polymer having at least one lower molecular weight component and at least one higher molecular weigh

专利摘要:
POLYMER COMPOSITIONS FOR BLOW MOLDING APPLICATIONS A polymer having a density of about 0.960 g/cc to about 0.965 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has an environmental stress fracture strength equal to or greater than about 150 hours when measured in accordance with ASTM D 1693 Condition B , 100% Igepal. A polymer having a density of about 0.955 g/cc to about 0.960 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has an environmental stress fracture toughness equal to or greater than about 500 hours when measured in accordance with ASTM D 1693 Condition B , 100% Igepal.
公开号:BR112013031561B1
申请号:R112013031561-0
申请日:2012-06-08
公开日:2021-05-18
发明作者:Qing Yang；Max P. Mcdaniel；William B. Beaulieu；Youlu Yu；Tony R. Crain
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present disclosure relates to polymeric compositions, more specifically to polyethylene compositions, and articles made from them. FUNDAMENTALS OF THE INVENTION
[002] Polymeric compositions, such as polyethylene compositions, are used for the production of a wide variety of articles. Often these articles are exposed to numerous stresses during their lifetime, and this exposure can result in fractures or breakages and negatively affect the usefulness of the article. The ability of the polymer composition to resist fracture or breakage is inversely proportional to the density of the polymer composition, creating a challenge for the user to balance durability (eg, resistance to fracture and breakage) and polymer density for a specific application. Thus, there is a continuing need to develop polymers which, at higher densities, exhibit a high level of resistance to the development of fractures or breaks. SUMMARY OF THE INVENTION
[003] Disclosed herein is a polymer having a density of about 0.960 g/cc to about 0.965 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has a fracture toughness under environmental stress equal to or greater than about 150 hours when measured in accordance with condition B of ASTM D 1693, 100% Igepal.
[004] Also disclosed in this document is a polymer having a density of about 0.955 g/cc to about 0.960 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has an environmental stress fracture toughness equal to or greater than about 500 hours when measured in accordance with ASTM D 1693 Condition B , 100% Igepal.
[005] Also disclosed in this document is a polymer having a density of about 0.950 g/cc to about 0.955 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has a fracture toughness under environmental stress equal to or greater than about 2000 hours when measured in accordance with ASTM D 1693 Condition B , 100% Igepal.
[006] Also disclosed in this document is a polymer having a density of about 0.950 g/cc to about 0.965 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., wherein an article formed from the polymer has a fracture toughness under environmental stress (Y), where Y > -75,078.088, 945x4+ 287,612,937,602x3 - 413,152,026,579x2 + 263,756,655,421x - 63,139,684,577 and where x is the density of the polymer.
[007] Also disclosed in this document is a polymer having at least one lower molecular weight component and at least one higher molecular weight component and comprising a copolymer of ethylene and a comonomer comprising 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene or combinations thereof; wherein the polymer comprises equal to or less than about 0.5 mol% comonomer; a lower molecular weight component present in an amount greater than about 60% by weight and less than about 100% by weight; a weight average molecular weight (Mw) of the lower molecular weight component ranging from about 50 kg/mol to about 120 kg/mol and a Mw of the higher molecular weight component ranging from about 800 kg/mol to about 2000 kg/mol; a polydispersity index of the highest molecular weight component from about 2 to about 4; and a ratio of short chain branching at a molecular weight (MW) of 1 x 106 and SCB at the polymer peak MW of more than about 3; and wherein the average short chain branching content of each 10 wt% fraction of the polymer increases with increasing molecular weight (MW) over a MW range greater than about 100 kg/mol. BRIEF DESCRIPTION OF THE FIGURES
[008] Figure 1 is a representation of catalyst structures designated MTE-1 and MTE-2.
[009] Figure 2 is a graphical representation of the molecular weight distribution profiles for the samples from Example 1.
[0010] Figure 3 is a graph of dynamic melt viscosity versus frequency for the samples from Example 1.
[0011] Figure 4 is a graph of fracture strength under environmental stress versus density for the samples in Example 1.
[0012] Figures 5-7 are graphs of the short chain branching (SCB) distribution of the samples from Example 1.
[0013] Figure 8 is a quadrant plot for the samples in Example 1. DETAILED DESCRIPTION
[0014] Polymers, polymeric compositions, polymeric articles and manufacturing methods thereof are disclosed in this document. The polymers and/or polymeric compositions of the present disclosure can comprise polyethylene or an ethylene copolymer. The polymers and/or polymeric compositions disclosed herein may comprise a mixture of polymer components and result in a polymer and/or polymeric composition that unexpectedly exhibits increased environmental stress fracture resistance (ESCR) when compared to a polymer and/or or otherwise similar polymeric composition at the same density. In the following, polymer refers to both the material collected and the product of a polymerization reaction and the polymeric composition comprising the polymer and one or more additives.
[0015] In one embodiment, a polymer of the present disclosure is produced by any olefin polymerization method, using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. Homopolymers and/or copolymers produced in the reactor can be referred to as resin and/or polymers. The various types of reactors include, but are not limited to, those that may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, autoclave, or other reactor and/or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical and/or horizontal cycles. High pressure reactors can comprise autoclave and/or tubular reactors. Reactor types can include batch and/or continuous processes. Continuous processes can use intermittent and/or continuous product discharge or transfer. Processes may also include direct partial or complete recycling of unreacted monomer, unreacted comonomer, catalyst and/or co-catalysts, diluents and/or other materials from the polymerization process.
[0016] The polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type, operated in any suitable configuration. The production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors can include either manual or automatic transfer of polymer from one reactor to a subsequent reactor or reactors for further polymerization. Alternatively, multi-stage or multi-stage polymerization can take place in a single reactor, where conditions are changed such that a different polymerization reaction takes place.
[0017] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the general process of producing the polymer of the present disclosure. Multiple reactor systems can include any combination, including but not limited to multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure with reactors cycle and/or gas. Multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and/or any combination of reactors can be employed to produce the polymer of the present disclosure.
[0018] According to an embodiment, the polymerization reactor system may comprise at least one slurry cycle reactor. These reactors are common and can comprise vertical or horizontal cycles. Monomer, diluent, catalyst system and optionally any comonomer can be fed continuously into a slurry loop reactor where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst and/or a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. Reactor effluent can be flushed through to remove liquids comprising the solid polymer diluent, monomer and/or comonomer. Several technologies can be used for this separation step, including, but not limited to, the quick pass which can include any combination of heat addition and pressure reduction; separation by cyclonic action into a cyclone or hydrocyclone; centrifugal separation; or other appropriate method of separation.
Typical slurry polymerization processes (also known as particle formation processes) are disclosed in U.S. Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, for example; each of which is incorporated in its entirety in this document for reference.
[0020] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some cycle polymerization reactions can take place under bulky conditions where no diluent is used. One example is the polymerization of propylene monomer, as disclosed in U.S. Patent No. 5,455,314, which is incorporated in its entirety herein by reference.
[0021] According to another embodiment, the polymerization reactor may comprise at least one gas-phase reactor. Such systems can employ a continuous recycle stream that contains one or more monomers cycled continuously through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be taken from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product can be withdrawn from the reactor and new or newly added monomer can be added to replace the polymerized monomer. Such gas phase reactors may comprise a process for the multi-step gas phase polymerization of olefins, in which the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones, while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Patent Nos. 4,588,790, 5,352,749, and 5,436,304, each of which are incorporated in their entirety herein by reference.
[0022] According to another embodiment, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have multiple zones where fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a reactor zone. Initiators, catalysts and/or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas streams can be mixed for polymerization. Heat and pressure can be appropriately employed to obtain optimal polymerization reaction conditions.
[0023] According to another embodiment, the polymerization reactor may comprise a solution polymerization reactor, in which the monomer is brought into contact with the catalyst composition by suitable stirring or by other means. A carrier, comprising an excess organic diluent or monomer, may be employed. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation can be employed to obtain better temperature control and keep the polymerization mixtures uniform throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[0024] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one raw material feed system, at least one feed system for the catalyst or catalyst components, and/or at least one feed system. polymer recovery. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, discharge, laboratory analysis and control of process.
[0025] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and amount of catalyst or co-catalyst, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature in accordance with the Gibbs Free Energy Equation. Typically, this includes from about 60°C to about 280°C, for example, and/or from about 70°C to about 110°C, depending on the type of polymerization reactor and/or polymerization process. .
[0026] Appropriate pressures will also vary, depending on the reactor and the polymerization process. Pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig. Pressure for gas phase polymerization is generally about 200 - 500 psig. High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region, generally taking place at higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.
[0027] The concentration of various reactants can be controlled to produce polymers with certain physical and mechanical properties. The proposed end use product that will be formed by the polymer and the method of forming that product can be varied to determine the desired properties of the end product. Mechanical properties include, but are not limited to tensile strength, flexural modulus, impact strength, creep, stress relaxation and hardness testing. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, fracture growth, short chain branching, branching of long chain and rheological measurements.
[0028] The concentrations of monomer, comonomer, hydrogen, co-catalyst, modifiers and electron donors are generally important in producing the specific properties of the polymer. Comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate toxics and/or control molecular weight. Toxic concentration can be minimized as poisons can affect reactions and/or otherwise affect polymer product properties. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
[0029] In one embodiment, a method of preparing a polymer comprises contacting an olefin and/or alpha-olefin monomer with a catalyst system under conditions suitable for forming a polymer of the type described herein. Any catalyst system compatible with and capable of producing a polymer having the characteristics disclosed herein can be employed. Typical catalyst compositions that may be employed include supported chromium catalysts, Ziegler-Natta catalysts, metallocene catalysts or combinations thereof.
[0030] In one embodiment, a catalyst composition for producing a polymer of the type disclosed herein may comprise at least two metallocene compounds; an activator support and an organoaluminium compound. The first metallocene can be used to produce the first component, and can be a firmly bridged metallocene containing a substituent that includes a terminal olefin or a non-olefin substituent. The second metallocene, which can be used to produce the second component, is generally unbridged and more responsive to chain-terminating reagents such as hydrogen than the first metallocene. In one embodiment, the first component has a greater molecular weight than the second component. Such metallocene compounds are described in more detail, for example, in US Pat. 7,589.162; 7,517,929; 7,619.047; 7,652,160 and 7,910,763, each of which is incorporated herein in its entirety by reference.
[0031] In one embodiment, the first metallocene compound has the formula:
where (X1) cyclopentadienyl, indenyl, or fluorenyl, (X2) is fluorenyl, and (X1) and (X2) are connected by a disubstituted bridging group comprising an atom bonded to both (X1) and (X2), in that the atom is carbon or silicon. A first substituent on the disubstituted bridging group is an aromatic or aliphatic group, having from 1 to about 20 carbon atoms. A second substituent of the disubstituted bridging group can be an aromatic or aliphatic group, having from 1 to about 20 carbon atoms, or the second substituent of the disubstituted bridging group is an unsaturated aliphatic group, having from 3 to about 10 atoms of carbon. R1 is H, or an aliphatic group, having from 3 to about 10 carbon atoms. R2 is H, an alkyl group having 1 to about 12 carbon atoms, or an aryl group; (X3) and (X4) are each independently 1) a halide; 2) a hydrocarbyl group having up to 20 carbon atoms, H or BH4; 3) a hydrocarbyloxide group, a hydrocarbylamino group or a trihydrocarbylsilyl group, any one of which has up to 20 carbon atoms; or 4) OBRA2 or SO3RA, where RA is an alkyl group or an aryl group, any of which has up to 12 carbon atoms; and M1 is Zr or Hf. The first substituent on the disubstituted bridging group can be a phenyl group. The second substituent of the disubstituted bridging group can be a phenyl group, an alkyl group, a butenyl group, a pentenyl group or a hexenyl group.
[0032] In one embodiment, the second metallocene compound has the formula:
wherein (X5) and (X6) are each independently a cyclopentadienyl, indenyl, substituted cyclopentadienyl or a substituted indenyl, each substituent in (X5) and (X6) is independently selected from a linear or branched alkyl group, or a linear or branched alkenyl group, in which the alkyl group or alkenyl group is substituted or unsubstituted, any substituent in (X5) and (X6) having from 1 to about 20 carbon atoms; (X7) and (X8) are, independently, 1) a halide; 2) a hydrocarbyl group having up to 20 carbon atoms, H or BH4; 3) a hydrocarbyloxide group, a hydrocarbylamino group or a trihydrocarbylsilyl group, any one of which has up to 20 carbon atoms; or 4) OBRA2 or SO3RA, where RA is an alkyl group or an aryl group, any of which has up to 12 carbon atoms; and M2 is Zr or Hf.
[0033] In one embodiment of the present disclosure, the ratio of the first metallocene compound to the second metallocene compound can be from about 1:10 to about 10:1. According to other aspects of the present disclosure, the ratio of the first metallocene compound to the second metallocene compound can be from about 1:5 to about 5:1. According to other aspects of the present disclosure, the ratio of the first metallocene compound to the second metallocene compound can be from about 1:2 to about 2:1.
[0034] In one aspect, the activating support comprises a chemically treated solid oxide. Alternatively, the activating support may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, a layered silicate mineral, a layered aluminosilicate mineral , an unlayered aluminosilicate mineral or any combination thereof.
[0035] Generally, chemically treated solid oxides exhibit enhanced acidity compared to the corresponding untreated solid oxide compound. Chemically treated solid oxide also functions as a catalyst activator compared to the corresponding untreated solid oxide. Since the chemically treated solid oxide activates the metallocene(s) in the absence of co-catalysts, it is not necessary to eliminate the co-catalysts from the catalyst composition. The activating function of the activating support is evident in the enhanced activity of the catalyst composition as a whole compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that chemically treated solid oxide can function as an activator even in the absence of an organoaluminium compound, aluminoxanes compounds, organoboron or organoborate, ionizing ionic compounds and the like.
[0036] The chemically treated solid oxide may comprise a solid oxide treated with an electron withdrawing anion. Since it is not intended to be bound by the following statement, it is believed that treatment of solid oxide with an electron withdrawing component increases or enhances the acidity of the oxide. Thus, the activating support exhibits a Lewis or Br0nsted acidity that is usually greater than the Lewis or Br0nsted acidic strength of the untreated solid oxide, or the activating support has a greater number of acidic sites than the untreated solid oxide, or both . One method to quantify the acidity of chemically treated and untreated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
[0037] The chemically treated solid oxides of this disclosure are generally formed from an inorganic solid oxide which exhibits Lewis acid or BrOnsted acid behavior and has a relatively high porosity. Solid oxide is chemically treated with an electron withdrawing component, usually an electron withdrawing anion, to form an activating support.
According to one aspect of the present disclosure, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc/g. In accordance with another aspect of the present disclosure, the solid oxide has a pore volume greater than about 0.5 cc/g. In accordance with another aspect of the present disclosure, the solid oxide has a pore volume greater than about 1.0 cc/g.
[0039] In another aspect, solid oxide has a surface area of about 100 m2/g to about 1000 m2/g. In another aspect, the solid oxide has a surface area from about 200 m 2 /g to about 800 m 2 /g. In another aspect of the present disclosure, the solid oxide has a surface area of from about 250 m2/g to about 600 m2/g.
[0040] The chemically treated solid oxide may comprise an inorganic solid oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or comprising oxygen and one or more elements selected from the lanthanide or actinide elements (See: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA , and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide may comprise oxygen and an element or elements selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
[0041] Suitable examples of solid oxide materials or compounds that can be used to form the chemically treated solid oxide include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3 , La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, including their mixed oxides and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides or any combination thereof.
[0042] The solid oxide of this disclosure encompasses oxide materials, such as alumina, "mixed oxide" compounds thereof, such as silica-alumina and combinations and mixtures thereof. Mixed oxide compounds such as silica-alumina can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator support of the present disclosure include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia and the like. The solid oxide of this disclosure also encompasses oxide materials, such as silica coated alumina, as described in U.S. Patent No. 7,884,163, the entire disclosure of which is incorporated herein by reference.
[0043] The electron withdrawing component used to treat solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide after treatment (compared to solid oxide that is not treated with at least one anion of electron withdrawal). In accordance with one aspect of the present disclosure, the electron withdrawing component is an electron withdrawing anion derived from a salt, an acid or other compound, such as a volatile organic compound, which serves as a source or precursor for this. anion. Examples of electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstate, and the like, including mixtures and combinations of these. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed in the present disclosure. It is envisioned that the electron withdrawing anion can be, or can comprise fluoride, chloride, bromide, phosphate, triflate, bisulfate or sulfate and the like, or any combination thereof, in some aspects of this disclosure. In other aspects, the electron withdrawing anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate and the like, or any combination thereof.
[0044] Thus, for example, the activating support (e.g., chemically treated solid oxide) used in catalyst compositions can be, or can comprise, fluorinated alumina, chlorinated alumina, bromide alumina, fluorinated silica-alumina, chlorinated silica-alumina , bromide silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, bromide-silica zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, coated alumina by phosphated silica and the like, or combinations thereof. In one aspect, the activator support can be, or can comprise, fluoridated alumina, sulfated alumina, fluoridated silica-alumina, sulfated silica-alumina, fluoridated silica coated alumina, sulfated silica coated alumina, phosphated silica coated alumina, and the like or any combination of these. In another aspect, the activating support comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluorinated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or alternatively comprises alumina coated with fluorinated silica.
[0045] When the electron withdrawing component comprises a salt of an electron withdrawing anion, the counterion or cation of this salt can be selected from any cation that allows the salt to revert or decompose back to the acid during calcination. Factors that determine the suitability of the specific salt to serve as a source for the electron-withdrawing anion include, but are not limited to, the solubility of the salt in the desired solvent, lack of adverse cation reactivity, ion-pairing effects. between the cation and the anion, hygroscopic properties transmitted to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the electron withdrawing anion salt include, but are not limited to, ammonium, trialkyl ammonium, tetra-alkyl ammonium, tetra-alkyl-phosphonium, H+, [H(OEt2)2]+, and the like.
[0046] Furthermore, combinations of one or more different electron-withdrawal anions, in varying proportions, can be used to adapt the specific acidity of the activating support to the desired level. Combinations of electron withdrawing components can be contacted with the oxide material simultaneously or individually, and in any order that provides the desired acidity of the chemically treated solid oxide. For example, one aspect of this disclosure is employing two or more electron withdrawing anion source compounds in two or more separate contact steps.
[0047] Thus, an example of such a process, by which a chemically treated solid oxide is prepared, is as follows: a selected solid oxide, or a combination of solid oxides, is contacted with a first anion source compound of electron withdrawal to form a first mixture; this first mixture is calcined and then contacted with a second electron withdrawing anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In this process, the first and second electron-withdrawing anion source compound can be the same or different compounds.
[0048] According to another aspect of the present disclosure, the chemically treated solid oxide comprises an inorganic solid oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which is chemically treated with an electron withdrawing component. and optionally treated with a metal source, including metal salts, metal ions or other metal-containing compounds. Non-limiting examples of metal or metal ions include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium and the like, or combinations thereof. Examples of chemically treated solid oxides that contain a metal or metal ion include, but are not limited to, zinc-impregnated chlorinated alumina, titanium-impregnated fluorinated alumina, zinc-impregnated fluorinated alumina, zinc-impregnated chlorinated silica-alumina, silica-alumina fluoridated zinc-impregnated alumina, zinc-impregnated sulfated alumina, chlorinated zinc aluminate, fluoridated zinc aluminate, sulfated zinc aluminate, silica-coated alumina treated with hexafluorotitanic acid, silica-coated alumina treated with zinc and then fluoridated, and the like, or any combination of these.
[0049] Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is brought into contact with a source of metal, usually a salt or metal-containing compound, may include, but is not limited to, gelling, co-gelling, impregnating one compound into another, and the like. If desired, the metal-containing compound is added or impregnated into the solid oxide in solution form and further converted to the supported metal after calcination. In this sense, the inorganic solid oxide may further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum and the like, or combinations of these metals. For example, zinc is often used to impregnate solid oxide because it can provide improved catalyst activity at a low cost.
[0050] The solid oxide can be treated with metal salts or compounds containing metals before, after or at the same time that the solid oxide is treated with the electron withdrawing anion. After any contact method, the contacted mixture of the solid compound, the electron withdrawing anion and the metal ion are normally calcined. Alternatively, a solid oxide material, an electron withdrawing anion source and the metal salt or metal-containing compound are contacted and calcined simultaneously.
[0051] Various processes are used to form the chemically treated solid oxide useful in the present disclosure. The chemically treated solid oxide can comprise the product of contacting one or more solid oxides with one or more electron withdrawing anion sources. It is not necessary for the solid oxide to be calcined before coming into contact with the electron withdrawing anion source. The contact product is usually calcined during or after the solid oxide is brought into contact with the electron withdrawing anion source. Solid oxide can be calcined or uncalcined. Various processes for preparing solid oxide activating supports that can be employed in this disclosure have been reported. For example, such methods are described in US Pat. 6,107.230; 6,165,929; 6,294,494; 6,300,271; 6,316,553; 6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987; 6,548,441; 6,548.442; 6,576,583; 6,613,712; 6,632,894; 6,667,274 and 6,750,302, the disclosures of which are incorporated in their entirety herein by reference.
[0052] In accordance with one aspect of the present disclosure, solid oxide material is chemically treated by contacting it with an electron withdrawing component, typically an electron withdrawing anion source. In addition, the solid oxide material optionally is chemically treated with a metal ion and then calcined to form a solid oxide containing metal or impregnated with chemically treated metal. In accordance with another aspect of the present disclosure, the solid oxide material and the electron withdrawing anion source are contacted and calcined simultaneously.
[0053] The method by which the oxide is brought into contact with the electron withdrawing component, usually a salt or an acid of an electron withdrawing anion, may include, but is not limited to, gelling, co-gelling, impregnation of one compound into another and the like. Thus, after any contact method, the contacted mixture of the solid oxide, the electron withdrawing anion and the optional metal ion are calcined.
[0054] The solid oxide activating support (i.e., chemically treated solid oxide), thus, can be produced by a process comprising: (1) contacting a solid oxide (or solid oxides) with a compound (or compounds ) from an electron withdrawing anion source to form a first mixture; and (2) calcining the first mixture to form the solid oxide activating support.
[0055] According to another aspect of the present disclosure, the solid oxide activator support (chemically treated solid oxide) is produced by a process comprising: (3) contacting a solid oxide (or solid oxides) with a first compound of source of electron withdrawing anion to form a first mixture; (4) calcining the first mixture to produce a calcined first mixture; (5) contacting the calcined first mixture with a second electron-withdrawing anion to form a second mixture; and (6) calcining the second mixture to form the solid oxide activating support.
[0056] According to another aspect of the present disclosure, the chemically treated solid oxide is produced or formed by contacting the solid oxide with the electron withdrawing anion source compound, where the solid oxide compound is calcined before, during or after contacting the electron withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds and ionizing ionic compounds.
[0057] The calcination of the treated solid oxide is generally conducted in an ambient atmosphere, usually in a dry ambient atmosphere, at a temperature of about 200°C to about 900°C and for a time of about 1 minute to about 100 hours. Calcination can be carried out at a temperature from about 300°C to about 800°C, or alternatively, at a temperature from about 400°C to about 700°C. Calcination can be carried out for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350°C to about 550°C. Any suitable ambient atmosphere can be employed during calcination. Calcination is generally conducted in an oxidizing atmosphere such as air. Alternatively, an inert atmosphere such as nitrogen or argon or a reducing atmosphere such as hydrogen or carbon monoxide can be used.
[0058] According to one aspect of the present disclosure, the solid oxide material is treated with a source of halide ion, sulfate ion or a combination of anions, optionally treated with a metal ion and then calcined to provide the oxide. chemically treated solid in the form of a particulate solid. For example, the solid oxide material can be treated with a sulphate source (referred to as "sulphating agent"), a chloride ion source (referred to as "chlorinating agent"), a fluoride ion source (referred to as "fluoridating agent"), or a combination of these, and calcined to provide the solid oxide activator. Useful acid activator supports include, but are not limited to, bromide alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, bromide silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia-silica , chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina treated with hexafluorotitanic acid, alumina coated with silica treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, acid-treated silica-alumina trifluoroacetic, boria-fluorinated alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluoride, chloride or sulfate; phosphated alumina or other aluminophosphates optionally treated with sulfate, fluoride or chloride; or some combination of the above. Furthermore, any of these activating supports can optionally be treated with a metal ion.
The chemically treated solid oxide may comprise a fluoridated solid oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting a solid oxide with a fluoridating agent. The fluoride ion can be added to the oxide, forming a slurry of the oxide in a suitable solvent such as alcohol or water, including, but not limited to, one to three carbon alcohols due to their volatility and low surface tension. Examples of suitable fluoridating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4 )2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4)2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, analogues and combinations thereof. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluoridating agent due to its ease of use and availability.
[0060] If desired, the solid oxide is treated with a fluoridating agent during the calcination step. Any fluorinating agent capable of completely coming into contact with the solid oxide during the calcination step can be used. For example, in addition to these fluoridating agents described above, volatile organic fluoridating agents can be used. Examples of volatile organic fluorinating agents useful in this aspect of the disclosure include, but are not limited to freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol and the like, and combinations thereof. Calcining temperatures generally must be high enough to decompose the compound and release the fluoride. Gaseous hydrogen fluoride (HF) or fluorine (F2) itself can also be used with solid oxide if it is fluoridated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4-) can also be used. A convenient method of bringing the solid oxide into contact with the fluoridating agent is to vaporize a fluoridating agent into a gas stream used to fluidize the solid oxide during calcination.
[0061] Similarly, in another aspect of this disclosure, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. Chlorinated solid oxide is formed by contacting a solid oxide with a chlorinating agent. Chloride ion can be added to the oxide, forming a slurry of the oxide in a suitable solvent. Solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a source of chloride and completely coming into contact with the oxide during the calcination step can be used, such as SiCl4, SiMe2Cl2, TiCl4, BCl3e similar, including their mixtures. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol and the like or any combination thereof. The gaseous hydrogen chloride or chlorine itself can also be used with the solid oxide during calcination. A convenient method of bringing the oxide into contact with the chlorinating agent is to vaporize a chlorinating agent into a gas stream used to fluidize the solid oxide during calcination.
[0062] The amount of fluoride or chloride ions present prior to calcining the solid oxide is generally from about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, eg silica-alumina , before calcination. According to another aspect of this disclosure, the amount of fluoride or chloride ions present prior to calcination of the solid oxide is from about 1 to about 25% by weight, according to another aspect of this disclosure, from about 2 to about 20% by weight. According to another aspect of this disclosure, the amount of fluoride or chloride ions present prior to calcining the solid oxide is from about 4 to about 10% by weight. Once impregnated with halide, the halide oxide can be dried by any suitable method, including but not limited to suction filtration followed by evaporation, vacuum drying, spray drying and the like, although it is also possible to start the calcination step immediately without drying the impregnated solid oxide.
[0063] The silica-alumina used to prepare treated silica-alumina typically has a pore volume greater than about 0.5 cc/g. In accordance with one aspect of the present disclosure, the pore volume is greater than about 0.8 cc/g, and in accordance with another aspect of the present disclosure, greater than about 1.0 cc/g. Furthermore, silica-alumina generally has a surface area greater than about 100 m2/g. In accordance with another aspect of this disclosure, the surface area is greater than about 250 m2/g. In yet another aspect, the surface area is greater than about 350 m2/g.
[0064] The silica-alumina used in the present disclosure typically has an alumina content of about 5 to about 95% by weight. In accordance with one aspect of this disclosure, the alumina content of silica-alumina is from about 5 to about 50%, or from about 8% to about 30% alumina by weight. In another aspect, high alumina silica-alumina compounds may be employed, in which the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or about 65 % to about 80% alumina by weight. In accordance with another aspect of this disclosure, the solid oxide component comprises alumina without silica, and, in accordance with another aspect of this disclosure, the solid oxide component comprises silica without alumina.
[0065] The sulfated solid oxide comprises sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with a metal ion, such that the calcined sulfated oxide comprises a metal. In accordance with one aspect of the present disclosure, the sulfated solid oxide comprises sulfate and alumina. In some cases, sulfated alumina is formed by a process in which the alumina is treated with a source of sulfate, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process is generally carried out by forming a slurry of alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of sulphating agent has been added. Suitable organic solvents include, but are not limited to one to three carbon alcohols due to their volatility and low surface tension.
[0066] According to one aspect of this disclosure, the amount of sulfate ions present prior to calcination is from about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. According to another aspect of this disclosure, the amount of sulfate ions present prior to calcination is from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and according to another aspect of this disclosure, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of solid oxide prior to calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method, including but not limited to suction filtration followed by evaporation, vacuum drying, spray drying and the like, although it is also possible to start the calcination step immediately. .
[0067] According to another aspect of the present disclosure, the activator support used in preparing the catalyst compositions of this disclosure comprises an ion exchangeable activator support, including, but not limited to silicate and aluminosilicate compounds or minerals, with structures in layers or without layers and their combinations. In another aspect of this disclosure, layered ion exchangeable aluminosilicates such as pillared clays are used as activating supports. When the acid activator support comprises an ion exchangeable activator support, it may optionally be treated with at least one electron withdrawing anion, such as those disclosed in this document, although normally the ion exchangeable activator support is not treated with an anion of electron withdrawal.
[0068] According to another aspect of the present disclosure, the activating support of this disclosure comprises clay minerals with exchangeable cations and layers capable of expanding. Typical clay mineral activating supports include, but are not limited to, layered ion exchangeable aluminosilicates such as pillared clays. Although the term "support" is used, it should not be interpreted as an inert component of a catalyst composition, but rather an active part of the catalyst composition, due to its intimate association with the metallocene component.
[0069] According to another aspect of this disclosure, the clay materials of this disclosure encompass materials both in their natural state and those that have been treated with various ions by wetting, ion exchange or reaction in pillars. Typically, the clay material activating support of this disclosure comprises clays that have had their ions exchanged for large cations, including polynuclear cations, of highly charged metal complex. However, the clay material activator supports of this disclosure also encompass clays that have had their ions exchanged for simple salts, including, but not limited to, Al(III), Fe(II), Fe(III) and Zn salts (II) with binders such as halide, acetate, sulfate, nitrate or nitrite.
[0070] According to another aspect of the present disclosure, the activator support comprises a pillared clay. The term "pillarized clay" is used to refer to clay materials that have had their ions exchanged for large, usually polynuclear, highly charged metal complex cations. Examples of such ions include, but are not limited to, Keggin ions which can have charges such as 7+, various polyoxometalates and other large ions. Thus, the term pillar reaction refers to a simple exchange reaction, in which the exchangeable cations of a clay material are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations are then immobilized within the clay interlayers and, when calcined, are converted to metal oxide "pillars", effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded reticular structure is maintained and the porosity is reinforced. The resulting pores can vary in shape and size depending on the reaction material in pillars and the source clay material used. Examples of reaction in pillars and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press, Inc., (1972); U.S. Patent Nos. 4,452,910; 5,376.611; and 4,060,480; which disclosures are incorporated in their entirety herein by reference.
[0071] The reaction process in pillars uses clay minerals with exchangeable cations and layers capable of expanding. Any pillared clay which can enhance the polymerization of olefins in the catalyst composition of the present disclosure can be used. Therefore, clay minerals suitable for the reaction in pillars include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and their derivatives, such as montmorillonites (bentonites), nontronites, hectorites or Laponites; halloysites; vermiculites; micas; fluoromerics; chlorites; mixed layer clays; fibrous clays, including but not limited to sepiolites, attapulgites and palygorskites; a serpentine clay; illite; laponite; saponite; and any combination of these. In one aspect, the pillared clay activator support comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[0072] Pillarized clay can be pretreated if desired. For example, a pillared bentonite is pretreated by drying at about 300°C under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this disclosure.
[0073] The activator support used to prepare the catalyst compositions of the present disclosure can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, inorganic phosphate oxides, and the like. In one aspect, typical support materials that are used include, but are not limited to silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, silica/titania co-precipitated, mixtures thereof or any combination thereof.
[0074] The manufacturing process of these activator supports may include precipitation, co-precipitation, impregnation, gelling, pore-gelling, calcination (up to 900°C), spray drying, instant drying, rotary drying and calcining, grinding, sieving and similar operations.
[0075] In one embodiment, the organoaluminium compound used with the present disclosure may have the formula:
in which (R3) is an aliphatic group, having from 2 to about 6 carbon atoms. In some cases, (R3) is ethyl, propyl, butyl, hexyl or isobutyl.
[0076] In one embodiment, catalysts are chosen from compounds such as those represented by chemical structures A and B with fluorinated alumina as the activating support, and with tri-isobutylaluminum (TIBA) as the co-catalyst.

[0077] In one embodiment, a monomer (eg, ethylene) is polymerized using the methodologies disclosed herein to produce a polymer of the type disclosed herein. The polymer can comprise a homopolymer, copolymer and/or combinations thereof. In one embodiment, the polymer is a copolymer comprising ethylene and one or more comonomers, such as, for example, alpha-olefins. Examples of suitable comonomers include, but are not limited to, unsaturated hydrocarbons having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl -1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and mixtures thereof. In one embodiment, the comonomer is 1-hexene. In one embodiment, the comonomer may be present in the polymer in an amount equal to or less than about 0.5 mol.%, alternatively less than about 0.4 mol.%, alternatively less than about 0.3 mol.% or alternatively less than about 0.2 mol.%.
[0078] The polymer may include other additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, slip agents, antiblockers, tacifiers, polymer processing aids and combinations thereof. Such additives can be used singly or in combination and can be included in the polymer before, during or after preparation of the polymer as described herein. Such additives can be added in any suitable amount to meet some user and/or process need. As will be understood by a person skilled in the art, additives can be chosen and included in amounts that meet the need of the user and/or the process, while not negatively affecting the advantageous properties of the disclosed compositions. Such additives can be added by any suitable technique, for example, during an extrusion or compounding step, such as during pelletizing or subsequent processing into an end-use article.
[0079] A polymer of the type described in this document can be of any modality. In this document, the "modality" of a polymer refers to the shape of its molecular weight distribution curve, that is, the appearance of the graph of the polymer weight fraction versus its molecular weight. Polymer weight fraction refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak may be referred to as a unimodal polymer, a polymer having a curve showing two distinct peaks may be referred to as a bimodal polymer, a polymer having a curve showing three distinct peaks may be referred to as a trimodal polymer, etc. Polymers having molecular weight distribution curves, showing more than one peak, may collectively be referred to as multimodal polymers.
[0080] A polymer of the type described in this document may have two or more components that may be distinguishable from each other, for example, based on their individual composition and/or molecular weight distribution. A molecular weight distribution curve can be prepared for each individual polymer component. For example, the molecular weight distribution curve for individual polymer components may exhibit a single peak and therefore be unimodal. The molecular weight distribution curves for the individual components can be overlaid on a common graph to form the molecular weight distribution curve for the polymer as a whole. For example, the overlapping molecular weight distribution curves for the individual components may show a single peak that is magnified compared to the curves for the individual components corresponding to polymer fractions having different but overlapping molecular weight distributions. In an alternative embodiment, until the molecular weight distribution curves overlap for the individual polymer components, the resulting profile shows n distinct peaks corresponding to n polymer components of different molecular weight distributions. Such compositions can have the modality correlated to the number of distinct peaks in the molecular weight distribution profile. For example, a bimodal polymer might show two distinct peaks, corresponding to two individual components, while a trimodal polymer composition might show three distinct peaks, corresponding to three individual polymer components.
[0081] In one aspect, the polymer comprises a first component and a second component. The first component can be of higher molecular weight relative to the second component, and the components are described below as a higher molecular weight component (HMW) and a lower molecular weight component (LMWH). In one embodiment, the LMW component is present in the polymer in an amount ranging from greater than about 60 percent by weight (% by weight) to less than about 100% by weight, based on the total weight of the polymer composition. ; alternatively greater than about 70% by weight to less than about 100% by weight; or alternatively greater than about 80% by weight to less than about 100% by weight, with the remainder being substantially comprised of the HMW component. In this document, "the remaining amount being substantially comprised of the HMW component" is defined as the amount of polymer that is remaining, since the LMW component that is accounted for is comprised of more than about 95, 96, 97, 98 , 99 or 99.5% by weight of the HMW component. For example, if the polymer comprises 80% by weight of the LMW component, then more than about 95% of the remaining 20% by weight of the polymer is the HMW component.
[0082] In one embodiment, the LMW component has a weight average molecular weight (Mw) greater than about 40 kg/mol; alternatively greater than about 50 kg/mol; alternatively greater than about 60 kg/mol; or alternatively, from about 50 kg/mol to about 120 kg/mol, while the HMW component has a Mw greater than about 800 kg/mol; alternatively greater than about 900 kg/mol; alternatively greater than about 1,000 kg/mol; or alternatively, from about 800 kg/mol to about 2000 kg/mol. Weight average molecular weight describes the molecular weight distribution of a polymer composition and is calculated according to equation 1:
where Ni is the number of molecules of molecular weight Mi.
[0083] In one embodiment, the polymer (comprising the LMW component and the HMW component) has a Mw from about 150 kg/mol to about 300 kg/mol, alternatively from about 160 kg/mol to about 300 kg/mol; or alternatively, from about 170 kg/mol to about 300 kg/mol; and a z-average molecular weight (Mz) of about 800 kg/mol or greater; alternatively, from about 800 kg/mol to about 2000 kg/mol; alternatively, from about 900 kg/mol to about 2000 kg/mol; or alternatively, from about 1000 kg/mol to about 2000 kg/mol. The z-average molecular weight is a higher order molecular weight average, which is calculated according to equation (2):
where Ni is the amount of substance of i-species, and Mi is the molecular weight of i-species.
[0084] The LMW component can be further characterized by a molecular weight distribution (MWD) greater than about 3, alternatively greater than about 3.5, alternatively greater than about 4, while the HMW component can be characterized still by a MWD of less than about 4; alternatively less than about 3; alternatively less than about 2.5. MWD is the ratio of Mw to the number average molecular weight (Mn), which is also referred to as the polydispersity index (PDI) or more simply as polydispersity. The number average molecular weight is the common average of the molecular weights of the individual polymers and can be calculated according to equation (3), where Ni is the number of molecules of the molecular weight Mi.

[0085] The polymer (comprising the LMW component and the HMW component) may have a PDI of more than about 8, alternatively greater than about 9, or alternatively greater than about 10.
[0086] The LMW component can be further characterized by an Mz/Mw ratio of from about 3 to about 5, or alternatively from about 3 to about 4, while the HMW component can be further characterized by the ratio of Mz/Mw of less than about 3; alternatively less than about 2.8; alternatively less than about 2.5. The Mz/Mw ratio is another indication of the amplitude of a polymer's MWD. The polymer (comprising the LMW component and the HMW component) may have an Mz/Mw ratio greater than about 5, alternatively greater than about 6, or alternatively greater than about 7.
[0087] In one embodiment, a polymer of the type described herein is characterized by a density of from about 0.950 g/cc to about 0.965 g/cc, alternatively from about 0.955 g/cc to about 0.965 g/cc, or alternatively from about 0.955 g/cc to about 0.962 g/cc. For example, the polymer may be a polyethylene homopolymer or copolymer, having a density greater than about 0.950 g/cc, alternatively greater than about 0.955 g/cc, or alternatively greater than about 0.960 g/cc.
[0088] In one embodiment, a polymer of the type described in this document has a melt index, MI, in the range of about 0.01 g/10 min. at about 1 g/10 min., alternatively at about 0.1 g/10 min. at about 0.8 g/10 min., alternatively at about 0.2 g/10 min. at about 0.8 g/10 min.; or alternatively about 0.2 g/10 min. at about 0.6 g/10 min. Melt Index (MI) refers to the amount of a polymer that can be forced through a 0.0825 inch diameter rheometer extrusion hole when subjected to a force of 2160 grams in ten minutes at 190°C , as determined in accordance with ASTM D 1238.
[0089] In one embodiment, a polymer of the type disclosed in this document has a shear response, or high charge melt index to melt index (HLMI/MI) in the range of about 50 to about 500 , alternatively from about 90 to about 300, or alternatively from about 100 to about 250. The HLMI represents the flow rate of a molten polymer through a 0.0825 inch diameter orifice when subjected to a force of 21,600 grams at 190°C as determined in accordance with ASTM D 1238.
[0090] The polymers of this disclosure can be further characterized by their rheological breadth. Rheological amplitude refers to the amplitude of the transition region between Newtonian and power law-type shear rate for a polymer or frequency dependence of the polymer's viscosity. Rheological amplitude is a function of the relaxation time distribution of a polymer which, in turn, is a function of the polymer's molecular structure or architecture. Assuming the Cox-Merz rule, rheological amplitude can be calculated by fitting the flow curves generated in linear viscoelastic dynamic oscillatory frequency sweep experiments with a modified Carreau-Yasuda (CY) model, which is represented by the following equation:
Where
the magnitude of the shear viscosity of the complex; ip is the zero-shear viscosity; TΠis the viscous relaxation time; a is an amplitude parameter; n is a parameter that fixes the slope of the final power law, which is fixed at 2/11 in this work; and o is an angular frequency of the oscillatory shear strain.
[0091] In order to facilitate the adjustment of the model, the constant power law is kept at a constant value. Details of the meaning and interpretation of the CY model and derived parameters can be found in: C.A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H Chiang, Polym. Eng. Sci., 32, 931 (1992); and R.B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987), each of which is incorporated in its entirety herein by reference.
[0092] In one embodiment, the polymers of this disclosure have a ratio of "eta at 0.1" (n 0.1) to "eta at 100" (n 100), (n 0.1/n 100), greater than about 20 ; alternatively greater than about 22, or alternatively greater than about 25. The ratio n0.1/n100 is indicative of the shear thinning behavior of a polymer.
[0093] In one embodiment, the polymers of this disclosure have a "CY-a" value less than about 0.30, alternatively less than about 0.25, alternatively less than about 0.2, where the viscosity Complex dynamics versus frequency sweep are fitted to the Carreau-Yasuda equation with an n value = 0.1818.
[0094] In one embodiment, the polymers of this disclosure are further characterized by quadrant plot values, where n 100 is less than about 1400 and N100 is greater than about 0.3; alternatively n100 is less than about 1400 and N100 is greater than about 0.35; alternatively n100 is less than about 1350 and N100 is greater than about 0.35; or alternatively n100 is less than about 1300 and N100 is greater than about 0.35. The quadrant plot is indicative of the processability of a blow molding polymer relative to process yield, where n100 is the shear viscosity at shear rate 100 and N100 is the slope of the logG* vs. curve. then at shear rate 100, where G* is the modulus of the complex, and o is the shear rate.
[0095] In one embodiment, the polymers of this disclosure are further characterized by a crossover modulus (CM) of about 1,000 Pascals (Pa) to about 160,000 Pa; alternatively from about 22,000 Pa to about 130,000 Pa; or alternatively, from about 29,000 Pa to about 70,000 Pa and a predicted extrudate swelling of about 25% to about 35%; alternatively from about 27% to about 33%; or alternatively, from about 28% to about 30%. Extruded swelling refers to the increase in diameter of a polymeric extrudate until it emerges from an extrusion die. The crossover modulus is determined by the graphical representation of the storage modulus and the loss modulus as a function of the shear rate. The storage modulus in viscoelastic materials measures stored energy and represents the elastic portion of the material. The loss modulus is related to the energy dissipated as heat and represents the viscous portion related to the amount of energy lost due to the viscous flow. The intersection of the storage and loss modulus is called the crossover modulus to which the extrudate swell is correlated. A correlation between crossover modulus (CM) and extrudate swell was observed and the two parameters measured during blowing from a standard 110g gallon milk bottle. The correlation is as follows: Predicted Flat Extension (LF) = 5.452+0.234CM/105 Measured Extruded Swelling = LF /(3.14*d/2)-1 where d is the die diameter and where the extrudate swell measured is the length, or flat extent, of the bottom emerging from the molded bottle divided by one-half the circumference of the matrix minus 1.
[0096] A polymer of the type disclosed in this document can be further characterized by the degree and nature of the branching present in the individual components of the polymer composition and/or in the polymer composition as a whole. Short chain branching (SCB) is known for its effects on polymer properties such as stiffness, tensile properties, heat resistance, hardness, permeation resistance, shrinkage, creep resistance, transparency, stress fracture resistance , flexibility, impact strength and solid state properties of semi-crystalline polymers such as polyethylene.
[0097] In one embodiment, the LMW component exhibits the SCB at a peak molecular weight (SCB@Mp) of about 0 to about 1 per 1000 total carbon atoms; alternatively, from about 0 to about 0.7; or alternatively, from about 0 to about 0.4. The SCB@Mp in this document is representative of the SCB content for the main body of the LMW component. Polymers of the type disclosed herein (comprising the LMW component and the HMW component) may exhibit a low to undetectable amount of SCB in the main body of the LMW component.
[0098] In one embodiment, the polymer (comprising the LMW component and the HMW component) exhibits a ratio of the SCB at a molecular weight (MW) of 106 and the SCB@Mp equal to or greater than about 3; alternatively equal to or greater than 4; or alternatively, equal to or greater than about 5. The SCB at a MW of 106 is indicative of the level of the SCB in the HMW component and the ratio between the SCB at a MW of 106 and the SCB@Mp is indicative of the effectiveness of the placement of the SCB selectively at the higher molecular weight end of the polymer.
[0099] In one embodiment, the polymers disclosed in this document exhibit unique SCB distribution characteristics in that the amount of SCB in the HMW component exceeds that found in the LMW component and, within the HMW component, the SCB level generally remains constant or increases as a function of molecular weight. As will be appreciated by one of skill in the art, SCB content as a function of molecular weight can be represented by a plurality of data points, such that the data set used to describe SCB content over a weight range molecular can be relatively large (ie, greater than about 100 data points). It is contemplated that the unique SCB distribution characteristics of a polymer of the type disclosed herein are observable over a range of molecular weights encompassed by the HMW component, notwithstanding any normal fluctuations in a specific subset of data. In one embodiment, the polymers disclosed in this document exhibit an SCB distribution characterized by an average SCB content for each 10 wt% fraction of polymer that increases with increasing polymer molecular weight at molecular weights greater than about 100 kg /mol.
[00100] The polymers disclosed in this document can be formed into various articles, including, but not limited to, bottles, drums, toys, household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes and liners. Various processes can be used to form such articles, including, but not limited to, blow molding, extrusion molding, rotational molding, thermoforming, mold molding and the like. In one embodiment, the polymers of this disclosure are manufactured into an article by a molding process such as blow molding, extrusion blow molding, injection blow molding, or stretch blow molding.
[00101] In one embodiment, a polymer of the type disclosed herein is formed into an article by extrusion blow molding (EBM). At EBM, a polymer is melted and extruded into a hollow tube (a parison). This parison is then captured, enclosing it in a chilled metal mold. Then air is blown into the parison, inflating it into the shape of the user's desired article.
[00102] In one embodiment, a polymer of the type disclosed in this document is formed into an article by injection blow molding (IBM). At IBM, a molten polymer composition is fed into a dispenser, where it is injected through nozzles into a hollow, heated preform mold. The preform mold constitutes the external shape and is fixed around a mandrel (the core shank), which constitutes the internal shape of the preform. The preform consists of a fully formed bottle/jar neck with a thick polymer tube attached, which will form the body. The preform mold opens and the core rod is rotated and fixed in the mold by hollow blow, cooled. The core rod opens and allows compressed air into the preform, which inflates it to the shape of the finished article.
[00103] In one embodiment, a polymer of the type disclosed herein is formed into an article by stretch blow molding (SBM). At SBM, the polymer is first molded into a "preform" using the injection molding process. These preforms are produced with the necks of the bottles, including fillets (the "finish") at one end. These preforms are packaged and fed later (after cooling) into a stretch blow molding machine with reheat. In the SBM process, preforms are heated above their glass transition temperature, then blown using high pressure air into the articles using metal blow molds.
[00104] In one embodiment, articles made from the polymers of this disclosure exhibit enhanced mechanical properties, such as increased environmental stress fracture resistance, when compared to an article made from a dissimilar polymer. In this document, dissimilar polymers refers to polymers having a similar density and monomer composition, but prepared using different methodology and/or different catalyst compositions. Environmental stress fractures refers to the premature initiation of fractures and embrittlement of a plastic due to the simultaneous action of stress, force, and contact with specific chemical environments. The Environmental Stress Fracture Resistance (ESCR) measures a polymer's resistance to this form of damage.
[00105] In one embodiment, a polymer resin of the type disclosed herein may have a density of about 0.950 g/ml to about 0.965 g/ml and a ratio of short chain branching to molecular weight that is characterized by the equation
where dy is the change in the amount of short chain branching and dx is the change in molecular weight, where when dy is a non-negative number and dx is greater than zero g(x) is a piecewise function such that g(x) depends on the molecular weight domain and where, when formed into an article, the resin has an environmental stress fracture toughness (ESCR) equal to or greater than about 100 hours. For example, g(x) within a first domain of MW might be a non-negative number; within a second domain of MW, g(x) can be greater than zero; and within a third domain of MW, g(x) can be a non-negative number or an increasing monotonic function, where MW increases from the first domain of MW, through the second domain of MW to the third domain of MW.
[00106] In one embodiment, a polymer of this disclosure exhibits an ESCR (Y) value, where Y > -75,078,088,945x4 + 287,612,937,602x3 - 413,152,026,579x2 + 263,756,655,421x - 63,139,684,577 and where x is the density of the polymer and the ESCR is measured conforms to ASTM D 1693 condition B, 100% Igepal, F50. Igepal refers to the active surface wetting solution used in the procedure described in condition B of ASTM D 1693.
[00107] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.950 g/cc to less than about 0.955 g/cc and an MI of about 0.2 g/10 min. at about 0.8 g/10 min., exhibits an ESCR of greater than about 1500 hours, alternatively greater than about 2000 hours, alternatively greater than about 2500 hours, as determined in accordance with Condition B of ASTM D1693, 100% Igepal, F50.
[00108] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.955 g/cc to about 0.960 g/cc and an MI of about 0.2 g/10 min. at about 0.8 g/10 min., exhibits an ESCR of greater than about 300 hours, alternatively greater than about 1000 hours, alternatively greater than about 1500 hours, as determined in accordance with condition B of ASTM D1693, 100% Igepal, F50.
[00109] In one embodiment, a polymer of the type described herein, having a density of about 0.958 g/cc to about 0.962 g/cc and an MI of about 0.2 g/10 min. at about 0.8 g/10 min., exhibits an ESCR of greater than about 100 hours, alternatively greater than about 300 hours, alternatively greater than about 700 hours, as determined in accordance with condition B of ASTM D1693, 100% Igepal, F50.
[00110] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.960 g/cc to about 0.965 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., when formed into an article, exhibits an ESCR equal to or greater than about 150 hours when measured according to ASTM D 1693, 100% Igepal, F50 condition B.
[00111] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.950 g/cc to about 0.955 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min. when formed into an article exhibits an ESCR equal to or greater than about 2000 hours when measured according to condition B of ASTM D 1693, 100% Igepal, F50.
[00112] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.955 g/cc to about 0.960 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., when formed into an article, exhibits an ESCR equal to or greater than about 500 hours when measured according to condition B of ASTM D 1693, 100% Igepal, F50.
[00113] In one embodiment, a polymer of the type disclosed herein, having a density of about 0.950 g/cc to about 0.965 g/cc and a melt index of about 0.2 g/10 min. at about 0.6 g/10 min., when formed into an article, exhibits an ESCR (Y), where Y > -75,078.088.945x4 + 287.612,937.602x3 - 413,152,026,579x2 + 263,756,655,421x - 63,139,684,577 and where x is the density of the polymer.
[00114] In one embodiment, a polymer of the type disclosed herein, having at least one minor LMW component and at least one HMW component and comprising a copolymer of ethylene and a comonomer comprising 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene or combinations thereof; and comprising equal to or less than about 0.5 mol% comonomer; and having the lower molecular weight component present in an amount greater than about 60% by weight and less than about 100% by weight; and having an Mw of the LMW component, ranging from about 50 kg/mol to about 120 kg/mol, and the Mw of the HMW component, ranging from about 800 kg/mol to about 2000 kg/mol, and having a polydispersity index of the HMW component from about 2 to about 4; and having the SCB@ MW ratio of 1 x 106 and SCB@Mp greater than 3 and with an SCB content of each fraction of 10% by weight of the polymer increasing with increasing molecular weight in a MW range greater than 100 kg /mol, when formed into an article, displays an ESCR greater than about 2000 hours. Alternatively, the ESCR is greater than about 500 hours when the comonomer is present in an amount less than about 0.3 mol.%; alternatively, the ESCR is greater than about 150 hours when the comonomer is less than about 0.2 mol.%. EXAMPLES
[00115] The subject having been described generally, the following examples are given as specific modalities of disclosure and to demonstrate their practices and advantages. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims below in any way. The following test procedures were used to evaluate the various polymers and compositions.
[00116] The high charge melt index (HLMI, g/10 min) was determined in accordance with condition E of ASTM D 1238 at 190°C with a weight of 21,600 grams.
[00117] Polymer density was determined in grams per cubic centimeter (g/cc) in a compression-molded sample, cooled to about 15°C per hour, and conditioned for about 40 hours at room temperature, in accordance with ASTM D 1505 and ASTM D 1928, procedure C.
[00118] Molecular weight and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW- columns 6E GPC (Waters, MA), operating at 145°C. The flow rate of 1,2,4-trichlorobenzene (TCB) mobile phase containing 2,6-di-t-butyl-4-methylphenol (BHT) from 0.5 g/L was defined as 1 mL/min and the concentration of polymer solutions generally remained in the range of 1.0-1.5 mg/mL, depending on the molecular weight. Sample preparation was carried out at 150°C for nominally 4 h with occasional gentle agitation before the solutions were transferred to the sample vials for injection. The integral calibration method was used to deduce molecular weights and molecular weight distributions, using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX BHB5003, as the broad standard. The comprehensive broad pattern table was pre-determined in a separate experiment with SEC-MALS.
[00119] The short chain branching (SCB) and SCB distribution through molecular weight distribution (SCBD) were determined through a GPC system detected by IR5 (IR5-GPC), in which the GPC system used was a PL220 GPC system /SEC (Polymer Labs, an Agilent company) equipped with three Styragel HMW-6E columns (Waters, MA) for polymer separation. For the GPC columns they were connected to a thermoelectric cooling (IR5) MCT IR5 detector (Polymer Char, Spain) via a hot transfer line. Chromatographic data is obtained from two output ports of the IR5 detector. First, the analog signal goes from the analog output port to a digitizer before connecting to Computer "A" for molecular weight determinations via Cirrus software (Polymer Labs, an Agilent company) and the integral calibration method using a Marlex™ BHB5003 (Chevron Phillips Chemical Company) wide MWD HDPE resin as the MW wide standard. Digital signals, on the other hand, go via a USB cable directly to Computer "B", where they are collected by LabView data collection software provided by Polymer Char. Chromatographic conditions are defined as follows: Column oven temperature: 145°C; flow rate: 1 mL/min; injection volume: 0.4 mL; polymer concentration: nominally at 2.0 mg/ml, depending on the molecular weight of the sample. The temperatures for the hot transfer and sample cell of the IR5 detector are set at 150°C, while for the IR5 detector electronics it is set at 60°C.
[00120] The short chain branching content was deduced through an internal method, using the intensity ratio between CH3 (ICH3) and CH2 (ICH2) coupled with a calibration curve. The calibration curve is a graph of the SCB content (%SCB) versus the intensity ratio between ICH3 / ICH2. To obtain a calibration curve, a polyethylene resin group (not less than 5) of the SCB level, ranging from zero to ca. 32 SCB/1,000 total carbons (SCB Standards) are used. All of these SCB Standards met SCB levels and flat SCB distribution profiles pre-determined separately by NMR and solvent-gradient fractionation coupled with NMR methods (SGF-NMR). Using the SCB calibration curves thus established, short chain branch distribution through molecular weight distribution (SCBD) profiles can be obtained for the resin fractionated by the IR5-GPC system under exactly the same chromatographic conditions as for these Standards. SCB. A relationship between the intensity ratio and elution volume can be converted to SCB distribution as a function of MWD using a predetermined SCB calibration curve (ie intensity ratio between ICH3/ICH2 vs. SCB content ) and the MW calibration curve (i.e. molecular weight vs. elution time) to convert the ICH3/ICH2 intensity ratio to the SCB content and the molecular weight, respectively.
[00121] Rheology measurements were made as follows:
[00122] Samples for measuring melt viscosity were compression molded at 182°C for a total of three minutes. The samples were allowed to melt at relatively low pressure for one minute and then subjected to high molding pressure for an additional two minutes. The molded samples were then cooled in a cold press (room temperature). 2mm x 25.4mm diameter discs were stamped out of the molded plates for rheological characterization. The fluff samples were stabilized with 0.1% by weight of BHT dispersed in acetone and vacuum dried prior to molding.
[00123] Low force oscillatory shear measurements were made on an ARES rheometer (Rheometrics Inc., now TA Instruments) or Anton Paar rheometers (Anton Paar GmbH), using parallel plate geometry. The rheometer test chamber was covered in nitrogen in order to minimize polymer degradation. Until sample loading and after oven heat equilibrium, specimens were squeezed between plates with a thickness of 1.6 mm and the excess was trimmed off. Dynamic shear viscosities were measured over an angular frequency range of 0.03 - 100 rad/s.
[00124] These data were fitted to the Carreau-Yasuda (CY) equation to determine the zero-shear viscosity (^0) and other rheological parameters such as the relaxation times (rq), and a measure of the relaxation amplitude of the relaxation time distribution (CY-a). See R. Byron Bird, Robert C. Armstrong, and Ole Hassager, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, (John Wiley & Sons, New York, 1987).
[00125] The intersection of the storage module and the loss module, both varied as a function of the shear rate, is called the crossing modulus, and is measured in Pascals. It was used to calculate the predicted extrudate swell. A correlation was observed between the crossover modulus and extrudate swelling measured during blowing of a standard 110 g 1 gallon milk bottle. The correlation is as follows:
[00126] Planned flat extension (LF) = 5.452+0.234CM/105, where CM = crossing module.
[00127] Expected extrudate swelling = LF/(3.14*2.75/2) - 1, where LF is the expected flat extension.
[00128] The measured extrudate swell is the length, or flat extent (LF), of the bottom emerging from the molded bottle divided by one half of the die circumference minus 1. That is: Measured extrude swell = LF/(3.14*d /2) - 1, where d is the diameter of the array. EXAMPLE 1
[00129] Polymers of the type described in this document were prepared using a catalyst system comprising at least two metallocene complexes, for example, MTE1/MTE2, a solid activating support (for example, alumina coated with fluorinated silica) and a trialkylaluminum (eg triisobutylaluminum). The structures of MTE-1 and MTE-2 are shown in Figure 1. The catalyst system was used to polymerize ethylene and 1-hexene in the presence of hydrogen in a hydrocarbon diluent (eg, isobutane). Three samples of polymers of the type described in this document were prepared and designated as Samples 1-3. The MI, HLMI, density, and ESCR of these samples are shown in Table 1. Also shown are values for a MARLEX HHM 5502BN comparative polyethylene resin, which is a high density polyethylene commercially available from Chevron Phillips Chemical Company LLC. Table 1

[00130] The molecular weight distribution and dynamic melt viscosity as a function of frequency for Samples 1-3 and the comparative sample are shown in Figures 2 and 3, respectively. Figure 4 is a plot of ESCR versus polymer density for Samples 1-3. EXAMPLE 2
[00131] Measurements of SCB and SCBD were made for Samples 1 and 3 of Example 1 and for the comparative polymer. The SCBD profile is shown in Figures 5, 6 and 7 for the comparative polymer, Sample 1 and Sample 3, respectively. The results demonstrate that the short chain branch in Samples 1 and 3 is primarily located at the higher molecular weight end.
[00132] The processability of the polymers was also investigated by preparing a quadrant chart of the samples from Example 1. The quadrant chart shown in Figure 8 demonstrates the processability of blow molding resins in relation to the yield of the process.
[00133] Once the embodiments of the invention have been shown and described, their modifications can be made without deviating from the spirit and teachings of the invention. The modalities and examples described in this document are exemplary only and are not intended to be limiting. Many variations and modifications of the invention disclosed in this document are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations shall be understood to include the iterative ranges or limitations of the magnitude covered by the expressly stated ranges or limitations (eg, from about 1 to about 10 includes 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term "optionally" in relation to any element of a claim is intended to mean that the subject element is necessary, or alternatively, not necessary. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as understand, include, having, etc. is to be understood to provide support for more limited terms, such as consisting of, consisting essentially of, substantially understood by, etc.
[00134] In this sense, the scope of protection is not limited by the description set out above, but is only limited by the following claims, this scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the detailed description of the present invention. The disclosures of all patents, patent applications, and publications cited in this document are hereby incorporated by reference, insofar as they provide exemplary, procedural or other details in addition to those presented herein.

权利要求:
Claims (7)
[0001]
1. Polymer having at least one lower molecular weight component and at least one higher molecular weight component and comprising a copolymer of ethylene and a comonomer comprising 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene or combinations thereof; characterized by the fact that the polymer comprises equal to or less than 0.5% mol of comonomer; a lower molecular weight component present in an amount greater than 60% by weight and less than 100% by weight; a weight average molecular weight (Mw) of the lower molecular weight component, ranging from 50 kg/mol to 120 kg/mol, and a Mw of the higher molecular weight component, ranging from 800 kg/mol to 2000 kg/mol; a polydispersity index of the largest molecular weight component from 2 to 4; a ratio of short chain branching at a molecular weight (MW) of 1 x 106 and SCB at peak MW for polymer greater than 3; and wherein the average short chain branching content of each 10 wt% fraction of the polymer increases with increasing molecular weight (MW) over a range of MW greater than 100 kg/mol.
[0002]
2. Polymer according to claim 1, characterized in that an article formed from the polymer has an ESCR greater than 2000 hours.
[0003]
3. Polymer according to claim 1, characterized in that it has less than 0.3 mol% comonomer, in which an article formed from the polymer has an ESCR greater than 500 hours.
[0004]
4. Polymer according to claim 1, characterized in that it has less than 0.2 mol% comonomer, in which an article formed from the polymer has an ESCR greater than 150 hours.
[0005]
5. Polymer according to claim 1, characterized in that it has an n 100 less than 1350 and an N100 greater than 0.35.
[0006]
6. Polymer according to claim 1, characterized in that it has an expected swelling of the extrudate from 25% to 35%.
[0007]
7. Polymer according to claim 1, characterized in that it has an Mz greater than 800 kg/mol and an Mz/Mw greater than 5.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3248179A|1962-02-26|1966-04-26|Phillips Petroleum Co|Method and apparatus for the production of solid polymers of olefins|

---

US3660530A|1968-08-28|1972-05-02|Dow Chemical Co|Blends of ethylene polymers with polyethylene-polybutene-1 block copolymers having improved stress crack resistance|

---

US3703565A|1971-02-22|1972-11-21|Dow Chemical Co|Blends of ethylene polymers having improved stress crack resistance|

---

US4060480A|1971-09-03|1977-11-29|Chevron Research Company|Hydrocarbon hydroconversion process employing hydroxy-aluminum stabilized catalysts supports|

---

US4501885A|1981-10-14|1985-02-26|Phillips Petroleum Company|Diluent and inert gas recovery from a polymerization process|

---

US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|

---

US4452910A|1982-06-15|1984-06-05|Standard Oil Company |Chromium expanded smectite clay|

---

US4461873A|1982-06-22|1984-07-24|Phillips Petroleum Company|Ethylene polymer blends|

---

US5565175A|1990-10-01|1996-10-15|Phillips Petroleum Company|Apparatus and method for producing ethylene polymer|

---

US5575979A|1991-03-04|1996-11-19|Phillips Petroleum Company|Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator|

---

KR930006091A|1991-09-18|1993-04-20|제이 이이 휘립프스|Polyethylene blends and films, bottles or pipes made therefrom|

---

CA2078366A1|1991-09-18|1993-03-19|Joel L. Martin|Polyethylene blends|

---

AU650787B2|1991-12-09|1994-06-30|Phillips Petroleum Company|Process for preparing a pillared chain silicate clay|

---

US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|

---

US5436304A|1992-03-19|1995-07-25|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|

---

US5455314A|1994-07-27|1995-10-03|Phillips Petroleum Company|Method for controlling removal of polymerization reaction effluent|

---

US6239235B1|1997-07-15|2001-05-29|Phillips Petroleum Company|High solids slurry polymerization|

---

JP3989066B2|1997-11-05|2007-10-10|旭化成ケミカルズ株式会社|Blow molding|

---

KR100531628B1|1998-03-20|2005-11-29|엑손모빌 케미칼 패턴츠 인코포레이티드|Continuous slurry polymerization volatile removal|

---

US6165929A|1998-05-18|2000-12-26|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6107230A|1998-05-18|2000-08-22|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6300271B1|1998-05-18|2001-10-09|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6294494B1|1998-12-18|2001-09-25|Phillips Petroleum Company|Olefin polymerization processes and products thereof|

---

US6262191B1|1999-03-09|2001-07-17|Phillips Petroleum Company|Diluent slip stream to give catalyst wetting agent|

---

US6355594B1|1999-09-27|2002-03-12|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6376415B1|1999-09-28|2002-04-23|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6395666B1|1999-09-29|2002-05-28|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6548441B1|1999-10-27|2003-04-15|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6391816B1|1999-10-27|2002-05-21|Phillips Petroleum|Organometal compound catalyst|

---

US6613712B1|1999-11-24|2003-09-02|Phillips Petroleum Company|Organometal catalyst compositions with solid oxide supports treated with fluorine and boron|

---

US6548442B1|1999-12-03|2003-04-15|Phillips Petroleum Company|Organometal compound catalyst|

---

US6750302B1|1999-12-16|2004-06-15|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6524987B1|1999-12-22|2003-02-25|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6667274B1|1999-12-30|2003-12-23|Phillips Petroleum Company|Polymerization catalysts|

---

US6632894B1|1999-12-30|2003-10-14|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6576583B1|2000-02-11|2003-06-10|Phillips Petroleum Company|Organometal catalyst composition|

---

US6388017B1|2000-05-24|2002-05-14|Phillips Petroleum Company|Process for producing a polymer composition|

---

US6982304B2|2003-12-22|2006-01-03|Union Carbide Chemicals & Plastics Technology Corporation|Blow molding resins with improved ESCR|

---

US20050272891A1|2004-02-13|2005-12-08|Atofina Research S.A.|Double loop technology|

---

US7307133B2|2004-04-22|2007-12-11|Chevron Phillips Chemical Company Lp|Polymers having broad molecular weight distributions and methods of making the same|

---

KR101205605B1|2004-04-22|2012-11-27|셰브론 필립스 케미컬 컴퍼니 엘피|Chromium based polymerization catalyst, the method to prepare it and polymers prepared therewith|

---

US8202940B2|2004-08-19|2012-06-19|Univation Technologies, Llc|Bimodal polyethylene compositions for blow molding applications|

---

US7517929B2|2004-12-03|2009-04-14|Momentive Performance Materials Inc.|Star-branched silicone polymers as anti-mist additives for coating applications|

---

US7858702B2|2005-06-14|2010-12-28|Univation Technologies, Llc|Enhanced ESCR bimodal HDPE for blow molding applications|

---

US20070027276A1|2005-07-27|2007-02-01|Cann Kevin J|Blow molding polyethylene resins|

---

US7312283B2|2005-08-22|2007-12-25|Chevron Phillips Chemical Company Lp|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

EP1940942B1|2005-08-24|2009-09-30|Dow Global Technologies Inc.|Polyolefin compositions, articles made therefrom and methods for preparing the same|

---

US7226886B2|2005-09-15|2007-06-05|Chevron Phillips Chemical Company, L.P.|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

US7517939B2|2006-02-02|2009-04-14|Chevron Phillips Chemical Company, Lp|Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching|

---

EP1992649A4|2006-02-15|2009-04-22|Mitsui Chemicals Inc|Ethylene resin and blow-molded article comprising the same|

---

US7619047B2|2006-02-22|2009-11-17|Chevron Phillips Chemical Company, Lp|Dual metallocene catalysts for polymerization of bimodal polymers|

---

US7589162B2|2006-02-22|2009-09-15|Chevron Philips Chemical Company Lp|Polyethylene compositions and pipe made from same|

---

EP1845110A1|2006-04-13|2007-10-17|Total Petrochemicals Research Feluy|Chromium-based catalysts|

---

US7449529B2|2006-07-11|2008-11-11|Fina Technology, Inc.|Bimodal blow molding resin and products made therefrom|

---

EP1972642A1|2007-03-19|2008-09-24|Total Petrochemicals Research Feluy|Homo-or co-polymers of ethylene with combination of processability and toughness properties|

---

US9175111B2|2007-12-31|2015-11-03|Dow Global Technologies Llc|Ethylene-based polymer compositions, methods of making the same, and articles prepared from the same|

---

US7884163B2|2008-03-20|2011-02-08|Chevron Phillips Chemical Company Lp|Silica-coated alumina activator-supports for metallocene catalyst compositions|US9371442B2|2011-09-19|2016-06-21|Nova ChemicalsS.A.|Polyethylene compositions and closures made from them|

---

US8815357B1|2013-02-27|2014-08-26|Chevron Phillips Chemical Company Lp|Polymer resins with improved processability and melt fracture characteristics|

---

US10577440B2|2013-03-13|2020-03-03|Chevron Phillips Chemical Company Lp|Radically coupled resins and methods of making and using same|

---

US10654948B2|2013-03-13|2020-05-19|Chevron Phillips Chemical Company Lp|Radically coupled resins and methods of making and using same|

---

US9169337B2|2014-03-12|2015-10-27|Chevron Phillips Chemical Company Lp|Polymers with improved ESCR for blow molding applications|

---

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---

US9505161B2|2014-04-10|2016-11-29|Fina Technology, Inc.|Solid-state stretched HDPE|

---

US9758653B2|2015-08-19|2017-09-12|Nova ChemicalsS.A.|Polyethylene compositions, process and closures|

---

US9493589B1|2015-09-09|2016-11-15|Chevron Phillips Chemical Company Lp|Polymers with improved ESCR for blow molding applications|

---

US9650459B2|2015-09-09|2017-05-16|Chevron Phillips Chemical Company Lp|Methods for controlling die swell in dual catalyst olefin polymerization systems|

---

US9540457B1|2015-09-24|2017-01-10|Chevron Phillips Chemical Company Lp|Ziegler-natta—metallocene dual catalyst systems with activator-supports|

---

US10000594B2|2016-11-08|2018-06-19|Chevron Phillips Chemical Company Lp|Dual catalyst system for producing LLDPE copolymers with a narrow molecular weight distribution and improved processability|

---

KR102095523B1|2016-11-24|2020-03-31|주식회사 엘지화학|Method for predicting property of polymers|

---

KR102068795B1|2016-11-24|2020-01-21|주식회사 엘지화학|Method for predicting property of polymers|

---

CN110191902A|2017-02-13|2019-08-30|尤尼威蒂恩技术有限责任公司|Bimodal polyethylene resins|

---

US20210155805A1|2019-11-26|2021-05-27|Behr Process Corporation|Primer topcoat|

法律状态:
2020-10-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-04-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-04| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/156,102|US8318883B1|2011-06-08|2011-06-08|Polymer compositions for blow molding applications|

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US13/156,102|2011-06-08|

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PCT/US2012/041466|WO2012170762A1|2011-06-08|2012-06-08|Polymer compositions for blow molding applications|

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