RU2806260C2 - Ethylene homopolymers with reverse distribution of short-chain branches - Google Patents

Abstract

FIELD: ethylene homopolymers.

SUBSTANCE: 2 embodiments of an ethylene homopolymer are proposed which have a density less than or equal to 0.925 g/cm³, a number of short chain branches (SCBs) ranging from 3 to 15 SCBs per 1000 carbon atoms in total, wherein at least 50% of the SCBs are methyl branches according to the first embodiment and have a density in the range from 0.90 g/cm³ to 0.925 g/cm³, the number of long chain branches (LCB) per 1000 carbon atoms in total is in the range from 0.3 to 2, the Mw/Mn ratio is in range from 2 to 100 according to the second embodiment, products containing the proposed ethylene homopolymers, and the method of polymerization of ethylene are also proposed.

EFFECT: obtaining linear low-density polyethylene, containing no or extremely small amounts of comonomer, and also having a wide molecular weight distribution.

20 cl, 2 dwg, 1 tbl, 1 ex

Description

BACKGROUND OF THE ART

Polyolefins, such as high-density polyethylene homopolymer (HDPE) and linear copolymer low-density polyethylene (LLDPE), can be produced using various combinations of catalyst systems and polymerization methods. In some end applications, it may be preferable for the catalyst system used to include short chain branching, without the use of a comonomer, to produce lower density ethylene homopolymers. In addition, it may be preferable for the ethylene homopolymer to have a broad molecular weight distribution (MWD), which results in good extrudability, polymer melt strength, and bubble stability in the production of blown films. Accordingly, the present invention is generally aimed at solving these problems.

BRIEF DESCRIPTION OF THE INVENTION

The present summary of the invention is provided to introduce, in a simplified form, a selection of concepts that are further presented in the detailed description below. This brief description is not intended to identify required or essential features of the claimed invention. Also, this brief description does not limit the scope of the claimed invention.

The present invention generally relates to ethylene homopolymers. In one aspect, the ethylene homopolymer may have a density less than or equal to about 0.94 g/cm ³ , an inverse short chain branching (RSBC) distribution, a number of short chain branches (SCBCs) ranging from about 2 to about 20 CBCs per a total of 1000 carbon atoms , and wherein at least about 50% of the CCRs are methyl branches. In another aspect, the ethylene homopolymer may have a density less than or equal to about 0.94 g/cm ³ , reverse short chain branching (RSBC), and a Mw/Mn ratio ranging from about 2 to about 100, and at least about 50 % CCRs are methyl branches. Such ethylene homopolymers can be used to produce a variety of products such as films (eg blown films), sheets, pipes and molded products.

The present invention also provides catalyst compositions. Such catalyst compositions may include catalyst component I containing a nickel diimine complex, catalyst component II containing a metallocene compound, an activator and, optionally, a cocatalyst. The present invention also contemplates and covers polymerization processes, for example, contacting a catalyst composition with ethylene and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer. A typically used catalyst composition may contain: any of the nickel diimine complexes, any of the metallocene compounds, and any of the activators described herein. Additionally, organoaluminum compounds or other cocatalysts can also be used in polymerization processes.

Both the above Brief Description of the Invention and the following Detailed Description are exemplary, and such descriptions are illustrative only. Accordingly, the above summary of the invention and the following detailed description should not be considered limiting. Moreover, in addition to the features and options described herein, other features or options may be offered. For example, certain aspects and embodiments may relate to various combinations and subcombinations of the features described in the detailed description.

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

In FIG. 1 shows a diagram of the molecular weight distribution and short-chain branching distribution of the polymer from Example 1.

Fig. 2 is a differential scanning calorimeter (DSC) plot for the polymer of Example 1.

DEFINITIONS

For a clearer understanding of the terms used in this document, the following definitions are provided. Unless otherwise noted, the following definitions apply to this specification. If any term is used in the specification that is not specifically defined herein, the definition given in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may be used, provided that such definition is not inconsistent with any other specification or definition. as used herein, or does not render vague or invalid any claim to which such definition applies. In the event that any definition or application given in any document incorporated herein by reference is inconsistent with a definition or application given herein, the definition or application given herein shall control.

Features of the subject matter are described herein such that combinations of various features may be contemplated within specific aspects. For each and every aspect and/or feature described herein, all combinations that do not adversely affect the polymers, compositions and methods described herein are included with or without a detailed description of the specific combination. In addition, unless expressly stated otherwise, any aspect and/or feature disclosed herein may be combined to describe polymers, compositions and methods consistent with this disclosure.

Although polymers, compositions and methods are described herein as “comprising” various properties, components or steps, said polymers, compositions and methods may also “consist essentially of” or “consist of” various properties, components or steps , unless otherwise specified. For example, the catalyst composition according to aspects of the present invention may contain; alternatively may consist essentially of; or alternatively may consist of a catalyst component I, a catalyst component II, an activator and a cocatalyst.

Terms in the singular include plural alternatives, such as at least one, unless otherwise noted. For example, the description of “support activator” or “metallocene compound” is intended to include one or a mixture, or combination of more than one support activator or metallocene compound, respectively, unless otherwise indicated.

In general, groups of elements are indicated using the numbering scheme specified in the version of the periodic table of the elements published in Chemical and Engineering News , 63(5), 27, 1985. In some cases, a group of elements may be indicated using the common name adopted for this group; for example, alkali metals for group 1 elements, alkaline earth metals for group 2 elements, transition metals for group 3-12 elements, and halogens or halides for group 17 elements.

For any particular compound described herein, the general structure or given name is also intended to include all structural isomers, conformational isomers, and stereoisomers that may result from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly stated otherwise; for example, a common reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a common reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. In addition, reference to the general structure or name includes all enantiomers, diastereomers and other optical isomers existing in enantiomeric or racemic forms, as well as mixtures of stereoisomers where permitted or required by the context. For any specific formula or name presented, any general formula or name presented also includes all conformational isomers, regioisomers and stereoisomers that can be formed from a particular set of substituents.

The term "polymer" is used herein generically and includes ethylene homopolymers, copolymers, terpolymers, and the like, as well as alloys and mixtures thereof. The term "polymer" also includes impact, block, graft, random and alternating copolymers. A copolymer is prepared from an olefin monomer and one olefin comonomer, and a terpolymer is prepared from an olefin monomer and two olefin comonomers. Accordingly, “polymer” includes copolymers and terpolymers derived from ethylene and any comonomer(s) described herein. Likewise, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Thus, the ethylene polymer may include ethylene homopolymers, ethylene copolymers (eg, ethylene/α-olefin copolymers), ethylene terpolymers, etc., as well as combinations or mixtures thereof. Thus, the ethylene polymer includes polymers often referred to in the art as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene). For example, an ethylene copolymer can be prepared from ethylene and a comonomer such as 1-butene, 1-hexene or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene/1-hexene copolymer. The term "polymer" also includes all possible geometric configurations unless otherwise noted, and such configurations may include isotactic, syndiotactic, and random symmetries. In addition, unless otherwise noted, the term "polymer" also includes polymers of all molecular weights and includes low molecular weight polymers or oligomers.

The term "metallocene" as used herein describes compounds containing at least one η ³ - η ⁵ -cycloalkadienyl moiety, wherein the η ³ - η ⁵ -cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of them. Possible substituents on these ligands may include H, thus the present invention includes ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, a metallocene is referred to simply as a "catalyst", much in the same way that the term "co-catalyst" is used in this context to describe, for example, an organoaluminum compound.

The terms “catalytic composition”, “catalytic mixture”, “catalytic system”, etc. independent of the actual product or composition resulting from contact or interaction of the starting components of the described or claimed catalyst composition/mixture/system, the nature of the active catalyst site, or changes in the cocatalyst, metallocene compound, nickel diimine complex, or activator (e.g., activator-support ), after combining the specified components. Therefore, the terms “catalytic composition”, “catalytic mixture”, “catalytic system”, etc. include the original starting components of the composition as well as any product(s) that can be obtained by contacting said initial starting components, said terms including both heterogeneous and homogeneous catalyst systems or compositions. The terms “catalytic composition”, “catalytic mixture”, “catalytic system”, etc. may be used interchangeably in this description.

Although any methods, devices, and materials similar or equivalent to those described herein are employed in the practice or testing of the invention, exemplary methods, devices, and materials are described herein.

All publications and patents referenced herein are incorporated herein by reference for purposes of description and disclosure, for example, of designs and methodologies described in such publications that may be used in connection with the invention described herein.

The present invention provides several types of ranges. If a range of any type is described or claimed, then each possible individual number that is included in the specified range is also described or claimed, including the end points of the range, as well as any subranges and combinations of subranges included therein. For example, if a chemical moiety containing a specified number of carbon atoms is described or claimed, each possible value that may fall within that range is assumed to be separately described or claimed in accordance with the invention as described. For example, the description that the fragment is a C ₁ -C ₁₈ hydrocarbon group, or, in other words, a hydrocarbon group containing from 1 to 18 carbon atoms, in this context refers to a fragment that may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms, and any range between these two values (for example, C ₁ -C ₈ hydrocarbon group), and also including any combination of ranges between these two values (eg, C ₂ -C ₄ and C ₁₂ -C ₁₆ hydrocarbon group).

Likewise, another illustrative example is presented for the Mz/Mw ratio of an ethylene polymer, in accordance with aspects of the present invention. The description that the Mz/Mw ratio can be from about 3 to about 6 includes mention that the Mz/Mw ratio can be any ratio in the specified range and, for example, can be equal to about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, or about 6. In addition, the Mz/Mw ratio can be from about 3 to about 6 (for example, from about 3.5 to about 5.5) and also includes any combination of ranges between about 3 and about 6 (for example, the Mz/Mw ratio may be from about 3 to about 4 or from about 5 to about 6). In addition, in all cases where a specific value is stated “about”, that value itself is described. Thus, the statement that the Mz/Mw value is from about 3 to about 6 also indicates a range of Mz/Mw from 3 to 6 (for example, from 3.5 to 5.5), which range also includes any combination ranges between 3 and 6 (for example, from 3 to 4 or from 5 to 6). By analogy, all other ranges described herein should be interpreted in the same way as the above examples.

The term “about” means that quantities, sizes, compositions, parameters and other quantities and characteristics are not and do not have to be exact, but may be approximate and/or larger or smaller if desired, reflecting tolerances, conversion factors, rounding, errors measurements and the like, as well as other factors known to those skilled in the art. Generally, a quantity, size, composition, parameter or other quantity or characteristic is “approximate” or “approximate”, regardless of whether it is explicitly stated. The term “about” also includes amounts that differ due to different equilibrium conditions for the composition obtained from a particular starting mixture. Claims, whether modified by the term “about” or not, include quantity equivalents. The term "about" may mean within 10% of the specified numerical value, preferably within 5% of the specified numerical value.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates generally to catalyst compositions, methods for preparing catalyst compositions, methods of using catalyst compositions in the polymerization of olefins, polymer resins prepared using such catalyst compositions, and articles made using these polymer resins. In particular, the present invention relates to the production of ethylene homopolymers having a combination of relatively low density and reverse distribution of short chain branches (RCSB).

ETHYLENE POLYMERS

In general, the polymers described herein are ethylene-based polymers or ethylene polymers, including homopolymers of ethylene, as well as copolymers, terpolymers, etc. of ethylene and at least one olefin comonomer. Comonomers that can be copolymerized with ethylene can often contain from 3 to 20 carbon atoms in the molecular chain. For example, typical comonomers may include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc. or combinations thereof. In one aspect, the olefin comonomer may comprise a C ₃ -C ₂₀ olefin; alternatively, the olefin comonomer may contain a C ₃ -C ₁₀ olefin; alternatively, the olefin comonomer may contain a C ₄ -C ₁₀ olefin; alternatively, the olefin comonomer may contain a C ₃ -C ₁₀ α-olefin; alternatively, the olefin comonomer may contain a C ₄ -C ₁₀ α-olefin; alternatively, the olefin comonomer may contain 1-butene, 1-hexene, 1-octene, or any combination thereof; or, alternatively, the comonomer may contain 1-hexene. Typically, the amount of comonomer, based on the total weight of monomer (ethylene) and comonomer, can be from about 0.1 to about 20% by weight, from about 0.1 to about 10% by weight, from about 0.5 to about 15 % wt., from about 0.5 to about 8% wt. or from about 1 to about 15% of the mass.

In one aspect, the ethylene polymer of the present invention may comprise (or consist essentially of, or consist of) an ethylene homopolymer, while in another aspect, the ethylene polymer may contain (or consist essentially of, or consist of) an ethylene/α-copolymer olefin, and in another aspect, the ethylene polymer may comprise (or consist essentially of, or consist of) an ethylene/α-olefin copolymer and an ethylene homopolymer. For example, the ethylene polymer may comprise ethylene/1-butene copolymer, ethylene/1-hexene copolymer, ethylene/1-octene copolymer, ethylene homopolymer, or any combination thereof; alternatively, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or any combination thereof; or, alternatively, an ethylene/1-hexene copolymer.

If the resulting polymer obtained according to the present invention is, for example, an ethylene homopolymer, its properties can be characterized using various analytical methods known and used in the polyolefin industry. Articles may be made from and/or contain ethylene polymers of the present invention, with typical properties of said polymers set forth below.

In particular aspects and unexpectedly, the ethylene homopolymers described herein often have a unique combination of low density and inverse distribution of short-chain branches. As used herein, ethylene homopolymer includes polymers derived from ethylene - without comonomer - and polymers in which minor amounts of α-olefin comonomer (eg, impurities) are also present during polymerization. Typically, the weight fraction of α-olefin comonomer, expressed as ethylene, is less than about 0.05% by weight. (500 ppm) or less than about 0.01 wt%. (100 ppm). An illustrative and non-limiting example of an ethylene homopolymer in accordance with aspects of the present invention may have a density less than or equal to about 0.94 g/cm ³ , an inverse short chain branching distribution (SBCD), and a number of short chain branches (SCBs) ranging from about 2 to about 20 CCR for a total of 1000 carbon atoms; and wherein at least about 50% of the CCRs are methyl branches. Another illustrative and non-limiting example of an ethylene homopolymer of the present invention may have a density less than or equal to about 0.94 g/cm ³ , an inverse short chain branching distribution (RSBCD), and a Mw/Mn ratio ranging from about 2 to about 100; and wherein at least about 50% of the CCRs are methyl branches. Such illustrative and non-limiting examples of ethylene homopolymers of the present invention may also have any of the homopolymer properties set forth below and in any combination unless otherwise noted.

The density of the ethylene homopolymers described herein is often less than or equal to about 0.94 g/cm ³ , for example, less than or equal to about 0.93 g/cm ³ or less than or equal to about 0.925 g/cm ³ . However, in particular aspects, the density may range from about 0.89 to about 0.94 g/ ^cm3 , from about 0.90 to about 0.94 g/ ^cm3 , from about 0.91 to about 0.94 g/cm ³ , from about 0.90 to about 0.932 g/cm ³ , from about 0.91 to about 0.932 g/cm ³ , from about 0.89 to about 0.93 g/cm ³ , from about 0.905 to about 0.93 g/ ^cm3 , about 0.91 to about 0.93 g/ ^cm3 , about 0.90 to about 0.925 g/ ^cm3 , or about 0.905 to about 0.922 g/ ^cm3 .

Without being limited to these values, the ethylene homopolymers described herein can often have a melt flow index (MFI) of from about 0 to about 25 g/10 min, from about 0 to about 10 g/10 min, or from about 0 to about 5 g/10 min. In other aspects, the ethylene homopolymers described herein may have a melt flow index (MFI) of from about 0.1 to about 5 g/10 min, from about 0.1 to about 3 g/10 min, from about 0.1 to about 1 g/10 min, from about 0.3 to about 5 g/10 min, from about 0.5 to about 4 g/10 min, or from about 0.5 to about 2 g/10 min.

In one aspect, the ethylene homopolymers described herein may have a Mw/Mn ratio or polydispersity index ranging from about 2 to about 100, from about 2 to about 20, from about 3 to about 30, from about 3 to about 20, from about 4 to about 100, about 4 to about 80, about 4 to about 30, about 4 to about 20, about 5 to about 75, or about 5 to about 50. In another aspect, the ethylene homopolymers described herein can have a Mw/Mn value ranging from about 5 to about 30, from about 5 to about 20, from about 6 to about 16, or from about 8 to about 15.

In one aspect, the ethylene homopolymers described herein may have a Mz/Mw ratio ranging from about 2 to about 8, from about 2 to about 7, or from about 2 to about 6. In another aspect, the ethylene homopolymers described herein , may have a Mz/Mw value of from about 2.5 to about 8, from about 2.5 to about 7, from about 2.5 to about 5, or from about 3 to about 6.

In one aspect, the ethylene homopolymers described herein may have a weight average molecular weight (Mw) of about 80,000 to about 800,000 g/mol, from about 80,000 to about 500,000 g/mol, or from about 85,000 to about 200,000 g/mol. In another aspect, the ethylene homopolymers described herein may have a Mw of from about 100,000 to about 750,000 g/mol, from about 100,000 to about 350,000 g/mol, from about 150,000 to about 800,000 g/mol, or from about 200,000 to about 600000 g/mol.

In one aspect, the ethylene homopolymers described herein may have a number average molecular weight (Mn) of from about 8,000 to about 70,000 g/mol, from about 10,000 to about 60,000 g/mol, from about 10,000 to about 40,000 g/mol, or from about 15,000 to about 55,000 g/mol. In another aspect, the ethylene homopolymers described herein may have a Mn value of from about 15,000 to about 45,000 g/mol, from about 15,000 to about 35,000 g/mol, or from about 20,000 to about 40,000 g/mol.

In one aspect, the ethylene homopolymers described herein may have a z-average molecular weight (Mz) of about 300,000 to about 3,000,000 g/mol, from about 400,000 to about 2,500,000 g/mol, from about 400,000 to about 2,000,000 g/mol or from about 500,000 to about 2,500,000 g/mol. In another aspect, the ethylene homopolymers described herein may have an Mz value of from about 500,000 to about 2,000,000 g/mol, from about 500,000 to about 1,500,000 g/mol, from about 750,000 to about 2,000,000 g/mol, or from about 750,000 to about 1250000 g/mol.

Despite the relatively low density, the disclosed ethylene homopolymers have a relatively high peak melting point, often falling in the range of about 118 to about 135°C, from about 118 to about 130°C, from about 120 to about 135°C, or from about 120 up to approximately 132°C. In additional aspects, the ethylene homopolymer often has a peak melting point in the temperature range of from about 120 to about 130°C, from about 122 to about 135°C, from about 122 to about 132°C, from about 122 to about 130°C, or from about 122 to about 128°C. The peak melting point is determined using DSC (differential scanning calorimetry) on the second heating.

Without limitation, the percentage crystallinity of the ethylene homopolymer often ranges from about 30% to about 75%. For example, the ethylene homopolymer may have a percentage crystallinity of from about 35% to about 70%; alternatively from about 40% to about 65%; alternatively from about 45% to about 60%; or, alternatively, from about 40% to about 55%. Percent crystallinity is the ratio of the enthalpy of fusion (DSC at second heat) to the enthalpy of fusion for 100% crystalline PE (taken as 290 J/g).

Ethylene homopolymers generally have a moderate content of long chain branches (LCBs). For example, the ethylene homopolymer may contain from about 0.05 to about 10, from about 0.1 to about 8, from about 0.4 to about 6, from about 0.4 to about 4, from about 0.2 to about 3 , from about 0.3 to about 2 or from about 0.5 to about 1.5, DCB per a total of 1000 carbon atoms. DSBs are determined by NMR, and DSBs span branches with six (6) or more carbon atoms.

Moreover, ethylene homopolymers typically have an inverse distribution of short-chain branches (inverse or reverse RCCR; increasing branching distribution); at higher molecular weights, relatively more branching is observed. Reverse RCCR may be characterized by a higher number of short chain branches (SCBs) per aggregate 1000 carbon atoms of ethylene homopolymer at Mw than at Mn, and/or a higher number of SCBs per aggregate 1000 carbon atoms of ethylene homopolymer at Mz than at Mn. In FIG. 1 shows an ethylene homopolymer with reverse RCCR.

Without limitation, the ethylene homopolymer may have from about 2 to about 20 short chain branches (SCBs) per a total of 1000 carbon atoms. In one aspect, the number of CCPs per a total of 1000 carbon atoms may be from about 3 to about 15 (or from about 3 to about 10), and in another aspect from about 4 to about 12 (or from about 4 to about 9), and in yet another aspect, from about 5 to about 15 (or from about 5 to about 12). The content of CCR is determined using NMR.

Often at least half of the CCRs in the homopolymer are methyl branches, and these can be up to 90%, 95% or more. In one aspect, the ethylene homopolymer may contain an amount of CCBs that are methyl branches, at least about 55% and in other aspects at least about 60%, at least about 70%, at least about 75%, at least at least about 80% or at least about 85% of the CCRs are methyl branches.

In general, ethylene homopolymers according to some aspects of the present invention may have a bimodal (or multimodal) molecular weight distribution (determined by gel permeation chromatography (GPC) or other suitable analytical technique).

In one aspect, the ethylene homopolymer described herein may be a reactor product (eg, a single reactor product), eg, not a post-reactor mixture of two polymers, eg, having different molecular weight characteristics. As will be understood by those skilled in the art, physical mixtures of two different polymer resins can be produced, but this requires additional processing that complicates production, which is not required for the reactor product.

In addition, the ethylene homopolymers described herein may contain one or more additives. Non-limiting examples of suitable additives may include an antioxidant, an acid scavenger, an anti-lock additive, a glidant additive, a colorant, a filler, a processing aid, an ultraviolet inhibitor, and the like, as well as combinations of these additives.

PRODUCTS AND PRODUCTS

Articles may be prepared from and/or may contain ethylene polymers (eg, ethylene homopolymers) according to the present invention and are accordingly included within the scope of the present invention. For example, articles that may contain the ethylene polymers of the present invention may include, but are not limited to, agricultural film, automotive part, bottle, chemical container, drum, fiber or fabric, food packaging film or container, food service product, fuel tank , geomembrane, household container, liner, molded article, medical device or material, outdoor storage product, outdoor play equipment, pipe, sheet or tape, toy or road barrier, etc. To obtain these products, various methods can be used. Non-limiting examples of such methods include injection molding, blow molding, rotomoulding, film extrusion, sheet extrusion, profile extrusion, thermoforming and the like. In addition, additives and modifiers are often added to these polymers to ensure good processability of the polymer or final product. These methods and materials are described in Modern Plastics Encyclopedia , Mid-November 1995 Issue, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties , TAPPI Press, 1992; the contents of which are incorporated herein by reference in their entirety. In some aspects of the present invention, the article of manufacture may comprise any of the ethylene polymers (e.g., ethylene homopolymers) described herein, and the article of manufacture may be or may comprise a film (e.g., blown film), tube, or molded article .

Also provided herein is a method of molding or producing an article containing the ethylene polymer described herein. For example, the proposed method may include (i) contacting a catalyst composition with ethylene and an olefin comonomer under polymerization conditions in a polymerization reactor system to produce an ethylene polymer, wherein the catalyst composition may comprise a catalyst component I, a catalyst component II, an activator (e.g., a support -an activator containing a solid oxide treated with an electron-withdrawing anion) and an optional cocatalyst (for example, an organoaluminum compound); and (ii) molding an article containing the ethylene polymer. The molding step may include mixing, melt molding, extrusion, casting or thermoforming, and the like, including combinations thereof.

CATALYTIC SYSTEMS AND POLYMERIZATION METHODS

In accordance with some aspects of the present invention, an ethylene polymer (eg, an ethylene homopolymer) can be produced using a dual catalyst system. In these aspects, catalyst component I may comprise any suitable nickel diimine complex or any nickel diimine complex described herein. Catalyst component II may contain any suitable metallocene compound or any metallocene compound described herein. The catalyst system may contain any suitable activator or any activator described herein, and optionally any suitable cocatalyst or any cocatalyst described herein.

Catalytic component I may contain, in certain aspects of the present invention, a nickel diimine complex. Catalytic component I, for example, may contain a compound having the following formula:

(I).

In formula (I), the transition metal M may be Ni; X ¹ and X ² independently may be a monoanionic ligand, or X ¹ and X ² taken together may form a bidentate dianionic ligand; R ¹ and R ⁴ independently may be C ₁ to C ₁₈ hydrocarbyl or substituted hydrocarbyl; and R ² and R ³ independently may be hydrogen or C ₁ to C ₁₈ ^hydrocarbyl or substituted hydrocarbyl, or R ² and R ³ taken together may be C ₂ to C ₁₈ hydrocarbylene or substituted hydrocarbyl, to form carbocyclic ring.

Ligands coordinated to the transition metal M (nickel) in the compound of formula (I) include X ¹ and X ² , which may be monoanionic ligands, but may also be bidentate or multidentate dianionic ligands. For example, X ¹ and X ² independently may be a halide, hydride, C ₁ -C ₁₈ hydrocarbyl or C ₁ -C ₁₈ hydrocarbyl oxide, or X ¹ and X ² taken together may be C ₁ -C ₁₈ hydrocarbylene dioxide. In one aspect, X ¹ and X ² can independently be a chloride, bromide, iodide, hydride, C ₁ -C ₁₈ hydrocarbyl, or C ₁ -C ₁₈ hydrocarbyl oxide. In another aspect, X ¹ and X ² may independently be a chloride, bromide, hydride, or C ₁ -C ₄ alkoxide. In yet another aspect, X ¹ and X ² taken together may be a lactate, glycolate, salicylate, catecholate, oxalate or malonate. In yet another aspect, X ¹ and X ² may be a chloride.

Ligands coordinated to the transition metal M (nickel) in compound (I) may include diimine ligands represented by the general formula:

.

In this formula, the substituents R ¹ and R ⁴ independently can be C ₁ to C ₁₈ hydrocarbyl or substituted hydrocarbyl. The substituents R ² and R ³ independently may be hydrogen, C ₁ to C ₁₈ hydrocarbyl or substituted hydrocarbyl, or R ² and R ³ taken together may be C ₂ to C ₁₈ hydrocarbylene or substituted hydrocarbyl to form a carbocyclic rings. For example, R ² and R ³ independently may be C ₂ to C ₁₈ hydrocarbyl or substituted hydrocarbyl, C ₃ to C ₁₈ hydrocarbyl or substituted hydrocarbyl, C ₄ to C ₁₆ hydrocarbyl or substituted hydrocarbyl, C ₅ to C hydrocarbyl ₁₄ or substituted hydrocarbyl, or C ₆ to C ₁₂ hydrocarbyl or substituted hydrocarbyl. In another example, R ² and R ³ taken together may form a carbocyclic ring as a C ₂ to C ₁₈ hydrocarbylene or substituted hydrocarbylene, a C ₄ to C ₁₈ hydrocarbylene or substituted hydrocarbylene, a C ₆ to C ₁₈ hydrocarbylene or substituted hydrocarbylene, or C ₁₀ to C ₁₈ hydrocarbylene or substituted hydrocarbylene. Therefore, in formula (I), R ¹ and R ⁴ may be different or, alternatively, R ¹ and R ⁴ may be the same.

As an example, R ¹ and R ⁴ can independently be aryl or substituted aryl, such as 2,6-disubstituted aryl or 2,4,6-trisubstituted aryl, and wherein either substituent is independently C ₁ -C ₁₂ hydrocarbyl. Thus, R ¹ and R ⁴ may independently be phenyl, 2,4,6-trimethylphenyl (mesityl), 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-ethyl-6-methylphenyl, 2-isopropyl-6 -methylphenyl, 2-isopropyl-6-ethylphenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2,6-diisopropyl-4-benzylphenyl, 2,6-diisopropyl-4-(1,1-dimethylbenzyl)-phenyl , 4-methylphenyl or 2-tert-butylphenyl.

Also by way of example, R ² and R ³ can independently represent hydrogen, C ₁ to C ₁₈ hydrocarbyl, or substituted hydrocarbyl. For example, R ² and R ³ independently can be hydrogen, methyl, ethyl, aryl or substituted aryl. In one aspect, R ² and R ³ taken together may be a C ₂ to C ₁₈ hydrocarbylene or a substituted hydrocarbylene to form a carbocyclic ring. For example, ^R2 and ^R3 taken together may represent a _C10 hydrocarbylene group having the following formula:

.

In some aspects, a nickel complex suitable for use as catalyst component I may have a diimine ligand represented by any of the following formulas:

, , , , , , , , including a combination of any of them, which can be used to form a mixture of nickel complexes having different combinations of these ligands.

Therefore, illustrative and non-limiting examples of nickel complexes suitable for use as catalyst component I may include the following compounds:

, ,

, , , , , , and similar compounds, as well as combinations thereof.

Catalytic component I is not limited to the nickel complexes described above. Other suitable nickel complexes are described in US Patent Publication No. 2017/0335022, which is incorporated herein by reference in its entirety.

Typically, catalyst component II may contain any suitable metallocene compound. For example, in one aspect, catalyst component II may comprise a zirconium- or hafnium-based bridged metallocene compound. In another aspect, catalyst component II may comprise a bridged zirconium- or hafnium-based metallocene compound with an alkenyl substituent. In another aspect, catalyst component II may comprise a monobridged metallocene compound containing a cyclopentadienyl group. In another aspect, catalyst component II may comprise a mono-bridged metallocene compound containing a fluorenyl group. In yet another aspect, catalyst component II may comprise a mono-bridged metallocene compound bearing an alkyl and/or aryl group substituent on the bridging atom (eg, a bridging carbon or silicon atom). In yet another aspect, catalyst component II may comprise a bridged zirconium or hafnium metallocene compound with a cyclopentadienyl group and a fluorenyl group, as well as an alkenyl substituent on the bridged group and/or on the cyclopentadienyl group.

In these and other aspects, any cyclopentadienyl group, indenyl group, or fluorenyl group on a bridged metallocene compound may independently be unsubstituted or may be substituted with any suitable substituent, any number of substituents, and at any position of the appropriate group, consistent with the rules of chemical valence. In addition, the bridging group may be a bridging atom (for example, carbon, silicon, or germanium) or a chain of bridging atoms, and the bridging atom or chain may be unsubstituted or may be substituted with any suitable substituent, any number of substituents, and at any position of the corresponding bridging group. groups corresponding to the rules of chemical valency.

Illustrative and non-limiting examples of bridged metallocene compounds suitable for use as catalyst component II may include the following compounds (Me=methyl, Ph=phenyl; t-Bu=tert-butyl):

etc., as well as their combinations.

Catalytic component II is not limited to the bridged metallocene compounds described above. Other suitable bridged metallocene compounds are described in US Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047, the entire contents of which are incorporated herein by reference.

Alternatively, catalyst component II may comprise a non-bridged metallocene compound, for example containing titanium, zirconium or hafnium. In another aspect, catalyst component II may comprise a non-bridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and indenyl group. In another aspect, catalyst component II may comprise a non-bridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups. In yet another aspect, catalyst component II may comprise a non-bridged zirconium- or hafnium-based metallocene compound containing two indenyl groups. In yet another aspect, catalyst component II may comprise a non-bridged zirconium- or hafnium-based metallocene compound containing cyclopentadienyl and indenyl groups. In some aspects, catalyst component II may comprise a non-bridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group.

Any cyclopentadienyl group, indenyl group or fluorenyl group on a non-bridged metallocene compound may independently be unsubstituted or may be substituted with any suitable substituent, any number of substituents and at any position of the corresponding group consistent with the rules of chemical valence. For example, an unbridged metallocene compound may contain two unsubstituted cyclopentadienyl groups (or two unsubstituted indenyl groups), or an unbridged metallocene compound may contain two substituted cyclopentadienyl groups (or two substituted indenyl groups), and these groups may have an alkyl substituent, for example, an alkyl-substituted cyclopentadienyl group . When the unbridged metallocene compound contains two cyclopentadienyl groups (or two indenyl groups), the cyclopentadienyl groups (or indenyl groups) may be the same or different.

Illustrative and non-limiting examples of non-bridged metallocene compounds suitable for use as catalyst component II may include the following compounds (Ph=phenyl):

and similar compounds, as well as combinations thereof.

Catalytic component I is not limited to the non-bridged metallocene compounds described above. Other suitable non-bridged metallocene compounds are described in US Pat. Nos. 7,199,073, 7,226,886, 7,312,283, and 7,619,047, the entire contents of which are incorporated herein by reference.

In accordance with one aspect of the present invention, the weight ratio of catalyst component I to catalyst component II in the catalyst composition can be from about 10:1 to about 1:10, from about 8:1 to about 1:8, from about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3; from about 2:1 to about 1:2, from about 1.5:1 to about 1:1.5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about 1:1,1.

In addition, the dual catalytic system contains an activator. For example, the catalyst system may contain an activator support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, and the like. or any combination thereof. The catalyst system may contain one or more than one activator.

In one aspect, the catalyst system may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or the like. or a combination thereof. Examples of such activators are described, for example, in US Pat. Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, and 8,114,946, the entire contents of which are incorporated herein by reference. In another aspect, the catalyst system may comprise an aluminoxane compound. In another aspect, the catalyst system may comprise an organoboron or organoborate compound. In another aspect, the catalyst system may comprise an ionizing ionic compound.

In other aspects, the catalyst system may comprise an activator support, for example, an activator support containing a solid oxide treated with an electron withdrawing anion. Examples of such materials are described, for example, in US Pat. Nos. 7294599, 7601665, 7884163, 8309485, 8623973 and 9023959, the entire contents of which are incorporated herein by reference. For example, the activator support may comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated alumina-silicon, chlorinated alumina-silicon, brominated alumina-silicon, sulfated alumina-silicon, fluorinated silica -zirconium, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium oxide, fluorinated-chlorinated silica-coated alumina, fluorinated-chlorinated silica-coated alumina, sulfated alumina silica, or alumina coated with phosphated silica, etc., as well as any combination thereof. In some aspects, the activator support may comprise a fluoridated solid oxide and/or a sulfated solid oxide. For example, the activator support may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, sulfated silica-coated alumina, or any combination thereof.

Various methods can be used to form the activator support useful in this invention. Methods for contacting a solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and amounts to be added, impregnation with metals or metal ions (for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc. . or combinations thereof), as well as various calcination procedures and conditions are described, for example, in US patents No. 6107230, 6165929, 6294494, 6300271, 6316553, 6355594, 6376415, 6388017, 6391816, 6395666, 65249 87, 6548441, 6548442, 6576583, 6613712 , 6632894, 6667274, 6750302, 7294599, 7601665, 7884163 and 8309485, the entire contents of which are incorporated herein by reference. Other suitable methods and techniques for preparing activator supports (eg, fluoridated solid oxides, sulfated solid oxides, etc.) are well known to those skilled in the art.

According to the present invention, catalyst compositions containing catalyst component I, catalyst component II, an activator (one or more) and, optionally, a co-catalyst can be used. If present, the cocatalyst may contain, without limitation, alkyl metal or organometallic cocatalysts, in which the metal includes boron, aluminum, zinc, and the like. Optionally, the catalyst systems provided herein may contain a co-catalyst or a combination of co-catalysts. For example, alkyl boron, alkyl aluminum and alkyl zinc compounds can often be used as cocatalysts in such catalyst systems. Exemplary boron compounds may include, without limitation, tri-n-butylborane, tripropylborane, triethylborane, and the like, and including combinations of two or more of these materials. Without limitation, exemplary aluminum compounds (e.g., organoaluminum compounds) may include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, etc., as well as any combinations thereof. Exemplary zinc compounds (e.g., organozinc compounds) that can be used as cocatalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di-(trimethylsilyl)-zinc, di-(triethylsilyl)-zinc, di -(triisopropylsilyl)-zinc, di-(triphenylsilyl)-zinc, di-(allyldimethylsilyl)-zinc, di-(trimethylsilylmethyl)-zinc, etc. or combinations thereof. Accordingly, in one aspect of the present invention, the dual catalyst composition may comprise catalyst component I, catalyst component II, an activator support, and an organoaluminum compound (and/or an organozinc compound).

In another aspect of the present invention, there is provided a catalyst composition that contains catalyst component I, catalyst component II, an activator support and an organoaluminum compound, wherein said catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds and/or other similar materials ; alternatively, is substantially free of aluminoxanes; alternatively, is substantially free of organoboron or organoborate compounds; or alternatively, is substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has the catalytic activity described herein in the absence of these additional materials. For example, the catalyst composition of the present invention may consist essentially of catalyst component I, catalyst component II, an activator support, and an organoaluminum compound, wherein said catalyst composition contains no other materials that increase/decreas the activity of the catalyst composition by more than about 10% relative to catalytic activity of the catalyst composition in the absence of these materials.

The catalyst compositions of the present invention typically have a catalytic activity of greater than about 5,000 grams of ethylene polymer (ethylene homopolymer and/or copolymer, as the context requires) per gram of nickel (or per gram of transition metal in the metallocene compound) per hour (abbreviated g/g /h). In another aspect, the catalytic activity may be greater than about 10,000, greater than about 15,000, or greater than about 20,000 g/g/hr, and can often be as high as 250,000-500,000 g/g/hr. Exemplary and non-limiting ranges of catalytic activity include: from about 5,000 to about 500,000, from about 10,000 to about 250,000, or from about 20,000 to about 100,000 g/g/h, and the like. These activities are measured under slurry polymerization conditions with triisobutylaluminum as a cocatalyst, using pentane as a diluent, at a polymerization temperature of about 60° C. and a reactor pressure of about 300 psig. (2.2 MPa g). Additionally, in some aspects, the activator support may comprise, but is not limited to, sulfated alumina, fluorinated alumina-silica, or fluorinated silica-coated alumina.

The present invention further includes methods for preparing said catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence. In one aspect, for example, the catalyst composition may be prepared by a process including contacting, in any order, catalyst component I, catalyst component II, and an activator, and in another aspect, the catalyst composition may be prepared by a process including contacting, in any order, catalytic component I, catalytic component II, activator and cocatalyst.

Ethylene polymers (eg, ethylene homopolymers) can be produced using the described catalyst systems using any suitable olefin polymerization process using different types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. One such olefin polymerization process for polymerizing olefins in the presence of a catalyst composition of the present invention may involve contacting said catalyst composition with ethylene and optionally an olefin comonomer (one or more) in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition may contain, as described herein, catalyst component I, catalyst component II, an activator, and an optional cocatalyst. The present invention also includes any ethylene polymers (eg, ethylene homopolymers) obtained using any of the polymerization methods described herein.

As used herein, the term "polymerization reactor" includes any polymerization reactor capable of polymerizing ethylene, alone or with a comonomer, to produce ethylene homopolymers, copolymers, terpolymers, and the like. Various types of polymerization reactors include batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor and the like. or combinations thereof; or, alternatively, the polymerization reactor system may comprise a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof. Polymerization conditions for various types of reactors are well known to those skilled in the art. Gas-phase reactors may include fluidized bed reactors or multi-stage horizontal reactors. Slurry reactors may include vertical or horizontal loops. High pressure reactors may include autoclave or tube reactors. Batch or continuous processes can be used in different types of reactors. Continuous processes may employ intermittent or continuous product discharge. Reactor systems and polymerization processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, and/or diluent.

The polymerization reactor system may include one or more reactors (2 reactors, more than 2 reactors, etc.) of the same or different types. For example, a polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, or a combination of two or more of these reactors. The multi-reactor production of polymers may include multiple steps in at least two separate polymerization reactors interconnected by a transfer device allowing the polymers produced in the first polymerization reactor to be transferred to the second polymerization reactor. The required polymerization conditions in one of the reactors may differ from the operating conditions in the other reactor(s). Alternatively, multi-reactor polymerization may involve manually transferring polymer from one reactor to subsequent reactors to continue polymerization. Multi-reactor systems may include any combination, including, without limitation, 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 reactors with loop and/or gas-phase reactors. Multiple reactors can be operated in series, in parallel, or in both configurations. Accordingly, the present invention covers polymerization reactor systems including one reactor, including two reactors, and including more than two reactors. In some aspects of the present invention, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, and multi-reactor combinations thereof.

In accordance with one aspect, the polymerization reactor system may include at least one slurry loop reactor comprising vertical or horizontal loops. The loop reactor in which the polymerization occurs can be fed continuously with monomer, diluent, catalyst and comonomer. In general, continuous processes may involve continuously introducing monomer/comonomer, catalyst and diluent into a polymerization reactor and continuously removing a slurry containing polymer particles and diluent from such reactor. The reactor effluent can be flashed to remove solid polymer from liquids containing diluent, monomer and/or comonomer. Various technologies may be used for this separation step, including, but not limited to, flashing, which may involve any combination of heat application and pressure reduction, separation by cyclone action in a cyclone or hydrocyclone, or separation by centrifugation.

An exemplary suspension polymerization process (also known as a particulate process) is described, for example, in US Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and 8,822,608, each of which is incorporated herein by reference in its entirety. .

Suitable diluents used in slurry polymerization include, but are not limited to, the polymerizable monomer and hydrocarbons, which are liquids 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 polymerization reactions in a loop reactor can occur in bulk, without the use of a diluent.

According to another aspect, the polymerization reactor system may comprise at least one gas phase reactor (eg, a fluidized bed reactor). Such reactor systems may employ a continuous recycle stream containing one or more monomers continuously circulated through a fluidized bed in the presence of a catalyst under polymerization conditions. The reused stream can be removed from the fluidized bed and returned to the reactor. At the same time, 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 may include multi-stage gas-phase olefin polymerization technology in which olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones, with the catalyst-containing polymer produced in the first polymerization zone being fed to a second polymerization zone. Exemplary gas phase reactors are described in US Pat. Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606, and 7,598,327, each of which is incorporated herein by reference in its entirety.

In accordance with another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, may include a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones into which fresh monomer, initiators or catalysts are introduced. The monomer can be entrained by a flow of inert gas and introduced into one of the reactor zones. Initiators, catalysts and/or catalyst components can be entrained in the gas stream and introduced into another zone of the reactor. For polymerization, the gas streams can be stirred. To achieve optimal conditions for the polymerization reaction, heat and pressure can be applied, respectively.

According to another aspect, the polymerization reactor system may include a solution polymerization reactor in which the monomer/comonomer is brought into contact with the catalyst composition through suitable agitation or other means. A carrier containing an inert organic diluent or an excess of monomer may be used. If desired, the monomer/comonomer can be brought into contact in the vapor phase with the catalytic reaction product in the presence or absence of liquid material. The polymerization zone can be maintained at a temperature and pressure that ensures the formation of a polymer solution in the reaction medium. Stirring can be used to improve temperature control and maintain homogeneity of the polymerization mixture in the polymerization zone. Appropriate means are used to dissipate the exothermic heat of polymerization.

The polymerization reactor system may further include any combination of at least one feedstock feed system, at least one catalyst or catalyst component feed system, and/or at least one polymer recovery system. Suitable reactor systems may further include systems for feed purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recirculation, storage, discharge, laboratory analysis and process control. Depending on the desired properties of the ethylene polymer, hydrogen may be added to the polymerization reactor as needed (eg, continuously, intermittently, etc.).

Polymerization conditions that can be adjusted to improve efficiency and achieve desired product properties may include temperature, pressure, and concentrations of various reagents. Polymerization temperature can affect catalyst performance, polymer molecular weight, and molecular weight distribution. Various polymerization conditions can be kept substantially constant, for example, to produce a particular grade of ethylene polymer (or ethylene homopolymer). A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically it is, for example, from about 60°C to about 280°C or from about 60°C to about 120°C, depending on the type of polymerization reactor(s). In some reactor systems, the polymerization temperature may generally be from about 70°C to about 100°C or from about 75°C to about 95°C.

Suitable pressure also varies depending on the reactor and type of polymerization. Liquid phase polymerization pressures in a loop reactor are typically less than 1000 psi. inch (6.9 MPa). Gas phase polymerization pressures are typically from about 200 to 500 psi. inch (1.4 to 3.4 MPa). High pressure polymerization in tubular or autoclave reactors is typically carried out at pressures ranging from about 20,000 to 75,000 psi. inch (from 138 to 517 MPa). Polymerization reactors can also operate in the supercritical region, which is typically at higher temperatures and pressures. Operating at conditions above the critical point on the pressure/temperature diagram (supercritical phase) can provide benefits to this polymerization reaction method.

Ethylene monomer and, if desired, olefin comonomer, can be used with the catalyst compositions and polymerization methods of the present invention. The olefin comonomer generally may include an olefin compound containing from 3 to 30 carbon atoms per molecule and containing at least one olefinic double bond. In one aspect, the olefin comonomer may comprise a C ₃ -C ₂₀ olefin; alternatively, a C ₃ -C ₁₀ alpha-olefin; alternatively, a C ₃ -C ₁₀ olefin; alternatively, a C ₃ -C ₁₀ alpha olefin; alternatively, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or any combination thereof; alternatively, 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, 1-butene; alternatively, 1-hexene; or alternatively 1-octene.

EXAMPLES

The present invention is further illustrated by the following examples, which should in no way be construed as limiting the scope of the present invention. Various other aspects, embodiments, modifications and equivalents thereof may be suggested by those skilled in the art upon examination of the description herein and do not depart from the spirit of the present invention or the scope of the appended claims.

Melt Flow Index (MFR, g/10 min) can be determined according to ASTM D1238 at 190°C at 2160 gram load, and Melt Flow Index at High Load (MFL, g/10 min) can be determined according to ASTM D1238 at 190°C at load 21600 grams. Density was determined in grams per cubic centimeter (g/cm ³ ) on a sample that was pressed into a mold, cooled at a rate of 15°C per hour, and held for 40 hours at room temperature, in accordance with ASTM D1505 and ASTM D4703 .

Peak melting temperature was determined using differential scanning calorimetry (DSC) as described in ASTM D3418 (2nd heat, ºC) at a heating rate of 10 °C/min. The percent crystallinity (%) was determined by dividing the enthalpy of fusion (in J/g) from the DSC curve for the 2nd heating, by 290 J/g (approximate enthalpy of 100% crystalline polyethylene).

The number of short chain branches (SCBs) per total 1000 carbon atoms was determined by NMR according to the procedure used in Jurkiewicz et al., Macromolecules 1999, 32 (17), 5471. The total number of SCBs per total 1000 carbon atoms was determined. and the number of methyl branches, ethyl branches, propyl branches, butyl branches and pentyl branches per collective 1000 carbon atoms. Long chain branches (LCBs) have also been determined by NMR, and for the purposes of this disclosure, LCBs include any branches with six (6) or more carbon atoms.

Molecular weight and molecular weight distribution values were determined on a PL-GPC 220 system (Polymer Labs, an Agilent Company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA), at 145 °C. The flow rate of the mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 g/l 2,6-di-tert-butyl-4-methylphenol (BHT) was set to 1 ml/min, the concentration of the polymer solutions was 1 .0-1.5 mg/ml depending on molecular weight. Sample preparation was carried out at 150°C for a nominal 4 hours with occasional gentle stirring, after which the solutions were transferred to sample tubes for sample injection. A sample injection volume of approximately 200 μL was used. An internal calibration method was used to determine the molecular weights and molecular weight distribution using Chevron Phillips Chemical Company's HDPE polyethylene resin MARLEX® BHB5003 as a reference standard. The integral table of standards was determined in advance in a separate experiment using size exclusion chromatography with multi-angle laser light scattering (SEC-MLS). Mn is the number average molecular weight, Mw is the mass average molecular weight, Mz is the z-average molecular weight, and Mp is the peak molecular weight (the position, by molecular weight, of the highest point on the molecular weight distribution curve).

The molecular weight distribution of short chain branches (SCBs) was determined using an IR5-detection GPC system (IR5-GPC), which GPC system was a PL220 GPC/SEC system (Polymer Labs, an Agilent Company) equipped with three Styragel columns HMW-6E (Waters, MA) for polymer separation. An IR5 MCT (IR5) detector (Polymer Char, Spain) with thermoelectric cooling was connected to the GPC columns using a heat transfer line. Chromatographic data was obtained from two output ports of the IR5 detector. The analog signal is first passed from the analog output port to the digitizer before connecting to computer "A" to determine the molecular weight using Cirrus software (Polymer Labs, now Agilent Company) and the integral calibration method using Marlex™ BHB5003 HDPE resin (Chevron Phillips Chemical) as a molecular weight standard. Digital signals, on the other hand, travel through a USB cable directly to Computer B, where they are received using LabView data acquisition software supplied by Polymer Char. The chromatogram recording conditions were chosen as follows: column oven temperature 145°C; flow rate 1 ml/min; sample injection volume 0.4 ml; and a polymer concentration of approximately 2 mg/ml, depending on the molecular weight of the sample. The temperature of the heat transfer line and the measuring cell of the IR5 detector was set to 150°C, and the temperature of the electronics of the IR5 detector was set to 60°C. The content of short-chain branches was determined using an in-house method using the intensity ratio of CH ₃ (I _CH3 ) to CH ₂ (I _CH2 ) in combination with a calibration curve. The calibration curve is a plot of the content of short-chain branches, SCB (x _SCB ), versus the intensity ratio I _CH3 /I _CH2 . To construct a calibration curve, a set of polyethylene resins (at least 5) with a CCR content from zero to approximately 32 CCR/a total of 1000 carbon atoms (standard CCR samples) was used. All of these standard QCR samples have known QCR contents and flat QCR profiles, previously obtained separately by NMR and solvent gradient fractionation coupled with NMR (SGR-NMR). Using the QCR calibration curves constructed in this manner, short-chain branching molecular weight distribution profiles were obtained for resins fractionated by the IR5-GPC system under exactly the same chromatogram recording conditions as for the QCR standards. The relationship between the intensity ratio and the elution volume was converted into a CCR distribution as a function of the MWD using a previously constructed CCR calibration curve (e.g., the intensity ratio I _CH3 /I _CH2 curve versus the CCR content) and the MW calibration curve (i.e., the molecular mass versus elution time) to convert the I _CH3 /I _CH2 intensity ratio and elution time into CCR content and molecular weight, respectively.

Activator substrates based on fluorinated silica-coated alumina (FASCO) were prepared as follows. Boehmite was purchased from W.R. Grace & Company under the name "Aluminum Oxide A" and had a surface area of 300 m ² /g, a pore volume of 1.3 ml/g and an average particle size of 100 microns. First, the aluminum oxide was calcined in dry air at about 600°C for about 6 hours, cooled to room temperature, and then brought into contact with tetraethyl orthosilicate in isopropanol to correspond to 25 wt%. _SiO2 . After drying, the aluminum oxide coated with silicon dioxide was calcined at 600°C for 3 hours. Fluorinated silica-coated alumina (7% wt. F) was prepared by impregnating calcined silica-coated alumina with a solution of ammonium bifluoride in methanol, drying, and then calcining for 3 hours at 600°C in dry air. Subsequently, fluorinated silica-coated alumina (FSCA) was collected and stored under dry nitrogen and used without access to the atmosphere.

EXAMPLE 1

The polymerization experiment of Example 1 was carried out for 60 minutes in a 500 ml reactor. First, 361 mg of OAPPDK and 0.30 ml of pure TIBA were added to the reactor with 100 ml of anhydrous n-pentane. Then 5.1 mg of diimine nickel catalyst (dissolved in a few ml of toluene) and 3.6 mg of a metallocene compound (dissolved in a few ml of toluene) were added to the reactor with 100 ml of anhydrous n-pentane. The structures of the nickel complex and zirconium-based metallocene are shown below.

The reactor was maintained at 300 psi ethylene pressure. inch at a reactor temperature of 26°C. With stirring, the reaction temperature quickly increased to 60°C and was maintained within 3 degrees with cooling during the 60-minute experiment. Ethylene was supplied as needed to maintain reactor pressure at 300 psi; no hydrogen or comonomer was added. After venting the reactor and removing the solvent, 33.1 g of polyethylene was isolated, which corresponds to a catalytic activity of 63,700 g/g/h (in terms of nickel) and 34,600 g/g/h (in terms of zirconium).

The reverse distribution of short-chain branches of the homopolymer from Example 1 is shown in FIG. 1, which shows the molecular weight distribution and the distribution of short-chain branches of the homopolymer. In FIG. 1 shows relatively more short chain branches (SCBs) at higher molecular weights; the amount of CCR per a total of 1000 carbon atoms (CA) of the polymer at Mw is greater than at Mn (and at Mz greater than at Mn).

Fig. 2 illustrates the 2nd heat differential scanning calorimeter (DSC) plot for the homopolymer from Example 1. The peak melting point was 126 ^° C. and the percent crystallinity was 51% (148.7 J/g divided by 290 J/g).

Table I summarizes some of the properties of the ethylene homopolymer from Example 1. Surprisingly, the homopolymer had the advantageous combination of a very low density (0.915 g/cm ³ , without comonomer), a wide molecular weight distribution (Mw/Mn 9.5) and a significant amount CCR (6.7 per combined 1000 carbons), of which 82% (5.5 divided by 6.7) were methyl branches. Moreover, as shown in FIG. 1-2 , the homopolymer also had a reverse RCCR and a high peak melting point.

By selecting a specific catalyst component I (nickel diimine complex) and a specific catalyst component II (metallocene compound) and their relative amounts (weight ratio of catalyst component I to catalyst component II), ethylene homopolymers having different densities, DCR content, CCR content can be obtained , methyl branch content, molecular weight distributions (Mw/Mn and Mz/Mw and Mw, Mn and Mz ratios), and thermal characteristics.

Table I. Example 1

Example Mn/1000
(g/mol) Mw/1000
(g/mol) Mz/1000
(g/mol) MP/1000
(g/mol) Mw/Mn Mz/Mw I.B. 1 27.4 261 1030 243 9.5 3.9 1.6

Table I. Example 1 (continued)

Example KCR
(at 1000 C) Methyl
(at 1000 C) Ethyl
(at 1000 C) I cut through
(at 1000 C) Butyl
(at 1000 C) Pentyl
(at 1000 C) C ₆₊
(at 1000 C) 1 6.7 5.5 1.2 0 0 0 0.9

Table I. Example 1 (continued)

Example Density
(g/ ^cm3 ) Peak melting point ( ^oC ) Crystallinity
(%) 1 0.915 126 51

The present invention has been described above with reference to numerous aspects and specific examples. Those skilled in the art will be able to suggest many modifications based on the above detailed description. All such obvious variations are within the intended full scope of the appended claims. Other aspects of the present invention may include, without limitation, the following (aspects are described as “comprising”, but alternatively they may “consist essentially of” or “consist of”):

Aspect 1. An ethylene homopolymer having (or characterized by):

density less than or equal to about 0.94 g/cm ³ ;

reverse distribution of short-chain branches (RCSB); And

a number of short chain branches (SCBs) ranging from about 2 to about 20 SCBs per a total of 1000 carbon atoms;

wherein at least about 50% of the CCRs are methyl branches.

Aspect 2. An ethylene homopolymer having (or characterized by):

density less than or equal to about 0.94 g/cm ³ ;

reverse distribution of short-chain branches (RCSB); And

a Mw/Mn ratio ranging from about 2 to about 100;

wherein at least about 50% of the CCRs are methyl branches.

Aspect 3. The homopolymer according to aspect 1 or 2, wherein said ethylene homopolymer has a density in any range described herein, for example, from about 0.89 to about 0.94 g/cm ³ , from about 0.90 to about 0.94 g/cm ³ , from about 0.91 to about 0.94 g/cm ³ , from about 0.905 to about 0.93 g/cm ³ , from about 0.91 to about 0.93 g/cm cm ³ , etc.

Aspect 4. A homopolymer according to any one of aspects 1-3, characterized in that said ethylene homopolymer has an inverse (or increasing) distribution of short chain branches, for example, the number of short chain branches (SCBs) per a total of 1000 carbon atoms of the polymer at Mw (or Mz) greater than with Mn.

Aspect 5. A homopolymer according to any of aspects 1-4, wherein said ethylene homopolymer has an amount of methyl branched CCBs in any range described herein, for example, at least about 55%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, etc.

Aspect 6. A homopolymer according to any of aspects 1-5, wherein said ethylene homopolymer has a number of short chain branches (SCBs) of a total of 1000 carbon atoms in any range described herein, for example, from about 2 to about 20, from about 3 to about 15, from about 4 to about 12, from about 5 to about 15, from about 5 to about 12, from about 4 to about 9 CCR, etc.

Aspect 7. A homopolymer according to any of aspects 1-6, wherein said ethylene homopolymer has an Mz/Mw ratio in any range described herein, for example, from about 4 to about 30, from about 4 to about 20, from about 5 to about 30, about 5 to about 20, about 8 to about 15, etc.

Aspect 8. A homopolymer according to any of aspects 1-7, wherein said ethylene homopolymer has a Mw in any range described herein, for example, from about 80,000 to about 800,000 g/mol, from about 80,000 to about 500,000 g/mol mole, from about 150,000 to about 800,000 g/mol, from about 200,000 to about 600,000 g/mol, etc.

Aspect 9. A homopolymer according to any of aspects 1-8, wherein said ethylene homopolymer has a Mn in any range described herein, for example, from about 10,000 to about 60,000 g/mol, from about 15,000 to about 55,000 g/mol mole, from about 15,000 to about 45,000 g/mol, from about 20,000 to about 40,000 g/mol, etc.

Aspect 10. A homopolymer according to any one of aspects 1-9, wherein said ethylene homopolymer has an Mz in any range described herein, for example, from about 300,000 to about 3,000,000, from about 500,000 to about 2,000,000, from about 500,000 to about 1,500,000, from about 750,000 to about 1,250,000 g/mol, etc.

Aspect 11. A homopolymer according to any of aspects 1-10, wherein said ethylene homopolymer has an Mz/Mw ratio in any range described herein, for example, from about 2 to about 8, from about 2.5 to about 7 , from about 2.5 to about 5 or from about 3 to about 6, etc.

Aspect 12. A homopolymer according to any of aspects 1-11, wherein said ethylene homopolymer has a melt flow index (MFI) in any range described herein, for example, from about 0 to about 25, from about 0 to about 5 , from about 0.1 to about 3, from about 0.1 to about 1 g/10 min, etc.

Aspect 13. A homopolymer according to any one of aspects 1-12, wherein in said ethylene homopolymer the number of long chain branches (LCBs) per a total of 1000 carbon atoms is within any range described herein, for example, from about 0.05 to about 10, about 0.1 to about 8, about 0.4 to about 6, about 0.4 to about 4, about 0.2 to about 3, or about 0.3 to about 2 DBR, etc.

Aspect 14. A homopolymer according to any one of aspects 1-13, wherein said ethylene homopolymer has a peak melting point in any melting temperature range described herein, for example, from about 120 to about 135°C, from about 120 to about 132°C, from about 120 to about 130°C, etc.

Aspect 15. A homopolymer according to any of aspects 1-14, wherein said ethylene homopolymer has a percentage crystallinity within any range described herein, for example, from about 30% to about 75%, from about 35% to about 70% , from about 45% to about 60%, etc.

Aspect 16. A homopolymer according to any of aspects 1-15, characterized in that said ethylene homopolymer has a bimodal or multimodal molecular weight distribution.

Aspect 17. A homopolymer according to any of aspects 1-16, wherein said ethylene homopolymer is a single reactor product, eg, not a post-reactor mixture of two polymers, eg having different molecular weight characteristics.

Aspect 18. A homopolymer according to any one of aspects 1-17, wherein said ethylene homopolymer further comprises at least one additive selected from an antioxidant, an acid scavenger, an antiblocking agent, a glidant, a colorant, a filler, a processing aid, an inhibitor ultraviolet radiation, etc. or any combination thereof.

Aspect 19. An article comprising an ethylene homopolymer according to any one of aspects 1-18.

Aspect 20. An article comprising an ethylene homopolymer according to any one of aspects 1-18, wherein said article is an agricultural film, an automobile part, a bottle, a chemical container, a drum, a fiber or fabric, a food packaging film or container, an article food service, fuel tank, geomembrane, household container, liner, molded article, medical device or material, outdoor storage product, outdoor play equipment, pipe, sheet or tape, toy or road barrier.

Aspect 21. A film, tube, or molded product comprising an ethylene homopolymer according to any one of aspects 1-18.

Aspect 22. Catalytic composition containing:

catalyst component I containing any suitable nickel diimine complex or any nickel diimine complex described herein, catalyst component II containing any suitable metallocene compound or any metallocene compound described herein, any suitable activator or any activator described herein document, and optionally any suitable cocatalyst or any cocatalyst described herein.

Aspect 23. The composition according to aspect 22, characterized in that said catalyst component II contains a bridged metallocene compound based on zirconium or hafnium.

Aspect 24. The composition according to aspect 22, characterized in that said catalyst component II contains a bridged metallocene compound based on zirconium or hafnium with an alkenyl substituent.

Aspect 25. The composition according to aspect 22, characterized in that said catalytic component II contains a monoatomic bridged metallocene compound containing an alkyl and/or aryl substituent group on the bridging atom.

Aspect 26. The composition of Aspect 22, wherein said catalyst component II comprises a mono-bridged metallocene compound containing a cyclopentadienyl group (eg, a bridged bis-cyclopentadienyl metallocene compound).

Aspect 27. The composition according to aspect 22, characterized in that said catalytic component II contains a monoatomic bridged metallocene compound containing a fluorenyl group.

Aspect 28. The composition of Aspect 22, wherein said catalyst component II comprises a non-bridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and indenyl group.

Aspect 29. The composition according to aspect 22, characterized in that said catalyst component II contains a non-bridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups.

Aspect 30. The composition according to aspect 22, characterized in that said catalyst component II contains a non-bridged zirconium- or hafnium-based metallocene compound containing two indenyl groups.

Aspect 31. The composition according to aspect 22, characterized in that said catalyst component II contains a non-bridged zirconium- or hafnium-based metallocene compound containing cyclopentadienyl and indenyl groups.

Aspect 32. A composition according to any of aspects 22-31, wherein said activator comprises an activator support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

Aspect 33. The composition according to any of aspects 22-32, characterized in that said activator contains an aluminoxane compound.

Aspect 34. The composition according to any of aspects 22-32, characterized in that said activator contains an organoboron or organoborate compound.

Aspect 35. A composition according to any of aspects 22-32, characterized in that said activator contains an ionizing ionic compound.

Aspect 36. A composition according to any of aspects 22-32, wherein said activator comprises an activator support, and said activator support comprises any solid oxide treated with any electron-withdrawing anion described herein.

Aspect 37. The composition according to any of aspects 22-32, wherein said activator comprises fluoridated alumina, chloridated alumina, brominated alumina, sulfated alumina, fluoridated alumina-silicon, chloridated alumina-silicon, brominated alumina -silicon, sulfated alumina-silicon oxide, fluoridated silica-zirconia, chloridated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium oxide, fluorinated silica-coated alumina, aluminum oxide, sulfated silica coated, phosphated silica coated alumina, or any combination thereof.

Aspect 38. The composition according to any of aspects 22-32, wherein said activator comprises fluorinated alumina, sulfated alumina, fluorinated alumina-silicon, sulfated alumina-silicon, fluorinated silica-coated alumina, alumina, coated with sulfated silica, or any combination thereof.

Aspect 39. A composition according to any of aspects 22-32, wherein said activator comprises a fluoridated solid oxide and/or a sulfated solid oxide.

Aspect 40. The composition according to any of aspects 36-39, wherein said activator further contains any metal or metal ion described herein, for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten , molybdenum, zirconium, or any combination thereof.

Aspect 41. A composition according to any of aspects 22-40, wherein said catalyst composition contains a cocatalyst, for example, any suitable cocatalyst.

Aspect 42. A composition according to any of aspects 22-41, wherein said cocatalyst contains any organoaluminum compound described herein.

Aspect 43. The composition according to aspect 42, characterized in that said organoaluminum compound contains trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.

Aspect 44. A composition according to any of aspects 36-43, wherein said catalyst composition comprises catalyst component I, catalyst component II, a solid oxide treated with an electron withdrawing anion, and an organoaluminum compound.

Aspect 45. A composition according to any of aspects 36-44, wherein said catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

Aspect 46. A composition according to any of aspects 22-45, wherein the weight ratio of catalyst component I to catalyst component II in said catalyst composition is within any range described herein, for example, from about 10:1 to about 1: 10, from about 5:1 to about 1:5, from about 2:1 to about 1:2, etc.

Aspect 47. A composition according to any of aspects 22-46, wherein said catalyst composition is prepared by a process comprising contacting, in any order, catalyst component I, catalyst component II, and an activator.

Aspect 48. The composition according to any of aspects 22-46, wherein said catalyst composition is prepared by a process comprising contacting, in any order, catalyst component I, catalyst component II, an activator and a cocatalyst.

Aspect 49. A composition according to any of aspects 22-48, wherein the catalytic activity of said catalyst composition is within any range described herein, for example, at least 15,000, from about 10,000 to about 250,000, from about 20,000 to approximately 100,000 grams, etc. ethylene polymer per gram of nickel (or per gram of transition metal in the metallocene compound) per hour, under slurry polymerization conditions, with a triisobutylaluminum cocatalyst, using pentane as a diluent and at a polymerization temperature of 60 °C and a reactor pressure of 300 psi hut (2.2 MPa g).

Aspect 50. A polymerization process comprising contacting a catalyst composition according to any one of aspects 22-49 with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

Aspect 51. The method of Aspect 50, wherein said olefin comonomer comprises a C ₃ -C ₂₀ alpha olefin.

Aspect 52. The method of Aspect 50, wherein the catalyst composition is contacted with ethylene and an olefin comonomer containing a C ₃ -C ₁₀ alpha olefin.

Aspect 53. The method of Aspect 50, wherein the catalyst composition is contacted with ethylene and an olefin comonomer containing 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 54. The method according to any one of aspects 50-53, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.

Aspect 55. A method according to any one of aspects 50-54, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

Aspect 56. The method according to any of aspects 50-55, wherein the polymerization reactor system comprises a loop slurry reactor.

Aspect 57. A method according to any of aspects 50-56, wherein the polymerization reactor system comprises a single reactor.

Aspect 58. The method according to any of aspects 50-56, characterized in that the polymerization reactor system contains 2 reactors.

Aspect 59. The method according to any of aspects 50-56, characterized in that the polymerization reactor system contains more than 2 reactors.

Aspect 60. A method according to any of aspects 50-59, wherein said ethylene polymer includes any ethylene polymer described herein.

Aspect 61. A method according to any one of aspects 50-60, wherein said ethylene polymer comprises an ethylene homopolymer.

Aspect 62. A method according to any of aspects 50-60, wherein said ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

Aspect 63. A method according to any one of aspects 50-62, wherein the polymerization conditions include a polymerization reaction temperature in the range of about 60 °C to about 120 °C and a reaction pressure in the range of about 200 to about 1000 psi hut (from about 1.4 to about 6.9 MPa).

Aspect 64. A method according to any of aspects 50-63, characterized in that the polymerization conditions are substantially constant, for example, for a particular grade of polymer.

Aspect 65. A method according to any one of aspects 50-64, characterized in that no hydrogen is added to the polymerization reactor system.

Aspect 66. A method according to any of aspects 50-64, characterized in that hydrogen is added to the polymerization reactor system.

Aspect 67. A method according to any of aspects 50-66, wherein the resulting ethylene polymer is defined in any of aspects 1-18.

Aspect 68. An ethylene polymer produced by the olefin polymerization process of any one of aspects 50-66.

Aspect 69. An ethylene homopolymer according to any one of aspects 1-18, prepared by a method according to any one of aspects 50-66.

Aspect 70. An article comprising a polymer as defined in any one of aspects 68-69.

Claims (57)

1. An ethylene homopolymer used to produce various products such as films, sheets, pipes and molded products, having: density less than or equal to 0.925 g/cm ³ ; number of short chain branches (SCBs) ranging from 3 to 15 SCBs per 1000 carbon atoms in total; wherein at least 50% of the CCRs are methyl branches. 2. The homopolymer according to claim 1, characterized in that said homopolymer is additionally characterized by the number of CCRs per a total of 1000 carbon atoms at Mz greater than at Mn. 3. Homopolymer according to claim 1, characterized in that: density ranges from 0.905 to 0.922 g/cm ³ ; the number of CCRs per a total of 1000 carbon atoms ranges from 4 to 12; at least 70% of the CCRs are methyl branches. 4. Product, including films, sheets, pipes and molded products, containing the homopolymer according to claim 3. 5. Homopolymer according to claim 1, characterized in that said homopolymer is additionally characterized by: Mw/Mn ratio in the range from 5 to 20; And ratio Mz/Mw in the range from 2.5 to 7. 6. Homopolymer according to claim 1, characterized in that said homopolymer is additionally characterized by: Mw in the range from 80,000 to 500,000 g/mol; Mn in the range from 10,000 to 60,000 g/mol; And Mz in the range from 500000 to 2000000 g/mol. 7. Homopolymer according to claim 1, characterized in that said homopolymer is additionally characterized by: the number of long-chain branches (LCBs) per a total of 1000 carbon atoms in the range from 0.1 to 8; peak melting point in the temperature range from 120 to 132°C; And percentage crystallinity ranging from 35 to 70%. 8. Product, including films, sheets, pipes and molded products, containing the homopolymer according to claim 7. 9. Ethylene homopolymer used to produce various products such as films, sheets, pipes and molded products, having: density in the range from 0.90 g/cm ³ to 0.925 g/cm ³ ; the number of long chain branches (LCBs) per a total of 1000 carbon atoms in the range from 0.3 to 2; And Mw/Mn ratio in the range from 2 to 100; wherein at least 50% of the CCRs are methyl branches. 10. Product, including films, sheets, pipes and molded products, containing the homopolymer according to claim 9. 11. The homopolymer according to claim 9, characterized in that said homopolymer is additionally characterized by the number of CCRs per a total of 1000 carbon atoms at Mz greater than at Mn. 12. Homopolymer according to claim 9, characterized in that: density ranges from 0.905 to 0.922 g/cm ³ ; the Mw/Mn ratio ranges from 6 to 16; And at least 75% of the CCRs are methyl branches. 13. Product, including films, sheets, pipes and molded products, containing the homopolymer according to claim 12. 14. Homopolymer according to claim 9, characterized in that the Mw/Mn ratio is in the range from 4 to 30. 15. Homopolymer according to claim 9, characterized in that said homopolymer is additionally characterized by: Mw in the range from 150,000 to 800,000 g/mol; Mn in the range from 15000 to 45000 g/mol; And Mz in the range from 500000 to 2000000 g/mol. 16. Homopolymer according to claim 9, characterized in that said homopolymer is additionally characterized by: the number of short-chain branches (SCBs) ranging from 4 to 9 per 1000 carbon atoms in total; peak melting point in the temperature range from 120 to 130°C; And percentage crystallinity ranging from 45 to 60%. 17. Product, including films, sheets, pipes and molded products, containing the homopolymer according to claim 16. 18. A method for polymerizing ethylene, including: bringing the catalyst composition into contact with ethylene in a polymerization reactor system under polymerization conditions to produce an olefin homopolymer, wherein: said catalytic composition contains a nickel diimine complex, a metallocene compound and an activator; And said ethylene homopolymer is characterized by: density less than or equal to 0.925 g/cm ³ ; the number of short-chain branches (SCBs) in the range from 3 to 15 SCBs per a total of 1000 carbon atoms; And wherein at least 50% of the CCRs are methyl branches. 19. The method according to claim 18, characterized in that: said ethylene polymer includes an ethylene homopolymer; said catalyst composition further includes a co-catalyst; And said polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof. 20. The method according to claim 19, characterized in that said ethylene homopolymer is additionally characterized by: Mw/Mn ratio from 5 to 30.