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 a polyolefin composition, and an injection molded article or a 3D printed article obtained therefrom. Background Art

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

[0003] Filled polyolefins have several advantageous properties such as high strength and high rigidity, and are widely used in many industrial fields, for example, they are used for injection molding of interior and exterior parts in the automotive field.

[0004] While the presence of inorganic fillers improves the mechanical properties of polyolefins, it adversely affects the environmental sustainability of the filler-containing material.

[0005] The mechanical properties of mechanically recycled glass fiber-filled polyolefins degrade over time because the fibers are damaged and shredded during each recycling step. Therefore, the life cycle of inorganic-filled plastic materials is shorter than that of unfilled materials, and they quickly become disposable waste.

[0006] In the case of chemical recycling, the inorganic filler needs to be separated from the polyolefin matrix, which complicates the process and reduces sustainability.

[0007] Furthermore, conventional plastics filled with inorganic fillers have a high density. The heavier the plastic material, the greater the vehicle mass when transporting the material. This increases fuel consumption in internal combustion engine vehicles and reduces the cruising range of electric vehicles, thereby increasing the environmental impact of filler logistics.

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

[0009] Timo Hees et al. published in Polymer, Volume 151, pp. 47-55, a total PE self-reinforced composite material created by combining conventional HDPE with a twin-peak reactor blend of UHMWPE (ultra-high molecular weight polyethylene) and HDPE wax. The resulting tripod-peaked self-reinforced polyethylene improves mechanical properties.

[0010] However, past attempts to reinforce polypropylene with UHMWPE have either yielded poor results due to the poor miscibility between UHMWPE and polypropylene, or they have involved the use of unconventional and energy-consuming processes.

[0011] X. Wang et al., Journal of Polymer Science, Vol. 1, 100, 3495-3509 (2006), achieved satisfactory results when melt-blending polyolefins in a co-rotating quadruple-screw extruder, ultimately reinforcing a propylene homopolymer with UHMWPE in the presence of EPDM. Conventional twin-screw extruders yielded 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] U.S. Patent Application No. 2014 / 0066574A1 teaches how to obtain reinforced injection molded articles by pultrusion molding 60–85 wt% high-flow thermoplastic resin into 15–40 wt% UHMWPE fibers. [Overview of the project] [Problems that the invention aims to solve]

[0014] In this case, there is still a need for reinforced polyolefins that have improved mechanical properties compared to the same unreinforced polyolefins, particularly increased tensile strength and impact resistance, as well as improved recyclability compared to low-density and inorganic-filled polyolefins.

[0015] Therefore, this disclosure is, (A) A heterogeneous polymer composition comprising 15 to 80% by weight, (a) Propylene homopolymer, ethylene and / or formula CH2=CHR 1 (However, R 1 A propylene polymer selected from the group consisting of a propylene copolymer with at least one α-olefin represented by (a) and mixtures thereof, wherein the copolymer contains at least 10.0% by weight, preferably 0.05 to 8.0% by weight, of the units derived from the ethylene and / or the α-olefin on a weight basis of (a), and at least one propylene polymer. 50 ~80% by weight, (b) Ethylene and the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl group. A copolymer of at least one α-olefin represented by (b), wherein the copolymer contains 10-40% by weight, preferably 20-35% by weight, of the units derived from the α-olefin, and at least 20-50% by weight of the at least one copolymer. Essentially, before The amounts of (a) and (b) are based on the total weight of (a) + (b), and consist of 15-80% by weight of the heterogeneous polymer composition. (B) A polyethylene composition comprising 20 to 85% by weight, (i) 25-85% by weight of polyethylene components whose weight-average molecular weight Mw(i) measured by gel permeation chromatography is 1,000,000 g / mol or more, (ii) A polyethylene component comprising 10 to 65% by weight, wherein the weight-average molecular weight Mw(ii) measured by gel permeation chromatography is 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) are based on the total weight of the polyethylene composition (B), which is 100%, and includes 20-85% by weight of the polyethylene composition. The amounts of the above (A) and (B) are based on the total weight of (A)+(B) Ori , The polyolefin composition (I) comprises 40 to 80% by weight of a heterogeneous polymer composition (A) and 20 to 60% by weight of a polyethylene composition (B). A polyolefin composition (I) is provided.

[0016] A process for producing a molded article is also provided, which comprises applying a shear rate of 50s -1 or higher to the flow of the molten polyolefin composition (I).

[0017] In another aspect, the present disclosure relates to a polyethylene composition (B) 20~85% by weight for use, wherein the 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 higher as measured by gel permeation chromatography; (ii) 10 to 65% by weight of a polyethylene component having a weight average molecular weight Mw(ii) of 5,000 g / mol or lower as measured by gel permeation chromatography, the polyethylene composition (B) comprises at least 70% by weight of the sum of (i) and (ii), and the amounts of (i) and (ii) are based on the total weight of the polyethylene composition (B), where the total weight is 100%, as a reinforcing masterbatch for the heterophasic polymer composition (A), (a) propylene polymer selected from the group consisting of propylene homopolymers, propylene copolymers with ethylene and / or at least one α-olefin represented by formula CH2=CHR 1 (wherein R 1 is a linear or branched C2-C8 alkyl), and mixtures thereof, wherein the copolymer comprises 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), at least one propylene polymer 50 to 80% by weight of (b) ethylene and a compound of formula CH2=CHR 1 (wherein R 1A copolymer of at least one α-olefin represented by (b), wherein the unit derived from the α-olefin is 10 to 40% by weight or less, preferably 20 to 35% by weight, and the copolymer is 20 to 50% by weight of at least one copolymer. Essentially , before Note( The amounts of a) and (b) are based on the total weight of (a) + (b). Furthermore, the amount of (B) is based on the total weight of (A) + (B). , provides use.

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

[0019] Furthermore, polyolefin composition (I) has a significantly lower density compared to conventional polyphase polyolefin composition (A) reinforced with inorganic fillers (e.g., glass fibers).

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

[0021] Furthermore, the mechanical properties of the polyolefin composition (I) do not deteriorate significantly after multiple processing cycles, enabling multiple recycling cycles of the polyolefin composition (I), thus improving environmental sustainability compared to conventional polyolefin compositions containing inorganic fillers.

[0022] While several embodiments are disclosed, further embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, all specific embodiments disclosed herein can be modified in various obvious ways without departing from the spirit and scope of the claims set forth herein. Therefore, the following detailed description should be considered as illustrative and not restrictive in nature. [Modes for carrying out the invention]

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

[0024] -When the term “contains” refers to a polymer, or a polymer composition, mixture, or blend, it should be interpreted as “contains, or essentially consists of.”

[0025] - The term "essentially composed" means that, in addition to the essential components, other components may be present in the polymer or polymer composition, mixture, or blend, provided that their presence does not substantially affect the essential properties of the polymer or composition, mixture, or blend. Examples of components that, when present in normal amounts, do not substantially affect the properties of the polymer or polyolefin composition, mixture, or blend include 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% by weight, preferably 50 to 70% by weight, of a heterogeneous polymer composition (A) and 20 to 60% by weight, preferably 30 to 50% by weight, of a polyethylene composition (B).

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

[0028] - The melt flow rate MFR(tot), measured in accordance with ISO 1133-2:2011 at a temperature of 230°C and a load of 2.16 kg, is 0.001 to 5.0 g / 10 min, and / or -The density measured in accordance with ASTM standard D792-08 is 1.00 g / cm³. 3 The following conditions must be met: In one embodiment, the density is 0.90 g / cm³. 3 That's all. and / or -The tensile modulus measured for injection-molded test specimens in accordance with ISO 527-1:2012 is at least 100%, preferably at least 150%, and more preferably at least 200% higher than the tensile modulus of heterogeneous polymer composition (A). In one embodiment, the tensile modulus of polyolefin composition (I) is 500% or less higher than the tensile modulus of heterogeneous 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 fiber reinforcing agents such as polyolefin fibers or wool.

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

[0031] The components of the polyolefin composition (I) are defined in more detail below. These components may be included in the polyolefin composition (I) in any combination.

[0032] The α-olefins that may be included in components (a) and (b) of the heterogeneous 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, and preferably the α-olefin is butene-1.

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

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

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

[0036] At a temperature of -25°C, the xylene-soluble fraction XS(a) 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, 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 heterogeneous polymer composition (A) is a copolymer or mixture of copolymers of ethylene and 1-butene.

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

[0041] - The weight-average molecular weight Mw measured by GPC shall be in the range of 50,000 g / mol or more, preferably 50,000 g / mol or more and less than 1,000,000 g / mol. and / or

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

[0043] In one embodiment, the heterogeneous polymer composition (A) preferably includes the following:

[0044] (a) Propylene homopolymer, ethylene and / or formula CH2=CHR 1 (However, R 1 A propylene polymer selected from the group consisting of a propylene copolymer with at least one α-olefin represented by (a), wherein the copolymer contains 10.0% by weight or less, preferably 0.05 to 8.0% by weight, of the ethylene and / or the α-olefin units on a weight basis of (a), and 35 to 70% by weight, preferably 40 to 65% by weight, of at least one propylene polymer. (b) Ethylene and the formula CH2=CHR 1 (However, R 1 is a linear or branched C2-C8 alkyl group. A copolymer of at least one α-olefin represented by (b), wherein the copolymer contains 10-40% by weight, preferably 20-35% by weight, of units derived from the α-olefin on a weight basis of (b), and at least one copolymer of 15-40% by weight, preferably 20-35% by weight, (c) Ethylene and / or formula CH2=CHR 1 (However, R 1 A propylene copolymer comprising at least one α-olefin represented by (c) and a mixture thereof, wherein the propylene copolymer contains 5 to 30% by weight, preferably 7 to 20% by weight, of at least one propylene copolymer, which contains 50% by weight or less, preferably 15 to 50% by weight, of the ethylene and / or units derived from the α-olefin on a weight basis of (c), The quantities (a), (b), and (c) above are based on the total weight of (a) + (b) + (c).

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

[0046] Preferably, the polyolefin composition may contain 3.0% by weight or less of at least one further additive selected from the group consisting of antistatic agents, antioxidants, light stabilizers, lubricants, acid inhibitors, melt stabilizers, and combinations thereof, the amount of the further additive being based on the total weight of the polyolefin composition containing the further additive.

[0047] The heterogeneous polymer composition (A) of this disclosure preferably has a melt flow rate (MFR) of 8.0 g / 10 min or more, measured at a temperature of 230°C and a load of 2.16 kg in accordance with the ISO 1133-2:2011 method. In one embodiment, the MFR (A) measured at a temperature of 230°C and a load of 2.16 kg in accordance with the ISO 1133-2:2011 method is 150 g / 10 min or less.

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

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

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

[0051] At a temperature of -25°C, the xylene-soluble fraction XS(A1) shall be 30% to 50% by 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, should be 5-20 g / 10 min, preferably 8-15 g / 10 min.

[0052] The heterogeneous polymer composition (A) is produced by melt-blending components (a), (b), and optionally (c) and (d), or by polymerizing the relevant monomers in at least two polymerization steps, each of which is carried out in the presence of the polymer produced and the catalyst used in the immediately preceding polymerization step, thereby obtaining a reactor blend of components (a), (b), and optionally (c), and optionally melt-blending the thus obtained reactor blend with component (d).

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

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

[0055] The solid catalyst component (1) preferably contains TiCl4 in an amount of 0.5 to 10% by weight relative to the total weight of the solid catalyst component (1).

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

[0057] Preferred donors are phthalate esters, particularly diisobutyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzylbutyl phthalate, and combinations thereof, as described in European Patent No. 45977A2 and European Patent No. 395083A2.

[0058] Fatty acid esters may be selected from malonic acid esters, such as those described in International Publication Nos. 98 / 056830, 98 / 056833, and 98 / 056834; glutaric acid esters, such as those disclosed in International Publication No. 00 / 55215; and succinic acid esters, such as those disclosed in International Publication No. 00 / 63261.

[0059] Certain types of diesters are derived from the esterification of aliphatic or aromatic diols, such as those described in International Publication No. 2010 / 078494 and U.S. Patent No. 7,388,061.

[0060] In some embodiments, the internal donor is selected from 1,3-diethers such as those described in European Patent No. 361493, European Patent No. 728769, and International Publication No. 02 / 100904.

[0061] Certain mixtures of internal donors, particularly mixtures of aliphatic or aromatic mono or dicarboxylic acid esters and 1,3-diethers disclosed in International Publication No. 07 / 57160 and International Publication No. 2011 / 061134, can be used as internal donors.

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

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

[0064] A preferred method for producing the solid catalyst component (1) is described in European Patent No. 395083A2.

[0065] Methods for producing catalyst components by general means are described, for example, in U.S. Patent No. 4,399,054, U.S. Patent No. 4,469,648, International Publication No. 98 / 44009A1, and European Patent No. 395083A2.

[0066] In some embodiments, the catalyst system includes an Al-containing co-catalyst (2) selected from Al-trialkyl, preferably 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 the embodiment, the catalyst system includes a further electron-donating compound (3) (external electron donor) selected from silicon compounds, ethers, esters, amines, heterocyclic compounds, particularly 2,2,6,6-tetramethylpiperidine, and ketones.

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

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

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

[0071] Phase polymerization can be carried out in a fluidized bed reactor, a stirred fixed-bed reactor, or a multi-zone circulating reactor, as described in European Patent No. 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 for the liquid phase process and 0.5 to 3.0 MPa for the gas phase process.

[0073] Polymerization processes suitable for producing heterogeneous polymer composition (A) are described in International Patent Applications No. 03 / 051984 and International Patent Applications No. 03 / 076511, which are incorporated herein by reference in their entirety.

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

[0075] In a preferred embodiment, the 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 the polyethylene composition (B), which is 100%.

[0076] Preferably, the polyethylene composition (B) has a melt flow rate (MFR) of up to 10 g / 10 min, preferably 0.00001 to 10 g / 10 min, measured in accordance with ISO 1133-2:2011 at a temperature of 190°C and a load of 2.16 kg.

[0077] The polyethylene composition (B) is preferably, (i) The polyethylene component, which has a weight-average molecular weight Mw(i) of 1000 g / mol or more as measured by gel permeation chromatography, is 25-85% by weight, preferably 60-75% by weight. (ii) A polyethylene component comprising 10 to 65% by weight, preferably 10 to 20% by weight, whose weight-average molecular weight Mw(ii) measured by gel permeation chromatography is 5,000 g / mol or less. (iii) comprising 100% by weight (including 100% by weight) of polyethylene components different from components (i) and (ii), The polyethylene composition (B) contains at least 70% by weight, preferably at least 75% by weight, and more preferably at least 80% by weight of (i) + (ii), where the amounts of (i) and (ii) are based on the total weight of the polyethylene composition (B), which is 100%.

[0078] Preferably, the polyethylene composition (B) has a Mw / Mn(B) value 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] Polyethylene components (i) to (iii) are ethylene homopolymer, CH2=CHR 1 (However, R 1The group consists of ethylene copolymers having at least one α-olefin (where is a linear or branched C2-C8 alkyl group), and mixtures thereof, which are independently selected.

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

[0081] In preferred embodiments, polyethylene components (i) to (iii) are ethylene homopolymers.

[0082] The densities of polyethylene components (i) and (ii), measured by the ASTMD792-08 method, were 0.900–0.965 g / cm³. 3 Preferably, it is 0.930 to 0.960 g / cm³. 3 It is preferable that it be so.

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

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

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

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

[0087] -MWD(ii) has a GPC peak (2) in the range of 500-1500 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 that exhibits a GPC peak (1) in the range of 10,000 g / mol to 3,000 g / mol, preferably 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 low Mw polyethylene, as reported in International Patent Application No. 01 / 021668 and International Patent Application No. 2011 / 089017 for UHMWPE component (i), and in European Patent No. 1188762 for component (ii).

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

[0092] The polyethylene component (i) is preferably produced by polymerizing the monomer using a polymerization catalyst consisting of a chromium cyclopentadienyl complex, and the η5 cyclopentadienyl portion, particularly [η 5 It is preferable that the catalyst component contains -3,4,5-trimethyl-1-(8-quinolinyl)-2-trimethylsilyl-cyclopentadienyl-chromium dichloride (CrQCp catalyst component).

[0093] The polyethylene component (ii) is preferably produced by polymerizing the relevant monomers using a polymerization catalyst that includes a chromium bis(imino)pyridine complex, 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, it may be either an organic solid or an inorganic solid, and a finely separated support is used. Examples include organic polymers such as silica gel, magnesium chloride, alumina, mesoporous material, aluminosilicate, hydrotalcite, polyethylene, polypropylene, polystyrene, and polytetrafluoroethylene, or polymers having polar functional groups such as ethylene and acrylic acid esters, acrolein, and vinyl acetate. The support material has a specific surface area of ​​10 to 1000 m². 2 It is preferable to use materials with a particle size of 0.1 to 5 ml / g, a pore volume of 0.1 to 5 ml / g, and an average particle size of 1 to 500 m.

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

[0096] Preferably, the catalyst component is brought into contact with a support in a suitable solvent to obtain a soluble reaction product, adduct, or mixture.

[0097] Suitable and preferred carrier materials, methods for manufacturing them, and their use for manufacturing supported catalysts are described in International Patent Application No. 2005 / 103096.

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

[0099] Particularly useful almoxanes are open-chain almoxane compounds of 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 R is independently selected from C1-C6 alkyl groups, preferably R 1 -R 4 I is independently selected from the group consisting of methyl, ethyl, n-butyl, and isobutyl, and I is an integer from 1 to 40, preferably from 4 to 25.

[0101] Methylaluminoxane (MAO) is preferred.

[0102] Suitable non-aluminoxane activators include alkylaluminum, alkylaluminum halides, anionic compounds of boron or aluminum, trialkylboron, and triarylboron compounds. 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 activator used is generally in the range of 0.01 to 10,000, preferably 1 to 5,000 moles per mole of catalyst.

[0104] These are each supplied to the polymerization region, supported on the carrier during the production of the unit catalyst, and / or can be pre-contacted with the unit catalyst.

[0105] In preferred embodiments, 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 catalyst centers and results in tight mixing of polyethylene components formed on each catalyst center.

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

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

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

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

[0110] Polyethylene components (i) to (iii) are produced by gas-phase polymerization, particularly in gas-phase fluidized bed reactors, solution polymerization, or suspension polymerization, particularly in loop reactors and stirred-tank reactors. Gas-phase polymerization can be carried out in condensation mode or supercondensation mode, in which a portion of the circulating gas is cooled below the dew point and recirculated to the reactor as a two-phase mixture.

[0111] Polyethylene components (i) to (iii) can also be produced in a gas-phase reactor called a multi-zone circulating reactor (MZCR) having two interconnected polymerization zones. Under rapid fluidization or transport conditions, polymer particles flow upward through a first polymerization zone called a “riser,” exit the riser, and enter a second polymerization zone called a “downcomer” where they flow in a compact form by gravity. Continuous circulation of the polymer is established between the riser and the downcomer. Generally, conditions for rapid fluidization are established in the riser by supplying a gas mixture containing the relevant monomers to the riser. The catalyst system is preferably supplied to the reactor at any point in the riser.

[0112] In a multi-zone circulating reactor, it is possible to obtain two polymerization zones with different compositions by supplying a gas / liquid stream (barrier stream) to 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 above the downcomer. The established 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 to form a polymerization cascade, as needed, for example, in the Hostalen® process. It is also possible to arrange reactors using two or more different or identical polymerization processes in parallel. Furthermore, conventional additives such as molar mass modifiers like hydrogen and antistatic agents can be used in polymerization.

[0114] Polymerization temperatures are generally in the range of -20°C to 115°C, and pressures are generally in the range of 1 to 100 bar.

[0115] In 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%. Polymerization may be carried out in a batch manner, such as in a stirred autoclave, or in a continuous manner, such as in a tubular reactor, or preferably in a loop reactor.

[0116] In one embodiment, the polyethylene composition (B) comprises at least one additional additive (iv) for the relevant art, 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 the polyethylene composition (B) in an amount of up to 6% by weight (including 6% by weight), preferably 0.1 to 1% by weight, relative to the total weight (100% by total weight) of the polyethylene composition (B) containing the additive.

[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) comprises 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 of another component (C), preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, and the other component (C) is (C1) Reinforcement agent, (C2) Preferably Polystyrene ( C2 A saturated or unsaturated styrene or α-methylstyrene block copolymer, comprising 30% by weight or less, preferably 10-30% by weight, of the above, (C3) The compatibilizer (D) is a polyolefin functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched dialkyl maleate, C1-C10 linear or branched dialkyl fumarate, itaconic anhydride, C1-C10 linear or branched itaconic acid, dialkyl esters, maleic acid, fumaric acid, itaconic acid, and mixtures thereof, (C4) Additives selected from the group consisting of pigments, dyes, spreading oils, flame retardants, UV inhibitors, UV stabilizers, lubricants, antiblocking agents, slip agents, and waxes, (C5) A combination of those, and selected from, 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, preferably all, of the following properties.

[0123] - The melt flow rate (MFR), measured in accordance with ASTM D1238 (230°C, 2.16 kg), is 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 ASTM2240 shall be 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 copolymer (C2) is prepared by ionic polymerization of the relevant monomers, and Kraton (登録商標) It is marketed under the brand name Kraton Polymers.

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

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

[0128] Modified polymers are known in the art and can be produced, for example, by a functionalization process carried out in solution, in a solid state, or preferably in a molten state, by reactive extrusion of the polymer in the presence of a graft compound and a free radical initiator. Functionalization of polypropylene and / or polyethylene with maleic anhydride is described, for example, in European Patent No. EP0572028A1.

[0129] An example of functionalized polyolefins is the commercially available product Amplify by Dow Chemical Company. (商標) TY, ExxonMobil Chemical Company's Exxelor (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 produced by tightly mixing components (A), (B), and optionally (C) using methods and apparatus known in the art, such as compounding the components at a temperature of 180° to 220°C, for example, using a mixture.

[0131] We found that by molding the polyolefin composition (I) under appropriate conditions, the tensile strength of the heterogeneous polymer composition (A) is improved by the flow-inducing enhancement effect of the polyethylene composition (B).

[0132] Therefore, this disclosure relates to the flow of the above-mentioned molten polyolefin composition (I) for 50 seconds. -1 The above is preferably 150s -1 This also relates to a manufacturing process for molded articles that includes the step of applying the above-mentioned shear rates.

[0133] In one embodiment, the flow of molten polyolefin composition (I) is 3 seconds -1 Preferably 8 seconds -1 This provides the above distortion rate.

[0134] The manufacturing process is preferably, - A step of melting the above polyolefin composition (I) at 180°C or higher, preferably in the range of 180°C to 220°C, - 50s in the flow of molten polyolefin composition (I) -1 The above is preferably 150s -1 The above steps involve applying the shear rate, - The process includes the steps of molding a molten polyolefin composition (I) and cooling it.

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

[0136] In the flow of molten polyolefin composition (I) for 50 seconds -1 It is preferable to perform the step of applying the above shear rate by injection molding, with the shear rate being 50 to 3000 s. -1 Preferably 200-2000s -1 That is the case.

[0137] In one embodiment, during the injection molding process, the above-mentioned molten polyolefin composition (I) is flowed for 3 to 200 seconds. -1 Preferably 8-120 seconds -1 Gives a distortion rate within this range.

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

[0139] Each component of the polyolefin composition (I) is supplied to an injection molding machine, or is preferably pre-mixed, more preferably densely pre-mixed in a molten state. Pre-mixing in a molten state is preferably carried out by mixing the components of the polyolefin composition (I) in a mixer of the type used in the art.

[0140] The extrusion-based process is preferably an extrusion-based 3D printing process, in which the molten polyolefin composition (I) is passed through a flow for 50 seconds. -1 The above steps for applying shear rates are performed by extrusion-based 3D printing, with shear rates ranging from 50 to 1,000 s. -1 Preferably 100-600s -1 It is preferable that this be the case.

[0141] In one preferred embodiment, the extrusion-based 3D printing process involves flowing a molten polyolefin composition (I) through a stream for 3 to 50 seconds. -1 Preferably 3 to 20 seconds -1 This includes providing a distortion rate within a certain range.

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

[0143] Each component of the polyolefin composition (I) is supplied to the 3D printer, or is preferably pre-mixed, more preferably densely pre-mixed in a molten state. Pre-mixing in a molten state is preferably carried out by mixing the components of the polyolefin composition (I) in a mixer of the type used in the art.

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

[0145] The molded articles obtained by the manufacturing process of this disclosure have significantly lower density and superior mechanical properties compared to conventional heterogeneous polymer compositions (A) reinforced solely with inorganic fillers, such as glass fibers.

[0146] In another aspect, the disclosure relates to using the polyethylene composition (B) above as a reinforcing masterbatch for the heterogeneous polymer composition (A) above.

[0147] A method for reinforcing a heterogeneous polymer composition (A) using a polyolefin composition (B) is: - A step to obtain a polyolefin composition (I) by adding 20-85% by weight, preferably 20-60% by weight, more preferably 30-50% by weight, of a polyethylene composition (B) to 15-80% by weight, preferably 40-80% by weight, more preferably 50-70% by weight of a heterogeneous polymer composition (A), wherein 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 flow of the molten polyolefin composition (I) is 50s -1 The above is preferably 150s -1 The above steps involve applying the shear rate, - The process includes the steps of molding a molten polyolefin composition (I) and cooling it.

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

[0149] The features describing the subject matter of this disclosure are not closely related to one another. Therefore, the priority of one feature does not necessarily correspond to the same priority of the remaining features of the same or different components. In this disclosure, the preferred range of features of components (A) and (B) from which the polyolefin composition (I) is obtained 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 herein.

[0150] Examples

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

[0152] Characterization methods

[0153] The following methods are used to determine the characteristics described 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 and a load of 2.16 kg, depending on the polymer. The melt flow rate (MFR(tot)) of the composition correlates with the melt flow rate of the components by the following formula.

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[0154] Density: Measured according to 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 magnetic stirrer. The temperature was raised to 135°C in 30 mins. The resulting clarified solution was kept under reflux and stirred for a further 30 mins. The solution was cooled in two stages. In the first stage, the temperature was lowered to 100°C over 10-15 mins with stirring in air. In the second stage, the flask was transferred to a thermostat-controlled water bath at 25°C over 30 mins. The temperature was lowered to 25°C without stirring for the first 20 mins, and then maintained at 25°C with stirring for the last 10 mins. The formed solid was filtered over 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 heating plate under a nitrogen stream to evaporate and remove the solvent. Next, the container was held under vacuum in an 80°C oven until it reached a certain weight. Then, the amount of polymer soluble in xylene at 25°C was calculated.

[0156] The xylene-soluble fraction (XS(tot)) of the composition correlates with the xylene-soluble fraction of the component according to the following formula.

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[0157] C2 and C4 content in polymers containing C3, C2, and C4: 13 The ¹³C NMR spectrum was acquired using a Bruker AV-600 spectrometer with a frozen probe operating at 120°C and 160.91 MHz in Fourier transform mode. 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 the sample was dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2 at 120°C, and 0.1 mg / ml of Irganox 1010 (AO1010) was added as an antioxidant. Each spectrum was acquired with a 90° pulse, with a 15-second delay between the pulse and the CPD to remove the 1H-13C coupling. Using a 9000 Hz spectral window, 512 transients were stored in 65K data points. The triad distribution was constructed using the following equation (potential overlap with peaks originating from AO1010 is considered).

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[0158] C2 and C3 polymers containing propylene and ethylene: 13 The ¹³C NMR spectrum was acquired using a Bruker AV-600 spectrometer with a frozen probe operating at 120°C and 160.91 MHz in Fourier transform mode. 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 the sample was dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2 at 120°C, and 0.1 mg / ml of 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 1H-13C coupling. Using a 9000 Hz spectral window, 512 transients were stored in 32K data points. Spectral assignment, evaluation of triad distribution, 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 (considering the possibility of overlap with peaks originating from AO1010).

number

number

[0159] Molecular weight characteristics: Average molecular weight Mw, Mn, and molecular weight distribution 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 chromatography columns were calibrated using 12 types of monodisperse polystyrene standards (Achillon Technology) with narrow molecular weight distributions, ranging from 580 g / mol to 11,600,000 g / mol. The calibration curve was adapted to polyethylene using the universal calibration method (Grubisic Z., Rempp P and Benoit H., J. Polymer Sci., 5, 753 (1967)). The Mark-Houwing parameters kPS=0.000121 dl / g and αPS=0.706 used for polystyrene, and kPE=0.000406 dl / g and αPE=0.725 used for polyethylene, are valid at TCB at 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, injection volume of 500 μL, polymer concentration of 0.01%~0.05% w / w, and 160°C.

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

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

[0162] Tensile properties at fracture: Tensile modulus and tensile strength were measured according to the ISO 527-1:2012 method using a ZWICK Z005 tensile testing machine and a makroXtens tensile meter (load cell 2.5kN). Six test specimens of the ISO 527-2:20125a geometric shape were tested at a tensile speed of 50 mm / min. Data were evaluated using TESTXPERT II V3.31 software. 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 using a Zwick 5102.100 / 00 pendulum impact tester according to the ISO 179-1:2010 method (notch impact at 23°C). Five test specimens were tested for each composition. After determining the cross-sectional area of ​​the notch, all test specimens were subjected to impact. The characteristics of the impact test were determined by the dissipated energy. The average of five measurements was taken as the impact resistance value. Shear rate: The shear rate applied to the polymer molten material during extrusion.

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[0164] raw materials:

[0165] HECO-1 - (Based on the total weight of (a) + (b) + (c)) heterogeneous polymers: (a) 56.5% by weight of propylene homopolymer with xylene-soluble fraction XS(a) at 3% by weight on a weight basis of (a) and MFR(a) of 70 g / 10 min (ISO 1133-2:2011, 230°C / 2.16 kg). (b) 23.0% by weight of ethylene-butene-1 copolymer, containing 27.4% by weight of units derived from butene-1 on the weight basis of (b). (c) 20.5% by weight of propylene-ethylene copolymer containing 41.5% by weight of units derived from ethylene on a weight basis as of (c).

[0166] HECO-1 is a reactor mixture of components (a), (b), and (c) described in Examples 1-3 of International Patent Application No. 03 / 076511A1, and has the following properties: At a temperature of -25°C, the xylene-soluble fraction XS(HECO-1) 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 according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, is 12.5 grams / 10 min. The total ethylene content based on the weight of -(a)+(b)+(c) is 25.2% by weight, and the total butene-1 content is 6.3% by weight. The numbers (a), (b), and (c) correspond to the division of the reactor, and the amounts of ethylene in component b) and component 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 manufactured as described for composition II-2 in Patent Application No. 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 manufacturing a mixed catalyst system Pore ​​volume is 1.5 ml / g, specific surface area is 400 m² 2 g -1 A mesoporous silica catalyst support (Grace's Sylopol XPO2107) was dried at 160°C for 14 hours in a Schlenk tube, and 20 mL of toluene was added, followed by high vacuum (10 -3 The suspension was sonicated for 10 minutes in toluene (bar). After adding the calculated amount of MAO (Al:Cr=300:1), the mixture was stirred for 30 minutes and sonicated for 5 minutes. After sedimentation, the MAO-treated catalyst support was washed with dry toluene, and the supernatant was removed and replaced. CrBIP was then sonicated in toluene (0.2 mg mL). -1 It was dissolved in (), pretreated with trimethylaluminum (TMA, 10 equivalents), and added by syringe. After stirring for 5 minutes, CrQCp (0.2 mg mL) was added to toluene. -1) was added, and the mixture was stirred again for 5 minutes. 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 start polymerization. Ethylene polymerization was carried out in a 2.6 L steel reactor (HITEC ZANG) equipped with a mechanical stirrer, thermostat, and software interface. Therefore, the reactor was heated to 90°C under high vacuum for 2 hours, packed 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 minutes at 40°C, an ethylene pressure of 5 bar, 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 reduced pressure at 60°C to a constant weight.

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

[0170] HECO-2 (component)- heterophase polyolefin composition containing the following (a) Propylene homopolymer 60% by weight, (b) 40% by weight of propylene-ethylene copolymer consisting of 68% by weight of ethylene on the weight basis of (b)

[0171] HECO-2 is a reactor mixture of components (a) and (b) obtained as described in Example 1-2 of International Patent Application No. 2005 / 014715, and has the following properties: The xylene-soluble fraction XS(HECO-2) is 31.2% by weight at a temperature of -25°C. 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 according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg, should be 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.

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

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

[0174] Dow Company Engage 7467 It contains 31% by weight of units derived from -butene-1, and has a density of 0.862 g / cm³. 3 It is an ethylene-butene copolymer having a melt index (ASTM D792) and (ASTM D1238, 190℃ / 2.16Kg).

[0175] Polybond 3200 -Supplied by SI Group, it is a maleic anhydride-modified polypropylene homopolymer (ASTM D1238, 190℃ / 2.16kg) with a maleic anhydride content in the range of 0.8-1.2% by weight (ASTM D6047) and an MFR of 115 g / 10 min.

[0176] Moplen HP500N- A propylene homopolymer supplied by LyondellBasell, with an MFR of 12 g / 10 min, measured according to ISO 1133 method at a temperature of 230°C and a load of 2.16 kg.

[0177] GF - Johns Manville (diemeter: 10 meters; length: 4 mm) glass fiber Thermoflow 636 EC10

[0178] Additive pack It consists of 5.0 wt% Irgafos168 (BASF) α-tris(2,4-di-tert-butylphenyl) phosphite, 7.5 wt% Irganox 1076 (BASF) α-octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, 2.5 wt% Tinuvin622 (BASF) α-oligohindered amine light stabilizer, 12.5 wt% talc, 25 wt% polydimethylsiloxane, 2.5 wt% magnesium oxide, and 45 wt% MoplenHF501N (LyondellBasell), both based on the weight of the additive pack.

[0179] Example E1 and Comparative Examples CE2-CE5

[0180] The components were melted and mixed in a DSM Xplore Compounder (5cc) at 200°C, 120 rpm, and held for 90 seconds. The mixture was then pelletized and injection molded.

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

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

Table 4

[0183] Comparative Examples CE12, CE13

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

Table 5

Table 6

[0185] Example E14 and Comparative Example CE15

[0186] The compositions of Example E8 and Comparative Example CE10 are subjected to four process cycles of granulation and injection molding in a DSM Xplore microcharger 5cc equipped with an injection molding system DSM Xplore 10cc, at 220°C, 0.8 MPa, with pressure holding for 8 seconds (mold temperature is 60°C). The values of tensile modulus and tensile strength 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 twin-screw extruder COLLIN TEACH-LINETM ZK25T equipped with a circular die (3.00 mm diameter) to obtain a filament for 3D printing. The extrusion parameters are shown in Table 6. The extruded filament was cooled with water and wound onto a printer coil. Table 6

Table 8

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

Table 9

[0190] Test specimens for tensile tests and Charpy impact tests were produced by 3D printing a filament having a patch pattern orientation parallel to the longest dimension of the specimen, which corresponds to a 0° orientation relative to the tensile / impact direction.

[0191] The values of tensile modulus and tensile strength measured for each printing / extrusion speed, and the shear and strain rates that the polymer melt undergoes 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) A heterogeneous polymer composition comprising 40 to 80% by weight, (a) Propylene homopolymer, ethylene and / or formula CH ２ =CHR １ (However, R １ A propylene polymer selected from the group consisting of a propylene copolymer with at least one α-olefin represented by (a) and mixtures thereof, wherein the copolymer contains at least 50 to 80% by weight of at least one propylene polymer, with units derived from the ethylene and / or the α-olefin in an amount of 10.0% by weight or less on a weight basis of (a), (b) Ethylene and CH ２ =CHR １ (However, R １ A copolymer of at least one α-olefin represented by (b), wherein the copolymer contains units derived from the α-olefin in an amount of 10 to 40% by weight or less on a weight basis of (b), and the copolymer essentially consists of 20 to 50% by weight of at least one copolymer. The amounts of (a) and (b) above are based on the total weight of (a) + (b), and consist of 40 to 80% by weight of the heterogeneous polymer composition. (B) A polyethylene composition comprising 20 to 60% by weight, (i) 25 to 85% by weight of polyethylene components having a weight-average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography, (ii) A polyethylene component comprising 10 to 65% by weight, wherein the weight-average molecular weight Mw(ii) measured by gel permeation chromatography is 5,000 g / mol or less. The polyethylene component is an ethylene homopolymer, The polyethylene composition (B) contains at least 70% by weight of (i) + (ii), the amounts of (i) and (ii) are based on the total weight of the polyethylene composition (B), which is 100%, and comprises 20-60% by weight of the polyethylene composition. Includes, The quantities of (A) and (B) above are based on the total weight of (A) + (B), in an injection-molded product.

2. An injection-molded article according to claim 1, comprising 50 to 70% by weight of a heterogeneous polymer composition (A) and 30 to 50% by weight of a polyethylene composition (B).

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

4. The product contains 40% by weight or less of component (C), and the said component (C) is (C1) Reinforcement agent, (C2) Saturated or unsaturated styrene or α-methylstyrene block copolymer, (C3) Polyolefins functionalized with compounds 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 itaconates, maleic acid, fumaric acid, itaconic acid, and mixtures thereof, (C4) Additives selected from the group consisting of pigments, dyes, spreading oils, flame retardants, UV inhibitors, UV stabilizers, lubricants, antiblocking agents, slip agents, and waxes, (C5) Those combinations and Selected from the group consisting of, The injection-molded article according to claim 1, wherein the amount of component (C) is based on the total weight of (A) + (B) + (C).

5. A flow of molten polyolefin composition (I) for 50 seconds －１ A process for manufacturing a molded article, comprising the step of providing the above-mentioned shear rates, The molten polyolefin composition (I) is (A) A heterogeneous polymer composition comprising 40 to 80% by weight, (a) A propylene polymer selected from the group consisting of a propylene homopolymer, a propylene copolymer of at least one α-olefin represented by the formula CH2=CHR1 (where R1 is a linear or branched C2-C8 alkyl group), and mixtures thereof, wherein the copolymer contains 50 to 80% by weight of at least one propylene polymer, with units derived from the ethylene and / or the α-olefin in an amount of 10.0% by weight or less on a weight basis of (a), (b) A copolymer of ethylene and at least one α-olefin represented by the formula CH₂=CHR₁ (where R₁ is a linear or branched C2-C8 alkyl group), wherein the copolymer essentially consists of 20-50% by weight of at least one copolymer, each copolymer containing units derived from the α-olefin in an amount of 10-40% by weight on a weight basis of (b). The amounts of (a) and (b) above are based on the total weight of (a) + (b), and consist of 40 to 80% by weight of the heterogeneous polymer composition. (B) A polyethylene composition comprising 20 to 60% by weight, (i) 25 to 85% by weight of polyethylene components having a weight-average molecular weight Mw(i) of 1,000,000 g / mol or more as measured by gel permeation chromatography, (ii) A polyethylene component comprising 10 to 65% by weight, wherein the weight-average molecular weight Mw(ii) measured by gel permeation chromatography is 5,000 g / mol or less. The polyethylene component is an ethylene homopolymer, The polyethylene composition (B) contains at least 70% by weight of (i) + (ii), the amounts of (i) and (ii) are based on the total weight of the polyethylene composition (B), which is 100%, and comprises 20-60% by weight of the polyethylene composition. Includes, A manufacturing process for molded products in which the quantities of (A) and (B) are based on the total weight of (A) + (B).

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

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