Reinforced polypropylene composition

Abstract

A polyolefin composition (I) having low density and improved mechanical properties, comprising: (A) 15-80 wt. % of a heterophasic polymer composition comprising (a) 50-80 wt. % of a propylene-based polymer and (b) 20-50 wt. % of a copolymer of ethylene and at least one α-olefin; and (B) 20-85 wt. % of a polyethylene composition, comprising: (i) 25-50 wt. % of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography. and (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) of 5,000 g / mol or less, measured by gel permeation chromatography, wherein the polyethylene composition (B) comprises at least 70% by weight of (i)+(ii), the amounts of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%, and 20 to 85% by weight of a polyethylene composition, wherein the amounts of (A) and (B) are based on the total weight of (A)+(B).

Description

[Technical Field]

[0001] The present disclosure relates to polyolefin compositions and injection molded or 3D printed articles obtained therefrom. [Background technology]

[0002] To compete with other engineering materials, polyolefins are often reinforced with inorganic fillers such as glass fibers or minerals.

[0003] Filled polyolefins have several advantageous properties, such as high strength and stiffness, and are widely used in many industrial sectors, including the automotive sector, where they are used for injection molding of interior and exterior parts.

[0004] While the presence of inorganic fillers improves the mechanical properties of polyolefins, it also negatively impacts the environmental sustainability of the fillers.

[0005] The mechanical properties of mechanically recycled glass-fiber-filled polyolefins deteriorate over time as the fibers are broken and shredded at each recycling step, so the life cycle of inorganically filled plastic materials is shorter than that of unfilled materials, which quickly become disposable waste.

[0006] In the case of chemical recycling, the inorganic filler needs to be separated from the polyolefin matrix, making the process more complex and less sustainable.

[0007] Furthermore, plastics filled with typical inorganic fillers are dense. The heavier the plastic material, the greater the vehicle mass required to transport the material. This increases the fuel consumption of internal combustion engine vehicles and reduces the range of electric vehicles, increasing the environmental impact of filling material logistics.

[0008] Self-reinforced polyolefin solutions have been developed to provide reinforced polyolefins that do not contain inorganic reinforcing agents.

[0009] Timo Hees et al., in Polymer, Volume 151, pp. 47-55, reported on an all-PE self-reinforced composite material in which conventional HDPE was blended with a twin-peak reactor blend of UHMWPE (ultra-high molecular weight polyethylene) and HDPE wax. The resulting trimodal self-reinforced polyethylene exhibited improved mechanical performance.

[0010] However, past attempts to reinforce polypropylene with UHMWPE have either met with poor results due to the poor miscibility of UHMWPE with polypropylene, or have required the use of unconventional, energy-intensive processes.

[0011] X. Wang et al., Journal of Polymer Science, Vol. 1, 100, 3495-3509 (2006), reported that when polyolefins were melt blended in a co-rotating four-screw extruder, satisfactory results were achieved in toughening propylene homopolymer with UHMWPE, ultimately in the presence of EPDM. A conventional twin-screw extruder produced poor results.

[0012] T. Hees et al., ACS Applied Polymer Materials, 2021, 3, 3455-3464, obtained poor results by enhancing iPP with a reactor mixture of low amounts of UHMWPE and PE wax.

[0013] US Patent Application No. 2014 / 0066574A1 teaches obtaining reinforced injection molded articles by pultrusion molding 60-85 wt% of a high flow thermoplastic resin into 15-40 wt% of UHMWPE fibers. Summary of the Invention [Problem to be solved by the invention]

[0014] In this case, there remains a need for reinforced polyolefins that have improved mechanical properties compared to the same unreinforced polyolefins, particularly simultaneously increased tensile strength and impact resistance, and improved recyclability compared to low density and inorganically filled polyolefins.

[0015] Thus, the present disclosure: (A) 15 to 80 wt. % of a heterophasic polymer composition, (a) propylene homopolymer, ethylene and / or a copolymer of the formula CH═CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) and a mixture thereof, wherein the copolymer comprises 55 to 80% by weight of at least one propylene polymer containing 10.0% by weight or less, preferably 0.05 to 8.0% by weight, of units derived from the ethylene and / or the α-olefin, based on the weight of (a); (b) Ethylene and the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl; and 20 to 50% by weight of at least one copolymer containing 10 to 40% by weight or less, preferably 20 to 35% by weight, of units derived from the α-olefin, based on the weight of (b); the amounts of (a) and (b) are based on the total weight of (a) + (b); the amounts of (a) and (b) being based on the total weight of (a)+(b), 15-80 wt. % of the heterophasic polymer composition; (B) 20 to 85% by weight of a polyethylene composition, (i) 25 to 85% by weight of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) measured by gel permeation chromatography of 5,000 g / mol or less, the polyethylene composition (B) comprising at least 70% by weight of (i) + (ii), the amount of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%, and 20 to 85% by weight of a polyethylene composition; The amounts of (A) and (B) are based on the total weight of (A)+(B) to provide polyolefin composition (I).

[0016] The flow of the molten polyolefin composition (I) is continued for 50 seconds. -1 Also provided is a process for producing a molded article comprising the step of applying a shear rate equal to or greater than the above.

[0017] In another aspect, the present disclosure relates to the use of polyethylene composition (B), wherein said polyethylene composition (B) comprises: (i) 25 to 85% by weight of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) measured by gel permeation chromatography of 5,000 g / mol or less, the polyethylene composition (B) comprises at least 70% by weight of (i)+(ii), the amounts of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%; As a reinforcing masterbatch for the heterophasic polymer composition (A), (a) propylene homopolymer, ethylene and / or a copolymer of the formula CH═CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) and a mixture thereof, wherein the copolymer comprises 55 to 80% by weight of at least one propylene polymer containing 10.0% by weight or less, preferably 0.05 to 8.0% by weight, of units derived from the ethylene and / or the α-olefin, based on the weight of (a); (b) Ethylene and the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) and 20 to 50% by weight of at least one copolymer containing 10 to 40% by weight or less, preferably 20 to 35% by weight of units derived from the α-olefin, based on the weight of (b); The amounts of components (a) and (b) are based on the total weight of (a)+(b), provided the use.

[0018] The polyolefin composition (I) of the present disclosure has improved mechanical properties, in particular high tensile modulus and tensile strength, and high impact resistance.

[0019] Furthermore, the polyolefin composition (I) has a significantly reduced density compared to the multiphase polyolefin composition (A) reinforced with a conventional inorganic filler (eg, glass fiber).

[0020] The polyolefin composition (I) can be readily converted into molded articles using conventional extruders, such as twin-screw extruders, with little or no modification to conventional processes and equipment settings.

[0021] Furthermore, the mechanical properties of the polyolefin composition (I) do not deteriorate significantly after multiple processing, making it possible to recycle the polyolefin composition (I) multiple times, and improving environmental sustainability compared to conventional polyolefin compositions containing inorganic fillers.

[0022] While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will become apparent, the specific embodiments disclosed herein are capable of modification in various obvious respects, all without departing from the spirit and scope of the claims set forth herein. Accordingly, the following detailed description is to be regarded as illustrative in nature and not restrictive. DETAILED DESCRIPTION OF THE INVENTION

[0023] In the context of this disclosure: - Unless otherwise stated, percentages are expressed by weight. The total weight of the composition must add up to 100% unless otherwise stated. With respect to polymers, "blend" refers to reactor-produced blends, i.e., blends of at least two polymer components obtained directly from a polymerization process, mechanical blends, i.e., blends obtained by melt-mixing at least two different polymer components, and combinations of both.

[0024] - When the term "comprises" refers to a polymer, or polymer composition, mixture or blend, it should be interpreted to mean "comprising or consisting essentially of."

[0025] The term "consisting essentially of" means that in addition to the essential components, other components may be present in the polymer or polymer composition, mixture, or blend, so long as the essential properties of the polymer or composition, mixture, or blend are not substantially affected by their presence. Examples of components that, when present in normal amounts, do not substantially affect the properties of the polymer or polyolefin composition, mixture, or blend are catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, and acid inhibitors.

[0026] In one preferred embodiment, the polyolefin composition (I) comprises 40 to 80 wt. %, preferably 50 to 70 wt. % of the heterophasic polymer composition (A) and 20 to 60 wt. %, preferably 30 to 50 wt. % of the polyethylene composition (B).

[0027] The polyolefin composition preferably has at least one of the following properties:

[0028] - A melt flow rate MFR(tot) of 0.001 to 5.0 g / 10 min measured at 230°C and a load of 2.16 kg according to ISO 1133-2:2011; and / or - Density measured according to ASTM standard D792-08 is 1.00 g / cm 3 In one embodiment, the density is 0.90 g / cm 3 That's all. And / or the tensile modulus, measured on injection-molded specimens according to the ISO 527-1:2012 method, is at least 100%, preferably at least 150%, more preferably at least 200% higher than the tensile modulus of the heterophasic polymer composition (A). In one embodiment, the tensile modulus of the polyolefin composition (I) is at most 500% higher than the tensile modulus of the heterophasic polymer composition (A).

[0029] In one embodiment, the polyolefin composition (I) does not contain inorganic reinforcing agents such as glass fibers or mineral fillers, and / or fibrous reinforcing agents such as polyolefin fibers or wool.

[0030] In one embodiment, the polyolefin composition (I) comprises only component (B) as a toughening agent.

[0031] Each component of the polyolefin composition (I) is defined in more detail below. The components may be contained in any combination in the polyolefin composition (I).

[0032] The α-olefins that may be included in components (a) and (b) of the heterophasic polymer composition (A) are preferably independently selected from the group consisting of butene-1, hexene-1,4-methyl-1-pentene, octene-1, and combinations thereof; preferably, the α-olefin is butene-1.

[0033] In one embodiment, component (a) of the heterophasic polymer composition (A) is a mixture of propylene polymers.

[0034] In one embodiment, component (a) of the heterophasic polymer composition (A) is a propylene homopolymer or a mixture of propylene homopolymers.

[0035] In a preferred embodiment, component (a) of polyolefin composition (A) has at least one, and more preferably all, of the following properties:

[0036] The xylene soluble fraction XS(a) at a temperature of -25°C is 5% by weight or less, preferably 3% by weight or less, based on the weight of (a). In one embodiment, for each upper limit, the lower limit is 0.1% by weight, based on the weight of (a). And / or The melt flow rate MFR(a) measured in accordance with ISO1133-2:2011 at a temperature of 230°C and a load of 2.16 kg is 50 g / 10 min or more, and preferably 50 g / 10 min to 300 g / 10 min.

[0037] In one embodiment, component (a) is a propylene homopolymer or a mixture of propylene homopolymers having all of the above properties.

[0038] Component (b) is an ethylene copolymer or a mixture of ethylene copolymers.

[0039] In one embodiment, component (b) of the heterophasic polymer composition (A) is a copolymer or mixture of copolymers of ethylene and 1-butene.

[0040] In a preferred embodiment, component (b) of the heterophasic polymer composition (A) has at least one, and preferably all, of the following properties:

[0041] a weight-average molecular weight Mw measured by GPC of at least 50,000 g / mol, preferably in the range of at least 50,000 g / mol but less than 1,000,000 g / mol; and / or

[0042] The xylene soluble fraction XS(b) at a temperature of -25°C is 40% by weight or more, preferably 65% ​​by weight or more, based on the weight of (b). In one embodiment, the upper limit of the xylene soluble fraction XS(b) at a temperature of 25°C is equal to 100% by weight for each lower limit.

[0043] In one embodiment, the heterophasic polymer composition (A) preferably comprises:

[0044] (a) propylene homopolymer, ethylene and / or a copolymer of the formula CH═CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) The copolymer comprises 35 to 70 wt%, preferably 40 to 65 wt%, of at least one propylene polymer containing 10.0% by weight or less, preferably 0.05 to 8.0% by weight, of units derived from ethylene and / or the α-olefin, based on the weight of (a); (b) Ethylene and the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) The copolymer comprises 15 to 40% by weight, preferably 20 to 35% by weight, of at least one copolymer containing 10 to 40% by weight or less, preferably 20 to 35% by weight, of units derived from the α-olefin based on the weight of (b); (c) ethylene and / or the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl.) and a mixture thereof, wherein the propylene copolymer comprises 5 to 30% by weight, preferably 7 to 20% by weight, of at least one propylene copolymer containing 50% by weight or less, preferably 15 to 50% by weight, of units derived from the ethylene and / or the α-olefin, based on the weight of (c); The amounts of (a), (b), and (c) are based on the total weight of (a)+(b)+(c).

[0045] In one preferred embodiment, said at least one propylene copolymer (c) is selected from the group consisting of propylene-ethylene copolymers.

[0046] Preferably, the polyolefin composition may contain up to 3.0 wt % of at least one additional additive selected from the group consisting of antistatic agents, antioxidants, light stabilizers, slip agents, acid inhibitors, melt stabilizers, and combinations thereof, the amount of additional additive being based on the total weight of the polyolefin composition including the additional additive.

[0047] The heterophasic polymer composition (A) of the present disclosure preferably has a melt flow rate MFR(A) of at least 8.0 g / 10 min, measured at 230° C. under a load of 2.16 kg according to ISO 1133-2:2011. In one embodiment, the MFR(A) is at most 150 g / 10 min, measured at 230° C. under a load of 2.16 kg according to ISO 1133-2:2011.

[0048] The heterophasic polymer composition (A) is a reactor blend or a melt blend or a combination thereof.

[0049] In one embodiment, the heterophasic polymer composition (A) is a reactor blend multiphase polyolefin composition (A1), which comprises: (a) 35 to 70% by weight, preferably 40 to 65% by weight, of a propylene homopolymer; (b) 15 to 40% by weight, preferably 20 to 35% by weight, of a copolymer of ethylene and 1-butene containing 10 to 40% by weight, preferably 20 to 35% by weight, of units derived from 1-butene, based on the weight of (b); (c) 5 to 30 wt %, preferably 7 to 25 wt %, of a propylene copolymer with ethylene, containing 50 wt %, preferably 15 to 50 wt %, of units derived from ethylene, based on the weight of (c); (d) optionally, 3.0 wt. % or less, preferably 0.01 wt. % to 3.0 wt. %, of at least one additional additive selected from the group consisting of antistatic agents, antioxidants, light stabilizers, slitting agents, anti-acid agents, melt stabilizers, and combinations thereof; The amounts of (a), (b), (c), and (d) are based on a total weight of 100% (a)+(b)+(c)+(d).

[0050] The heterophasic polyolefin composition (A1) has at least one, and preferably all, of the following properties:

[0051] The xylene soluble fraction XS (A1) at a temperature of -25°C is 30% to 50% by weight based on the weight of (A1); and / or The intrinsic viscosity of the xylene-soluble fraction XSIV(A1) at -25°C is 1.50 to 3.00 dL / g, preferably 2.00 to 2.50 dL / g; and / or The melt flow rate MFR(A1) measured in accordance with ISO1133-2:2011 at a temperature of 230°C and a load of 2.16 kg is 5 to 20 g / 10 min, preferably 8 to 15 g / 10 min.

[0052] The heterophasic polymer composition (A) is prepared by melt blending components (a), (b), and optionally (c) and (d), or by polymerizing the relevant monomers in at least two polymerization stages, the second, and optionally each subsequent polymerization stage being carried out in the presence of the polymer prepared and the catalyst used in the immediately preceding polymerization stage, thereby obtaining a reactor blend of components (a), (b) and optionally (c), and optionally melt blending the reactor blend thus obtained with component (d).

[0053] In one embodiment, the heterophasic polymer composition (A) is a reactor mixture of components (a), (b), and optionally (c).

[0054] The monomers are polymerized in the presence of a catalyst selected from metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems, and combinations thereof, preferably in the presence of a highly stereospecific Ziegler-Natta catalyst system comprising: (1) a solid catalyst component comprising a magnesium halide support on which a Ti compound having at least a Ti-halogen bond is present, and a sterically controlling internal donor; (2) an optional but preferably Al-containing cocatalyst, and (3) Optionally but preferably, a further electron donor compound (external donor).

[0055] The solid catalyst component (1) preferably contains TiCl4 in an amount such that Ti is present in an amount of 0.5 to 10% by weight based on the total weight of the solid catalyst component (1).

[0056] The solid catalyst component (1) comprises at least one stereocontrolling internal electron donor compound selected from monodentate or bidentate organic Lewis bases, preferably selected from esters, ketones, amines, amides, carbamates, carbonates, ethers, nitriles, alkoxysilanes, and combinations thereof.

[0057] Preferred donors are esters of phthalic acid, as described in EP 45977 A2 and EP 395083 A2, in particular diisobutyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl butyl phthalate, and combinations thereof.

[0058] The esters of fatty acids may be selected from esters of malonic acid such as those described in WO 98 / 056830, WO 98 / 056833, WO 98 / 056834, esters of glutaric acid such as those disclosed in WO 00 / 55215, and esters of succinic acid such as those disclosed in WO 00 / 63261.

[0059] A particular type of diester is one derived from the esterification of aliphatic or aromatic diols, such as those described in WO 2010 / 078494 and U.S. Pat. No. 7,388,061.

[0060] In some embodiments, the internal donor is selected from 1,3-diethers such as those described in EP 361493, EP 728769 and WO 02 / 100904.

[0061] Certain mixtures of internal donors can be used as internal donors, in particular the mixtures of aliphatic or aromatic mono- or dicarboxylic acid esters and 1,3-diethers disclosed in WO 07 / 57160 and WO 2011 / 061134.

[0062] The preferred magnesium halide support is magnesium dihalide.

[0063] The amount of the internal donor fixed on the solid catalyst component (1) is 5 to 20 mol % relative to the magnesium dihalide.

[0064] A preferred method for preparing the solid catalyst component (1) is described in EP 395083 A2.

[0065] The preparation of catalyst components by conventional methods is described, for example, in US Pat. No. 4,399,054, US Pat. No. 4,469,648, WO 98 / 44009 A1, and EP 395083 A2.

[0066] In some embodiments, the catalyst system includes an Al-containing cocatalyst (2) selected from Al-trialkyls, preferably selected from the group consisting of Al-triethyl, Al-triisobutyl, and Al-tri-n-butyl. The Al / Ti weight ratio in the catalyst system is 1 to 1000, preferably 20 to 800.

[0067] In an embodiment, the catalyst system comprises a further electron donor compound (3) (external electron donor) selected from silicon compounds, ethers, esters, amines, heterocyclic compounds, in particular 2,2,6,6-tetramethylpiperidine, and ketones.

[0068] Preferred silicon compounds are selected from methylcyclohexyldimethoxysilane (C donor), dicyclopentyldimethoxysilane (D donor), and mixtures thereof.

[0069] The polymerization to obtain the single components (a), (b) and optionally (c), or the sequential polymerization process to obtain the heterophasic polymer composition (A), can be carried out in either the liquid or gas phase, continuously or batchwise.

[0070] Liquid phase polymerization can be carried out in either slurry, solution, or bulk (liquid monomer).

[0071] The phase polymerization can be carried out in a fluidized bed reactor or a stirred fixed bed reactor, or in a multi-zone circulation reactor, as shown in EP 1012195.

[0072] The reaction temperature is preferably in the range of 40°C to 90°C, and the polymerization pressure is 3.3 to 4.3 MPa in a liquid phase process and 0.5 to 3.0 MPa in a gas phase process.

[0073] Suitable polymerization processes for producing the heterophasic polymer composition (A) are described in International Patent Application Nos. WO 03 / 051984 and WO 03 / 076511, which are incorporated herein by reference in their entirety.

[0074] Composition (B) is a multimodal polyethylene composition comprising a UHMWPE fraction (i) and a PE-wax (ii).

[0075] In a preferred embodiment, polyethylene composition (B) comprises at least 75% by weight, more preferably at least 80% by weight, of (i)+(ii), where the amounts of (i) and (ii) are based on the total weight of polyethylene composition (B), the total weight being 100%.

[0076] Preferably, the polyethylene composition (B) has a melt flow rate MFR(B) measured in accordance with ISO1133-2:2011 at a temperature of 190°C under a load of 2.16 kg of up to 10 g / 10 min, preferably 0.00001 to 10 g / 10 min.

[0077] The polyethylene composition (B) is preferably (i) 25 to 85% by weight, preferably 60 to 75% by weight, of a polyethylene component having a weight average molecular weight Mw(i) of 1000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight, preferably 10 to 20% by weight, of a polyethylene component having a weight-average molecular weight Mw(ii) of 5,000 g / mol or less as measured by gel permeation chromatography; (iii) 100% by weight (inclusive) of a polyethylene component different from component (i) and component (ii), Polyethylene composition (B) comprises at least 70% by weight, preferably at least 75% by weight, more preferably at least 80% by weight of (i)+(ii), the amounts of (i) and (ii) being based on the total weight of polyethylene composition (B), the total weight being 100%.

[0078] Preferably, the polyethylene composition (B) has a value of Mw / Mn(B) of 300 or more, and preferably in the range of 300 to 1500, where Mw is the weight of the polyethylene composition (B) measured by GPC, and Mn is the number average molecular weight.

[0079] The polyethylene components (i) to (iii) are ethylene homopolymers, CH₂=CHR 1 (However, R 1is a straight or branched chain C2-C8 alkyl), and mixtures thereof.

[0080] The α-alpha-olefin is preferably selected from the group consisting of butene-1, hexene-1, 4-methyl-1-pentene, octene-1, and combinations thereof.

[0081] In a preferred embodiment, the polyethylene components (i)-(iii) are ethylene homopolymers.

[0082] The density of the polyethylene components (i) and (ii) measured by ASTM D792-08 method is 0.900 to 0.965 g / cm 3 It is preferable that the density is 0.930 to 0.960 g / cm 3 It is more preferable that:

[0083] Preferably, the polyethylene component (i) has at least one, and preferably all, of the following properties:

[0084] - the molecular weight distribution MWD(i) has a GPC peak (1) measured by gel permeation chromatography in the range of 1000 g / mol to 3000 g / mol, preferably 1500 g / mol to 3000 g / mol; and / or

[0085] The value of Mw / Mn(i) is 5, preferably 1.2 to 5, more preferably 1.5 to 4.5, and Mn is the number average molecular weight measured by gel permeation chromatography.

[0086] The polyethylene component (ii) preferably has at least one, and more preferably all, of the following properties:

[0087] - MWD(ii) has a GPC peak (2) comprised in the range of 500 to 1500 g / mol, where MWD(ii) is measured by gel permeation chromatography; and / or

[0088] The value of Mw / Mn(ii) is 5 or less, preferably 1.2 to 5, more preferably 1.5 to 4.5, and Mn is the number average molecular weight measured by gel permeation chromatography.

[0089] More preferably, the polyethylene composition (B) is a multimodal polyethylene composition exhibiting a GPC peak (1) having an MWD in the range of 10,000 g / mol to 3,000 g / mol, preferably in the range of 15,000 g / mol to 3,000 g / mol, and a GPC peak (2) in the range of 500 to 1,500 g / mol.

[0090] The polyethylene components (i) to (iii) are preferably obtained by a polymerization process using a unit catalyst such as the low Mw polyethylene reported in WO 01 / 021668 and WO 2011 / 089017 for the UHMWPE component (i) and in EP 1188762 for this component (ii).

[0091] The polyethylene component (iii) is preferably obtained from the polymerization process that produces the polyethylene component (i) and / or the polyethylene component (ii).

[0092] The polyethylene component (i) is preferably produced by polymerizing the monomer using a polymerization catalyst comprising a cyclopentadienyl complex of chromium, and the η cyclopentadienyl moiety, particularly [η 5 Preferably, the catalyst component comprises chromium dichloride (CrQCp catalyst component) containing 3,4,5-trimethyl-1-(8-quinolinyl)-2-trimethylsilyl-cyclopentadienyl.

[0093] The polyethylene component (ii) is preferably prepared by polymerizing the relevant monomers using a polymerization catalyst comprising a bis(imino)pyridine complex of chromium, preferably 2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridinechromium(III) trichloride (CrBIP catalyst component).

[0094] The catalyst component is preferably supported on a solid component. Preferably, a finely divided support is used, which may be either an organic solid or an inorganic solid. Examples of such a support include silica gel, magnesium chloride, alumina, mesoporous materials, aluminosilicates, hydrotalcite, organic polymers such as polyethylene, polypropylene, polystyrene, and polytetrafluoroethylene, and polymers having polar functional groups such as ethylene and acrylic esters, acrolein, and vinyl acetate. The support material should preferably have a specific surface area of ​​10 to 1,000 m. 2 It is preferable to use one having a pore volume of 0.1 to 5 ml / g and an average particle size of 1 to 500 μm.

[0095] The preparation of supported catalysts is carried out by physical adsorption or chemical reaction, i.e., covalent bonding of components to reactive groups on the support surface.

[0096] The catalyst components are preferably contacted with the support in a suitable solvent to provide a soluble reaction product, adduct, or mixture.

[0097] Suitable and preferred support materials, their preparation methods and their use for preparing supported catalysts are described in WO 2005 / 103096.

[0098] The catalyst components, particularly the CrQCp and CrBIP components, generally need to be contacted with an activator, preferably selected from the group consisting of aluminoxane and non-aluminoxane activators, to achieve high polymerization productivity.

[0099] Particularly useful alumoxanes are open-chain alumoxane compounds of the general formula (1): [ka] Alternatively, it is a cyclic aluminoxane compound represented by the following general formula (2). [ka]

[0100] However, here, R 1 -R 4 are independently selected from C1 to C6 alkyl groups, preferably R 1 -R 4 is independently selected from the group consisting of methyl, ethyl, n-butyl and isobutyl, and I is an integer of 1 to 40, preferably 4 to 25.

[0101] Methylaluminoxane (MAO) is preferred.

[0102] Suitable non-alumoxane activators include alkylaluminums, alkylaluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, etc. Examples include triethylaluminum, trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, lithium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)aluminate, tris(pentafluorophenyl)boron, and tris(pentabromophenyl)boron.

[0103] The amount of the activator used is generally in the range of 0.01 to 10,000, preferably 1 to 5,000 mol per 1 mol of unit catalyst.

[0104] These may be fed to the polymerization zone, supported on said carrier during the preparation of the unit catalyst, and / or pre-contacted with the unit catalyst, respectively.

[0105] In a preferred embodiment, the polyethylene components (i) to (iii) are produced in a single polymerization step by supporting two unit catalyst components (particularly CrQCp and CrBIP) on the same support, thereby obtaining a two-position catalyst component that ensures relatively close spatial proximity of the catalyst centers and results in intimate mixing of the polyethylene components formed on each catalyst center.

[0106] Thus, in a preferred embodiment, the polyethylene composition (B) is a reactor blend of the polyethylene components (i) to (iii).

[0107] The relative amounts of the polyethylene components (i) to (iii) reported previously can be determined by appropriately setting the relative amounts of the two unit catalyst components, particularly CrQCp and CrBIP, to determine the amounts of the components (i) to (iii) in the polyethylene composition (B).

[0108] The CrBIP / CrQCp molar ratio is preferably in the range of 0.1-20, more preferably 0.3-10, and particularly preferably 0.5-8.

[0109] In a less preferred alternative, polyethylene components (i)-(iii) are prepared separately by polymerizing the relevant monomers in the presence of their respective unit catalysts, and polyethylene composition (B) is prepared by melt-mixing the individual components.

[0110] The polyethylene components (i) to (iii) are produced by gas-phase polymerization, especially in gas-phase fluidized-bed reactors, or solution or suspension polymerization, especially in loop and stirred-tank reactors. Gas-phase polymerization can be carried out in condensed or hypercondensed mode, in which part of the cycle gas is cooled below the dew point and recycled to the reactor as a two-phase mixture.

[0111] Polyethylene components (i)-(iii) can also be produced in a gas-phase reactor known as a multi-zone circulation reactor (MZCR), which has two interconnected polymerization zones. Polymer particles flow upward under fast fluidization or transport conditions through a first polymerization zone, called the "riser," and exit the riser into a second polymerization zone, called the "downcomer," where they flow in a dense form by gravity. Continuous circulation of the polymer is established between the riser and the downcomer. Rapid fluidization conditions are typically established within the riser by feeding a gas mixture containing the relevant monomers into the riser. The catalyst system is preferably fed into the reactor at any point in the riser.

[0112] In a multi-zone circulation reactor, two polymerization zones with different compositions can be obtained by feeding a gas / liquid stream (barrier stream) into the top of the downcomer. The gas / liquid flow acts as a barrier to the gas phase from the riser, establishing an upward pure gas flow at the top of the downcomer. This upward gas flow has the effect of preventing the gas mixture present in the riser from entering the downcomer. Such a reactor is described, for example, in International Patent Application No. 97 / 04015.

[0113] Different or identical polymerization zones can be connected in series, if desired, to form a polymerization cascade, as in the Hostalen® process. It is also possible to arrange reactors using two or more different or identical polymerization processes in parallel. Conventional additives, such as molar mass regulators (e.g., hydrogen) and antistatic agents, can also be used in the polymerization.

[0114] The polymerization temperature is generally in the range of from −20° C. to 115° C., and the pressure is generally in the range of from 1 to 100 bar.

[0115] In the case of suspension polymerization, the suspension medium is preferably an inert hydrocarbon such as isobutane, a mixture of hydrocarbons, or the monomer itself. The solids content of the suspension is generally in the range of 10-80%. The polymerization can be batchwise, such as in a stirred autoclave, or continuous, such as in a tubular reactor, or preferably in a loop reactor.

[0116] In one embodiment, polyethylene composition (B) comprises at least one additional additive (iv) for a related technical field, preferably selected from processing stabilizers, light stabilizers, heat stabilizers, lubricants, antioxidants, antiblocking agents, antistatic agents, pigments, dyes, and mixtures thereof. The additive is contained in polyethylene composition (B) in an amount of up to 6% by weight (including 6% by weight), preferably 0.1 to 1% by weight, based on the total weight of polyethylene composition (B) containing the additive (total weight 100%).

[0117] In one preferred embodiment, the polyethylene composition (B) does not contain any polymers other than polyethylene.

[0118] In another embodiment, the polyethylene composition (B) consists of the polyethylene components (i) to (iii) and optionally another additive (iv).

[0119] In one embodiment, the polyolefin composition (I) may contain 40% by weight or less, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight of another component (C), and the other component (C) is (C1) a strengthening agent; (C2) a saturated or unsaturated styrene or α-methylstyrene block copolymer containing 30% by weight or less, preferably 10 to 30% by weight, of polystyrene based on the weight of (d1); (C3) The compatibilizer (D) comprises a polyolefin functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched maleate dialkyl, C1-C10 linear or branched fumarate dialkyl, itaconic anhydride, C1-C10 linear or branched itaconic acid, dialkyl ester, maleic acid, fumaric acid, itaconic acid, and mixtures thereof; (C4) an additive selected from the group consisting of pigments, dyes, extender oils, flame retardants, UV inhibitors, UV stabilizers, lubricants, antiblocking agents, slip agents, and waxes; (C5) a combination thereof; The amount of component (C) is based on the total weight of (A)+(B)+(C).

[0120] The reinforcing agent (C1) is preferably an inorganic reinforcing agent selected from the group consisting of inorganic fibers (e.g., glass fibers), mineral fillers (e.g., talc), and combinations thereof. The reinforcing agent (C1) is preferably glass fibers.

[0121] The saturated or unsaturated styrene or α-methylstyrene block copolymer (C2) preferably contains 10% to 30% by weight of styrene based on the weight of (C2). Preferably, (C2) is selected from the group consisting of polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly(ethylene-butylene)-polystyrene (SEBS), polystyrene-poly(ethylene-propylene)-polystyrene (SEPS), polystyrene-polyisoprene-polystyrene (SIS), polystyrene-poly(isoprene-butadiene)-polystyrene (SIBS), and mixtures thereof. More preferably, the styrene block copolymer (C2) is polystyrene-poly(ethylene-butylene)-polystyrene (SEBS).

[0122] The styrene block copolymer (C2) preferably has at least one, and preferably all, of the following properties:

[0123] a melt flow rate (MFR) measured according to ASTM D1238 (230°C, 2.16 kg) in the range of 5 to 80 g / 10 min, preferably 10 to 60 g / 10 min, more preferably 10 to 30 g / 10 min; and / or

[0124] The Shore A value (30s) measured in accordance with ASTM 2240 is 70 or less, preferably in the range of 30 to 70, and more preferably in the range of 30 to 60.

[0125] Styrene or alpha-methylstyrene block copolymers (C2) are prepared by ionic polymerization of related monomers, Kraton (登録商標) It is marketed by Kraton Polymers under the trade name

[0126] The functionalized polyolefin (C3) is preferably selected from polyethylene, polypropylene, and C1-C10 linear or branched itaconic acid, dialkyl esters, maleic acid, fumaric acid, itaconic acid, and mixtures thereof, functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched maleic dialkyl, C1-C10 linear or branched dialkyl fumarate, itaconic anhydride.

[0127] In a preferred embodiment, the functionalized polyolefin (C3) is polyethylene and / or polypropylene grafted with maleic anhydride (MAH-g-PP and / or MAH-g-PE).

[0128] The modified polymers are known in the art and can be prepared by functionalization processes carried out in solution, in the solid state, or preferably in the melt, for example by reactive extrusion of the polymer in the presence of a grafting compound and a free radical initiator. The functionalization of polypropylene and / or polyethylene with maleic anhydride is described, for example, in EP 0 572 028 A1.

[0129] An example of a functionalized polyolefin is the commercial product Amplify by The Dow Chemical Company. (商標) TY, Exxelor by ExxonMobil Chemical Company (商標) , Scona by Byk (Altana Group) (登録商標) TPPP, Bondyram by Polyram Group (登録商標) (and Polybond by Chemtura (登録商標) , and combinations thereof.

[0130] The polyolefin composition (I) is prepared by intimately mixing components (A), (B), and, optionally, (C) using methods and equipment known in the art, e.g., blending the components at a temperature of 180° to 220°C.

[0131] It has been found that by molding the polyolefin composition (I) under appropriate conditions, the tensile properties of the heterophasic polymer composition (A) can be improved by the flow-inducing enhancing effect of the polyethylene composition (B).

[0132] Therefore, the present disclosure provides a method for producing the molten polyolefin composition (I) in a stream of 50 s -1 More than 150s, preferably -1 The present invention also relates to a process for producing a molded article, which comprises the step of applying a shear rate equal to or greater than the above.

[0133] In one embodiment, the flow of the molten polyolefin composition (I) is -1 More than 8 seconds, preferably -1 A strain rate of at least

[0134] The manufacturing process preferably comprises: - melting the polyolefin composition (I) at a temperature of 180°C or higher, preferably in the range of 180°C to 220°C; - The flow of the molten polyolefin composition (I) is continued for 50 seconds. -1 More than 150s, preferably -1 applying a shear rate equal to or greater than - shaping and cooling the molten polyolefin composition (I).

[0135] The flow of the molten polyolefin composition (I) is continued for 50 seconds. -1 The step of applying the above shear rate is preferably carried out by a process using injection molding or extrusion molding.

[0136] The flow of the molten polyolefin composition (I) is continued for 50 seconds. -1 The step of applying the above shear rate is preferably carried out by injection molding, and the shear rate is 50 to 3000 s -1 , preferably 200 to 2000 s -1 is.

[0137] In one embodiment, in the injection molding process, the flow of the molten polyolefin composition (I) is added for 3 to 200 s. -1 , preferably 8 to 120 seconds -1 gives strain rates in the range

[0138] The injection molding process is advantageously carried out by melt-mixing the polyolefin composition (I) in a conventional twin-screw extruder, preferably a conventional twin-screw co-rotating extruder.

[0139] The components of the polyolefin composition (I) are fed to an injection molding machine individually or preferably premixed, more preferably intimately premixed in a molten state, preferably by mixing the components of the polyolefin composition (I) in a mixer of the type commonly used in the art.

[0140] The extrusion-based process is preferably an extrusion-based 3D printing process, in which the flow of the molten polyolefin composition (I) is -1 The shear rate step was performed by extrusion-based 3D printing, with the shear rate ranging from 50 to 1,000 s -1 , preferably 100 to 600 s -1 It is preferable that:

[0141] In one preferred embodiment, the extrusion-based 3D printing process comprises adding a stream of molten polyolefin composition (I) to the stream for 3 to 50 seconds. -1 , preferably 3 to 20 seconds -1 This involves applying a strain rate in the range

[0142] The 3D printing process is preferably a fused filament fabrication (FFF) process, also known as fused deposition modeling (FDM), and is carried out using commercially available extrusion-based 3D printers.

[0143] The components of the polyolefin composition (I) are either individually fed into the 3D printer or preferably premixed, more preferably intimately premixed in a molten state, preferably by mixing the components of the polyolefin composition (I) in a mixer of the type commonly used in the art.

[0144] In another aspect, the present disclosure relates to an extrusion-based 3D printing filament, also called extrusion-based additive manufacturing, comprising or consisting of the polyolefin composition (I) described above.

[0145] The molded article obtained by the manufacturing process of the present disclosure has a significantly reduced density and excellent mechanical properties compared to a heterophasic polymer composition (A) reinforced only with a conventional inorganic filler, such as glass fiber.

[0146] In another aspect, the present disclosure relates to the use of the above polyethylene composition (B) as a reinforcing masterbatch of the above heterophasic polymer composition (A).

[0147] The method of using a polyolefin composition (B) to reinforce a heterophasic polymer composition (A) comprises the steps of: - adding 20 to 85% by weight, preferably 20 to 60% by weight, more preferably 30 to 50% by weight of a polyethylene composition (B) to 15 to 80% by weight, preferably 40 to 80% by weight, more preferably 50 to 70% by weight of a heterophasic polymer composition (A), in which the amounts of (A) and (B) are greater than the total weight of (A)+(B), Preferably, the polyolefin composition (I) is melted at a temperature of 180°C or higher, and the molten polyolefin composition (I) is allowed to flow for 50 seconds. -1 More than 150s, preferably -1 applying a shear rate equal to or greater than - shaping and cooling the molten polyolefin composition (I).

[0148] Preferably, in the method, the step of cooling and melting the polyolefin composition comprises molding the polyolefin composition by an extrusion-based process or injection molding. More preferably, the extrusion-based process is 3D printing.

[0149] The features described in the subject matter of this disclosure are not necessarily closely related to one another. Therefore, the priority of one feature does not necessarily relate to the same priority of the remaining features of the same or different components. In this disclosure, the preferred ranges of the features of components (A) and (B) that result in polyolefin composition (I) can be combined regardless of the level of preference, and components (A) and (B) can be combined with any possible additional components and their features described in this disclosure.

[0150] Example

[0151] The following examples are illustrative only and are not intended to limit the scope of the present disclosure in any way.

[0152] Characterization Method

[0153] The following methods are used to determine the properties set forth in the specification, claims, and examples. Melt flow rate: Measured according to ISO 1133-2:2011 method at a temperature of 230°C or 190°C depending on the polymer, with a load of 2.16 kg. The melt flow rate of a composition (MFR(tot)) correlates to the melt flow rates of the components according to the following formula:

number

[0154] Density: Measured in accordance with ASTM D 792-08 method.

[0155] Solubility in xylene at 25°C: 2.5 g of polymer sample and 250 ml of xylene were introduced into a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature rose to 135°C in 30 min. The resulting clear solution was maintained under reflux and stirred for an additional 30 min. The solution was cooled in two stages. In the first stage, the temperature was reduced to 100°C over 10-15 min with stirring in air. In the second stage, at 25°C, the flask was transferred to a thermostatically controlled water bath over 30 min. The temperature was reduced to 25°C without stirring for the first 20 min and maintained at 25°C for the final 10 min with stirring. The formed solid was filtered on a rapid filter paper (e.g., Whatman filter paper grade 4 or 541). 100 ml of the filtered solution (S1) was poured into a pre-weighed aluminum container and heated to 140°C on a hot plate under a nitrogen flow to evaporate the solvent. The container was then placed under vacuum in an oven at 80°C until a constant weight was reached. The amount of polymer soluble in xylene at 25°C was then calculated.

[0156] The xylene soluble fraction of a composition (XS(tot)) is related to the xylene soluble fraction of a component by the following formula:

number

[0157] C2 and C4 content in polymers containing C3, C2, and C4: 13 C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe operating at 160.91 MHz in Fourier transform mode at 120 °C. δδ The carbon peak (nomenclature follows "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode" CJ Carman, RA Harrington and CE Wilkes, Macromolecules, 1977, 10, 536) was used as an internal reference at 29.9 ppm. Approximately 30 mg of sample was dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2 at 120 °C, with 0.1 mg / ml Irganox 1010 (AO1010) added as an antioxidant. Each spectrum was acquired with a 90° pulse, with a 15-second delay between the pulse and CPD to remove 1H-13C coupling. A spectral window of 9000 Hz was used, and 512 transients were saved to 65K data points. The triad distribution was generated using the following equation (taking into account possible overlap with peaks derived from AO1010):

number

number

[0158] C2 and C3 polymers containing propylene and ethylene: 13 C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe operating at 160.91 MHz in Fourier transform mode at 120 °C. δδ The carbon peak (nomenclature follows "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode" CJ Carman, RA Harrington and CE Wilkes, Macromolecules, 1977, 10, 536) was used as an internal reference at 29.9 ppm. Approximately 30 mg of sample was dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2 at 120 °C, and 0.1 mg / ml Irganox 1010 (AO1010) was added as an antioxidant. Each spectrum was acquired with a 90° pulse, a 15-second delay between pulses, and CPD to remove H-C coupling. Using a 9000 Hz spectral window, 512 transients were saved to 32K data points. Spectral assignment, triad distribution evaluation, and composition were performed according to M. Kakugo, Y. Naito, K. Mizunuma, and T. Miyatake, Macromolecules, 1982, 15, 4, 1150-1152, using the following equation (taking into account possible overlap with peaks derived from AO1010):

number

number

[0159] Molecular weight characteristics: Average molecular weights Mw, Mn, and molecular weight distributions were measured by gel permeation chromatography (GPC) on a PL-220 high-temperature gel permeation chromatograph (HT-GPC Agilent) equipped with three PLGel Olexis columns and a triple detection system (differential refractive index detector, differential viscometer 210R (Viskotek), and low-angle light scattering). The chromatographic columns were calibrated using 12 narrow, monodisperse polystyrene standards (Achillon Technology) in the range of 580 g / mol to 11,600,000 g / mol. Calibration curves were matched to polyethylene using the universal calibration method (Grubisic Z., Rempp P and Benoit H., J. Polymer Sci., 5, 753 (1967)). The Mark-Houwing parameters used for polystyrene were kPS = 0.000121 dl / g, αPS = 0.706, and kPE = 0.000406 dl / g, αPE = 0.725, valid at a TCB of 135 °C. Data recording, calibration, and calculations were performed using NTGPC_Control_V6.02.03 and NTGPC_V6.4.24 (hs GmbH, Hauptstrasse 36, D-55437 Ober-Hilbersheim, Germany), respectively. Sample measurements were performed in 1,2,4-trichlorobenzene (stabilized with 0.2 wt% 2,6-di-tert-butyl-(4-methylphenol, BHT)) at a flow rate of 1.0 mL / min, an injection volume of 500 μL, and polymer concentrations of 0.01%–0.05% w / w at 160 °C.

[0160] Injection molding of test specimens: Tensile impact test specimens were prepared by injection molding the compositions using a DSM Xplore Microcharger 5cc equipped with a DSM Xplore 10cc injection molding system at 220°C, 0.8 MPa, and 8 seconds of dwell pressure. The mold temperature was 60°C.

[0161] Compression molding: A Collin 200P compression molding system was used to obtain plates of 110 x 80 x 2 and 4 mm, operated at 200 °C, 0.8 MPa, and a holding time of 20 min. Tensile specimens conforming to ISO 527-2:2012, Type 5A geometry were cut from the 2 mm thick plates. Impact specimens conforming to ISO 179-1 / 1EA were cut from the 4 mm thick plates.

[0162] Tensile properties at break: Tensile modulus and tensile strength were measured according to ISO 527-1:2012 using a ZWICK Z005 tensile testing machine and a makroXtens tensile tester (2.5 kN load cell). Six specimens with ISO 527-2:20125a geometry were tested at a tensile speed of 50 mm / min. The data were evaluated using the software TESTXPERT II V3.31. The average of the six measurements was used as the test attribute value.

[0163] Impact test: Charpy impact strength was measured on test specimens ISO 179-1 / 1eA according to the ISO 179-1:2010 method (notched impact at 23°C) using a Zwick 5102.100 / 00 pendulum impact tester. Five specimens were tested for each composition. After determining the cross-sectional area of ​​the notch, all specimens were impacted. The impact test properties were determined by the dissipated energy. The average value of five measurements was taken as the impact test resistance value. Shear rate: the shear rate applied to the polymer melt during extrusion

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[0164] raw materials:

[0165] HECO-1 - a heterophasic polymer comprising (based on the total weight of (a)+(b)+(c)): (a) 56.5 wt. % of a propylene homopolymer having a xylene soluble fraction XS(a) of 3 wt. % based on the weight of (a) and an MFR(a) of 70 g / 10 min (ISO 1133-2:2011, 230°C / 2.16 Kg). (b) 23.0 wt. % of a copolymer of ethylene and butene-1 containing 27.4 wt. % of units derived from butene-1, based on the weight of (b). (c) 20.5 wt. % of a propylene-ethylene copolymer containing 41.5 wt. % of units derived from ethylene, based on the weight of (c).

[0166] HECO-1 is a reactor mixture of components (a), (b) and (c) as described in Examples 1-3 of International Patent Application No. 03 / 076511 A1 and has the following properties: The xylene soluble fraction XS (HECO-1) at -25°C is 35.2% by weight. The intrinsic viscosity of the xylene soluble fraction XSIV (HECO-1) at -25°C is 2.26 dl / g. - The melt flow rate MFR(HECO-1) measured in accordance with ISO 1133 at 230°C and a load of 2.16 kg is 12.5 grams / 10 min; and - The total ethylene content, based on the weight of (a) + (b) + (c), is 25.2 wt.% and the total butene-1 content is 6.3 wt.%. The numbers (a), (b), and (c) correspond to the divisions of the reactor, and the amount of ethylene in components b) and c) and the amount of butene-1 in component c are calculated from the total amounts of ethylene C2(tot) and butene-1 C4(tot) measured in HECO-1 using the following formula:

number

[0167] Component B The polyethylene composition is prepared as described for composition II-2 in patent application 2020 / 169423A1.

[0168] 2,6-Bis-[1-(2,6-dimethylphenylimino)ethyl]pyridinechromium(III) trichloride (CrBIP) was synthesized according to Esteruelas MA, et al. Organometallics 2003;22(3):395-406. [η 5 -3,4,5-Trimethyl-1-(8-quinolyl)-2 trimethylsilyl-cyclopentadienyl-chromium dichloride (CrQCp) was synthesized according to Enders et al. Organometallics 2004; 23(16):3832-9, and Fernandez et al. Organometallics 2007; 26(18):4402-12. Method for producing a mixed catalyst system Pore ​​volume is 1.5 ml / g, specific surface area is 400 m 2 g -1 A mesoporous silica catalyst support (Grace's Sylopol XPO2107) was dried at 160 °C for 14 h in a Schlenk tube, and 20 mL of toluene was added. The tube was then heated under high vacuum (10 -3 The suspension was sonicated for 10 min at 10 bar. After adding the calculated amount of MAO (Al:Cr = 300:1), the mixture was stirred for 30 min and sonicated for 5 min. After settling, the MAO-treated catalyst support was washed with dry toluene, and the supernatant was removed and replaced. CrBIP was dissolved in toluene (0.2 mg mL -1 ), pretreated with trimethylaluminum (TMA, 10 equiv.), and added via syringe. After stirring for 5 min, CrQCp (0.2 mg mL) in toluene was added. -1) was added, and the mixture was stirred again for 5 min. The CrBIP / CrQCp molar ratio was 3.0. After settling, the activated catalyst was collected in n-heptane (20 mL) and transferred to the reactor to initiate polymerization. Ethylene polymerization was carried out in a 2.6 L steel reactor (HITEC ZANG) equipped with a mechanical stirrer, thermostat, and software interface. The reactor was heated to 90 °C under high vacuum for 2 h, filled with n-heptane (580 mL) and triisobutylaluminum (TiBAl, 3 mL, 1 M in n-hexane), and saturated with ethylene (5 bar). After transferring the prepared catalyst to the reactor, polymerization was carried out for 120 min at 40 °C, 5 bar ethylene pressure, and a stirring speed of 200 rpm. The polymer was stabilized in methanol with BHT (2,6-di-tert-butyl-4-methylphenol), filtered, and dried under vacuum at 60 °C to constant weight.

[0169] The properties of the polyethylene composition are shown in Table 1. Table 1 [Table 2]

[0170] HECO-2 (component)- A heterophasic polyolefin composition comprising: (a) 60% by weight of propylene homopolymer; (b) 40% by weight of a propylene-ethylene copolymer consisting of 68% by weight of ethylene, based on the weight of (b).

[0171] HECO-2 is a reactor mixture of components (a) and (b) obtained as described in Example 1-2 of WO 2005 / 014715 and has the following properties: At -25°C, the xylene soluble fraction XS (HECO-2) is 31.2% by weight. The intrinsic viscosity of the xylene soluble fraction XSIV (HECO-2) at -25°C is 2.29 dL / g; and - The melt flow rate MFR(HECO-1) measured in accordance with ISO 1133 at a temperature of 230°C and a load of 2.16 kg is 11.3 g / 10 min. The amount of ethylene C2(b) in component (b) is calculated from the total amount of ethylene C2(tot) measured by HECO-2 using the following formula:

number

[0172] Metocene MF650Y -Propylene homopolymer provided by LyondellBasell with a very narrow molecular weight distribution and MFR (ISO1133, 230℃ / 2.16Kg) of 1800g / 10min.

[0173] Kraton(TM) G1657 V—A linear styrene triblock copolymer based on styrene and ethylene / butylene containing 13% by weight of polystyrene, with an MFR (ASTM D1238; 230°C, 5Kg) of 22 g / 10 min and a Shore A value (ASTM D2240, 10 sec) of 47.

[0174] Dow Engage 7467 -Contains 31% by weight of units derived from butene-1 and has a density of 0.862 g / cm 3 (ASTM D792) and melt index (ASTM D1238, 190°C / 2.16Kg).

[0175] Polybond 3200 -Supplied by SI Group, it is a maleic anhydride-modified polypropylene homopolymer (ASTM D1238, 190°C / 2.16 kg) with a maleic anhydride content ranging from 0.8 to 1.2 wt% (ASTM D6047) and an MFR of 115 g / 10 min.

[0176] Moplen HP500N-Propylene homopolymer supplied by LyondellBasell and having an MFR of 12 g / 10 min measured according to ISO 1133 method at 230°C and 2.16 Kg load.

[0177] GF -Johns Manville Thermoflow 636 EC10 fiberglass (10 meter diameter; 4 mm length)

[0178] Additive Pack consisted of 5.0 wt. % Irgafos 168 (BASF) alpha tris(2,4-di-tert-butylphenyl)phosphite, 7.5 wt. % Irganox 1076 (BASF) alpha octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionic acid ester, 2.5 wt. % Tinuvin 622 (BASF) alpha oligohindered amine light stabilizer, 12.5 wt. % talc, 25 wt. % polydimethylsiloxane, 2.5 wt. % magnesium oxide, and 45 wt. % Moplen HF 501N (LyondellBasell), both based on the weight of the additive pack.

[0179] Example E1 and Comparative Examples CE2 to CE5

[0180] The ingredients were melt mixed in a DSM Xplore Compounder 5cc at 200°C, 120 rpm with a 90 second hold time, pelletized and injection molded.

[0181] Table 2 shows the composition of the test specimens and the test results for tensile and impact properties. Table 2 [Table 3]

[0182] Examples E6 to E9 and Comparative Examples CE10 and CE11 The components were melt-mixed in a 5cc DSM Xplore Compounder at 200°C, 120 rpm, and a holding time of 90 seconds, and then pelletized. The pellets were injection molded to prepare test specimens. The composition of the test specimens and the test results for tensile and impact properties are shown in Table 3. Table 3 [Table 4]

[0183] Comparative example CE12, CE13

[0184] The components were melt mixed in a 5cc DSM Xplore Compounder at 200°C, 120 rpm, and a holding time of 90 seconds, and then pelletized. Test specimens were obtained by compression molding of the pellets. The test specimen compositions and test results are shown in Tables 4 and 4a. Table 4 [Table 5] Table 4a [Table 6]

[0185] Example E14 and Comparative Example CE15

[0186] The compositions of Example E8 and Comparative Example CE10 were subjected to four process cycles of granulation and injection molding in a DSM Xplore Microcharger 5cc equipped with a DSM Xplore 10cc injection molding system at 220°C, 0.8 MPa, and 8 seconds of dwell time (mold temperature 60°C). The tensile modulus and tensile strength values ​​measured at the end of each process cycle are shown in Table 5. Table 5 [Table 7]

[0187] Examples E16 to E18 and Comparative Examples CE19 to CE21

[0188] Pellets of the composition produced in Example E8 and the composition produced in Example CE10 were extruded on a COLLIN TEACH-LINE™ ZK25T twin-screw extruder with a circular die (3.00 mm diameter) to obtain filaments for 3D printing. The extrusion parameters are shown in Table 6. The extruded filaments were quenched with water and wound onto a printer coil. Table 6 [Table 8]

[0189] The 3D printed parts were produced on an Ultimaker2+ FFF printer using 100% infill and a 0.8 mm diameter nozzle. The printing parameters are listed in Table 7. Table 7 [Table 9]

[0190] Tensile and Charpy impact test specimens were fabricated by 3D printing filaments with a patch pattern orientation parallel to the longest dimension of the specimen, corresponding to a 0° orientation relative to the tensile / impact direction.

[0191] The tensile modulus and tensile strength values ​​measured for each printing / extrusion speed, as well as the shear and strain rates experienced by the polymer melt during the process, are shown in Table 8. Table 8 [Table 10]

Claims

1. An injection-molded article comprising a polyolefin composition (I), The polyolefin composition (I) is (A) 40 to 80 wt. % of a heterophasic polymer composition, (a) propylene homopolymer, ethylene and / or a polymer of formula CH ２ = CHR １ (However, R １ is a linear or branched C2-C8 alkyl; and mixtures thereof, wherein the copolymer comprises 50 to 80% by weight of at least one propylene polymer containing 10.0% by weight or less of units derived from the ethylene and / or the α-olefin, based on the weight of (a); (b) Ethylene and a compound of formula CH ２ = CHR １ (However, R １ is a linear or branched C2-C8 alkyl; and a copolymer of at least one α-olefin represented by the formula (b), wherein the copolymer consists essentially of 20 to 50 wt. % of at least one copolymer containing 10 to 40 wt. % or less of units derived from the α-olefin, based on the weight of (b); 40-80 wt. % of the heterophasic polymer composition, the amounts of (a) and (b) being based on the total weight of (a)+(b); (B) 20 to 60% by weight of a polyethylene composition, (i) 25 to 85% by weight of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) measured by gel permeation chromatography of 5,000 g / mol or less; the polyethylene component is an ethylene homopolymer; 20 to 60 wt. % of a polyethylene composition (B), wherein the polyethylene composition (B) comprises at least 70 wt. % of (i) and (ii), the amounts of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%; and Including, The amounts of (A) and (B) are based on the total weight of (A) + (B).

2. 2. The injection molded article of claim 1, comprising 50 to 70 wt. % of the heterophasic polymer composition (A) and 30 to 50 wt. % of the polyethylene composition (B).

3. 2. The injection-molded article according to claim 1, wherein the polyethylene composition (B) has a value of Mw / Mn(B) of 300 or greater, the polyethylene components (i) and (ii) each have an Mw / Mn independently selected from values ​​of 5 or less, wherein Mw is a weight average molecular weight measured by GPC, and Mn is a number average molecular weight measured by GPC.

4. The composition comprises 40% by weight or less of a component (C), wherein the component (C) is (C1) a reinforcing agent; (C2) a saturated or unsaturated styrene or α-methylstyrene block copolymer; (C3) a polyolefin functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched dialkyl maleates, C1-C10 linear or branched dialkyl fumarates, itaconic anhydride, C1-C10 linear or branched dialkyl itaconic acid esters, maleic acid, fumaric acid, itaconic acid, and mixtures thereof; (C4) an additive selected from the group consisting of pigments, dyes, extender oils, flame retardants, UV inhibitors, UV stabilizers, lubricants, antiblocking agents, slip agents, and waxes; (C5) combinations thereof; and is selected from the group consisting of 2. The injection-molded article of claim 1, wherein the amount of component (C) is based on the total weight of (A)+(B)+(C).

5. The flow of the molten polyolefin composition (I) is －１ A process for producing a molded article, comprising the step of applying a shear rate of at least The molten polyolefin composition (I) is (A) 40 to 80 wt. % of a heterophasic polymer composition, (a) 50 to 80% by weight of at least one propylene polymer selected from the group consisting of propylene homopolymers, propylene copolymers with ethylene and / or at least one α-olefin represented by the formula CH 2 ═CHR 1 , where R 1 is a linear or branched C2 to C8 alkyl, and mixtures thereof, said copolymers containing no more than 10.0% by weight of units derived from said ethylene and / or said α-olefin, based on the weight of (a); (b) a copolymer of ethylene and at least one α-olefin represented by the formula CH 2 ═CHR 1 , wherein R 1 is a linear or branched C2-C8 alkyl, said copolymer consisting essentially of 20 to 50 weight percent of at least one copolymer containing 10 to 40 weight percent or less of units derived from said α-olefin, based on the weight of (b); 40-80 wt. % of the heterophasic polymer composition, the amounts of (a) and (b) being based on the total weight of (a)+(b); (B) 20 to 60% by weight of a polyethylene composition, (i) 25 to 85% by weight of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) measured by gel permeation chromatography of 5,000 g / mol or less; the polyethylene component is an ethylene homopolymer; 20 to 60 wt. % of a polyethylene composition (B), wherein the polyethylene composition (B) comprises at least 70 wt. % of (i) and (ii), the amounts of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%; and Including, The amount of (A) and (B) is based on the total weight of (A) + (B).

6. Use of 20 to 85 wt. % of a polyethylene composition (B) as a reinforcing masterbatch for a heterophasic polymer composition (A) in an injection-molded article, comprising: The polyethylene composition (B) is (i) 25 to 85% by weight of a polyethylene component having a weight average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) measured by gel permeation chromatography of 5,000 g / mol or less; the polyethylene composition (B) comprises at least 70% by weight of (i) plus (ii), the amounts of (i) and (ii) being based on the total weight of the polyethylene composition (B), the total weight being 100%; the polyethylene component is an ethylene homopolymer; The heterophasic polymer composition (A) comprises (a) propylene homopolymer, ethylene and / or a polymer of formula CH ２ = CHR １ (However, R １ is a linear or branched C2-C8 alkyl; and mixtures thereof, wherein the copolymer comprises 50 to 80% by weight of at least one propylene polymer containing 10.0% or less by weight of units derived from the ethylene and / or the α-olefin, based on the weight of (a); (b) Ethylene and a compound of formula CH ２ = CHR １ (However, R １ is a linear or branched C2-C8 alkyl; and 20 to 50 wt. % of at least one copolymer having 10 to 40 wt. % or less of units derived from said α-olefin, based on the weight of (b); The amounts of (a) and (b) are based on the total weight of (a)+(b), and the amount of (B) is based on the total weight of (A)+(B).

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