Polyolefin compositions and use thereof

Abstract

The present disclosure relates to polyolefin compositions, articles made therefrom, and their use in non-film applications. The polyolefin compositions have a high filler loading and a metallocene-catalyzed LLDPE as a toughness promoter.

Description

Technical Field

[0001] This disclosure relates to polyolefin compositions and their use in non-film applications. The polyolefin compositions feature high filler loadings and metallocene-catalyzed LLDPEs as toughening promoters. Background Technology

[0002] Polyolefin compositions have been used in a wide range of applications, including various films (e.g., cast films, shrink films, and blown films), sheets, membranes such as geomembranes, bags, pipes (e.g., heat-resistant polyethylene (PE-RT) pipes, utility pipes, and gas distribution pipes), rotational molded parts, blow-molded flexible bottles or other containers, and various other blow-molded / extruded products such as bottles, drums, cans, and other containers.

[0003] In various non-film applications such as pipes, blow-molded bottles, extruded sheets, and injection-molded products, inorganic fillers such as calcium carbonate are frequently added to polyolefin compositions to save costs and improve the properties of the polyolefin composition, such as heat resistance, rigidity, dimensional stability, and surface hardness. However, high filler loadings often sacrifice the mechanical properties of the final product, leading to product failure due to insufficient toughness. The reduction in product toughness, which limits the amount of filler used, is a problem that needs to be addressed in formulation design.

[0004] Furthermore, metallocene catalysts and linear low-density polyethylene (also known as mLLDPE) prepared using metallocene catalysts are known. See, for example, U.S. Patent Application Publication No. US2007 / 0260016 and U.S. Patent No. 6,476,171. However, the prior art does not teach the application of mLLDPE in improving the mechanical properties of resin compositions with high inorganic filler loadings.

[0005] Therefore, there is still a need for additives that can improve the mechanical properties of resin compositions with high inorganic filler loadings, such as cantilever beam impact resistance and environmental stress cracking resistance. Invention Overview

[0006] The inventors have discovered that materials selected from metallocene-catalyzed linear low-density polyethylene can be used as toughness promoters to compensate for the reduction in mechanical properties caused by inorganic fillers. In particular, the addition of said toughness promoters helps to significantly improve cantilever beam impact (Izod) performance and environmental stress cracking (ESCR) performance at room temperature and low temperature, thereby allowing for a further increase in the filler loading in the polyolefin composition, thus completing the present invention.

[0007] Therefore, one object of the present invention is to provide a polyolefin composition comprising:

[0008] 1) 0-75% by weight of base polyolefin resin;

[0009] 2) 20-50% by weight of inorganic fillers; and

[0010] 3) 5-50% by weight of a toughening accelerator selected from metallocene-catalyzed linear low-density polyethylene.

[0011] The percentages are based on the total weight of the polyolefin composition.

[0012] Another object of the present invention is to provide an article prepared from the polyolefin composition of the present invention described above.

[0013] Another object of the present invention is to provide the use of the above-described polyolefin compositions of the present invention in non-film applications such as pipes, blow-molded bottles, extruded sheets, and injection-molded articles.

[0014] These and other features and advantages of the invention will become clear from the following detailed description. Brief description of the attached figures

[0015] Figure 1 The dimensions of a notched cantilever beam test specimen according to some embodiments of this disclosure are shown. Invention Details

[0016] The embodiments described and discussed herein provide polyolefin compositions that, while having a high content of inorganic fillers such as calcium carbonate, possess good mechanical properties such as good toughness and / or resistance to environmental stress cracking. The embodiments described and discussed herein also include methods for producing polyolefin compositions and for forming articles from said polyolefin compositions.

[0017] definition

[0018] "Olefin" (also called "olefin") is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is in its polymerized form. For example, when a copolymer is claimed to have 35% to 55% by weight of "ethylene," it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and said derived units are present at 35% to 55% by weight based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. The term "different" used to refer to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of a copolymer includes terpolymers, etc. Similarly, as used herein, the definition of a polymer includes copolymers, etc. Therefore, as used herein, the terms “polyethylene,” “ethylene polymer,” “ethylene copolymer,” and “ethylene-based polymer” mean a polymer or copolymer containing at least 50 mol% ethylene units (at least 70 mol% ethylene units, at least 80 mol% ethylene units, at least 90 mol% ethylene units, at least 95 mol% ethylene units, or 100 mol% ethylene units (in the case of homopolymers)). Furthermore, the term “polyethylene composition” means a blend containing one or more polyethylene components.

[0019] As used herein, the terms “polypropylene,” “propylene polymer,” “propylene copolymer,” and “propylene-based polymer” mean a polymer or copolymer containing at least 50 mol% propylene units (at least 70 mol% propylene units, at least 80 mol% propylene units, at least 90 mol% propylene units, at least 95 mol% propylene units, or 100 mol% propylene units (in the case of homopolymers)).

[0020] As used herein, the terms “polybutene,” “butene polymer,” “butene copolymer,” and “butene-based polymer” mean a polymer or copolymer containing at least 50 mol% butene units (at least 70 mol% butene units, at least 80 mol% butene units, at least 90 mol% butene units, at least 95 mol% butene units, or 100 mol% butene units (in the case of homopolymers)).

[0021] Typically, it has a concentration of 0.86 g / cm³. 3 Ethylene polymers with a density of 0.86 or less are called ethylene elastomers or elastomers; having a density greater than 0.86 and less than 0.910 g / cm³. 3Ethylene polymers with a density of 0.910 to 0.930 g / cm³ are called ethylene plastites or ethylene plastides; 3 Ethylene polymers with a density greater than 0.930 g / cm³ are called low-density polyethylene (LDPE); 3 or greater than 0.940 g / cm 3 Ethylene polymers with a density of [specific value] are called high-density polyethylene (HDPE). For these definitions, density is determined using the methods described in the following test methods.

[0022] Overlap density range, for example, 0.890 to 0.930 g / cm³ 3 Polyethylene (which is linear and contains little or no long-chain branching) is called "linear low-density polyethylene" (LLDPE) and can be prepared using conventional Ziegler-Natta catalysts, vanadium catalysts, or metallocene catalysts in gas-phase reactors and / or slurry reactors and / or in solution reactors using any publicly available catalyst. "mLLDPE" is LLDPE made with metallocene catalysts.

[0023] "Metallocene" catalyst compounds are transition metal catalyst compounds that have one, two, or three (e.g., one or two) substituted or unsubstituted cyclopentadienyl ligands bonded to a transition metal. For example, metallocene catalysts are organometallic compounds containing at least one π-bonded cyclopentadienyl structural moiety (or a substituted cyclopentadienyl structural moiety).

[0024] The term "cyclopentadienyl," also known as "Cp," refers to a class of coordination complexes that are monovalent anions derived from cyclopentadiene hydrides and capable of forming metallocene compounds with transition metals. Cp has five π electrons in its five out-of-plane p orbitals on the carbon atom.

[0025] Melt index (MI) represents, for example, the molecular weight of a polymer, while melt index ratio (MIR) represents the molecular weight distribution. Polymers exhibiting a higher MI have shorter polymer chain lengths. As the MIR increases, the molecular weight distribution (MWD) of the polymer widens. Polymers exhibiting a narrower molecular weight distribution have a lower MIR.

[0026] "Linear polymer" refers to a polymer having few (if any) long chain branches and a branching index (g') of about 0.95 or higher, such as about 0.967 or higher, such as about 0.979 or higher, such as about 0.98 or higher. vis The branching index was determined using high-temperature gel permeation chromatography (GPC-4D) equipped with three online detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.

[0027] In this article, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. Molecular weight distribution (MWD), also known as polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0028] As used in this disclosure, the term "room temperature" means 23 ± 2 °C.

[0029] In one aspect, this disclosure provides a polyolefin composition comprising, substantially comprising, or comprising the following components:

[0030] 1) 0-75% by weight of basic polyolefin polymers;

[0031] 2) 20-50% by weight of inorganic fillers; and

[0032] 3) 5-50% by weight of a toughening accelerator selected from linear low-density polyethylene prepared using metallocene catalysts.

[0033] The percentages are based on the total weight of the polyolefin composition.

[0034] The base polyolefin polymer in the compositions disclosed herein may be any of those polyolefin polymers known in the art as suitable for a wide range of non-film applications. The selection of a suitable base polyolefin polymer based on the intended use of the polyolefin composition is within the knowledge of those skilled in the art.

[0035] In some embodiments, the base polyolefin polymer is selected from the group consisting of: high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), isotactic polypropylene, high-isotactic polypropylene, syndiotactic polypropylene, and random copolymers of propylene with ethylene and / or butene and / or hexene.

[0036] In some specific embodiments, the toughness accelerator itself is also used as the base polyolefin polymer. In such cases, the content of component 1) the base polyolefin polymer in the polyolefin composition can be as low as 0% by weight.

[0037] In some embodiments, the base polyolefin polymer is HDPE. The HDPE may have a content greater than 0.930 g / cm³. 3 The density, for example, is at least 0.935 g / cm³. 3The density is specified. Additionally, the HDPE may have a melt index (MI) of about 0.01 dg / min to about 100 dg / min, for example, about 0.05 dg / min to about 20 dg / min, or about 0.1 dg / min to about 8 dg / min, or about 0.2 dg / min to about 5 dg / min. Alternatively, the HDPE may have a melt index (MI) of about 0.01 dg / min to about 10 dg / min. Alternatively, the HDPE may have a melt index (MI) of about 1 dg / min to about 100 dg / min. Alternatively, the HDPE may have a melt index (MI) of about 0.05 to 800 dg / min and, in other embodiments, from 0.1 to 100 dg / min. In this document, the melt index (MI) is measured according to ASTM D1238 (190°C, 2.16 kg).

[0038] In some embodiments, the polyolefin compositions of this disclosure comprise 20-50% by weight of inorganic filler, based on the total weight of the polyolefin composition. The lower limit of the inorganic filler content range can be 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, and 35% by weight, and the upper limit of the inorganic filler content range can be 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50% by weight, based on the total weight of the polyolefin composition. Exemplary ranges of inorganic filler content include 20-45% by weight, 20-40% by weight, 20-35% by weight, 25-50% by weight, 25-45% by weight, 30-50% by weight, 30-45% by weight, and 30-40% by weight, based on the total weight of the polyolefin composition.

[0039] In some embodiments, the inorganic filler is selected from the group consisting of: carbonates and carbides, such as calcium carbonate (including heavy calcium carbonate and light calcium carbonate); silicates, such as clay (e.g., kaolin, porcelain clay, white clay, saponin), talc, asbestos powder, wollastonite, mica; silica; titanium dioxide; alumina; magnesium oxide; sulfates, such as barium sulfate, calcium sulfate; inorganic hollow microspheres, such as alumina, silica, zirconium oxide, magnesium oxide, glass, ceramics, carbon, sodium silicate, flue ash, borate or phosphate hollow microspheres; and metal powders, such as lead, bronze (copper-zinc alloy), zinc, copper, aluminum powder. Exemplary inorganic fillers include titanium dioxide, calcium carbonate, barium sulfate, silica, silica, carbon black, sand, glass beads, mineral aggregates, talc, clay, etc.

[0040] In some embodiments, the inorganic filler may be or include titanium dioxide, silicon carbide, silicon oxide (and other oxides of precipitated or non-precipitated silicon oxide), antimony oxide, lead carbonate, zinc white, zinc barium white, zircon, corundum, spinel, apatite, barite powder, barium sulfate, magnesite, carbon black, dolomite, calcium carbonate, talc, and hydrated or non-hydrated hydrotalcite compounds of ionic Mg, Ca, or Zn with Al, Cr, or Fe and CO3 and / or HPO4, quartz powder, magnesium carbonate hydrochloride, glass fiber, clay, alumina and other metal oxides and carbonates, metal hydroxides, chromium-containing, phosphorus-containing and brominated flame retardants, antimony trioxide, silicon oxide, silicones, and blends thereof. These fillers may particularly include any other fillers and porous fillers and supports known in the art, and in one embodiment may have a modifier pre-contacted or pre-absorbed into the filler prior to addition to the olefin polymer.

[0041] In some preferred embodiments, the inorganic filler is calcium carbonate. The calcium carbonate may be untreated or surface-treated with organic surfactants such as fatty acids, fatty acid esters, amines, lignin, etc., or inorganic substances such as silicon compounds, phosphates, etc.

[0042] Various inorganic fillers, such as calcium carbonate fillers, and their preparation and use as extenders and property modifiers in plastics processing are well known to those skilled in the art.

[0043] According to the present invention, a material selected from mLLDPE is used as a toughening promoter for the polyolefin composition. mLLDPE is a copolymer of ethylene and a small amount of higher α-olefins such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc., polymerized under high pressure or low pressure in the presence of a metallocene catalyst. Such copolymers have a substantially linear main chain with only a small amount or no long branches, but contain some short branches derived from comonomers.

[0044] In some embodiments, the mLLDPE may have a comonomer content of 1-20 mol%, for example 2-15 mol%.

[0045] The mLLDPEs that can be used in this invention can be obtained from many suppliers or can be prepared by methods that are inherently known. For example, exemplary mLLDPEs that can be used in embodiments of this invention include those sold by ExxonMobil Chemical Company of Houston, Texas, including those ENABLE. TM EXACT TM EXCEED TM ESCORENE TM EXXCO TM ESCORTM PAXON TM and OPTEMA TM Those products sold under the product name.

[0046] In some embodiments, the mLLDPE has a concentration of 0.890-0.930 g / cm³. 3 The preferred concentration is 0.900-0.928 g / cm³. 3 Or 0.900-0.925 g / cm³ 3 Or 0.900-0.920 g / cm³ 3 Density within the specified range. In this paper, density is determined according to ASTM D1505 using a density gradient column on compression-molded specimens (the compression-molded specimens have been slowly cooled to room temperature (e.g., over a period of 10 minutes or longer) and aged for a sufficient time to ensure that the density remains constant within + / - 0.001 g / cm³). 3 Within.

[0047] In some embodiments, the mLLDPE may have an M of 20,000 g / mol or greater, for example, 20,000 to 1,000,000 g / mol, 30,000 to 750,000 g / mol, 40,000 to 500,000 g / mol, 50,000 to 250,000 g / mol, 70,000 to 200,000 g / mol, or 80,000 to 150,000 g / mol. w , measured by size exclusion chromatography according to the procedure described and discussed below.

[0048] In some embodiments, the mLLDPE may have Mw / Mn of 1 to 40, 1 to 8, 1.6 to 20, 1.8 to 10, 1.8 to 4, or 1.8 to 3, as measured by size exclusion chromatography as described below in the Test Methods section.

[0049] In some embodiments, the mLLDPE may have a Tm of 30°C to 150°C, 30°C to 140°C, 50°C to 140°C, 60°C to 135°C, 80°C to 135°C, 90°C to 135°C, 100°C to 135°C, 100°C to 130°C, 100°C to 125°C, or 100°C to 120°C, as measured by the DSC method described below.

[0050] In some embodiments, the mLLDPE may have an intramolecular mass (MI) of 0.02 dg / min to 800 dg / min, or in other embodiments 0.05 dg / min to 500 dg / min, or in other embodiments 0.1 dg / min to 100 dg / min. In some embodiments, the mLLDPE may have an MI of 20 dg / min or less, 7 dg / min or less, 5 dg / min or less, 2 dg / min or less, or less than 2 dg / min.

[0051] Available mLLDPEs include those described in U.S. Patent Application Publication No. 2007 / 0260016 and U.S. Patent No. 6,476,171, such as copolymers of ethylene and at least one α-olefin having at least four carbon atoms obtained by continuous polymerization using an activated metallocene catalyst in the absence of substantially alkylaluminum-based scavengers (e.g., triethylaluminum, trimethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, etc.).

[0052] Usable mLLDPE copolymers can be prepared in solution, slurry, high pressure, or gas phase using mono- or di-cyclopentadienyl transition metal catalysts together with aluminoxane and / or non-coordinated anionic activators. The catalysts and activators can be supported or unsupported, and the cyclopentadienyl ring can be substituted or unsubstituted.

[0053] In some embodiments, the polyolefin composition of this disclosure comprises 5-50% by weight of mLLDPE as a toughening promoter, based on the total weight of the polyolefin composition. The lower limit of the mLLDPE content range can be 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10% by weight, and the upper limit of the mLLDPE content range can be 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 16, 17, 18, 19, 20, 22, 25, 28, 30, 35, 40, 45, and 50% by weight, based on the total weight of the polyolefin composition. Exemplary ranges of mLLDPE content include 5-25% by weight, 6-20% by weight, 7-20% by weight, 7-15% by weight, 8-25% by weight, 8-20% by weight, and 8-15% by weight, based on the total weight of the polyolefin composition.

[0054] additive

[0055] In addition to the inorganic fillers, the polyolefin composition may also contain other additives. These additives include antioxidants, nucleating agents, acid scavengers, stabilizers, corrosion inhibitors, plasticizers, foaming agents, cavitation agents, surfactants, auxiliaries, binders, anti-blocking agents, UV absorbers such as chain-breaking antioxidants, oils, quenchers, antistatic agents, slip agents, processing aids, UV stabilizers, neutralizers, lubricants, waxes, masterbatches, pigments, dyes, and curing agents such as peroxides. In one or more embodiments, each additive may be present individually in amounts ranging from 0.01% to 50% by weight in one embodiment, from 0.01% to 10% by weight in other embodiments, and from 0.1% to 6% by weight in other embodiments, based on the weight of the composition. In one or more embodiments, industrially common dyes and other colorants may be present in amounts ranging from 0.01% to 10% by weight in one embodiment and from 0.1% to 6% by weight in other embodiments, based on the weight of the composition.

[0056] Specifically, antioxidants and stabilizers such as organophosphites, hindered amines, and phenolic antioxidants may be present in the polyolefin composition in one embodiment from 0.001% to 2% by weight, in other embodiments from 0.01% to 0.8% by weight, and in yet another embodiment from 0.02% to 0.5% by weight. Non-limiting examples of suitable organophosphites are tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS168) and pentaerythritol diphosphite (ULTRANOX 626). Non-limiting examples of hindered amines include poly[2-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine-4-(1-amino-1,1,3,3-tetramethylbutane)triazine] (CHIMASORB 944) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TINUVIN 770). Non-limiting examples of phenolic antioxidants (e.g., sterically hindered phenols) include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANOX-1076); pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANOX1010); and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate) (IRGANOX 3114); fluoropolymers, fluoroelastomers, and mixtures thereof (e.g., mixtures of polyethylene glycol and one or more fluoroelastomers) (DYNAMAR) TMFX5920A); their derivatives; or any combination thereof. In one or more embodiments, the polyolefin composition contains an additive in a concentration of about 0.001% by weight to about 2% by weight, based on the weight of the polyolefin composition.

[0057] Metal salts of fatty acids may also be present in the polyolefin composition. The amount of such salt present in one embodiment may be from 0.001% to 1% by weight of the composition and in another embodiment from 0.01% to 0.8% by weight. Examples of fatty acids include lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid, any monocarboxylic acid aliphatic saturated or unsaturated acids having a chain length of 7 to 22 carbon atoms, their esters, their salts, or any combination thereof. Suitable metals include Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, etc. In some examples, the metal salts of fatty acids are magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.

[0058] In one or more embodiments, the lubricating additive may be present in the polyolefin composition. In some examples, the lubricating additive is present at 0.001 wt% to 1 wt% (10 ppm to 10,000 ppm), 0.01 wt% to 0.5 wt% (100 ppm to 5,000 ppm), or 0.1 wt% to 0.3 wt% (1,000 ppm to 3,000 ppm) based on the weight of the composition. Desired lubricating additives may be or include saturated fatty acid amides (e.g., palmitamide, stearamide, arachidamide, behenamide, stearylstearamide, palmityl palmitamide, and stearyl arachidamide); saturated ethylene bisamides (e.g., stearamide-ethyl-stearamide, stearamide-ethyl-palmitamide, and palmamide-ethyl-stearamide); unsaturated fatty acid amides (e.g., oleamide, erucamide, and linoleamide); unsaturated ethylene-bisamides (e.g., ethylene-bisstearamide, ethylene-bisoleamide, stearyl-erucamide, erucamide-ethyl-erucamide, oleamide-ethyl-oleamide). Erucamide-ethyl-oleamide, oleamide-ethyl-erucamide, stearamide-ethyl-erucamide, erucamide-ethyl-palmitamide, and palmamide-ethyl-oleamide); glycols; polyether polyols (e.g., Carbowax); aliphatic hydrocarbon acids (e.g., adipic acid and sebacic acid); aromatic or aliphatic hydrocarbon esters (e.g., glyceryl monostearate and pentaerythritol monooleate); styrene-α-methylstyrene; fluoropolymers (e.g., polytetrafluoroethylene, fluorinated oils, and fluorinated waxes); silicone compounds (e.g., silanes and silicone polymers, including silicone oils, modified silicones, and cured silicones); sodium alkyl sulfates, alkyl phosphates; and mixtures thereof. An exemplary slip additive is an unsaturated fatty acid amide, which can be obtained from Crompton (KEKAMIDE). TM Lubricating additives), Croda Universal (CRODAMIDE) TM (lubricating additives) and Akzo Nobel Amides Co. Ltd. (ARMOSLIP) TM Lubricating additives are commercially available. In particular, lubricating additives include unsaturated fatty acid amides having the following chemical structures:

[0059] CH3(CH2)7CH=CH(CH2) x CONH2,

[0060] Where x is 5 to 15. Exemplary variants include: 1) erucamide, where x is 11, also known as cis-13-docosahexaenoamide (commercially available as ARMOSLIP E); 2) oleamide, where x is 8; and 3) oleamide, where x is 7, also known as N-9-octadecenyl-hexadecamide. In other embodiments, stearamide is also an exemplary slip additive. Other slip additives include those described in WO 2004 / 005601A1.

[0061] Other polymers

[0062] In some embodiments, the polyolefin compositions described and discussed herein may be blended with one or more other polymers, including one or more thermoplastic polymers and / or one or more elastomers.

[0063] The term "thermoplastic polymer" refers to polymers whose solid properties do not change significantly before and after heating and subsequent cooling. Thermoplastic polymers typically include polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene ethers, polyphenylene sulfides, styrene-acrylonitrile resins, styrene-maleic anhydride, polyimides, aromatic polyketides, or mixtures of two or more of these. Polyolefins include those containing one or more linear, branched, or cyclic C2-C bonds. 40 Polymers of olefins, containing one or more C3-C 40 Olefins, C3-C 20 α-olefins, C3-C 10 Polymers of ethylene copolymerized with α-olefins. A particular example is polybutene. In some examples, the polyolefin is polypropylene. Exemplary polyolefins include those containing ethylene (including those with C3-C4 bonds). 40 Olefins, C3-C 20 Polymers of ethylene (copolymers of α-olefins, propylene, butene, hexene and / or octene).

[0064] The term "elastomer" refers to all natural and synthetic rubbers, including those defined in ASTM D1566. Examples of elastomers include ethylene propylene rubber, ethylene propylene diene monomer rubber, styrene block copolymer rubbers (including SEBS, SI, SIS, SB, SBS, SIBS, etc., where S = styrene, EB = random ethylene + butene, I = isoprene, B = butadiene), butyl rubber, halogenated butyl rubber, copolymers of isobutylene and p-alkylstyrene, halogenated copolymers of isobutylene and p-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene and acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and polybutadiene rubber (cis and trans).

[0065] In other embodiments, the blend containing the modifier may also be combined with one or more polymers that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol and / or polyisobutylene.

[0066] Tackifiers can be blended with polyolefin compositions. Examples of usable tackifiers include aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, rosin, rosin esters, wood rosin, wood rosin esters, tall oil rosin, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolic resins, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resins, hydrogenated aliphatic aromatic resins, hydrogenated terpenes, modified terpenes, and hydrogenated rosin esters. In some embodiments, the tackifier is hydrogenated. In other embodiments, the tackifier is nonpolar. (Non-polar means that the tackifier is substantially free of monomers having polar groups. In some instances, polar groups are absent; however, if polar groups are present, they are present in amounts of less than 5 wt%, less than 2 wt%, less than 0.5 wt%, or as little as about 1 ppm, based on the weight of the tackifier.) In some embodiments, the tackifier has a softening point of 80°C to 140°C or 100°C to 130°C (ring and ball method, measured by ASTM E-28). If present, the tackifier is typically present in amounts of 1 wt% to 50 wt%, 10 wt% to 40 wt%, or 20 wt% to 40 wt%, based on the weight of the blend. However, in some instances, the tackifier is absent, or if present, it is present in amounts of less than 10 wt%, less than 5 wt%, or less than 1 wt%.

[0067] Blending and processing

[0068] The compositions and blends described herein can be formed using conventional equipment and methods, such as by dry mixing the individual components and subsequently melt-mixing them in a mixer, or by directly mixing the components together in a mixer, such as a Banbury mixer, Haake mixer, Brabender internal mixer, or a single-screw or twin-screw extruder, which may include compounding extruders and side-arm extruders used directly downstream of the polymerization process. Additionally, additives may be included in the blends, in one or more components of the blends, and / or in the product formed from the blends, such as the desired film. Such additives are known in the art and may include, for example, fillers, antioxidants (e.g., hindered phenols such as IRGANOX, available from BASF).TM 1010 or IRGANOX TM 1076), phosphites (e.g., IRGAFOS available from BASF) TM 168), anti-blocking additives, tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates, and hydrogenated rosin, UV stabilizers, heat stabilizers, anti-blocking agents, mold release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, fillers, talc, etc.

[0069] The polymers suitable for use can be in any physical form when used for blending with the modifier. In one embodiment, reactor pellets (defined as pellets of polymer separated from the polymerization reactor prior to any processing procedure) are used for blending with the modifier. Reactor pellets typically have an average diameter from 50 μm to 10 mm in one embodiment and from 10 μm to 5 mm in another embodiment. In other embodiments, the polymer is in granular form formed from the melt extrusion of the reactor pellets, for example, granules having an average diameter from 1 mm to 10 mm.

[0070] The components can be blended by any suitable means, and are typically blended to produce a closely mixed composition, which can be a homogeneous single-phase mixture. For example, they can be blended in a static mixer, a batch mixer, an extruder, or a combination thereof, which is sufficient to achieve adequate dispersion of the modifier in the polymer.

[0071] The blending step may include first dry blending using, for example, a tumble blender, where the polymer and modifier are initially brought into contact without close mixing, followed by melt blending in an extruder. Another method for blending components is to directly melt blend the polymer pellets and modifier in an extruder or batch mixer. A "masterbatch" method may also be included, where the final modifier concentration is achieved by combining pure polymer with an appropriate amount of modified polymer, which has previously been prepared at a higher modifier concentration. The blending step may be performed as part of a processing method for manufacturing articles, such as in an extruder on an injection molding machine, blown film production line, or fiber production line.

[0072] In one or more embodiments, the polyolefin composition and / or ethylene polymer may also be “dry-blended” with the modifier using a drum mixer, twin-cone mixer, belt mixer, or other suitable mixer. Alternatively, in other embodiments, the polyolefin composition and / or ethylene polymer and modifier are “melt-blended” in an apparatus such as an extruder (single-screw or twin-screw) or a batch mixer. In other embodiments, the polyolefin composition and / or ethylene polymer and modifier are blended by a combination of methods (e.g., drum followed by extrusion). Exemplary blending methods include the final stage of blending as part of the article manufacturing step (e.g., in an extruder used for melting and conveying the composition for molding steps such as injection molding or blow molding). This may include injecting the modifier directly into the extruder before or after the polyethylene is fully melted. Extrusion techniques for polyethylene are described in more detail, for example, in PLASTICS EXTRUSION TECHNOLOGY 26-37 (edited by Friedhelm Hensen, Hanser Publisees 1988).

[0073] In other embodiments, the polyethylene composition can be blended in solution by any suitable means, using a solvent that largely dissolves both components. Blending can occur at any temperature or pressure where the modifier and ethylene polymer are held in solution. Exemplary conditions include blending at high temperatures (e.g., 10°C or greater, or 20°C or greater, above the melting point of the ethylene polymer). Such solution blending will be particularly useful in methods where the ethylene polymer is prepared by solution processing and the modifier is added directly to the finishing train rather than together with the dried polymer in a separate blending step. Such solution blending will also be particularly useful in methods where the ethylene polymer is prepared in bulk or high-pressure processes, where both the polymer and the modifier are soluble in the monomer. When using a solution process, the modifier is added directly to the finishing train rather than together with the dried polymer in a separate blending step.

[0074] Therefore, when manufacturing articles using methods including extrusion, such as injection molding or blow molding, any means of combining polyethylene compositions to achieve a desired composition works just as well as integrally formulated pre-blended granules, since the formation methods involve remelting and mixing the raw materials; example compositions include simple blends of pure polymer granules and modifiers, simple blends of pure polymer pellets and modifiers, simple blends of pure polymer granules and pre-blended granules, and simple blends of pure polymer pellets and pre-blended granules. Here, "pre-blended granules" means granules of a polyethylene composition containing a certain concentration of modifier and ethylene polymer. However, during compression molding, almost no mixing of melt components occurs, and pre-blended granules can be used instead of simple blends of component granules (or pellets) and modifiers. Those skilled in the art will be able to determine the appropriate procedures for blending polymers to balance the need for close mixing of component components with the expectation of process economy.

[0075] In a second aspect, the present disclosure provides an article of manufacture prepared from the polyolefin composition of the present disclosure described above, and in a third aspect, the present disclosure provides the use of the polyolefin composition of the present disclosure in non-film applications.

[0076] Articles disclosed herein include, for example, transparent articles such as cooking and storage utensils, and other articles such as furniture, automotive parts, toys, sportswear, medical devices, sterilizable medical devices and sterilization containers, nonwoven fibers and fabrics such as curtains, gowns, filters, hygiene products, diapers, sheets, tubing, pipes and other articles, wherein softness, high impact strength and impact strength below freezing point are important.

[0077] Additional examples of desired articles made from polyolefin compositions include sheets, fibers, woven and nonwoven fabrics, automotive parts, furniture, sporting equipment, food storage containers, transparent and translucent articles, toys, pipes and tubes, sheets, bags, coatings, caps, closures, crates, trays, cups, non-food containers, barrels, insulators, and medical devices. Further examples include automotive parts, cable sheaths, pipes, toys, sporting equipment, medical devices, tubing, extruded pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and sports field equipment, boat and marine components, and other such articles. In particular, polyolefin compositions are suitable for automotive parts such as bumpers, grilles, trim parts, dashboards and instrument panels, exterior door and hood parts, spoilers, windshields, hubcaps, mirror covers, body panels, protective side moldings, and other interior and exterior parts associated with automobiles, trucks, boats, and other vehicles.

[0078] Polyolefin compositions can also be used to manufacture other articles and items, such as crates, containers, packaging, laboratory equipment, such as roller flasks and culture media bottles for culturing growth, office mats, instrument sample racks and sample windows; liquid storage containers, such as bags, sacs and bottles for storing blood or solutions and for IV infusions. Other usable items include medical tubing and valves for any medical device (including infusion kits, catheters and respiratory therapy), and for irradiated medical devices or food (including trays and packaging materials for stored liquids, particularly water, milk or juice), including containers for single servings and large-capacity storage containers, and delivery devices such as tubing, pipes, etc.

[0079] These articles can be manufactured from polyolefin compositions by processes such as injection molding, extrusion, thermoforming, blow molding, rotational molding (rotomolding), fiber spinning, spin bonding or meltblown bonding (e.g., for nonwoven fabrics), profile shaping, coating (threads and cables), compression molding, calendering, foaming, lamination, transfer molding, pultrusion, protrusion, draw reduction, and other commonly used processing methods, or combinations thereof, such as those known in the art and described, for example, in PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986). Thorough mixing should be performed to ensure a closely mixed, homogeneous blend is produced before conversion into the final product.

[0080] Molded and extruded products

[0081] The polyolefin compositions described and discussed herein can be used to prepare molded products in any molding method, including injection molding, gas-assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion, and profile extrusion. Injection molding methods are well known to those skilled in the art.

[0082] The polyolefin compositions described and discussed herein can be molded into articles for the desired end use by any suitable means known in the art. Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming with matching die molding, injection molding, spraying technology, profile co-extrusion, or combinations thereof are commonly used methods.

[0083] Thermoforming is a method of shaping at least one flexible plastic sheet into a desired shape. In one or more embodiments, a thermoforming process for processing polyolefin compositions is further described. First, an extruded film of the polyolefin composition (and any other layers or materials) is placed on a shuttle to hold it in place during heating. Before forming, the shuttle indexes to an oven preheating the film. Once the film is heated, the shuttle indexes back to the forming tool. The film is then evacuated onto the forming tool to hold it in place, and the forming tool is closed. The forming tool can be a "male" or "female" type tool. The tool remains closed to cool the film and then the tool is opened. The formed laminated material is then removed from the tool. Once the material sheet reaches the thermoforming temperature, typically from 140°C to 185°C or higher, thermoforming is completed by vacuum, positive air pressure, plunger-assisted vacuum forming, or combinations and variations thereof. A pre-stretched film bubble step is used, particularly for large parts, to improve material distribution. In one embodiment, a clamping frame lifts the heated laminate toward the male forming tool with the aid of a vacuum applied through a hole in the male forming tool. Once the laminate is firmly formed into the male forming tool, the thermoformed laminate is typically cooled using a blower. Plunger-assisted forming is commonly used for small, deep-drawn parts. The choice of plunger material, design, and timing can be critical for process optimization. Plungers made of insulating foam prevent premature hardening of the plastic. The plunger shape is typically similar to the mold cavity, but smaller and without part details. A rounded plunger base typically promotes uniform material distribution and uniform sidewall thickness. For semi-crystalline polymers, a fast plunger speed typically provides optimal material distribution in the part. The formed laminate is then cooled in the mold. Sufficient cooling is desired to maintain the mold temperature at 30°C to 65°C. In some instances, in one embodiment, the part is cooled at below 90°C to 100°C before discharge. The formed laminate is then trimmed to remove excess laminate.

[0084] Blow molding is another suitable molding method, which includes injection blow molding, multilayer blow molding, extrusion blow molding, and stretch blow molding, and is particularly suitable for substantially closed or hollow objects, such as gas tanks and other fluid containers. Blow molding is described in more detail, for example, in CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING (edited by Jacqueline I. Kroschwitz, John Wiley & Sons 1990).

[0085] In another embodiment of the forming and molding process, profile co-extrusion can be used. The profile co-extrusion process parameters are as described above for the blow molding process, except that the die temperature (both top and bottom zones) ranges from 150°C to 235°C, the feed block temperature ranges from 90°C to 250°C, and the water cooling tank temperature ranges from 10°C to 40°C.

[0086] In one or more embodiments of the injection molding process, the molded laminated material is placed in an injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material has a melt temperature of about 180°C to 300°C or about 200°C to 250°C and is injected into the mold at an injection rate of about 2 seconds to about 10 seconds. After injection, the material is compressed or held at a predetermined time and pressure to ensure the part is dimensionally and aesthetically correct. Typical time periods are 5 seconds to 25 seconds and pressures are 1,000 kPa to 15,000 kPa. The mold is cooled between 10°C and 70°C to cool the substrate. The temperature will depend on the desired gloss and desired appearance. Typical cooling times are 10 seconds to 30 seconds, depending in part on the thickness. Finally, the mold is opened and the molded composite article is ejected.

[0087] Similarly, molded articles can be manufactured by injecting a blend of molten polyolefin polymer into a mold that shapes and solidifies the molten polymer into an article of desired geometry and thickness. Sheets can be prepared by extruding a substantially flat profile from a die onto cooling rollers or alternatively by calendering. Sheets will generally be considered to have a thickness from 10 mil to 100 mil (254 μm to 2,540 μm), although sheets can be substantially thicker. Tubes or pipes can be obtained by profile extrusion for medical, drinking water, land drainage, and other applications. Profile extrusion methods involve extruding molten polymer through a die. The extruded tubes or pipes are then solidified into continuous extruded articles by cooling water or cooling air. The outer diameter of the tubes will generally be in the range of 0.31 cm to 2.54 cm and the wall thickness will be in the range of 254 μm to 0.5 cm. The outer diameter of the pipes will generally be in the range of 2.54 cm to 254 cm and the wall thickness will be in the range of 0.5 cm to 15 cm. In one or more instances, containers can be formed using one or more sheets prepared from polyolefin compositions. Such containers can be formed by thermoforming, solid-state compression molding, stamping, and other forming techniques. The sheets can also be formed to cover floors, walls, or other surfaces.

[0088] In embodiments of the thermoforming method, the oven temperature is between 160°C and 195°C, the time in the oven is between 10 and 20 seconds, and the die (typically the male die) temperature is between 10°C and 71°C. The final thickness of the cooled (room temperature) molded laminate is from 10 μm to 6000 μm in one embodiment, from 200 μm to 6000 μm in other embodiments, from 250 μm to 3000 μm in other embodiments, and from 500 μm to 1550 μm in other embodiments; the desired range is any combination of any upper and lower thickness limit.

[0089] In embodiments of the injection molding method, wherein a substrate material is injection molded into a tool comprising a molding laminate, the melt temperature of the substrate material is between 190°C and 255°C in one embodiment and between 210°C and 250°C in another embodiment; the filling time is 2 to 10 seconds in one embodiment and 2 to 8 seconds in another embodiment; and the tool temperature is 25°C to 65°C in one embodiment and 27°C to 60°C in another embodiment. In some instances, the substrate material is heated to a temperature sufficiently high to melt any tie-layer material or backing layer to achieve adhesion between the layers.

[0090] In other embodiments, a blow molding operation can be used to fix the polyolefin composition to a substrate material. Blow molding is particularly useful in applications such as the manufacture of closures, including fuel tanks and other fluid containers, sports equipment, outdoor furniture, and small enclosed structures.

[0091] Because it includes linear low-density polyethylene, ethylene elastomers and ethylene plasmons selected from metallocene-catalyzed materials as toughening promoters, the polyolefin compositions / articles of this disclosure exhibit improved mechanical properties compared to comparative compositions / articles that do not include such toughening promoters, particularly improved cantilever beam impact (Izod) properties at room temperature and low temperature and improved environmental stress cracking (ESCR) properties.

[0092] In some embodiments, the polyolefin compositions / articles of this disclosure show an increase of at least 10%, for example 12-100%, for example 15-90%, in Izod values ​​(including at least one of the Izod values ​​at room temperature and the Izod values ​​at low temperature) compared to a comparative composition / article that does not include the toughness promoter.

[0093] In some embodiments, the polyolefin compositions / articles of this disclosure show an ESCR value increase of at least 15%, for example, at least 20% or at least 25%, compared to a comparative composition / article that does not include the toughness accelerator. Alternatively, the polyolefin compositions / articles of this disclosure show an ESCR value increase of at least 10 hours, for example, at least 20 hours or at least 30 hours, compared to a comparative composition / article that does not include the toughness accelerator.

[0094] This disclosure may further include the following non-restrictive embodiments.

[0095] Implementation Scheme 1. A polyolefin composition comprising:

[0096] 1) 0-75% by weight of base polyolefin resin;

[0097] 2) 20-50% by weight of inorganic fillers; and

[0098] 3) 5-50% by weight of a toughening modifier, selected from metallocene-catalyzed linear low-density polyethylene.

[0099] The percentages are based on the total weight of the polyolefin composition.

[0100] Implementation Scheme 2. The polyolefin composition of Implementation Scheme 1, wherein the base polyolefin polymer is selected from the group consisting of: high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), isotactic polypropylene, high-isotactic polypropylene, syndiotactic polypropylene, and random copolymers of propylene with ethylene and / or butene and / or hexene.

[0101] Implementation Scheme 3. The polyolefin composition of Implementation Scheme 1, wherein the base polyolefin is high-density polyethylene, which preferably has a content greater than 0.930 g / cm³. 3 For example, at least 0.935 g / cm³ 3 The density, determined according to ASTM D1505; and / or the melt index (MI), of about 0.01 dg / min to about 100 dg / min or about 0.05 to 20 dg / min or 0.1 to 8 dg / min or 0.2 to 5 dg / min, measured according to ASTM D1238 at 190°C and a 2.16 kg load.

[0102] Implementation Scheme 4. The polyolefin composition of Implementation Scheme 1, comprising 25-45% by weight of inorganic filler, based on the total weight of the polyolefin composition.

[0103] Implementation Scheme 5. The polyolefin composition of Implementation Scheme 1, comprising 30-40% by weight of inorganic filler, based on the total weight of the polyolefin composition.

[0104] Implementation Scheme 6. The polyolefin composition of Implementation Scheme 1, wherein the inorganic filler is selected from the group consisting of: carbonates and carbides, such as calcium carbonate; silicates, such as clay, talc, asbestos powder, wollastonite, mica; silicon dioxide; titanium dioxide; aluminum oxide; magnesium oxide; sulfates, such as barium sulfate, calcium sulfate; inorganic hollow microspheres, such as aluminum oxide, silicon dioxide, zirconium oxide, magnesium oxide, glass, ceramics, carbon, sodium silicate, flue ash, borate or phosphate hollow microspheres; and metal powders, such as lead, bronze, zinc, copper, aluminum powders.

[0105] Implementation Scheme 7. The polyolefin composition of Implementation Scheme 6, wherein the inorganic filler is calcium carbonate, which is either untreated or surface-treated with organic surfactants such as fatty acids, fatty acid esters, amines, lignin, or inorganic substances such as silicon compounds and phosphates.

[0106] Implementation Scheme 8. The polyolefin composition of Implementation Scheme 1, comprising 6-20% by weight of metallocene-catalyzed linear low-density polyethylene, based on the total weight of the polyolefin composition.

[0107] Implementation Scheme 9. The polyolefin composition of Implementation Scheme 1, comprising 7-15% by weight of metallocene-catalyzed linear low-density polyethylene, based on the total weight of the polyolefin composition.

[0108] Implementation Scheme 10. The polyolefin composition of Implementation Scheme 1, wherein the metallocene-catalyzed linear low-density polyethylene has:

[0109] 0.890-0.930 g / cm³ 3 For example, 0.900-0.920 g / cm³ 3 The density between these values ​​was determined according to ASTM D 1505;

[0110] 20,000 g / mol or greater M w , determined by size exclusion chromatography;

[0111] Mw / Mn of at least 1 but less than 8, for example 1.5 to 7 or 1.8 to 6 or 2.0 to 5, is determined by size exclusion chromatography;

[0112] Tm at temperatures ranging from 30°C to 150°C was determined by DSC; and / or

[0113] MI from 0.02 dg / min to 800 dg / min, measured according to ASTM D1238 at 190°C and 2.16 kg load.

[0114] Implementation Scheme 11. The polyolefin composition of Implementation Scheme 1, wherein the base polyolefin resin is high-density polyethylene, and the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.025 g / cm³. 3 Preferably greater than 0.030 g / cm³ 3 More preferably greater than 0.040 g / cm³ 3 .

[0115] Implementation Scheme 12. The polyolefin composition of Implementation Scheme 1 further comprises additives selected from the group consisting of: antioxidants, nucleating agents, acid scavengers, stabilizers, corrosion inhibitors, plasticizers, foaming agents, cavitation agents, surfactants, auxiliaries, binders, anti-blocking agents, UV absorbers such as chain-breaking antioxidants, oils, quenchers, antistatic agents, slip agents, processing aids, UV stabilizers, neutralizers, lubricants, waxes, masterbatches, pigments, dyes, and curing agents such as peroxides.

[0116] Implementation Scheme 13. The polyolefin composition of Implementation Scheme 1, comprising:

[0117] 1) 50-60% by weight of high-density polyethylene, which has a density of 0.960-0.965 g / cm³. 3 The density, determined according to ASTM D1505; and the melt index (MI), from about 0.5 dg / min to about 5 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg;

[0118] 2) 30-40% by weight of heavy calcium carbonate; and

[0119] 3) 8-12 wt% metallocene-catalyzed linear low-density polyethylene with a density of 0.900-0.920 g / cm³. 3 The density between 2.0 and 5.0 was determined according to ASTM D 1505; Mw / Mn was determined by size exclusion chromatography; and MI was measured according to ASTM D1238 at 190°C and 2.16 kg load.

[0120] Implementation Scheme 14. The polyolefin composition of Implementation Scheme 13, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.025 g / cm³. 3 Preferably greater than 0.030 g / cm³ 3 More preferably greater than 0.040 g / cm³3 .

[0121] Implementation Scheme 15. The polyolefin composition of Implementation Scheme 1, comprising:

[0122] 1) Approximately 55% by weight of high-density polyethylene, which has a density of 0.960-0.965 g / cm³. 3 The density, determined according to ASTM D1505; and the melt index (MI), from about 0.5 dg / min to about 5 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg;

[0123] 2) Approximately 35% by weight of heavy calcium carbonate; and

[0124] 3) Approximately 10% by weight of metallocene-catalyzed linear low-density polyethylene, which has a density of 0.910-0.920 g / cm³. 3 The density was determined according to ASTM D 1505; the Mw / Mn ratio was 3.0 to 5.0, determined by size exclusion chromatography; and the MI was 0.1 dg / min to 2 dg / min, measured according to ASTM D1238 at 190°C and a 2.16 kg load.

[0125] Implementation Scheme 16. The polyolefin composition of Implementation Scheme 1, comprising:

[0126] 1) Approximately 55% by weight of high-density polyethylene, which has a density of 0.960-0.965 g / cm³. 3 The density, determined according to ASTM D1505; and the melt index (MI), from about 0.5 dg / min to about 5 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg;

[0127] 2) Approximately 35% by weight of heavy calcium carbonate; and

[0128] 3) Approximately 10% by weight of metallocene-catalyzed linear low-density polyethylene, which has a density of 0.895-0.905 g / cm³. 3 The density between 2.2 and 2.8 was determined according to ASTM D 1505; Mw / Mn was determined by size exclusion chromatography from 2.2 to 2.8; and MI was measured according to ASTM D1238 at 190°C and 2.16 kg load from 1.0 dg / min to 1.5 dg / min.

[0129] Implementation Scheme 17. An article prepared from the polyolefin composition described in any one of Implementation Schemes 1-16.

[0130] Implementation Scheme 18. Use of the polyolefin composition described in any one of Implementation Schemes 1-16 in non-film applications such as pipes, blow-molded bottles, extruded sheets, and injection-molded articles.

[0131] Test methods

[0132] Density was determined according to ASTM D 1505 using a density gradient column on the molded specimen (the molded specimen had been slowly cooled to room temperature (e.g., over a period of 10 minutes or longer) and aged for a sufficient time to ensure that the density remained constant at + / - 0.001 g / cm³). 3 Within.

[0133] Unless otherwise specified, the melt index (MI, also known as I2) is measured at 190°C under a load of 2.16 kg according to ASTM D1238. The unit of MI is g / 10 min or dg / min.

[0134] High load melt index (HLMI, also known as I) 21 HLMI is the melt flow rate measured according to ASTM D-1238 at 190°C under a load of 21.6 kg. The unit of HLMI is g / 10 min or dg / min.

[0135] Melt Index Ratio (MIR) is the ratio of the high-load melt index to the melt index, or I. 21 / I2.

[0136] Density is measured by a density gradient column on a compression-molded specimen (which has been cooled to room temperature according to ASTM D4703-10a, procedure C, and then conditioned for 40 hours according to ASTM D618-08 (23°C ± 2°C and 50 ± 10% relative humidity) prior to testing, as described in ASTM D1505.

[0137] Differential scanning calorimetry (DSC)

[0138] Crystallization temperature (Tc) and melting temperature (Tm) were measured using differential scanning calorimetry (DSC) with a TA Instruments DSC Discovery 2500. Typically, 6–10 mg of the molding or plasticizing polymer is sealed in an aluminum dish and loaded into the instrument at room temperature. Melting data are obtained by heating the sample at a rate of 10 °C / min to at least 30 °C above its melting temperature (typically 180 °C for polyethylene) (first heating). The sample is held at this temperature for at least 1 minute to eliminate its thermal history. Crystallization data are obtained by cooling the sample from the melt to at least 50 °C below the crystallization temperature (typically -90 °C for polyethylene) at a rate of 10 °C / min. The sample is held at this temperature for at least 1 minute and then finally heated at 10 °C / min to obtain additional melting data (second heating). The endothermic melt transition (first and second heating) and exothermic crystallization transition are analyzed to obtain the transition onset and peak temperatures. Unless otherwise stated, the reported melting temperatures are the peak melting temperatures from the second heating. For polymers exhibiting multiple peaks, the melting point (or melting temperature) is defined as the peak melting temperature from the DSC melt trace (i.e., related to the thermal response of the maximum endothermic heat within that temperature range); similarly, the crystallization temperature is defined as the peak crystallization temperature from the DSC crystallization trace (i.e., related to the thermal response of the maximum exothermic heat within that temperature range).

[0139] The area under the DSC curve is used to determine the heat of transformation (heat of fusion Hf at melting or heat of crystallization Hc at crystallization; if the Hf value from melting differs from the Hf value obtained from the heat of crystallization, the value from melting (Tm) should be used), which can be used to calculate the degree of crystallinity (also known as percentage crystallinity). The percentage crystallinity (X%) is calculated using the following formula: [Area under the curve (in J / g) / H° (in J / g)] * 100, where H° is the heat of fusion of the homopolymer of the major monomer component. These H° values ​​are obtained from the Polymer Handbook (4th edition) published by John Wiley and Sons (New York) in 1999, except that a value of 290 J / g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene.

[0140] Gel permeation chromatography

[0141] Unless otherwise indicated, the molecular weight distribution and moments (Mw, Mn, Mw / Mn, etc.), comonomer content (C2, C3, C6, etc.), and branching index (g') were determined by high-temperature gel permeation chromatography (Polymer Char GPC-IR) using an infrared detector IR5 equipped with a multi-channel bandpass filter, an 18-angle Wyatt Dwan Heleos light scattering detector, and a four-capillary viscometer with a Wheatstone bridge structure.vis Polymer separation was achieved using three Agi-lent PLgel 10 μm mixed-B LS columns. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm Teflon filter and degassed with an in-line degasser before entering the GPC instrument. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 μL. The entire system, including the transfer lines, columns, and viscometer detector, was housed in an oven maintained at 145 °C. The polymer sample was weighed and sealed in a standard vial containing 80 μL of flow marker (heptane). After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument containing 8 mL of added TCB solvent. For polypropylene samples, continuous agitation at 160 °C for approximately 2 hours was used to dissolve the polymer. The concentration (c) at each point in the chromatogram is calculated from the IR5 broadband signal intensity (I) minus the baseline using the following equation: c = βI, where β is the mass constant. The mass recovery is calculated from the ratio of the integral area within the elution volume of concentration chromatography to the injection mass (which equals the predetermined concentration multiplied by the injection loop volume). The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with column calibration (which uses a range of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole). The MW at each elution volume is calculated using the following equation:

[0142]

[0143] Variables with the subscript "PS" represent polystyrene, while those without subscripts represent the test sample. In this method, α PS =0.67 and K PS =0.000175, while as disclosed and calculated in the literature (Sun, T. et al. Macromolecules 2001, 34, 6812), α and K for other materials are 0.695 and 0.000579 for linear ethylene polymers, and 0.705 and 0.0002288 for linear propylene polymers. Unless otherwise stated, concentrations are expressed in g / cm³. 3 Units are expressed as follows: molecular weight is expressed in g / mole, and intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g. Unless otherwise specified, concentrations here are expressed in g / cm³. 3 The units are expressed as g / mole, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed as dL / g.

[0144] The comonomer composition was determined by the ratio of IR5 detector intensities corresponding to the CH2 and CH3 channels (calibrated using a series of PE and PP homopolymer / copolymer standards with predetermined nominal values ​​by NMR or FTIP). Specifically, this provides the number of methyl groups / 1000 total carbons as a function of molecular weight (CH3 / 1000TC). The short-chain branching (SCB) content per 1000TC as a function of molecular weight (SCB / 1000TC) was then calculated by applying chain-end correction to the CH3 / 1000TC function, assuming each chain is linear and capped at each end with a methyl group.

[0145] The molecular weight (M) of LS at each point in the chromatogram was determined by analyzing the output of LS using the Zimm model for static light scattering.

[0146]

[0147] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined from IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K... o These are the optical constants of the system:

[0148]

[0149] Where N A is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145 °C and λ = 665 nm is n = 1.500. For the analysis of PE polymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015.

[0150] Specific viscosity was determined using a high-temperature Polymer Char viscometer, which has four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, and the other sensor, placed between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer was calculated from their outputs. s From the equation [η] = η s / c calculates the intrinsic viscosity [η] at each point in the chromatogram, where c is the concentration and is determined by the output of the IR5 broadband channel.

[0151] The branching index (g') is calculated using the output of the following GPC-IR5-LS-VIS method. vis The average intrinsic viscosity of the sample [η]. avg Through the following calculations:

[0152]

[0153] The sum is taken from all chromatographic slices i between the integration limits. Branching index g' vis Defined as:

[0154]

[0155] Where M v The viscosity-average molecular weight is based on the molecular weight determined by LS analysis and is disclosed and calculated in the literature (Sun, T. et al. Macromolecules 2001, 34, 6812) for reference linear polymers, except that for linear ethylene polymers α = 0.695 and K = 0.000579, and for linear propylene polymers α = 0.705 and K = 0.0002288.

[0156] T. Sun, P. Brant, R.R. Chance, and W.W. Graessley (Macromolecules, 2001, Vol. 34(19), pp. 6812-6820) describe experimental and analytical details not described above, including how to calibrate the detector and how to calculate the compositional dependence of the Mark-Houwink parameter and the second virial coefficient.

[0157] Cantilever beam test (ExxonMobil test method, refer to ASTM D256)

[0158] The dimensions of the notched cantilever beam test specimen are displayed. Figure 1 middle.

[0159] Hammer weight: 2.75J

[0160] • For room temperature tests, place the notched sample into the device and release the hammer, then record the results.

[0161] • For low temperature (-20°C) tests, place the sample in a refrigerator overnight, then test it as you would for room temperature tests and record the results.

[0162] Environmental stress cracking resistance (ExxonMobil test method, refer to ASTM D-1693)

[0163] The mixed granules are pressed into sheets 1.75–2.00 mm thick at 177°C. Within 24 hours, strips measuring 38 ± 2.5 mm x 13 ± 0.8 mm are punched from the sheets using a die-cutting machine. The strips are then placed in an ASTM environment (temperature 23 ± 2°C, humidity 50 ± 10%) for at least 40 hours but no more than 96 hours, and then a 0.30–0.40 mm notch is cut into the strips.

[0164] Ten samples were placed in a 10% CO 630 solution (Igepal CO 630 is a surfactant with a density of 1.06 g / cm³) in a 50°C water bath. 3 The 10% CO 630 was prepared as follows: 100 ml of Igepal CO 630 and 900 ml of water were mixed in a 1 L container, and then the number of hours when half of the samples broke was recorded. Example

[0165] The materials listed in Table 1 below were used in the following embodiments:

[0166] Table 1. Materials used in the formulation

[0167]

[0168] In addition, commercially available 400-mesh heavy calcium carbonate filler was used.

[0169] Examples 1-2

[0170] Following the formulations listed in Tables 2 and 3 below, the components of the composition were thoroughly mixed and granulated using a Koperon ZSK26 twin-screw mixer with a screw diameter of 25.4 mm and an L / D of 52.

[0171] Use a DEMAG 150 / 500 injection molding machine with a screw diameter of 40mm and an L / D of 20 to produce injection molded specimens that meet ASTM size requirements.

[0172] Table 2. Formulation of Example 1

[0173] Test No. formula Ref 1-1 70% Paxon 60-007 + 30% CaCO3 Ref 2-1 60%Paxon60-007+10%LL1001AV+30%CaCO3 Ref 3-1 55%Paxon60-007+10%LL1001AV+35%CaCO3 Ref 4-1 50%Paxon60-007+10%LL1001AV+40%CaCO3 EM 1-1 60%Paxon60-007+10%Exceed 1012MA+30%CaCO3 EM 2-1 55%Paxon60-007+10%Exceed 1012MA+35%CaCO3 EM 3-1 50%Paxon60-007+10%Exceed 1012MA+40%CaCO3 EM 4-1 60%Paxon60-007+10%Exceed XP 8656ML+30%CaCO3 EM 5-1 55%Paxon60-007+10%Exceed XP 8656ML+35%CaCO3 EM 6-1 50%Paxon60-007+10%Exceed XP 8656ML+40%CaCO3 EM 7-1 60%Paxon60-007+10%Exceed XP 7052ML+30%CaCO3 EM 8-1 55%Paxon60-007+10%Exceed XP 7052ML+35%CaCO3 EM 9-1 50%Paxon60-007+10%Exceed XP 7052ML+40%CaCO3 EM 10-1 60%Paxon60-007+10%Exact 3132+30%CaCO3 EM 11-1 55%Paxon60-007+10%Exact 3132+35%CaCO3 EM 12-1 50%Paxon60-007+10%Exact 3132+40%CaCO3 Ref 5-1 60%Paxon60-007+10%Enable 4009MC+30%CaCO3

[0174] Table 3. Formulation of Example 2

[0175]

[0176]

[0177] The impact performance and environmental stress cracking resistance of the cantilever beam were determined according to the procedure described above, and the results are shown in Tables 4 and 5 below.

[0178] Table 4. Results of the formulation in Example 1

[0179]

[0180]

[0181] *F50 indicates the time it took for 50% of the samples in the sample group to break.

[0182] Table 5. Results of the formulation in Example 2

[0183]

[0184] Compared with typical HDPE-based formulations Reference 1-1, EM1-1 to EM12-1 using mLLDPE according to this disclosure exhibit better Izod and ESCR properties at room temperature and low temperature, indicating that mLLDPE can improve the toughness of high filler loading matrices.

[0185] Compared with references 2-1, 3-1, and 4-1 of LLDPE using Z / N catalysis, EM1-1 to EM12-1 showed advantages in Izod and ESCR performance at room temperature and low temperature, demonstrating the value of mLLDPE as a toughening promoter compared with Z / N catalyzed LLDPE.

[0186] Compared to typical HDPE-based formulations (references 1-2), EM1-2 to EM12-2 using mLLDPE according to this disclosure exhibit better Izod impact at room temperature and better Izod impact at low temperature, indicating that mLLDPE can improve the toughness of high filler loading matrices.

[0187] Compared with references 2-2, 3-2 and 4-2 of LLDPE using Z / N catalysis, EM1-2 to EM12-2 using mLLDPE according to this disclosure exhibited better Izod impact at room temperature and better Izod impact at low temperature, indicating that mLLDPE can improve the toughness of high filler loading matrices.

[0188] Unless otherwise specified, the phrase "consisting essentially of..." does not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in this specification, provided that such steps, elements, or materials do not affect the essential and novel features of this disclosure. Furthermore, this phrase does not exclude impurities and variations that typically accompany the elements and materials used.

[0189] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range beginning with any lower bound can be combined with any upper bound to describe a range not explicitly mentioned, and a range beginning with any lower bound can be combined with any other lower bound to describe a range not explicitly mentioned. Similarly, a range beginning with any upper bound can be combined with any other upper bound to describe a range not explicitly mentioned. Furthermore, every point or value within a range, even if not explicitly mentioned, can be included. Therefore, each point or value can be used as its own lower or upper bound, combined with any other point or value or any other lower or upper bound to describe a range not explicitly mentioned.

[0190] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they are not inconsistent with this document. As will be apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of this disclosure, although the form of this disclosure has been illustrated and described. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, when a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also contemplate the same composition or group of elements, wherein the composition, element, or group of elements is preceded by the transitional phrase “substantially constitutes…,” “consisting of…,” “selected from the group of…,” or “is,” and vice versa.

[0191] Although this disclosure has been described with reference to numerous embodiments and examples, those skilled in the art who have an interest in this disclosure will understand that other embodiments may be suggested without departing from the spirit and scope of this disclosure.

Claims

1. A polyolefin composition comprising: 1) 50-60% by weight of high-density polyethylene, with a density of 0.960-0.965 g / cm³. 3 The density, determined according to ASTM D 1505; and the melt index (MI) of 0.05 to 20 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg. 2) 30-40% by weight of inorganic fillers, wherein the inorganic fillers are selected from the group consisting of: carbonates and carbides; silicon dioxide; titanium dioxide; alumina; magnesium oxide; inorganic hollow microspheres; and metal powders; and 3) 8-12% by weight of metallocene-catalyzed linear low-density polyethylene, which has a density of 0.890-0.930 g / cm³. 3 The density was determined according to ASTM D 1505; and the MI was measured according to ASTM D1238 at 190°C and a load of 2.16 kg, ranging from 0.1 dg / min to 7 dg / min. The percentages are based on the total weight of the polyolefin composition.

2. The polyolefin composition of claim 1, wherein the high-density polyethylene has a melt index (MI) of 0.1 to 8 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg.

3. The polyolefin composition of claim 1, wherein the high-density polyethylene has a melt index (MI) of 0.2 to 5 dg / min, measured according to ASTM D1238 at 190°C and a load of 2.16 kg.

4. The polyolefin composition of claim 1, wherein the inorganic hollow microspheres are selected from alumina, silicon dioxide, zirconium oxide, magnesium oxide, glass, ceramics, carbon, sodium silicate, flue dust, borate and phosphate hollow microspheres.

5. The polyolefin composition of claim 1, wherein the metal powder is selected from lead, bronze, zinc, copper and aluminum powders.

6. The polyolefin composition of claim 1, wherein the inorganic filler is calcium carbonate, which is either untreated or surface-treated with a surfactant.

7. The polyolefin composition of claim 6, wherein the surfactant is an organic surfactant or an inorganic substance, wherein the organic surfactant is selected from fatty acids, fatty acid esters, amines and lignin, and wherein the inorganic substance is selected from silicon compounds and phosphates.

8. The polyolefin composition of claim 1, comprising 8-11.5% by weight of metallocene-catalyzed linear low-density polyethylene, based on the total weight of the polyolefin composition.

9. The polyolefin composition of claim 1, wherein the metallocene-catalyzed linear low-density polyethylene has: 0.900-0.920 g / cm³ 3 The density between these values ​​was determined according to ASTM D 1505; 20,000 g / mol or greater M w , determined by size exclusion chromatography; Mw / Mn of at least 1 but less than 8 was determined by size exclusion chromatography. Tm at temperatures ranging from 30°C to 150°C was determined by DSC; and / or MI from 0.1 dg / min to 5 dg / min, measured according to ASTM D1238 at 190°C and 2.16 kg load.

10. The polyolefin composition of claim 9, wherein the metallocene-catalyzed linear low-density polyethylene has a Mw / Mn ratio of 1.5 to 7, as determined by size exclusion chromatography.

11. The polyolefin composition of claim 9, wherein the metallocene-catalyzed linear low-density polyethylene has a Mw / Mn ratio of 1.8 to 6, as determined by size exclusion chromatography.

12. The polyolefin composition of claim 9, wherein the metallocene-catalyzed linear low-density polyethylene has a Mw / Mn ratio of 2.0 to 5, as determined by size exclusion chromatography.

13. The polyolefin composition of claim 1, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.025 g / cm³. 3 .

14. The polyolefin composition of claim 13, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.030 g / cm³. 3 .

15. The polyolefin composition of claim 13, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.040 g / cm³. 3 .

16. The polyolefin composition of claim 1, further comprising additives selected from the group consisting of nucleating agents, stabilizers, corrosion inhibitors, plasticizers, foaming agents, cavitation agents, surfactants, binders, antistatic agents, processing aids, masterbatches, pigments, and dyes.

17. The polyolefin composition of claim 1, further comprising additives selected from the group consisting of antioxidants, antiblocking agents, slip agents, UV stabilizers, neutralizers, and lubricants.

18. The polyolefin composition of claim 1, further comprising additives selected from the group consisting of acid scavengers, UV absorbers, quenchers, and waxes.

19. The polyolefin composition of claim 1, comprising: 1) 50-60% by weight of high-density polyethylene, with a density of 0.960-0.965 g / cm³. 3 The density was determined according to ASTM D 1505; and the melt index (MI) was measured according to ASTM D1238 at 190°C and a load of 2.16 kg. 2) 30-40% by weight of heavy calcium carbonate; and 3) 8-12% by weight of metallocene-catalyzed linear low-density polyethylene, which has a density of 0.900-0.920 g / cm³. 3 The density between 2.0 and 5.0 was determined according to ASTM D 1505; Mw / Mn was determined by size exclusion chromatography; and MI was measured according to ASTM D1238 at 190°C and 2.16 kg load.

20. The polyolefin composition of claim 19, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.025 g / cm³. 3 .

21. The polyolefin composition of claim 20, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.030 g / cm³. 3 .

22. The polyolefin composition of claim 20, wherein the density difference between the high-density polyethylene and the metallocene-catalyzed linear low-density polyethylene is greater than 0.040 g / cm³. 3 .

23. The polyolefin composition of claim 1, comprising: 1) 55% by weight of high-density polyethylene, with a content of 0.960-0.965 g / cm³. 3 The density was determined according to ASTM D 1505; and the melt index (MI) was measured according to ASTM D1238 at 190°C and a load of 2.16 kg. 2) 35% by weight of heavy calcium carbonate; and 3) 10% by weight of metallocene-catalyzed linear low-density polyethylene, which has a molecular weight ratio of 0.910-0.920 g / cm³. 3 The density was determined according to ASTM D 1505; the Mw / Mn ratio was 3.0 to 5.0, determined by size exclusion chromatography; and the MI was 0.1 dg / min to 2 dg / min, measured according to ASTM D1238 at 190°C and a 2.16 kg load.

24. The polyolefin composition of claim 1, comprising: 1) 55% by weight of high-density polyethylene, with a content of 0.960-0.965 g / cm³. 3 The density was determined according to ASTM D 1505; and the melt index (MI) was measured according to ASTM D1238 at 190°C and a load of 2.16 kg. 2) 35% by weight of heavy calcium carbonate; and 3) 10% by weight of metallocene-catalyzed linear low-density polyethylene, which has a density of 0.895-0.905 g / cm³. 3 The density was determined according to ASTM D 1505; the Mw / Mn ratio was 2.2 to 2.8, determined by size exclusion chromatography; and the MI was 1.0 dg / min to 1.5 dg / min, measured according to ASTM D1238 at 190°C and a 2.16 kg load.

25. An article prepared from the polyolefin composition according to any one of claims 1-24.

26. Use of the polyolefin composition according to any one of claims 1-24 in non-film applications.

27. The use of claim 26, wherein the non-film application is selected from tubing, blow-molded bottles, extruded sheets, or injection-molded articles.

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