Polymer composition for injection molding

Abstract

The present disclosure relates to a polyolefin composition having a high balance of melt flow and impact resistance, the polyolefin composition comprising: A) 88% to 99% by weight of an ethylene polymer having a MIP of 5 g / 10 min or greater, where the MIP is a melt flow rate at 190°C and a 5 kg load determined in accordance with 1133-2:2011; and B) 1% to 12% by weight of a butene-1 polymer having a MIE of 800 g / 10 min or greater, where the MIE is a melt flow rate at 190°C and a 2.16 kg load determined in accordance with 1133-2:2011; and the amount of A) and B) is the total weight of A) + B).

Description

Technical Field

[0001] The present disclosure relates to a polymer composition for injection molding, comprising an ethylene polymer and a low amount of butene-1 polymer having a very high melt flow rate value.

[0002] The incorporation of the butene-1 polymer makes it possible to achieve an improved melt flow index in the injection molding process and improves some mechanical properties of the ethylene polymer.

Background Art

[0003] Generally, injection molding is used for the production of various polymer molded articles, especially those having complex shapes.

[0004] Polyolefins, including polyethylene, are the most widely used plastics in injection molding.

[0005] In the injection molding process, heat and pressure are applied to the polymer to melt and flow it. The melt is injected into a mold under high pressure.

[0006] Pressure is maintained on the material in the cavity until it cools and solidifies. When the temperature has sufficiently dropped below the deformation temperature of the polymer, the mold is opened and the molded article is ejected.

[0007] Therefore, in the design of polyolefins for injection molding, it is clear that high melt flowability is required to obtain high-quality and uniform final molded articles under feasible pressure and temperature conditions and to reduce the cycle time.

[0008] In the case of polyethylene, such effects are achieved by appropriately setting the molecular weight and molecular weight distribution, but there is a continuous effort to obtain the optimum possible melt flowability under injection molding process conditions without degrading the mechanical properties.

[0009] Paraffin waxes such as Fischer-Tropsch wax are generally used as additives to improve the melt flowability of polyethylene in the injection molding process.

[0010] However, when wax is added to polyethylene in an amount exceeding about 2% by mass, it becomes more difficult to obtain a uniform blend, and the improvement in melt flowability is limited.

[0011] Also, the final mechanical properties usually deteriorate.

[0012] As described in WO2010025918 and WO2007082817, it is known that adding a small amount of butene-1 polymer to polyethylene can be used to produce tubes, films and fibers, but in the art, the use of butene-1 polymer as a processing aid in injection molding compositions has not been considered.

[0013] It has been found that adding a butene-1 polymer having a very high melt flow rate value to an ethylene polymer results in a polymer composition for injection molding having an unintended property distribution.

Summary of the Invention

[0014] Accordingly, the present disclosure provides a polymer composition comprising A) and B), A) 88% to 99% by mass, preferably 90% to 98.5% by mass, more preferably 92% to 98.5% by mass of an ethylene polymer having a MIP of 5 g / 10 min or more, preferably 6 g / 10 min or more, more preferably 8 g / 10 min or more, where MIP is the melt flow rate at 190 °C and a load of 5 kg determined according to ISO 1133-2:2011, B) 1% to 12% by mass, preferably 1.5% to 10% by mass, more preferably 1.5% to 8% by mass of a butene-1 polymer having a melt index (MIE) of 800 g / 10 min or more, preferably 1000 g / 10 min or more, particularly 800 to 3000 g / 10 min, or 1000 to 3000 g / 10 min, where MIE is the melt flow rate at 190 °C and a load of 2.16 kg determined according to ISO 1133:2011, A) and B) are provided in an amount such that the total weight of A) + B) is a polymer composition.

[0015] The composition has a melt flowability measured at a high helix length and an impact resistance value measured by Charpy impact strength.

DETAILED DESCRIPTION OF THE INVENTION

[0016] As used herein, the term "ethylene polymer" includes polymers selected from the group consisting of ethylene homopolymers and ethylene copolymers, where the ethylene copolymer contains an α-olefin comonomer different from ethylene and preferably has 3 to 8 carbon atoms (preferably in an amount of 1% to 10% by mass based on the total weight of the copolymer), and mixtures thereof. Examples of the α-olefin comonomer having 3 to 8 carbon atoms include propene, butene-1, pentene-1, hexene-1, octene-1, and 4-methylpentene-1.

[0017] Butene-1 and hexene-1 are preferred.

[0018] The term "ethylene polymer" is also intended to cover polymers consisting of a single component, alternatively referred to as "monomodal" polymers in the art, and polymer compositions containing two or more ethylene polymer components that are "bimodal" or "multimodal" polymers, preferably having different molecular weights.

[0019] As used herein, the term "butene-1 polymer" includes polymers selected from the group consisting of butene-1 homopolymers and butene-1 copolymers containing a butene-1 and an α-olefin comonomer different from butene-1, preferably selected from the group consisting of ethylene, propene, α-olefins having 5 to 10 carbon atoms, and mixtures thereof.

[0020] Ethylene is particularly preferred.

[0021] Examples of the α-olefin having 5 to 10 carbon atoms include hexene-1 and octene-1.

[0022] The term "butene-1 polymer" is also intended to cover, alternatively, polymers consisting of a single component and polymers (polymer compositions) containing two or more butene-1 polymer components, preferably having different amounts of comonomer.

[0023] Particularly preferred amounts of A) and B) are - 88% to 97% by mass of A) and 3% to 12% by mass of B), or - 90% to 97% by mass of A) and 3% to 10% by mass of B), or - 92% to 97% by mass of A) and 3% to 8% by mass of B), where the contents of A) and B) are based on the total weight of A) + B).

[0024] Preferred values for the density of ethylene polymer A) measured at 23 °C in accordance with ISO 1183-1:2012 are 0.930 to 0.970 g / cm 3 , particularly 0.940 to 0.965 g / cm 3 .

[0025] Particularly preferred values for the MIP of ethylene polymer A) are - 5 to 20 g / 10 min, or - 5 to 15 g / 10 min, or - 6 to 20 g / 10 min, or - 6 to 15 g / 10 min, or - 8 to 20 g / 10 min, or - 8 to 15 g / 10 min.

[0026] Optionally, ethylene polymer A) may have at least one of the following further additional features: - A MIF value of 50 to 200 g / 10 min, or 50 to 150 g / 10 min, preferably 60 to 200 g / 10 min, or 60 to 150 g / 10 min, more preferably 80 to 200 g / 10 min, or 80 to 150 g / 10 min, where MIF is the melt flow rate at 190 °C and a load of 21.60 kg determined according to ISO 1133-2:2011, - A MIE value of 1 to 10 g / 10 min, or 1 to 8 g / 10 min, preferably 2 to 10 g / 10 min, or 2 to 8 g / 10 min, - A MIF / MIP ratio of 5 or more, especially 5 to 20 or 5 to 15, - A MIF / MIE ratio of 20 or more, especially 20 to 40 or 20 to 35.

[0027] Commercially available ethylene polymers A) of the present invention can be used. It belongs to the family of polymers (homopolymers and copolymers) obtained by a polymerization process in the presence of a coordination catalyst. The said process and the polymers obtained therefrom are widely described in the art.

[0028] In particular, the polymerization process can be carried out in the presence of a Ziegler-Natta catalyst.

[0029] As is well known, a Ziegler-Natta polymerization catalyst contains the reaction product of an organic compound of metals of Groups I to III of the periodic table (for example, alkylaluminum) and an inorganic compound of transition metals of Groups IV to VIII of the periodic table (for example, titanium halide), and is preferably supported on magnesium halide. The polymerization conditions for using such catalysts in combination are also generally known.

[0030] The polymerization can be carried out in a single step to produce a unimodal ethylene polymer or in two or more steps under different polymerization conditions to produce a multimodal ethylene polymer.

[0031] The butene-1 polymer B) of the present invention preferably has a Brookfield viscosity of 1500 to 20000 mPa·sec, particularly 2000 to 15000 mPa·sec, or 2500 to 10000 mPa·sec at 190°C.

[0032] In one embodiment, the butene-1 polymer B) may be a copolymer having a copolymer monomer content with copolymerization, particularly an ethylene content in the copolymerization of 0.5 mol% to 4.0 mol%, preferably 0.7 mol% to 3.5 mol%.

[0033] In a further embodiment, the butene-1 polymer B) may be a butene-1 copolymer composition comprising B1) and B2), B1) is a homopolymer of butene-1 or a copolymer of butene-1 and at least one comonomer selected from the group consisting of ethylene, propene, α-olefins having 5 to 10 carbon atoms, and mixtures thereof, and has a comonomer content (C A1 ) with copolymerization of at most 2 mol%, B2) is a copolymer of butene-1 and at least one comonomer selected from the group consisting of ethylene, propene, α-olefins having 5 to 10 carbon atoms, and mixtures thereof, and has a comonomer content (C A2 ) with copolymerization of 3 to 5 mol%, The total comonomer content with total polymerization in the composition is 0.5 mol% to 4.0 mol%, preferably 0.7 mol% to 3.5 mol%, and is referred to as the sum of B1) + B2).

[0034] The relative amounts of B1) and B2) may be in the range of 10% to 40% by mass of B1), particularly 15% to 35% by mass, and 90% to 60% by mass of B2), particularly 85% to 65% by mass, and the amounts are the sum of B1) + B2).

[0035] Particularly preferred MIP values for the butene-1 polymer B) are 1800 g / 10 min or more, particularly 1800 to 3000 g / 10 min.

[0036] Preferably, the butene-1 polymer B) may have at least one of the following additional features: a) The molecular weight distribution (Mw / Mn) is less than 4, preferably less than 3, more preferably less than 2.5, and in all cases the lower limit is preferably 1.5. b) The melting point (TmII) is less than 110 °C, preferably less than 100 °C, more preferably less than 90 °C. c) The melting point (TmII) is higher than 80 °C. d) The glass transition temperature (Tg) is in the range of -40 °C to -10 °C, preferably -30 °C to -10 °C. e) Operates at 150.91 MHz 13 The isotactic pentad (mmmm) measured by C-NMR is higher than 90%, particularly higher than 93% or 95%. f) Operates under 150.91 MHz 13 No 4,1 insertion is detected by C-NMR. g) The X-ray crystallinity is 25% to 65%.

[0037] Optionally, the butene-1 polymer B) may have at least one of the following further additional features: i) The intrinsic viscosity (IV) measured with tetralin (THN) at 135 °C is 0.6 dl / g or less, preferably included between 0.2 and 0.6 dl / g. ii) Mw is 30,000 g / mol or more, particularly 30,000 to 100,000 g / mol. iii) The density is 0.885 to 0.925 g / cm 3 Particularly 0.890 to 0.920 g / cm 3 And Butene-1 polymer B) can be obtained by polymerizing a monomer in the presence of a metallocene catalyst system, which can be obtained by contacting the following substances: - A stereorigid metallocene compound, - An aluminoxane or a compound capable of forming an alkylmetallocene cation, and optionally - An organoaluminum compound.

[0038] Preferably, the stereorigid metallocene compound belongs to the following formula (I),

Chemical formula

[0039] X, which may be the same or different from each other, is a hydrogen atom, a halogen atom, R, OR, OR’O, OSO2CF3, OCOR, SR, NR2 or PR2 group, where R is a linear or branched, saturated or unsaturated C1-C 20 - Alkyl group, C3-C 20 - Cycloalkyl group, C6-C 20 - Aryl group, C7-C 20 - Alkylaryl group or C7-C 20 - Arylalkyl radical, and optionally contains a heteroatom belonging to Groups 13-17 of the periodic table of elements, and R’ is a C1-C 20 - Alkylene group, C6-C 20 - Arylene group, C7-C 20 - Alkylarylene group or C7-C 20 - Arylalkylene radical, preferably X is a hydrogen atom, a halogen atom, OR’O or R group, more preferably X is a chlorine or methyl radical, R, which may be the same or different from each other, 1 R, 2 R, 5 R, 6 R, 7 R, 8 and R9 is a hydrogen atom, or a straight-chain or branched, saturated or unsaturated C1-C 20 -alkyl group, C3-C 20 -cycloalkyl group, C6-C 20 -aryl group, C7-C 20 -alkylaryl group or C7-C 20 -arylalkyl radical, optionally containing a heteroatom belonging to Groups 13-17 of the Periodic Table of the Elements, or R 5 and R 6 and / or R 8 and R 9 can optionally form a saturated or unsaturated 5- or 6-membered ring, said ring optionally bearing a C1-C 20 alkyl radical, provided that at least one of R 6 or R 7 is a straight-chain or branched, saturated or unsaturated C1-C 20 -alkyl group, optionally containing a heteroatom belonging to Groups 13-17 of the Periodic Table of the Elements, and a C1-C 10 -alkyl radical is preferred, R 3 and R 4 which are the same as or different from each other, are straight-chain or branched, saturated or unsaturated C1-C 20 -alkyl radicals, optionally containing a heteroatom belonging to Groups 13-17 of the Periodic Table of the Elements, and preferably, R 3 and R 4 are C1-C 10 -alkyl radicals, more preferably, R 3 is a methyl or ethyl radical, and R 4 is a methyl, ethyl or isopropyl radical.

[0040] Preferably, the compound of formula (I) has formula (Ia),

Chemical formula

[0041] Specific examples of metallocene compounds include dimethylsilyl group{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopentadiene[1,2-b:4,3-b’]-bithiophene)}zirconium dichloride, dimethylsilanediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopentadiene[1,2-b:4,3-b’]-bithiophene)}zirconium dichloride and dimethylsilanediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopentadiene[1,2-b:4,3-b’]-bithiophene)}dimethylzirconium.

[0042] Examples of aluminoxane include methylaluminoxane (MAO), tetra-(isobutyl)aluminoxane (TIBAO), tetra-(2,4,4-trimethyl-pentyl)aluminoxane (TIOAO), tetra-(2,3-dimethylbutyl)aluminoxane (TDMBAO) and tetra-(2,3,3-trimethylbutyl)aluminoxane (TTMBAO).

[0043] Compounds capable of forming an alkylmetallocene cation include the compound of formula D + E - where D +is a Bronsted acid that can provide a proton and irreversibly react with the substituent X of the metallocene of formula (I), and E - is a compatible anion that can stabilize the active catalyst substance derived from the reaction of two compounds and is sufficiently unstable to be removable by an olefin monomer. Preferably, the anion E - contains one or more boron atoms.

[0044] Specific examples of the organoaluminum compound include trimethylaluminum (TMA), triisobutylaluminum (TIBA), tris(2,4,4-trimethyl-pentyl)aluminum (TIOA), tris(2,3-dimethylbutyl)aluminum (TDMBA), and tris(2,3,3-trimethylbutyl)aluminum (TTMBA).

[0045] For specific examples of the catalyst system and the polymerization process using such a catalyst system, see WO2004099269 and WO2009000637.

[0046] The polymerization process can be carried out with the said catalyst in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase, using a fluidized bed or by operating a gas-phase reactor with mechanical stirring.

[0047] The hydrocarbon solvent may be aromatic (e.g., toluene) or aliphatic (e.g., propane, hexane, heptane, isobutane, cyclohexane, 2,2,4-trimethylpentane, isododecane, etc.).

[0048] Preferably, the polymerization process is carried out by using liquid butene-1 as the polymerization medium. The polymerization temperature may be between 20°C and 150°C, particularly between 50°C and 90°C, for example, between 65°C and 82°C.

[0049] The hydrogen concentration in the liquid phase of the polymerization reaction (mol ppm H2 / butene-1 monomer) is usually from 1800 ppm to 6000 ppm, particularly from 1900 ppm to 5500 ppm.

[0050] When the butene-1 polymer of the present invention contains the above-described two components B1) and B2), they may be separately produced, and may be blended together in a molten state using known polymer processing apparatuses such as a single-screw extruder and a twin-screw extruder.

[0051] However, the butene-1 polymer of the present invention containing the above components can be directly produced in the polymerization.

[0052] Therefore, in this case, the polymerization process includes at least two consecutive stages carried out in two or more reactors connected in series, where components B1) and B2) are prepared in separate subsequent stages and operate in the presence of the formed polymer and the catalyst used in the previous stage in each stage except the first stage.

[0053] The catalyst may be added only to the first reactor or may be added to a plurality of reactors.

[0054] Specific examples of the butene-1 polymer B) having an MIE of 800 g / 10 min or more are disclosed in WO2006045687, WO2018007279, WO2018007280, WO2020016143, and WO2020016144.

[0055] The polymer composition of the present invention can be produced by melting and blending the components, and the blending is usually carried out at a temperature of 180 to 310 °C, preferably 190 to 280 °C, more preferably 200 to 250 °C in a blending apparatus. All known apparatuses and techniques can be used for this purpose.

[0056] Useful melt blending apparatuses in this context are, in particular, extruders or kneaders, and in particular twin-screw extruders are preferred. It is also possible to premix the respective components at room temperature in a mixing apparatus.

[0057] This method can omit the previous melt blending step by directly introducing the polymer composition of the present invention in the form of a premixed component into a processing apparatus for producing a final molded article.

[0058] When producing the polymer composition, in addition to components A) and B) and any other polymer components, additives commonly used in the art such as stabilizers (heat, light, UV), plasticizers, antacids, antistatic agents, water repellents, and pigments may be introduced.

[0059] As described above, the polymer composition of the present invention has high impact resistance values.

[0060] In particular, - At -23 °C, Charpy of 5 to 70 kJ / m 2 of, - At 0 °C, Charpy of 4 to 50 kJ / m 2 of, - At -20 °C, Charpy of 2 to 40 kJ / m 2 It is preferred to have at least one of the Charpy values.

[0061] The Charpy values are measured according to ISO 179 / 1eA 48 hours after molding.

[0062] The polymer composition of the present invention further has a relatively low flexural modulus value, which is preferably lower than the flexural modulus of component A) and is converted into improved flexibility.

[0063] In particular, the polymer composition of the present invention preferably has a flexural modulus of 500 to 1000 MPa, more preferably 500 to 900 MPa, measured according to ISO 178:2019 48 hours after molding.

[0064] The polymer composition of the present invention can be processed by a conventional injection molding machine. The surface roughness of the obtained molded article is uniform and can be further improved by increasing the injection speed or raising the mold temperature.

[0065] Due to its high melt fluidity, it can also be used in the production of extruded articles, particularly extruded cable coatings.

[0066] Therefore, the present disclosure further provides an injection molded article or an extruded article comprising the polymer composition of the present invention.

[0067] Specific Examples The various examples, compositions, and methods provided herein are disclosed in the following specific examples. These specific examples are merely illustrative in nature and do not limit the scope of the present invention.

[0068] The following analytical methods are used to characterize the polymer composition.

[0069] MIF, MIE and MIP It is determined at 190 °C and a specified load in accordance with standard ISO 1133-2:2011.

[0070] Density It is measured at 23 °C based on ISO 1183-1:2012.

[0071] Brookfield viscosity It is measured at 190 °C using a cylindrical spindle rotational viscometer HA equipped with a drive motor capable of varying the test speed and a set of spindles capable of achieving and maintaining approximately 80% torque, Ametek / Benelux scientific model DV2T.

[0072] The selected spindle / chamber combination is SC4-27 / SC4-13R / RP.

[0073] During the test, the sample is incrementally rotated until it reaches and maintains approximately 80% of the torque value. Start rotating at 10 RPM and then gradually increase by 2 RPM every 5 seconds.

[0074] The Brookfield viscosity, expressed in mPa*s, is calculated as the shear stress (mPa) / shear rate (sec-1) ratio and is determined by the results obtained during the last 20 minutes of acquisition (1 data point / minute).

[0075] Intrinsic viscosity (IV) Determined at 135 °C based on standard ASTM D 2857 in tetralin.

[0076] Copolymer monomer content Component A) The copolymer monomer content is determined by IR using a Tensor 27 FT-IR spectrometer from Bruker, based on ASTM D 6248 98. Component B) The copolymer monomer content is determined by FT-IR.

[0077] The spectrum of the polymer press film is recorded as absorbance vs. wavenumber (cm -1 ). Calculate the ethylene content with the following measurements. a) The area (A -1 ) of the composite absorption band between 4482 and 3950 cm t used for spectral normalization of the film thickness. b) The subtraction factor (FCR C2 ) of the digital subtraction between the spectrum of the polymer sample and the absorption bands of sequences BEE and BEB (B: 1, butene unit, E: ethylene unit) due to the methylene group (CH2 shake vibration). c) The area (A C2、ブロック ) of the remaining band after subtracting the C2PB spectrum. It is derived from the sequence EEE (CH2 shake vibration) of the methylene group.

[0078] Equipment A Fourier Transform Infrared Spectrophotometer (FTIR) capable of providing the above-described spectrum measurement is used. A hydraulic press (Carver or equivalent) having a platen that can be heated to 200 °C is used.

[0079] Method Calibration of (BEB + BEE) sequence %(BEB + BEE) wt vs. FCR C2 / A t By plotting, a calibration straight line is obtained. The slope G r and the intercept I r are calculated by linear regression. Calibration of EEE sequence %(EEE) wt vs. A C2、ブロック / A t By plotting, a calibration straight line is obtained. The slope G H and the intercept I H are calculated by linear regression.

[0080] Sample preparation Using a hydraulic press, a thick sheet is obtained by pressing a sample of g 1.5 between two aluminum foils. If there are uniformity problems, it is proposed to perform at least two pressing operations. A very small part is cut out from this sheet to form a film. The recommended film thickness is 0.1 - 0.3 mm. The pressing temperature is 140 ± 10 °C. Since crystal phase modification occurs over time, it has been proposed to collect the IR spectrum of the sample film once it is formed.

[0081] Program The data collection parameters of the instrument are as follows: Purge time: at least 30 seconds. Collection time: at least 3 minutes. Apodization: Happ - Genzel. Resolution: 2 cm -1 . Collect the IR spectrum of the sample with respect to the air background. Calculation Calculate the weight concentration of the BEE + BEB sequence of ethylene units.

Number

Number

Number

[0082] Thermal properties (melting temperature and enthalpy) As described below, differential scanning calorimetry (D.S.C.) is determined using a Perkin Elmer DSC-7 instrument. - To determine -TmII (the melting temperature measured in the second heating run), the weighted sample (5 - 10 mg) obtained by polymerization is sealed in an aluminum pan and heated at a scanning rate corresponding to 10 °C / min at 200 °C. The sample is held at 200 °C for 5 minutes so that all microcrystals are completely melted, thereby removing the thermal history of the sample. Next, after cooling to -20 °C at a scanning rate corresponding to 10 °C / min, the peak temperature is taken as the crystallization temperature (Tc). After standing at -20 °C for 5 minutes, the sample is heated for the second time at 200 °C at a scanning rate corresponding to 10 °C / min. In this second heating run, the measured peak temperature is taken as TmII. If multiple peaks are present, the highest (strongest) peak is taken as TmII. The area at the peak (or peaks) is taken as the total melting enthalpy (DH TmII). - The melt enthalpy and melting temperature after aging are also measured as follows by differential scanning calorimetry (D.S.C.) using a PerkinElmer DSC-7 instrument. A weighted sample (5 - 10 mg) obtained by polymerization is sealed in an aluminum pan and heated at a scanning rate corresponding to 10 °C / min at 200 °C. The sample is held at 200 °C for 5 minutes so that all microcrystals are completely melted. Then the sample is stored at room temperature for 10 days. After 10 days, the sample is subjected to DSC, cooled to -20 °C, and then heated at 200 °C at a scanning rate corresponding to 10 °C / min. In this heating operation, the peak temperature is taken as the melting temperature (TmI). When there are multiple peaks, the highest (strongest) peak is taken as TmI. The area at the peak (or peaks) is taken as the total melt enthalpy after 10 days (DH TmI).

[0083] NMR analysis of chain structure 13 The 13C NMR spectra are acquired on a Bruker AV-600 spectrometer operating at 150.91 MHz in Fourier transform mode at 120 °C and equipped with a cryoprobe.

[0084] T bd The carbon peaks (by the nomenclature of C. J. Carman, R. A. Harrington, and C. E. Wilkes, <Macromolecules>, 10, 3 , 536 (1977)) are utilized at 37.24 ppm as an internal reference. The sample is dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 8% wt / v at 120 °C. Each spectrum is acquired with a 90° pulse, with a 15-second delay between pulses and CPD to 1 H- 13 remove 1H-13C coupling. Using a spectral window of 9000 Hz, approximately 512 transients are stored in 32K data points.

[0085] Kakugo [M. Kakugo, Y. Naito, K. Mizunuma, and T. Miyatake, <Macromolecules>, 16, 4, based on [1160 (1982)] and Randall [J. C. Randall, <Macromol. Chem. Phys.>, C30, 211 (1989)], values are assigned to the spectrum using the following terms, and the ternary distribution and composition are evaluated. BBB = 100 (T bb ) / S = I5 BBE = 100T bd / S = I4 EBE = 100 P dd / S = I14 BEB = 100 S bb / S = I13 BEE = 100 S ad / S = I7 EEE = 100(0.25 S gd +0.5 S dd ) / S = 0.25 I9 + 0.5I10

[0086]

Table 1

[0087] For the first approximation, mmmm is calculated with 2B2 carbons as follows.

Table 2

[0088] Determination of molecular weight by GPC It is measured with 1,2,4-trichlorobenzene (TCB) by gel permeation chromatography (GPC). The molecular weight parameters (Mn, Mw) and the molecular weight distribution Mw / Mn of all samples are measured using a GPC-IR apparatus from PolymerChar, which is equipped with a column group of four PLgel Olexis mixed beds (Polymer Laboratories) and an IR5 infrared detector (PolymerChar). The column size is 300 × 7.5 mm, and the particle size is 13 μm. The mobile phase flow rate is maintained at 1.0 mL / min. All measurements are carried out at 150 °C. The solution concentration is 2.0 mg / mL (at 150 °C), and 0.3 g / L of 2,6-di-tert-butyl-4-methylphenol is added to prevent decomposition. For GPC calculations, a universal calibration curve is obtained using 12 polystyrene (PS) standard samples (peak molecular weight range 266 - 1220000) provided by PolymerChar. The experimental data is interpolated with a third-degree polynomial fitting to obtain the relevant calibration curve. Data collection and processing are performed using Empower 3 (Waters). The Mark-Houwink relationship is used to determine the molecular weight distribution and the related average molecular weights. The K values of PS and polybutene (PB) are K PS = 1.21 × 10 -4 dL / g and K PB = 1.78 × 10 -4 dL / g, respectively, and the Mark-Houwink exponent a = 0.706 for PS and a = 0.725 for PB are used in combination.

[0089] In the case of butene / ethylene copolymers, for data evaluation, it is assumed that the composition of each sample is constant over the entire molecular weight range, and the K value of the Mark-Houwink relationship is calculated using the linear combination reported below.

Equation

[0090] Determination of X-ray crystallinity The X-ray crystallinity is measured using a powder X-ray diffractometer (XDPD) with Cu-Kα1 radiation having a fixed slit, and collecting the spectrum between diffraction angles 2Θ = 5° and 2Θ = 35° at a step size of 0.1° every 6 seconds.

[0091] The sample is a magnetic disk manufactured by pressing, with a thickness of about 1.5 - 2.5 mm and a diameter of 2.5 - 4.0 cm. The magnetic disk is aged at room temperature (23°C) for 96 hours.

[0092] After this preparation, the sample is inserted into the XDPD sample holder. The XRPD spectrum of the sample is collected from diffraction angle 2Θ = 5° to 2Θ = 35° at a step size of 0.1° using a counting time of 6 seconds, and the XRPD apparatus is adjusted to collect the final spectrum at the end.

[0093] Define the total area between the spectral profile and the baseline, Ta, represented in counts / sec·2Θ, the total amorphous area, Aa, represented in counts / sec·2Θ, and Ca is the total crystalline area represented in counts / sec·2Θ.

[0094] Analyze the spectrum or diffraction pattern in the following steps: 1) Define an appropriate linear baseline for the entire spectrum, calculate the total area (Ta) between the spectral profile and the baseline, 2) Define an appropriate amorphous profile that separates the amorphous region from the crystalline region based on the phase model along the entire spectrum, 3) Calculate the amorphous area (Aa), which is the area between the amorphous contour and the baseline, 4) Calculate the crystalline area (Ca), for example Ca = Ta - Aa, as the area between the spectral contour and the amorphous contour, 5) Calculate the crystallinity (%) of the sample using the following formula: %Cr = 100 x Ca / Ta

[0095] Fix a 76 mm × 13 mm × 1 mm molded sample on the DMTA machine via the glass transition point of DMTA (Dynamic Mechanical Thermal Analysis) and use it for tensile stress. Fix the tensile force and the dependent frequency of the sample at 1 Hz. DMTA converts the elastic response of the sample from -100 °C to 130 °C. In this way, a graph of the elastic response against temperature can be created. Define the elastic modulus of the viscoelastic material as E = E’ + iE”. DMTA can divide the temperature into two components E’ and E” via their resonance and the graphs E’ and E’ / E” = tan (δ). Assume that the glass transition point Tg is the temperature of the curve E’ / E” = tan (δ) with respect to the maximum value of the temperature.

[0096] Charpy impact strength Measure at 23 °C, 0 °C, and -20 °C after 48 hours of molding according to ISO 179 / 1eA.

[0097] Flexural modulus Measure after 48 hours of molding according to ISO 178:2019.

[0098] Helical fluidity test (helix length) Conduct a helical fluidity test using a Ripress FL 170 HES device equipped with a helical mold with a helical thickness of 2.5 mm.

[0099] Inject the polymer test object into the cavity of the helical mold through a 3 mm press mold under the following conditions: - Raw material temperature 230 °C, - By setting the injection position to 0.1 mm, the projection step is eliminated, - The hydraulic holding pressure of 29 bar to 126 bar corresponds to the pressure on the polymer material of 300 bar to 1220 bar, - Screw diameter 50 mm, - Mold temperature 40 °C, and - Closing pressure 170 t.

[0100] The screw length is the length of the solid polymer screw taken out of the screw mold after cooling.

[0101] The longer the screw length, the easier it is for the polymer to be processed under the injection molding process conditions.

[0102] Specific Examples 1 to 6 and Comparative Examples 1 to 4

[0103] Use the materials described below. Ethylene polymer A) High-density polyethylene has a density of 0.955 g / cm 3 density, 11.0 g / 10 min MIP, 105 g / 10 min MIF and 4 g / 10 min MIE, and is sold by Basell under the trademark Hostalen GD 7255 LS. Butene-1 polymer B) Use two different polymers, namely butene-1 polymer B)-I and butene-1 polymer B)-II. Butene-1 polymer B)-I

[0104] Prepare as described below. Preparation of catalyst solution Under a nitrogen atmosphere, a 33 g / L solution of triisobutylaluminum (TIBA) in isododecane (6400 g) and a 30% wt / wt solution of methylaluminoxane (MAO) in toluene (567 g) are charged into a 20 L glass reactor with a jacket, stirred by an anchor stirrer, and stirred and reacted at room temperature for about 1 hour. Then, 1.27 g of metallocene dimethylsilyl group {(2,4,7-trimethyl-l-indenyl)-7-(2,5-dimethyl-cyclopentadiene[l,2-b:4,3-b’]-bithiophene)} zirconium dichloride prepared based on Specific Example 32 of WO0147939 was added, and stirred for about 30 minutes to dissolve it. The final solution is discharged from the reactor into the cylinder through a filter to remove the final solid residue. Composition of the obtained solution:

Table 3

[0105] Polymerization The polymerization is carried out in two stirred reactors operating in series, in which the above catalyst solution with liquid butene-1 constituting the liquid medium is fed into the two reactors. The polymerization conditions are described in Table 1. The butene-1 / ethylene copolymer is recovered from the solution as a melt and cut into pellets. Further, the copolymer is characterized and the data is recorded in Table 2.

[0106]

Table 4

[0107]

Table 5

[0108] Butene-1 polymer B)-II Using the same catalyst solution and the same polymerization apparatus as for butene-1 polymer B)-I, polymerization is carried out in the two stirred reactors operating in series, wherein liquid butene-1 constitutes the liquid medium. The catalyst solution is injected into the two reactors, and polymerization is continuously carried out at a polymerization temperature of 75 °C. The residence time in each reactor is in the range of 120÷200 min. The hydrogen concentration during polymerization is 4900 ppm mol H2 / (C 4- ) body, where C 4- = butene-1. The comonomer is charged into the reactor in an amount of C 2- / C 4- 0.35% wt. The ethylene comonomer copolymerizes almost immediately (C 2- "stoichiometric" charged into the reactor). The catalyst yield (moles) is 2000 kg / g of metallocene active ingredient. The butene-1 copolymer is recovered from the solution as a melt and cut into pellets. Further, the copolymer is characterized and the data are recorded in Table 3.

[0109]

Table 6

[0110] Wax (comparison) The Fischer-Tropsch wax has a dropping melting point of 116 °C (measured according to ASTM D 3954), a penetration at 25 °C of 0.1 mm (measured according to ASTM D 1321), and a Brookfield viscosity at 135 °C of 12 CP (measured by the Sasol Wax 011 method), and Sasol is sold under the trademark EnHance FG.

[0111] Preparation of polymer composition

[0112] Specific Examples 1 to 6

[0113] The butene-1 polymers B)-I and B)-II are blended with the ethylene polymer A) in the amounts described in Table 4 below, and the final properties of the resulting polymer compositions are also described.

[0114] Comparative Examples 1 to 4

[0115] In the following Table 5, the properties of the pure ethylene polymer A) in Comparative Example 1 are described.

[0116] In Comparative Examples 2 to 4, the Fischer-Tropsch wax is blended with the ethylene polymer A) in the amounts described in Table 5, and the final properties of the resulting polymer compositions are also described.

[0117] The amounts described in Tables 4 and 5 are expressed as weight percentages based on the total weight of the polymer composition.

[0118] The compositions of Specific Examples 1 to 6 and Comparative Examples 2 to 4 are prepared by blending the components offline and charging them into the hopper of an injection molding apparatus used for a spiral flow test.

[0119] Therefore, the melt blending step is carried out in the injection molding apparatus.

[0120]

Table 7

[0121]

Table 8

Claims

1. A polymer composition comprising A) and B), wherein A) is an ethylene polymer of 88% to 99% by mass, having an MIP of 5 g / 10 min or more, where MIP is the melt flow rate at 190 °C and a load of 5 kg determined according to ISO 1133-2:2011, B) is a butene-1 polymer of 1% to 12% by mass, having a melting point (TmII) higher than 80 °C, a melting point (TmII) less than 110 °C, a molecular weight distribution (Mw / Mn) less than 4, and an MIE of 800 g / 10 min or more, where MIE is the melt flow rate at 190 °C and a load of 2.16 kg determined according to ISO 1133-2:2011, The amounts of A) and B) are based on the total weight of A) + B), the polymer composition.

2. The Brookfield viscosity of the butene-1 polymer B) at 190 °C is 1500 to 20000 mPa·sec, the composition according to claim 1.

3. The butene-1 polymer B) is selected from the group consisting of a butene-1 homopolymer and a copolymer of butene-1 and an α-olefin comonomer different from butene-1, the composition according to claim 1 or 2.

4. The content of the α-olefin comonomer different from butene-1 in the butene-1 polymer B) having copolymerization is 0.5 mol% to 4.0 mol%, the composition according to claim 3.

5. The butene-1 polymer B) has at least one of the following additional characteristics, namely, d) the glass transition point (Tg) is in the range of -40 °C to -10 °C, e) the isotactic pentad (mmmm) measured by 13C-NMR operating at 150.91 MHz is higher than 90%, f) no 4,1 insertion is detected by 13C-NMR operating at 150.91 MHz, g) the X-ray crystallinity is 25% to 65%, the composition according to claim 1 or 2.

6. The ethylene polymer A) has a density of 0.930 to 0.970 g / cm3 measured at 23 °C according to ISO 1183-1:2012, the composition according to claim 1 or 2.

7. The ethylene polymer A) has the following additional characteristics, namely, - MIF value of -50 to 200 g / 10 min, or 50 to 150 g / 10 min, where MIF is the melt flow rate at 190 °C and a load of 21.60 kg determined in accordance with ISO 1133-2:2011, - MIE value of -1 to 10 g / 10 min, or 1 to 8 g / 10 min, - MIF / MIP ratio of 5 or more, - The composition according to claim 1 or 2 having at least one of an MIF / MIE ratio of 20 or more.

8. A molded article comprising the polyolefin composition according to any one of claims 1 to 7.

9. The molded article according to claim 8, which is an injection molded article or an extrusion molded article.

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