), d'une fraction XSA soluble dans le xylène à 25°C ;

    B) 45 à 75% d'un copolymère d'éthylène et de propylène contenant de 45% à 70% d'éthylène et 60% ou plus d'une fraction XSB soluble dans le xylène à 25°C, les quantités à la fois d'éthylène et de XSB se référant au poids de B) ;

    les quantités de A) et B) se référant au poids total de A) + B).
     
    2. Composition de polymère d'éthylène selon la revendication 1, le polymère d'éthylène A) étant un homopolymère (i) d'éthylène ou un copolymère (ii) d'éthylène et d'un ou de plusieurs comonomères choisis parmi les oléfines de formule CH2=CHR, où R représente un radical alkyle, linéaire ou ramifié, comprenant 1 à 10 atomes de carbone, ou un mélange de (i) et (ii).
     
    3. Composition de polymère d'éthylène selon la revendication 1, le polymère d'éthylène A) présentant une densité de 0,930 à 0,960 g/cm3, déterminée selon la norme ISO 1183 à 23°C.
     
    4. Composition de polymère d'éthylène selon la revendication 1, présentant un pic de fusion à une température Tm de 120°C ou plus, mesurée par calorimétrie différentielle à balayage à une vitesse de chauffage de 20°C par minute.
     
    5. Composition de polymère d'éthylène selon la revendication 1, la viscosité intrinsèque [η] de la fraction XSB étant de 2 dl/g ou plus.
     
    6. Composition de polymère d'éthylène selon la revendication 1, présentant une valeur de MFR de 0,3 à 5 g/10 min, déterminée selon la norme ISO 1133 à 230°C sous une charge de 2,16 kg.
     
    7. Composition de polymère d'éthylène selon la revendication 1, présentant une valeur de module de flexion de 90 à 200 MPa, mesurée selon la norme ISO 178 sur des éprouvettes préparées par moulage par injection selon la norme ISO 1873-2:1989, 24 heures après moulage.
     
    8. Procédé de polymérisation pour la préparation de la composition de polymère d'éthylène selon la revendication 1, comprenant au moins deux étapes séquentielles, les constituants A) et B) étant préparés dans des étapes ultérieures distinctes, chaque étape étant mise en œuvre, à l'exception de la première étape, en présence du polymère formé et du catalyseur utilisé dans l'étape précédente.
     
    9. Composition de polyoléfine comprenant la composition de polymère d'éthylène selon la revendication 1 et au moins 50% en poids, par rapport au poids total de la composition de polyoléfine, d'une ou de plusieurs polyoléfines supplémentaires.
     
    10. Composition de polyoléfine selon la revendication 9, la polyoléfine ou les polyoléfines supplémentaire(s) étant choisie(s) parmi les homopolymères et les copolymères de propylène.
     
    11. Articles formés comprenant la composition de polyoléfine selon les revendications 9 et 10.
     
    12. Articles formés selon la revendication 11, sous forme d'articles moulés par injection.
     




    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description