巴西专利BR112014004959B1 bimodal polymer comprising polyethylene and food packaging container

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POLYMER COMPOSITIONS HAVING IMPROVED BARRIER PROPERTIES. A polymer having a melt index of approximately 0.5 g / 10 min to about 4.0 g / 10 min and a density greater than or equal to 0.96 g / cc, which, when formed on a film of 1 thousand, exhibits a moisture vapor transmission rate ranging from greater than or equal to 0 to equal to or approximately 20% greater than X, where X = k1 {-61.95377 + 39.52785 (Mz / Mw) - 8.16974 (Mz / Mw) 2 + 0.55114 (Mz / Mw) 3} + k2 {-114.01555 (Tau) + 37.68575 (Mz / Mw) (Tau) - 2.89177 (Mz / Mw) 2 (Tau)} + k3 {120.37572 (Tau) 2 - 25.91177 (Mz / Mw) (Tau) 2} + k4 {18.03254 (Tau) 3} when Mw is from about 100 kg / mol to about 180 kg / mol; Mz is about 300 kg / mol to about 1000 kg / mol; Tau is about 0.01 s to about 0.35 s; k1 is 1 g / 100 in2 day; k2 is 1 g / 100 in2 "days"; k3 is 1 g / 100 in2 "day" s2; and k4 is 1 g / 100 in2 "day" s3.
公开号:BR112014004959B1
申请号:R112014004959-9
申请日:2012-09-04
公开日:2021-01-19
发明作者:Qing Yang；Guylaine St Jean；Mark L Hlavinka；Brooke A Gill；Deloris R. Gagan
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED REQUESTS
[0001] This application claims priority for Provisional Patent Application Serial No. US 61 / 530,711 filed on September 2, 2011 by Hlavinka et al. and entitled "Polymer Compositions Having Improved Barrier Properties," which is incorporated herein by reference as if reproduced in its entirety. TECHNICAL FIELD
[0002] The present disclosure refers to polymeric compositions, more specifically, this disclosure refers to polyethylene (PE) compositions and articles made of the same. FUNDAMENTALS
[0003] Polyolefins are plastic materials, useful for making a wide variety of valued products due to their combination of rigidity, ductility, barrier properties, temperature resistance, optical properties, availability and low cost. One of the most valued products is plastic films. In particular, PE is one of the most widely consumed polymers in the world. It is a versatile polymer that offers high performance compared to other polymers and alternative materials, such as glass, metal or paper. Plastic films, such as PE films, are mainly used in packaging applications, but they also find use in the agricultural, medical and engineering fields.
[0004] PE films are manufactured in a variety of grades that are generally differentiated by the density of the polymer, so that PE films can be designated, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE ), medium density polyethylene (MDPE) and high density polyethylene (HDPE), where each density range has a unique combination of properties, making it suitable for a particular application.
[0005] Despite the many positive attributes of PE, the film product remains permeable to gases, such as oxygen or carbon dioxide, and / or moisture (for example, water). Thus, it would be desirable to develop a PE film product exhibiting improved barrier properties. SUMMARY
[0006] Disclosed here is a polymer having a melt index of about 0.5 g / 10 min to about 4.0 g / 10 min and a density greater than or equal to 0.96 g / cc, which, when formed on a 1 mil (0.0254 mm) film, it exhibits a moisture vapor transmission rate ranging from greater than or equal to 0 to equal to or approximately 20% greater than X, where X = k1 {- 61.95377 + 39.52785 (Mz / Mw) -8.16974 (Mz / Mw) 2 + 0.55114 (Mz / Mw) 3} + k2 {-114.01555 (T) + 37.68575 (Mz / Mw) (T) - 2.8 917 7 (Mz / Mw) ) 2 (T)} + ka {120.37572 (T) 2 - 2 5.91177 (MZ / MW) (T) 2} + k4 {18.03254 (T) 3} when Mw is about 100 kg / mol to about 180 kg / mol; Mz is about 300 kg / mol to about 1000 kg / mol; t is about 0.01s to about 0.35s; ki is 1 g / 100 in2 day; k2 is 1 g / 100 in2 ^ dia ^ s; ka is 1 g / 100 in2 dia2 s2; and k4 is 1 g / 100 in2 ^ dia ^ s3. BRIEF DESCRIPTION OF THE FIGURES
[0007] Figure 1 is a graphical representation of molecular weight distribution profiles for the samples in Example 1.
[0008] Figure 2 is a graph of dynamic fluidity viscosity as a frequency function for the samples in Example 1. DETAILED DESCRIPTION
[0009] Polymers, polymeric compositions, polymeric articles and methods for making them are disclosed here. The polymers and / or polymeric compositions of the present disclosure can comprise polyethylene. The polymers and / or polymeric compositions disclosed herein may comprise a mixture of polymer components and result in a polymer and / or polymeric composition which, interestingly, exhibits barrier properties when compared to a similar polymer composition otherwise prepared under different conditions. Hereinafter, the 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.
[00010] In one embodiment, a polymer of the present disclosure is produced by any method of polymerizing olefins, 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 can be referred to as batch, mud, gas phase, solution, high pressure, tubular, autoclave, or other reactor and / or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal staged reactors. Mud reactors can comprise vertical and / or horizontal cycles. High pressure reactors may comprise autoclave and / or tubular reactors. Reactor types can include batch and / or continuous processes. Continuous processes can use intermittent and / or continuous product transfer or discharge. Processes may also include direct partial or complete recycling of the unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents, and / or other materials from the polymerization process.
[00011] 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. 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 polymers resulting from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors may include the transfer, manually or automatically, of polymer from one reactor to the reactor or subsequent reactors for further polymerization. Alternatively, multiple-stage or multiple-stage polymerization can take place in a single reactor, where conditions are changed so that a different polymerization reaction takes place.
[00012] 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 polymer production process of the present disclosure. Multiple reactor systems may include any combination, including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of gas and cycle phase reactors, multiple high pressure reactors or a combination of high pressure reactors pressure with cycled and / or gas reactors. The 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.
[00013] According to one embodiment, the polymerization reactor system may comprise at least one slurry reactor in a cycle. Such reactors are common and can comprise vertical or horizontal cycles. Monomer, diluent, catalyst system and, optionally, any comonomer can be continuously fed to a cycle sludge 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 a suspension comprising polymer particles and the diluent from that reactor. Effluent from the reactor can be abruptly evaporated to remove liquids that comprise the polymer diluent, monomer and / or solid comonomer. Various technologies can be used for this separation step, including, but not limited to, sudden evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or hydrocyclone; centrifugation separation; or another appropriate method of separation.
[00014] Typical sludge polymerization processes (also known as particle-shaped processes) are disclosed in Patent Nos. US3,248,179, US4,501,885, US5,565,175, US5,575,979, US6,239,235, US6,262,191 and US6,833,415, for example; each of which is incorporated herein by reference in its entirety.
[00015] Suitable diluents used in sludge polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under 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 occur under mass conditions, where no diluents are used. An example is polymerization of propylene monomer, as disclosed in Patent No. US5,455,314, which is incorporated herein by reference in its entirety.
[00016] According to yet another modality, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream that contains one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product can be removed from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors can comprise a process for a multi-stage gas phase olefin polymerization, in which 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. A type of gas phase reactor is disclosed in Patent Nos. US4,588,790, US5,352,749 and US5,436,304, each of which are incorporated herein by reference in their entirety.
[00017] According to yet another modality, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators or catalysts are added. Monomer can be entrained in an inert gas stream and introduced into a reactor zone. Primers, catalysts and / or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas streams can be intermixed for polymerization. Heat and pressure can be used appropriately to obtain optimal polymerization reaction conditions.
[00018] According to yet another embodiment, the polymerization reactor can comprise a solution polymerization reactor, in which the monomer is contacted with the catalyst composition by suitable stirring or other means. A carrier that comprises an excess organic diluent or monomer can be employed. If desired, the monomer can be placed, in the vapor phase, in 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 used to obtain better temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[00019] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feedstock for catalyst or catalyst components, and / or at least one feedstock recovery system polymer. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor refrigeration, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control.
[00020] 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 the concentrations of various reagents. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to 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.
[00021] Adequate pressures will also vary according to the reactor and polymerization process. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig. Pressure for polymerization of the gas phase is generally around 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 occurring at higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
[00022] The concentration of various reagents 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 for forming that product can be varied to determine the properties of the desired end product. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, deformation, stress relaxation and hardness tests. Physical properties include, but are not limited to density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack increase, short chain branching, chain branching and rheological measurements.
[00023] Concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in the production of specific polymer properties. 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 toxins and / or control molecular weight. The concentration of toxicants can be minimized, since toxicants can impact reactions and / or affect polymer product properties in another way. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
[00024] In one embodiment, a method for preparing a polymer comprises contacting an olefin and / or alpha-olefin monomer with a catalyst system under conditions suitable for the formation of a polymer of the type described herein. In one embodiment, a catalyst system for producing a polymer of the type disclosed herein can comprise at least two metallocene compounds; an activator support and an organoaluminium compound. Here, the term "metallocene" describes a compound comprising at least a fraction of the type ^ 3 to r5-cycloalkadienyl, wherein fractions ^ 3 to ^ 5-cycloalkadienyl include cyclopentadienyl binders, indenyl binders, fluorenyl binders and the like, including partially derivatives saturated or substituted or analogous to any of these. Possible substituents on these binders include hydrogen; therefore, the description "substituted derivatives thereof" in this disclosure comprises partially saturated binders, such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially substituted saturated indenyl, partially substituted saturated fluorenyl and the like.
[00025] In one embodiment, the catalyst comprises a first metallocene compound hereinafter referred to as MTE-A. In one embodiment, MTE-A can be represented by the general formula:
where M1 is Ti, Zr or Hf; X1 and X2 are each independently F, Cl, Br, I, methyl, benzyl, phenyl, H, BH4, a hydrocarbonoxide group having up to 20 carbon atoms, a hydrocarbilamino group having up to 20 carbon atoms, a trihydrocarbylsilyl group having up to 20 carbon atoms, OBR'2 where R 'can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms and SO3R ", where R" can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms; and Cp1 and Cp2 are each independently a substituted or unsubstituted cyclopentadienyl group, or a substituted or unsubstituted indenyl group, where any substituent on Cp1 and Cp2 is H, a hydrocarbyl group having up to 18 carbon atoms or a hydrocarbylsilyl group having up to 18 carbon atoms.
[00026] In one embodiment, MTE-A is a dinuclear compound in which each metallic fraction has the same structural characteristic described here previously. In one embodiment, MTE-A is a metallocene without bridges (nonbridged metallocene). Non-limiting examples of compounds suitable for use in this disclosure as MTE-A are represented by structures (1) - (13):

[00027] Other non-limiting examples of metallocene compounds that can be properly employed as MTE-A for the preparation of a polymer of the type disclosed herein include hafnium bis (cyclopentadienyl) dichloride; bis (n-butylcyclopentadienyl) bis (di-t-butyl starch) hafnium; bis (n-propylcyclopentadienyl) zirconium dichloride; bis (pentamethylcyclopentadienyl) zirconium dichloride; bis (1-propylindenyl) zirconium dichloride; or any combination thereof. In one embodiment, MTE-A comprises bis (1-propylindenyl) zirconium dichloride, alternatively MTE-A comprises the compound represented by structure (2). Henceforth, the disclosure will refer predominantly to the use of the compound represented by structure (5) as MTE-A, although other metallocenes of the types described here are also contemplated for use in the teachings of this disclosure.
[00028] In one embodiment, the catalyst system comprises a second metallocene compound hereinafter referred to as MTE-B. In one embodiment, MTE-B is a bridged metallocene. In one modality, MTE-B can be represented by the general formula:
where M2 is Ti, Zr or Hf; X3 and X4 are independently F, Cl, Br, I, methyl, phenyl, benzyl, H, BH4, a hydrocarbiloxy group having up to 20 carbon atoms, a hydrocarbilamino group having up to 20 carbon atoms, a trihydrocarbylsilyl group having up to 20 atoms carbon, OBR'2 where R 'can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms, or SO3R ”where R" can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms; R1 and R2 are independently hydrogen or a hydrocarbon group having up to 18 carbon atoms; Cp3 is a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, a substituted fluorenyl group or unsubstituted, where any substituent in Cp3 is H, a hydrocarbyl group having up to 18 carbon atoms or a hydrocarbylsilyl group having up to 18 carbon atoms; and E represents a bridging group that may comprise (i) a cyclic or heterocyclic moiety having up to 18 carbon atoms, (ii) a group represented by the general formula EAR3AR4A, where EA is C or Si and R3A and R4A are independently H or a hydrocarbon group having up to 18 carbon atoms, (iii) a group represented by general formula —CR3BR4B — CR3CR4C—, where R3B, R4B, R3C, and R4C are H independent or a hydrocarbon group having up to 10 carbon atoms, (iv) a group represented by the general formula - SiR3DR4D — SiR3ER4E—, where R3D , R4D, R3E, and R4E are independently H or a hydrocarbon group with up to 10 carbon atoms and in which at least one of R3A, R3B, R4A, R4B, R3C, R4C, R3D, R4D, R3E, R4E, or the substituent in Cp3 it is (1) a terminal alkenyl group having up to 12 carbon atoms or (2) a dinuclear compound where each metallic fraction has the same structural characteristic as MTE-B. Non-limiting examples of compounds suitable for use in this disclosure as MTE-B are represented by structures (14) - (29):

[00029] In one embodiment, MTE-B is a compound represented by the structure (16). In one embodiment, MTE-B is further characterized as a catalyst that works to produce a PE polymer having a higher average molecular weight compared to a PE polymer produced by MTE-A under otherwise similar conditions. In one embodiment, MTE-A is further characterized as a catalyst that exhibits a positive hydrogen response compared to MTE-B under otherwise similar conditions.
[00030] In one embodiment, the catalyst system comprises MTE-A, which comprises the compound represented by structure (5), and MTE-B, which comprises the compound represented by structure (16).
[00031] In one aspect, the support-activator comprises a chemically treated solid oxide. Alternatively, the support-activator 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, an aluminosilicate mineral in layers, an aluminosilicate mineral without layers or any combination thereof.
[00032] Generally, chemically treated solid oxides exhibit enhanced acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide also functions as a catalyst activator in comparison to the corresponding untreated solid oxide. Since the chemically treated solid oxide activates the metallocene (s) in the absence of cocatalysts, it is not necessary to eliminate the cocatalysts from the catalyst composition. The activation function of the support-activator 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 the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminium compound, aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds and the like.
[00033] The chemically treated solid oxide may comprise a solid oxide treated with an electron-withdrawing anion. Although it is not intended to be limited by the following statement, it is believed that treatment of the solid oxide with an electron-removing component increases or intensifies the acidity of the oxide. Thus, the support-activator exhibits Lewis or Br0nsted acidity that is typically greater than the Lewis or Br0nsted acid strength of untreated solid oxide, or the support-activator has a greater number of acid sites than 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.
[00034] Chemically treated solid oxides of this disclosure are generally formed from an inorganic solid oxide which exhibits Lewis acid or Br0nsted acid behavior and has a relatively high porosity. The solid oxide is chemically treated with an electron withdrawing component, typically an electron withdrawing anion, to form an activator support.
[00035] 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. According to another aspect of the present disclosure, solid oxide has a pore volume greater than about 0.5 cc / g. In accordance with yet another aspect of the present disclosure, the solid oxide has a pore volume greater than about 1.0 cc / g.
[00036] In another aspect, the solid oxide has a surface area of about 100 m2 / g to about 1000 m2 / g. In yet another aspect, the solid oxide has a surface area of about 200 m2 / g to about 800 m2 / g. In yet another aspect of the present disclosure, solid oxide has a surface area of about 250 m2 / g to about 600 m2 / g.
[00037] The chemically treated solid oxide may comprise a solid inorganic 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 which comprises 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, inorganic oxide can 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.
[00038] Suitable examples of solid oxide materials or compounds that can be used to form 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 mixed oxides of the same and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boron, zinc oxide, mixed oxides thereof or any combination thereof. .
[00039] The solid oxide of this disclosure encompasses oxide materials, such as alumina, compounds of "mixed oxide" 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-boron, silica-boron, 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 Patent No. US7,884,163, the disclosure of which is incorporated herein by reference in its entirety.
[00040] The electron withdrawing component used to treat the solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide by treatment (in comparison to the solid oxide that is not treated with at least one electron withdrawing anion ). According to one aspect of the present disclosure, the electron withdrawing component is an electron withdrawing anion derived from a salt, acid or other compound, such as a volatile organic compound, which serves as a source or a precursor for that 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, phosphorungates and similar compounds and compounds themselves. 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 contemplated that the electron withdrawing anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate and the like, or any combination thereof, in some aspects of this disclosure. In other respects, 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.
[00041] Thus, for example, the support-activator (for example, chemically treated solid oxide) used in the catalyst compositions may be, or may comprise, fluoridated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluoridated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina-coated sulfated, phosphate-coated silica-alumina and the like, or combinations thereof. In one aspect, the support-activator may be, or may comprise, fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphate-silica-coated alumina and the like or any combination thereof. In another aspect, the support-activator comprises fluoridated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, it comprises fluoridated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluoridated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or, alternatively, it comprises alumina coated with fluoridated silica.
[00042] When the electron-withdrawing component comprises a salt from an electron-withdrawing anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert or decompose back to acid during calcination . Factors that dictate the suitability of the particular 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, the lack of adverse cation reactivity, ionic pairing effects between the cation and the anion, hygroscopic properties conferred 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, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H +, [H (OEt2) 2] +, and the like.
[00043] Additionally, combinations of one or more different electron withdrawing anions, in varying proportions, can be used to adjust the specific acidity of the activator 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 to employ two or more electron-withdrawing anion source compounds in two or more separate contact steps.
[00044] Thus, an example of such a process by which a chemically treated solid oxide is prepared is as follows: a selected solid oxide, or combination of solid oxides, is contacted with a first electron-withdrawing anion source compound 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 such a process, the first and second electron-withdrawing anion source compounds can be the same or different compounds.
[00045] According to another aspect of the present disclosure, the chemically treated solid oxide comprises a solid inorganic 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 compounds containing metals. Non-limiting examples of metal or metal ion 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, chlorinated zinc-impregnated alumina, fluorinated titanium-impregnated alumina, fluoridated zinc-impregnated alumina, chlorinated zinc-impregnated silica-alumina, silica-alumina impregnated with fluorinated zinc, alumina impregnated with sulfated zinc, chlorinated zinc aluminate, fluorinated 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 thereof.
[00046] Any method for impregnating the solid oxide material with a metal can be used. The method by which the oxide is contacted with a metal source, typically a metal-containing salt or compound, may include, but is not limited to, gelation, cogelification, impregnation of one compound into another, and the like. If desired, the metal-containing compound is added or impregnated in the solid oxide as a solution and subsequently converted to the supported metal by calcination. Consequently, the solid inorganic oxide can additionally 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 catalytic activity at a low cost.
[00047] The solid oxide can be treated with metallic 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 solid compound, electron withdrawing anion and the metal ion is typically calcined. Alternatively, a solid oxide material, an electron-withdrawing anion source, and the metal salt or metal-containing compound are contacted and calcined simultaneously.
[00048] Various processes are used to form the chemically treated solid oxide useful in the present disclosure. The chemically treated solid oxide may comprise the contact product of one or more solid oxides with one or more electron withdrawing anion sources. It is not required that the solid oxide be calcined before contacting the electron withdrawing anion source. The contact product is typically calcined during or after the solid oxide is brought into contact with the electron-withdrawing anion source. The solid oxide can be calcined or non-calcined. Several processes for preparing solid oxide support-activators that can be employed in this disclosure have been reported. For example, these methods are described in Patent Nos. US6,107,230; US6,165,929; US6,294,494; US6,300,271; US6,316,553; US6,355,594; US6,376,415; US6,388,017; US6,391,816; US6,395,666; US6,524,987; US6,548,441; US6,548,442; US6,576,583; US6,613,712; US6,632,894; US6,667,274; and US6,750,302; whose disclosures are hereby incorporated by reference in their entirety.
[00049] According to one aspect of the present disclosure, the 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 is optionally chemically treated with a metal ion and then calcined to form a chemically treated solid oxide containing metal or impregnated with metal. According to another aspect of the present disclosure, the solid oxide material and the electron-withdrawing anion source are brought into contact and calcined simultaneously.
[00050] The method by which the oxide is contacted with the electron-withdrawing component, typically a salt or acid from an electron-withdrawing anion, may include, but is not limited to, gelation, cogelification, impregnation of one compound into another, and the like. Thus, after any contact method, the contacted mixture of the solid oxide, electron withdrawing anion and optional metal ion is calcined.
[00051] The support-activator of the solid oxide (i.e., chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with an anion-removing source compound electron (or compounds) to form a first mixture; and 2) calcining the first mixture to form the solid oxide support-activator.
[00052] According to another aspect of the present disclosure, the solid oxide activator support (chemically treated solid oxide) is produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with a first electron withdrawing anion to form a first mixture; 2) calcining the first mixture to produce a first calcined mixture; 3) contacting a solid oxide (or solid oxides) with a second electron-withdrawing anion source compound to form a second mixture; 4) calcining the second mixture to form the solid oxide support-activator.
[00053] According to yet another aspect of the present disclosure, 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 contact with the electron-withdrawing anion source, and where there is a substantial absence of aluminoxane, organoboro or organoborate compounds and ionizing ionic compounds.
[00054] 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 conducted at a temperature of about 300 ° C to about 800 ° C, or alternatively, at a temperature of about 400 ° C to about 700 ° C. Calcination can be conducted 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 used during calcination. Generally, calcination is 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.
[00055] 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 solid oxide chemically treated as a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called "sulfating agent"), a chloride ion source (called "chlorinating agent"), a fluoride ion source (called "fluoridating agent"), or a combination thereof, and calcined to provide the solid oxide activator. Useful acidic support-activators include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, hexafluorotitanic acid-treated alumina, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated , fluorinated boria- 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 fluorine, chloride or sulfate; phosphate alumina or other aluminophosphates optionally treated with sulphate, fluoride or chloride; or some combination of the above. In addition, any of these support-activators can optionally be treated with a metal ion.
[00056] The chemically treated solid oxide may comprise a fluoridated solid oxide in the form of a particulate solid. Fluoridated solid oxide can be formed by contacting a solid oxide with a fluoridating agent. The fluoride ion can be added to the oxide by forming a fluid oxide slurry in a suitable solvent, such as alcohol or water, including, but not limited to, one to three carbon alcohols due to its 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) (( 2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4) 2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, analogues of the same and the same. Triflic acid and ammonium triphylate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as the fluoridating agent, due to its ease of use and availability.
[00057] If desired, the solid oxide is treated with a fluoridating agent during the calcination step. Any fluoridating agent capable of coming into full contact with the solid oxide during the calcination step can be used. For example, in addition to these fluoridating agents previously described, volatile organic fluoridating agents can be used. Examples of volatile organic fluoridating agents useful in this aspect of the disclosure include, but are not limited to, frees, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. Calcination temperatures should generally be high enough to decompose the compound and release fluoride. Hydrogen gas fluoride (HF) or fluorine (F2) itself can also be used with solid oxide, if fluoridated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4-) can also be used. A convenient method for contacting the solid oxide with the fluoridating agent is to vaporize a fluoridating agent in a gas stream used to fluidize the solid oxide during calcination.
[00058] Similarly, in another aspect of this disclosure, the chemically treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. The chlorinated solid oxide is formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming a fluid oxide slurry in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a chloride source and completely contacting the oxide during the calcination step can be used, such as SiCl4, SiMe2Cl2, TiCl4, BCl3 and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include, but are not limited to, certain frees, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like or any combination thereof. Hydrogen chloride gas or chlorine itself can also be used with solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent is to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
[00059] The amount of fluoride or chloride ion present before calcination of the solid oxide is generally about 1 to about 50% by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica- alumina before calcination. According to another aspect of this disclosure, the amount of fluoride or chloride ion present before calcination of the solid oxide is from about 1 to about 25% by weight, and according to another aspect of this disclosure, from about 2 to about 20% by weight. According to yet another aspect of this disclosure, the amount of fluoride or chloride ion present before calcination of 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 step calcination immediately without drying the impregnated solid oxide.
[00060] The silica-alumina used to prepare the treated silica-alumina typically has a pore volume greater than about 0.5 cc / g. According to one aspect of the present disclosure, the pore volume is greater than about 0.8 cc / g and, according to another aspect of the present disclosure, greater than about 1.0 cc / g. In addition, silica-alumina generally has a surface area greater than about 100 m2 / g. According to 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.
[00061] The silica-alumina used in the present disclosure normally has an alumina content of about 5 to about 95% by weight. According to a disclosure aspect, the alumina content of silica-alumina is from about 5 to about 50%, or from about 8% to about 30% of alumina by weight. In another aspect, silica-alumina compounds with a high alumina content can be employed, in which the alumina content of these silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80% alumina by weight. According to yet another aspect of this disclosure, the solid oxide component comprises alumina without silica and, according to another aspect of this disclosure, the solid oxide component comprises silica without alumina.
[00062] 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 additionally treated with a metal ion, so that the calcined sulfated oxide comprises a metal. According to 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 sulfate source, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process is usually performed by forming a fluid slurry of alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of the sulfating 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.
[00063] According to one aspect of this disclosure, the amount of sulfate ion present before calcination is 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 ion present before 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 yet 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 the solid oxide before 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.
[00064] According to another aspect of the present disclosure, the activator support used in the preparation of the catalyst compositions of this disclosure comprises an exchangeable ion activator support, including, but not limited to, silicate and aluminosilicate compounds or minerals, with structures in layers or without layers, and combinations thereof. In another aspect of this disclosure, layered exchangeable ion aluminosilicates, such as pillared clays, are used as support-activators. When the acid activating support comprises an exchangeable ion activating support, it can optionally be treated with at least one electron withdrawing anion, such as those disclosed in this document, although typically the exchangeable ion activating support is not treated with an electron withdrawing anion.
[00065] According to another aspect of the present disclosure, the activator support of this disclosure comprises clay minerals having exchangeable cations and layers capable of expanding. Typical clay mineral support-activators include, but are not limited to layered exchangeable ion aluminosilicates, such as pillared clays. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, but rather, it should be considered an active part of the catalyst composition due to its close association with the metallocene component.
[00066] According to another aspect of the present disclosure, the clay materials of this disclosure include materials in their natural state or that have been treated with different ions by wetting, ion exchange or pillarization. Typically, the clay material activator support in this disclosure comprises clays that have ions exchanged with large cations, including highly charged polynuclear metal complex cations. However, the clay material activating supports in this disclosure also include clays that have ions exchanged with simple salts, including, but not limited to, Al (III), Fe (II), Fe (III) and Zn ( II) with binders such as halide, acetate, sulfate, nitrate or nitrite.
[00067] According to another aspect of the present disclosure, the activator support comprises a pillared clay. The term "pillared clay" is used to refer to clay materials that have exchanged ions with large, highly charged, complex, typically polynuclear metal cations. Examples of such ions include, but are not limited to, Keggin ions which may have charges such as 7+, various polyoxometalates and other large ions. Thus, the term pilarizing 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 interlayer and, when calcined, are converted into 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 as a function of the pillar material and the precursor clay material used. Examples of pillar and pillar clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.)) C. 3, pp. 55-99, Academic Press, Inc., (1972); Patent Nos. US4,452,910; US5,376,611; and US 4,060,480; whose disclosures are hereby incorporated by reference in their entirety.
[00068] The pillarizing process uses clay minerals having exchangeable cations and layers capable of expanding. Any pillarized clay that can enhance the polymerization of olefins in the catalyst composition of the present disclosure can be used. Therefore, clay minerals suitable for pillaring include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof, such as montmorillonites (bentonites), nontronites, hectorites or laponites; haloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous clays including, but not limited to, sepiolites, atapulgites and paligorschites; a serpentine clay; illita; laponite; saponite; and any combination thereof. In one aspect, the pillarized clay support-activator comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[00069] The pillared clay can be pretreated, if desired. For example, a pillarized 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 here, it should be understood that preheating can be performed at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this disclosure.
[00070] 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, phosphate inorganic 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, boron, thorium, aluminum phosphate, aluminum phosphate, silica-titania, coprecipitated silica / titania , mixtures thereof or any combination thereof.
[00071] The production process for these activating supports can include precipitation, coprecipitation, impregnation, gelation, pore gelation, calcination (up to 900 ° C), spray drying, instant drying, rotary drying and calcination, crushing, sieving and similar operations.
[00072] In one embodiment, an organoaluminium compound suitable for use in the present disclosure comprises an alkylaluminum compound. For example, the organoaluminium compound can comprise a trialkylaluminium compound, having the general formula AIR3. Non-limiting examples of trialkylaluminum compounds suitable for use in this disclosure include triisobutylaluminum (TiBA or TiBAl); tri-n-butylaluminium (TNBA); Tri-octyl-butylaluminium (TOBA); triethyl aluminum (TEA); and / or other appropriate alkyl aluminum complexes and combinations thereof. In addition, partially hydrolyzed alkyl aluminum compounds and / or aluminum oxanes can be used. In one embodiment, the organoaluminium compound comprises a compound represented by the general formula: Al (X5) p (X6) q
[00073] where X5 is a halide, hydrocarbiloxide group, hydrocarbilamino group or combinations thereof; X6 is a hydrocarbyl group having up to 18 carbon atoms; p ranges from 0 to 2; and q is 3 - p.
[00074] In one embodiment, a process for the preparation of a polymer of the type disclosed herein comprises polymerization of an olefin monomer in the presence of a catalyst system comprising at least two metallocene complexes. In such embodiments, the first and second metallocene complexes are of the type described in this document (ie, MTE-A and B-MTE) and result in the formation of the two components of the polymer when both catalysts are employed in a single reactor.
[00075] In one embodiment, a monomer (for example, ethylene) is polymerized using the methodologies disclosed here to produce a polymer of the type disclosed here. The polymer can comprise a homopolymer. In one embodiment, the polymer is a homopolymer. It should be understood that an insignificant amount of comonomer may be present in the polymers disclosed here and the polymer is still considered a homopolymer. Here, an insignificant amount of a comonomer refers to an amount that does not substantially affect the properties of the polymer disclosed herein. For example, a comonomer may be present in an amount of less than about 0.5% by weight, 0.1% by weight or 0.01% by weight based on the total weight of the polymer.
[00076] The polymer can include other additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, non-stick agents, tachyants, 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 by any suitable technique, for example, during an extrusion or composition phase, such as during pelletizing or subsequent processing on an end-use article.
[00077] In one embodiment, a polymer of the type described here is characterized by a density greater than or equal to about 0.960 g / cc, alternatively greater than about 0.9615 g / cc, alternatively greater than about 0.9625 g / cc as determined according to ASTM D 1505.
[00078] A polymer of the type described here can be a multimodal resin. Here, the "modality" of a polymer resin refers to the shape of its molecular weight distribution curve, that is, the appearance of the graph of the polymer's weight fraction as a function of its molecular weight, as can be displayed for example, gel permeation chromatography (GPC). The weight fraction of the polymer refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak can be referred to as a unimodal polymer, a polymer having a curve showing two distinct peaks can be referred to as a bimodal or bimodal-like polymer, a polymer having a curve showing three distinct peaks can be referred to as trimodal polymer, etc. Polymers having molecular weight distribution curves, showing more than one peak, can be collectively referred to as multimodal polymers or resins. It is recognized that, in some cases, a multimodal polymer may appear to have a single peak through, for example, GPC analysis, when, in fact, the polymer itself is multimodal. In such cases, overlapping peaks can obscure the presence of other peaks and may imply unimodality, when in fact multimodality is a more accurate representation of the nature of the polymer or polymers.
[00079] In one embodiment, the polymer is characterized as a bimodal resin. Such a bimodal resin can show two distinct peaks attributable to a higher molecular weight component (HMW) and a lower molecular weight component (LMW). In one embodiment, the LMW component is present in the polymer composition in an amount from about 60% to about 90%, alternatively from about 65% to about 90%, or alternatively from about 70% to about 88%. In one embodiment, the HMW component is present in the polymer in an amount of about 10% to about 40%, alternatively from about 10% to about 35% or, alternatively, from about 12% to about 30% .
[00080] In one embodiment, a polymer of the type described here has a weighted average molecular weight (Mw) of about 100 kg / mol to about 180 kg / mol; alternatively from about 110 kg / mol to about 170 kg / mol; or, alternatively from about 120 kg / mol to about 160 kg / mol. The weighted average molecular weight describes the molecular weight distribution of a polymer and is calculated according to equation 1:
where Ni is the number of molecules in molecular weight Mi.
[00081] A polymer of the type described here can be characterized by a molecular weight distribution (MWD) of about 6 to about 20; alternatively from about 7 to about 18, or alternatively from about 7.5 to about 16. MWD is the ratio between Mw and the average molecular weight (Mn), which is also referred to as the polydispersity index ( PDI), or more simply as polydispersity. The average molecular weight is the common average of the molecular weights of the individual polymers and can be calculated according to equation (2):
where Ni is the number of molecules in molecular weight Mi.
[00082] A polymer of the type described here can be further characterized by a ratio between the average molecular weight-z (Mz) and Mw (Mz / Mw) from about 3 to about 7, alternatively from about 3.5 to about from 6.5, or alternatively from about 4.5 to about 6. The average z-molecular weight is a higher-order molecular weight average that is calculated according to equation (3): where Ni is the number of molecules in molecular weight Mi. The Mz / Mw ratio is another indication of the extent of a polymer's MWD. In one embodiment, a polymer of the type described here has an Mz of about 300 kg / mol to about 1000 kg / mol; alternatively from about 500 kg / mol to about 900 kg / mol; or alternatively from about 600 kg / mol to about 850 kg / mol.
[00083] In one embodiment, a polymer of the type described here has a melt index, MI, in the range of about 0.5 grams for 10 minutes (g / 10 min) to about 4.0 g / 10 min, alternatively from about 0.5 g / 10 min to about 3.0 g / 10 min, or alternatively from about 0.75 g / 10 min to about 2.5 g / 10 min. The flow index (MI) refers to the amount of a polymer that can be forced through a flow index hole of 0.0825 inches in diameter when subjected to a force of 2160 grams in ten minutes at 190 ° C, as determined according to ASTM D 1238.
[00084] In one embodiment, a polymer of the type described in this document has a zero shear viscosity (E) in the range of about 8000 Pa-s to about 50000 Pa-s, alternatively from about 10,000 Pas to about 45000 Pa-s, or alternatively from about 15000 Pa-s to about 40,000 Pa-s as determined according to the Carreau-Yasuda (CY) model, which is represented by equation (4):
where E = viscosity = (Pa-s) y = shear rate (1 / s) a = rheological amplitude parameter t = relaxation time (s) [describes the time location of the transition region] E = shear viscosity zero (Pa s) [defines the Newtonian plateau] n = power law constant [defines the final slope of the high shear rate region].
[00085] To facilitate model adaptation, the power law constant n is maintained at a constant value. Details of the significance and interpretation of the CY model and derived parameters can be found at: 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 herein by reference in its entirety.
[00086] The zero shear viscosity refers to the viscosity of the polymeric composition at a zero shear rate and is indicative of the molecular structure of the materials. In addition, for polymer melts, zero shear viscosity is often a useful indicator of processing attributes, such as melt strength in foam and blow molding technologies and bubble stability in film blowing. For example, the higher the zero shear viscosity, the better the melt resistance or bubble stability.
[00087] In one embodiment, a polymer of the type described here has a CY-a value, as defined by Equation (4), greater than about 0.2, alternatively greater than about 0.26, or alternatively greater than about 0.30.
[00088] In one embodiment, a polymer of the type described here has a rheological relaxation time (T), defined by Equation (4), in the range of approximately 0.01 s to about 0.35 s, alternatively about 0 , 03 s at about 0.35 s, or alternatively from about 0.05 s to about 0.35 s. The relaxation rate refers to the viscous relaxation times of the polymer and is indicative of a distribution of relaxation times associated with the broad distribution of molecular weights.
[00089] Polymers of the type disclosed herein can be formed into articles of manufacture or articles of end use using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and casting.
[00090] In one embodiment, the polymers disclosed here are formed on a film using any technology suitable for preparing a film. For example, the film can be produced by a coextrusion melt film process, in which melt polymers of the type disclosed here are coextruded through a slit or matrix to form a thin extruded sheet. The sheet or film is extruded on a cold roll cooled by water. The cold roll works to immediately cool the sheet or film from its molten state to a solid state.
[00091] In one embodiment, the sheet or film can then be passed through rollers designed to stretch the sheet in different axial directions to produce biaxially oriented films, which can be additionally trimmed and rolled up for transportation or storage.
[00092] In one embodiment, polymers of the type disclosed here are formed into a film through a film process produced by blowing. In a blown film process, plastic molten material is extruded through an annular matrix, usually vertically, to form a walled tube. The size of the tube is a function of the blowing ratio that is controlled by the amount of air introduced into the die. The bubble then moves upward until it passes through pinch rollers where the tube is flattened. This flattened tube is then collected in a rolled form. In some cases, the edges of the tube are narrow, forming two flat sheets, which are then collected in the form of a roll. The cooling of the film tube produced by blowing is carried out through the use of an air ring that is on top of the die and blows cold air against the outer surface of the tube. On higher outlet lines, fresh cooled air can be continuously circulated within the bubble, allowing for higher outlet rates. This way of cooling the bubble is known as Internal Bubble Cooling (IBC). Typically, the blowing ratio between die and blown bubble would be 1.5 to 4 times the diameter of the die. The drawdown between the wall thickness of the molten material and the thickness of the cooled film occurs both in the radial and longitudinal directions and is easily controlled by changing the volume of air inside the bubble and by changing the escape velocity of the line.
[00093] The film formed from polymer resins of this disclosure can be of any thickness desired by the user. For example, the film can have a thickness ranging from about 0.75 mils (0.01905 mm) to about 3 mils (0.0762 mm); alternatively from about 1 mil (0.0254 mm) to about 2.5 mil (0.0635 mm); or alternatively from about 1.5 mils (0.0381 mm) to about 2.0 mils (0.0508 mm).
[00094] In one embodiment, films formed from polymers of this disclosure may exhibit enhanced barrier properties. For example, such films may exhibit reduced moisture vapor transmission rates (MVTR).
[00095] In one embodiment, polymers of the type disclosed here having a density of 0.960 g / cc to about 0.967 g / cc are formed in films with a thickness of 1 mil (0.0254 mm) through a film process produced by breath. Conventional polymers having densities in the range of 0.960 g / cc to about 0.967 g / cc can exhibit a moisture vapor transmission rate of X, where X = k1 {-61.95377 + 39.52785 (Mz / Mw) - 8.16974 (Mz / Mw) 2 + 0.55114 (Mz / Mw) 3} + k2 {- 114.01555 (1) + 37.68575 (Mz / Mw) (T) - 2.89177 (MZ / MW) 2 (T)} + ka {120.37572 (T) 2 - 25.91177 (MZ / MW) (T) 2} + k4 {18.03254 (T) 3} when Mw is from about 100 kg / mol to about 180 kg / mol; Mz is about 300 kg / mol to about 1000 kg / mol; T is about 0.01 s to about 0.35 s. The constants k1, k2, k3, and k4 are defined as follows: k1 is 1 g / 100 in2 ^ day; k2 is 1 g / 100 in2 ^ dia ^ s; ka is 1 g / 100 in2 dia2 s2; and k4 is 1 g / 100 in2 ^ dia ^ s3. Polymers of the type disclosed here having a density of 0.960 g / cc to about 0.967 g / cc, when formed in films of 1 mil (0.0254 mm) thickness through a blowing film process, exhibit varying MVTR values from 0 to 20% greater than X. In one embodiment, films formed from polymers of the type disclosed here may exhibit an MVTR less than or equal to about 0.55 mm grams per 100 square inches per day (g-mil / 100 in2 / day), alternatively less than or equal to about 0.50 g-mil / 100 in2 / day, or alternatively less than or equal to about 0.46 g-mil / 100 in2 / day, as measured according to ASTM F 1249. MVTR measures the passage of H2O gas through a barrier. MVTR can also be referred to as the water vapor transmission rate (WVTR). Typically, MVTR is measured in a special chamber, vertically divided by the substrate / barrier material. A dry atmosphere is in one chamber, and a wet atmosphere is in the other. A 24-hour test is performed to see how much moisture passes through the substrate / barrier from the "wet" chamber to the "dry" chamber under conditions that can specify any of the five combinations of temperature and humidity in the "wet" chamber.
[00096] Films produced from polymers of this disclosure can be used in the formation of any variety of articles for end use. For example, the polymer can be extruded into a sheet, which is then thermoformed into an end-use article, such as a container, cup, tray, palette, toy or component from another product. Other non-limiting examples of end-use items that can be produced from the films in this release include merchandise bags, t-shirt bags, garbage bags, grocery bags, product bags, food packaging for content such as cereals, cookies , cheese, meat, etc., retractable plastic and other items. In one embodiment, the polymers disclosed here (for example, polyethylene) can be formed into films that can be useful in food packaging. EXAMPLE 1
[00097] Polymers of the type described herein were prepared using a catalyst system comprising at least two metallocene complexes (for example, MTE-A and MTE-B), a solid oxide (for example, sulfated alumina) and an organoaluminium compound (for example, tri-isobutylaluminium (Tiba)). Specifically, 4 samples, designated Samples 1-4, of polyethylene homopolymers were prepared as disclosed herein. Various properties of the polymer have been evaluated and the results are shown in Table 1. Also shown are the values for a comparative polyethylene resin MARLEX 9659, which is a high density polyethylene commercially available from Chevron Phillips Chemical Company LLC. The molecular weight distribution profiles and a graph of dynamic fluidity viscosity as a frequency function for the samples are shown in Figures 1 and 2, respectively. Table 1

[00098] Although modalities of the invention have been shown and described, modifications of them can be made without departing from the spirit and teachings of the invention. The modalities and examples described here are exemplary only and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where ranges or numerical limitations are expressly indicated, such ranges or expressed limitations should be understood to include iterative ranges or limitations of similar magnitude that are within the ranges or limitations expressly indicated (for example, 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" with respect to any element of a claim is intended to mean that the element of the subject is required or, alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms, such as comprises, includes, having, etc., is to be understood as providing support for more restricted terms, such as consisting of, consisting essentially of, substantially understood by, etc.
[00099] In this sense, the scope of protection is not limited by the description defined above, but is limited only by the claims that follow, this scope including all equivalents of the subject of the claims. Each and every claim is incorporated into the specification as a form of the present invention. Thus, the claims are an additional 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 incorporated herein by reference, insofar as they provide exemplary details, procedures or other complementary to those presented in this document.

权利要求:
Claims (15)
[0001]
1. Bimodal polymer comprising polyethylene characterized by the fact that it has a melt index of 0.5 g / 10 min to 4.0 g / 10 min and a density greater than or equal to 0.96 g / cc, which, when formed on a 0.0254 mm film, exhibits a moisture vapor transmission rate ranging from greater than or equal to 0 to equal to or 20% greater than X, where X = k1 {-61.95377 + 39.52785 (Mz / Mw ) - 8.16974 (Mz / Mw) 2 + 0.55114 (Mz / Mw) 3} + k2 {-114.01555 (T) + 37.68575 (Mz / Mw) (T) - 2.89177 (Mz / Mw) 2 (T)} + k3 {120.37572 (T) 2 - 25.91177 (Mz / Mw) (T) 2} + k4 {18.03254 (t) 3} when Mw is from 100 kg / mol to 180 kg / mol; Mz is from 300 kg / mol to 1000 kg / mol; t is 0.01 s to 0.35 s; k1 is 1 g / 100 in2 day; k2 is 1 g / 100 in2 ^ dia ^ s; k3 is 1 g / 100 in2 dia2 s2; and k4 is 1 g / 100 in2 ^ dia ^ s3 and where the polymer has a ratio between the average molecular weight z and the weighted average molecular weight of 3 to 7.
[0002]
2. Polymer according to claim 1, characterized by the fact that it has a higher molecular weight component (HMW) and a lower molecular weight component (LMW).
[0003]
3. Polymer according to claim 2, characterized by the fact that the HMW component is present in an amount of 60% to 90% based on the total weight of the polymer and the LMW component is present in an amount of 10% to 40% based on the total weight of the polymer.
[0004]
4. Polymer according to claim 1, characterized by the fact that it has a polydispersity index of 6 to 20 or a rheological relaxation time of 0.01 s to 0.35 s.
[0005]
5. Polymer according to claim 1, characterized by the fact that the polymer comprises an ethylene homopolymer.
[0006]
6. Polymer according to claim 1, characterized by the fact that it has a weighted average molecular weight from 100 kg / mol to 180 kg / mol.
[0007]
7. Polymer according to claim 1, characterized by the fact that it has an average molecular weight of 300 kg / mol to 1000 kg / mol.
[0008]
8. Polymer according to claim 1, characterized by the fact that it has a zero shear viscosity from 8000 Pa-s to 50,000 Pa-s or has a CY-a value greater than 0.2.
[0009]
9. Polymer, according to claim 1, characterized by the fact that, when formed in a 0.0254 mm thick film, it exhibits a moisture vapor transmission rate of less than or equal to 0.55 g-mil / 100 in2 in 24 hours, as determined according to ASTM F 1249.
[0010]
10. Polymer, according to claim 1, characterized by the fact that, formed in a 0.0254 mm thick film, it exhibits a moisture vapor transmission rate less than or equal to 0.50 g-mil / 100 in2 in 24 hours, as determined according to ASTM F 1249.
[0011]
11. Polymer according to claim 1, characterized by the fact that it has a ratio between the average molecular weight-z and the weighted average molecular weight of 3.5 to 6.
[0012]
12. Polymer, according to claim 1, characterized by the fact that it was prepared by contacting a monomer with a catalyst system in a single reactor under conditions suitable for the formation of the polymer.
[0013]
13. Polymer according to claim 12, characterized in that the catalyst system comprises at least two metallocene complexes.
[0014]
14. Polymer according to claim 12, characterized by the fact that the reactor employed a sludge cycle process.
[0015]
15. Food packaging container, characterized by the fact that it comprises the film as defined in claim 1.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

2020-05-26| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

2021-01-05| B09A| Decision: intention to grant|

2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US201161530711P| true| 2011-09-02|2011-09-02|

US61/530,711|2011-09-02|

US13/306,321|US9284391B2|2011-09-02|2011-11-29|Polymer compositions having improved barrier properties|

US13/306,321|2011-11-29|

PCT/US2012/053608|WO2013033690A1|2011-09-02|2012-09-04|Polymer compositions having improved barrier properties|

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