RU2799876C2 - Dual catalytic system for producing long chain branched high-density polyethylenes - Google Patents

Abstract

FIELD: polymers.

SUBSTANCE: invention relates to copolymers of ethylene with an alpha-olefin, where the alpha-olefin is selected from 1-butene, 1-hexene, 1-octene, or a combination thereof, as well as to industrial products containing such a copolymer. At the same time, the ethylene copolymer has: a melt flow index of 1 g/10 min or less, a density in the range from 0.93 to 0.965 g/cm³, the parameter CY-a at 190°C that is 0.2 or less, the average number of short chain branches (SCB) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range of 400,000 to 600,000 g/mol, which exceeds their number in a molecular weight in the range of 40,000 up to 60,000 g/mol, and the average number of long chain branches (LCB) per 1,000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number at a molecular weight in the range from 4,000,000 to 6,000,000 g/mol. Moreover, the specified ethylene copolymer has an average number of LCB in the range from 0.015 to 0.085 LCB per 1000 atoms of all carbon atoms at a molecular weight in the range from 400,000 to 600,000 g/mol. The average number of LCB in an ethylene copolymer can be from 0.01 to 0.06 long chain branches per 1000 atoms of all carbon atoms. The ethylene copolymer can be characterized by M_n in the range from 10,000 to 40,000 g/mol, M_w in the range from 100,000 to 300,000 g/mol, M_z in the range from 750,000 to 1,500,000 g/mol.

EFFECT: provision of ethylene copolymers characterized by improved dilution characteristics shear strength, melt strength and sleeve stability suitable for end applications such as pipe extrusion, blow moulding and blown film.

20 cl, 8 dwg, 5 tbl, 61 ex

Description

BACKGROUND OF THE INVENTION

Polyolefins such as high density homopolymer and copolymer polyethylene (HDPE) and copolymer linear low density polyethylene (LLDPE) can be produced using various combinations of catalyst systems and polymerization processes. Chromium-based Ziegler-Natta catalyst systems, for example, produce ethylene polymers having good extrusion performance, polymer melt strength in pipeline and blow molding applications, and film stability in blown film production, typically due to a broad molecular weight distribution (MWD). For example, metallocene-based catalyst systems produce ethylene polymers having excellent impact strength and toughness properties, but at the expense of poor extrusion performance, melt strength, and sleeve stability.

In some end applications, such as pipe extrusion, blow molding, and blown film, it can be advantageous to have the properties of medium density or high density copolymers produced using metallocene catalysts, but also improved processability, shear thinning, melt strength, and sleeve stability. Accordingly, the present invention as a whole is directed to these objects.

BRIEF DESCRIPTION OF THE INVENTION

The present summary is provided to introduce selected concepts in a simplified form, which are further described below in the detailed description. It is intended that this brief description may omit required or essential features of the claimed invention. It is also understood that this brief description does not limit the scope of the claimed invention.

Настоящее изобретение в целом относится к этиленовым полимерам (например, сополимерам этилена/α-олефина), характеризующимся показателем текучести расплава примерно 1 г/10 мин или менее, плотностью в диапазоне от примерно 0,93 до примерно 0,965 г/см ³ , параметром CY-a при 190°C, составляющим примерно 0,2 или менее, средним числом короткоцепочечных разветвлений (КЦР) на 1000 атомов углерода в целом в полимере с молекулярной массой в диапазоне от 400000 до 600000 г/моль, превышающим (например, по меньшей мере на 25% или по меньшей мере на 100%) их число в полимере с молекулярной массой в диапазоне от 40000 до 60000 г/моль, и средним числом длинноцепочечных разветвлений (ДЦР) на 1000 атомов углерода в целом в полимере с молекулярной массой в диапазоне от 400000 до 600000 г/моль, превышающей (например, по меньшей мере на 50% или по меньшей мере на 200%) их число в полимере с молекулярной массой в диапазоне от 4000000 до 6000000 г/моль. Preferably, in general, more SCBs are present in the higher molecular weight cuts of the ethylene polymer compared to the low molecular weight cuts, and in addition, a significant amount of LCB is present in these higher molecular weight cuts of the ethylene polymer, but not in the very high molecular weight cut (often referred to as the high molecular weight tail of the molecular weight distribution). The ethylene polymers described herein can be used to make a variety of industrial products such as films (eg, blown films), sheets, pipes, geomembranes, and blow molded products.

Another aspect of the present invention relates to a dual catalyst system, and according to said aspect, the dual catalyst system may contain a catalyst component I containing a metallocene compound with one bridging atom or two bridging carbon atoms containing two indenyl groups or an indenyl group and a cyclopentadienyl group, a catalyst component II containing a metallocene compound with one bridging atom containing a fluorenyl group and a cyclopentadienyl group with an alkenyl group. a substituent, an activator, and optionally a co-catalyst.

According to another aspect, a process for the polymerization of olefins is provided, and according to said aspect, the method may include contacting any of the catalyst systems described herein with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. For example, the olefin monomer may be ethylene and the olefin comonomer may be 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Both the foregoing brief description and the following detailed description provide examples that are provided solely for purposes of explanation. Accordingly, the foregoing summary and the following detailed description should not be construed as limiting. In addition, features or variations other than those described herein may be suggested. For example, certain aspects and embodiments may refer to various combinations and subcombinations of the features described in the Detailed Description.

BRIEF DESCRIPTION OF GRAPHICS

FIG. 1 is a plot of dynamic rheological properties (viscosity versus shear rate) at 190°C for polymers according to examples 37-38, 41, 65 and 76.

FIG. 2 is a plot of the molecular weight distribution for the polymers of Examples 37-38, 41, 65 and 76.

FIG. 3 is a plot of long chain branches in molecular weight distribution for the polymer of Example 41.

FIG. 4 is a plot of long chain branches in molecular weight distribution for the polymer of Example 60.

FIG. 5 is a plot of long chain branches in molecular weight distribution for the polymer of Example 61.

FIG. 6 is a plot of short chain branches in molecular weight distribution for the polymer of Example 41.

FIG. 7 is a plot of short chain branches in molecular weight distribution for the polymer of Example 60.

FIG. 8 is a plot of short chain branches in molecular weight distribution for the polymer of Example 61.

DEFINITIONS

For a more precise understanding of the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present invention. If a term is used herein that is not specifically defined herein, then the definition from the IUPAC Handbook of Chemical Terminology, 2nd Ed. (1997) unless this definition conflicts with any other description or definition used herein, or introduces uncertainty or makes impossible any claimed subject matter to which the definition applies. If any definition or use of a term proposed in any document incorporated herein by reference conflicts with a definition or use of a term proposed herein, then the definition or use of a term proposed herein shall prevail.

In this document, the features of the subject matter are described in such a way that a combination of different features can be considered within specific aspects. For each and every aspect and/or feature described herein, all combinations are intended that do not adversely affect the configurations, compositions, processes and/or methods described herein, with or without an explicit description of the particular combination. In addition, unless expressly stated otherwise, any aspects and/or features described herein may be combined to describe the proposed features corresponding to the present invention.

Although compositions and methods are described herein as "comprising" various components or steps, compositions and methods may also "consist essentially of" or "consist of" different components or steps, unless otherwise stated. For example, the catalyst composition according to aspects of the present invention may contain; alternatively, may consist essentially of; or, alternatively, may consist of: catalyst component I, catalyst component II, activator and co-catalyst.

The singular forms (corresponding to the English terms "a", "an", "the", etc.) are intended to include plural alternatives, for example at least one, unless specifically stated otherwise. For example, descriptions of "support activator" or "metallocene compound" are intended to include one(s) or mixtures or combinations of more than one support activator or metallocene compound, respectively, unless specifically noted otherwise.

In general, groups of elements are indicated using the numbering scheme given 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 by a common name given to the 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 name provided is also intended to include all structural isomers, conformational isomers, and stereoisomers that may exist with a particular set of substituents, unless specifically noted otherwise. Thus, a general description of a compound includes all structural isomers unless explicitly stated otherwise; for example, the general description of pentane includes n-pentane, 2-methylbutane and 2,2-dimethylpropane, while the general description of the butyl group includes n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. In addition, the description of the general structure or name includes all enantiomers, diastereomers and other optical isomers in both enantiomeric and racemic forms, as well as mixtures of stereoisomers, if the context allows or requires it. For any particular formula or name presented, any formula or name presented also includes all conformational isomers, regioisomers and stereoisomers that may exist with a particular set of substituents.

The term "substituted", when used to describe a group, for example, a substituted analogue of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen atom in the specified group; and is non-limiting. The group or groups may also be described herein as "unsubstituted(s)" or equivalent terms such as "unsubstituted(s)" and refers to a parent group in which a non-hydrogen moiety does not replace a hydrogen atom. Unless specifically stated otherwise, "substituted" is intended to be non-limiting and includes inorganic substituents or organic substituents, as will be understood by those skilled in the art.

The term "hydrocarbon", both in the present description and in the claims, refers to a compound containing only carbon and hydrogen atoms. Other definitions may be used to indicate the presence of specific groups in a hydrocarbon (for example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms that replace an equivalent number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl group" is used herein in accordance with the definition given by IUPAC: a monovalent group formed by the removal of a hydrogen atom from a hydrocarbon (ie, a group containing only carbon and hydrogen atoms). Non-limiting examples of hydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups, among others.

The term "polymer" is used herein in a broad sense and includes olefin homopolymers, copolymers, terpolymers, etc., as well as their alloys and mixtures. The term "polymer" also includes impact, block, graft, random, and alternating copolymers. The copolymer is made from an olefin monomer and one olefin comonomer, while the terpolymer is made from an olefin monomer and two olefin comonomers. Accordingly, "polymer" includes copolymers and terpolymers derived from any of the olefin monomers and comonomers described herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Thus, the ethylene polymer includes ethylene homopolymers, ethylene copolymers (eg, ethylene/α-olefin copolymers), ethylene terpolymers, etc., as well as combinations or mixtures thereof. Thus, ethylene polymer includes polymers often referred to in the art as LLDPE (Linear Low Density Polyethylene) and HDPE (High Density Polyethylene). For example, an olefin copolymer such as an ethylene copolymer can be made from ethylene and a comonomer such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, then the resulting polymer can be classified as an ethylene/1-hexene copolymer. The term "polymer" also includes all possible geometric configurations, unless otherwise stated, and these configurations may include isotactic, syndiotactic and statistical symmetry. In addition, unless otherwise stated, the term "polymer" is also intended to include polymers of any molecular weight, including polymers of lower molecular weight.

The term "co-catalyst" is used in a broad sense herein to describe compounds such as alumoxane compounds, organoboron or organoboron compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, etc., which can form a single component of the catalyst composition when used, for example, in conjunction with an activator support. The term "cocatalyst" is used regardless of the actual function of the compound or any chemical mechanism by which the compound may act.

The terms "chemically treated solid oxide", "treated solid oxide compound", etc. used herein to refer to a solid inorganic oxide of relatively high porosity, which may have the properties of a Lewis acid or Bronsted acid, and which is treated with an electron-withdrawing component, typically an anion, and which is calcined. The electron-withdrawing component is typically an electron-withdrawing anion source compound. Thus, the chemically treated solid oxide may comprise the calcined product of contacting at least one solid oxide with at least one electron-withdrawing anion source compound. Typically, the chemically treated solid oxide contains at least one acidic solid oxide compound. The "activator-substrate" according to the present invention may be a chemically treated solid oxide. The terms "support" and "activator-support" are not used to indicate that these components are inert, and these components should not be considered as an inert component of the catalyst composition. The term "activator" as used herein refers broadly to a substance that can convert a metallocene component into a catalyst that can polymerize olefins, or can convert the product of bringing a metallocene compound into contact with a component that provides an activated ligand (e.g., alkyl, hydride) in the metallocene, if the metallocene compound does not already contain said ligand, into a catalyst that can polymerize olefins. This term is used regardless of the actual activation mechanism. Exemplary activators include support activators, alumoxanes, organoboron or organoboron compounds, ionizing ionic compounds, and the like. Alumoxanes, organoboron or organoboron compounds, and ionizing ionic compounds are generally referred to as activators when they are used in a catalyst composition that lacks an activator-support. If the catalyst composition contains a support activator, then the alumoxane, organoboron or organoboron compound, and ionizing ionic materials are generally referred to as cocatalysts.

The term “metallocene” as used herein describes compounds containing at least one η ³ -η ⁵ -cycloalkadienyl moiety, where η ³ -η ⁵ -cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, etc., including partially saturated or substituted derivatives or analogs of any of these moieties. Possible substituents for 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, etc. In some contexts, the metallocene is simply referred to as "catalyst", in much the same way that the term "co-catalyst" herein refers to, for example, an organoaluminum compound.

The terms "catalyst composition", "catalyst mixture", "catalyst system", etc., do not depend on the actual product or composition formed (s) as a result of bringing into contact or interaction of the starting components of the described or claimed catalyst composition/mixture/system, the nature of the active catalytic site, or a change in the co-catalyst, catalyst component I, catalyst component II or activator (for example, activator-substrate), after combining these components. Thus, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc., include the initial starting components of the composition, as well as any (s) product (s) that (s) can (may) be formed as a result of bringing into contact of these initial starting components, including heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc., can be used interchangeably in the present invention.

The term "contact product" as used herein describes compositions in which the components are brought into contact with each other in any order in any manner for any period of time, unless specifically stated otherwise. For example, the components may be brought into contact by agitation or mixing. In addition, bringing any component into contact can be carried out in the presence or absence of any other component of the compositions described herein. The combination of additional materials or components can be carried out in any suitable manner. In addition, the term "contact product" includes mixtures, combinations, solutions, suspensions, reaction products, etc. or their combinations. While the "engaging product" may include interaction products, the respective components need not interact with each other. Likewise, the term "contacting" as used herein refers to materials that can be agitated, mixed, suspended, dissolved, brought into contact, processed, or otherwise combined.

While any methods, devices, and materials similar or equivalent to those described herein may be used to practice or study the invention, exemplary methods, devices, and materials are described herein.

The contents of all publications and patents mentioned herein are incorporated by reference to describe and describe, for example, designs and techniques that are described in publications that can be used in connection with the invention described herein.

The present invention describes several types of ranges. If a range of any type is described or claimed, it is the intent to describe or claim individually each possible numerical value that can reasonably be included in the specified range, including the endpoints of the range, as well as any subranges and combinations of subranges included therein. For example, if a chemical moiety is described or claimed to contain a certain number of carbon atoms, then the goal is to describe or claim separately each possible number that can be included in the specified range, in accordance with the invention described herein. For example, the description of a moiety that is a C ₁ -C ₁₈ hydrocarbyl group, or, alternatively, a hydrocarbyl group containing from 1 to 18 carbon atoms, herein refers to a moiety that may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between two of the indicated numbers (for example, to C ₁ -C ₈ hydrocarbyl group) and further includes any combination of ranges between two of the indicated numbers (for example, to C ₂ -C ₄ and C ₁₂ -C ₁₆ hydrocarbyl group).

Similarly, another representative example is given for the Mw/Mn ratio of an ethylene polymer according to aspects of the present invention. The purpose of describing the Mw/Mn ratio, which may range from about 5 to about 15, is to indicate that the Mw/Mn ratio may be any ratio within the specified range and, for example, may be about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, or about 15. In addition, the Mw/Mn ratio can be in any range from about 5 up to about 15 (for example, from about 6 to about 15) and also includes any combination of ranges from about 5 to about 15 (for example, the Mw/Mn ratio can be in the range from about 6 to about 9, or from about 11 to about 14). In addition, in all cases where "about" a specific value is described, the given value itself is also described. Thus, indicating that the Mw/Mn ratio may be from about 5 to about 15 also describes an Mw/Mn ratio of 5 to 15 (e.g., 6 to 15) and also includes any combination of the ranges from 5 to 15 (e.g., the Mw/Mn ratio may be in the range of 6 to 9 or 11 to 14). Likewise, all other ranges described herein should be construed in the same way as these examples.

The term "about" means that amounts, sizes, compositions, parameters, and other quantities and characteristics are and are not and need not be precise, but may be approximate values and/or be larger or smaller, as desired, to account for errors, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. Generally, an amount, size, composition, parameter, or other quantity or characteristic is "approximate" or "approximate" whether or not it is explicitly stated. The term "about" also includes amounts that differ due to different equilibrium conditions in the compositions obtained from a particular initial mixture. Claims include quantitative equivalents, whether modified by the term "about" or not. 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

The present invention relates generally to ethylene-based medium and high density polymers having excellent strength and mechanical toughness properties, but also improved processability, shear thinning, melt strength and sleeve stability. Articles made from these ethylene-based polymers may include pipes, blow molded products, and blown films.

Preferably, the ethylene polymers described herein may contain a higher number of short chain branches (SBCs) in the higher molecular weight fractions of the ethylene polymer (e.g., in the range of 400,000-600,000 g/mol) compared to the lower molecular weight fractions (e.g., in the range of 40,000-60,000 g/mol). In addition, in this overall high molecular weight range (400,000-600,000 g/mol), the ethylene polymer can also have a higher number of long chain branches (LCBs) per 1,000 carbon atoms overall compared to a very high molecular weight tail (e.g., in the range of 4,000,000-6,000,000 g/mol). Thus, relatively large amounts of both long chain branches and long chain branches are concentrated in a particular high molecular weight fraction of said ethylene polymers.

Said ethylene polymers can be produced, for example, using a dual metallocene catalyst system in a single reactor. It has been found that the use of a first metallocene catalyst, which preferably produces a lower molecular weight polyethylene with a relatively high content of LCB, in combination with a second metallocene catalyst, which preferably produces a higher molecular weight polyethylene with a relatively high level of comonomer incorporation, can provide a unique combination of the polymer properties described herein.

ETHYLENE POLYMERS

In general, the polymers described herein are ethylene-based or ethylene polymers, including homopolymers of ethylene as well as copolymers, terpolymers, etc., of ethylene and at least one olefin comonomer. The molecular chain of comonomers that can be copolymerized with ethylene may contain from 3 to 20 carbon atoms. For example, exemplary 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 ₁₈ 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 0.01 to about 20 wt. %, from about 0.1 to about 10 wt. %, from about 0.5 to about 15 wt. %, from about 0.5 to about 8 wt. % or from about 1 to about 15 wt. %.

In one aspect, the ethylene polymer of the present invention may comprise an ethylene/α-olefin copolymer, wherein in another aspect the ethylene polymer may comprise an ethylene homopolymer, and in yet another aspect, the ethylene polymer of the present invention may comprise an ethylene/α-olefin copolymer and an ethylene homopolymer. For example, the ethylene polymer may comprise an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, an 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.

Иллюстративный и неограничивающий пример этиленового полимера (например, содержащего сополимер этилена) согласно настоящему изобретению может иметь показатель текучести расплава примерно 1 г/10 мин или менее, плотность в диапазоне от примерно 0,93 до примерно 0,965 г/см ³ , параметр CY-a при 190°C, составляющий примерно 0,2 или менее, среднее число короткоцепочечных разветвлений (КЦР) на 1000 атомов углерода в целом в полимере с молекулярной массой в диапазоне от 400000 до 600000 г/моль, которое превышает их число в диапазоне молекулярных масс от 40000 до 60000 г/моль, и среднее число длинноцепочечных разветвлений (ДЦР) на 1000 атомов углерода в целом в полимере с молекулярной массой в диапазоне от 400000 до 600000 г/моль, которое превышает их число в диапазоне молекулярных масс от 4000000 до 6000000 г/моль. These illustrative and non-limiting examples of ethylene polymers according to the present invention may also have any of the properties of the polymers listed below in any combination, unless otherwise indicated.

The density of the ethylene-based polymers described herein is often about 0.93 g/cm ³ or more, such as about 0.935 g/cm ³ or more, or about 0.94 g/cm ³ or more. Also, in specific aspects, the density may be from about 0.93 to about 0.962 g/cm ³ , from about 0.93 to about 0.958 g/cm ³ , from about 0.935 to about 0.965 g/cm ³ , from about 0.94 to about 0.958 g/cm ³ , or from about 0.95 to about 0.96 g/cm ³ .

The ethylene polymers described herein can often have a melt flow index (MFR) of about 1 g/10 min or less, about 0.7 g/10 min or less, or about 0.5 g/10 min or less. In additional aspects, the ethylene polymers described herein may have a melt flow index (MFR) of about 0.35 g/10 min or less, about 0.25 g/10 min or less, in the range of about 0.05 to about 1 g/10 min, in the range of about 0.05 to about 0.5 g/10 min, in the range of about 0.02 to about 0.7 g/10 min, or in the range of about 0.02 to about 0.35 g/10 min.

Without being limited to these values, the ethylene polymer may have a melt flow index at high shear stress (MFR-MST) in the range from about 2 to about 50 g/10 min; alternatively, from about 3 to about 40 g/10 min; alternatively, from about 10 to about 45 g/10 min; or, alternatively, from about 12 to about 35 g/10 min.

The ratio of high shear melt flow index (MFR-MFR) to melt flow index (MFR), referred to as the MFR-MSR/MFR ratio, is not particularly limited, but is generally about 60 to about 400, about 80 to about 400, about 90 to about 300, about 75 to about 250, or about 100 to about 250. In the specified ratio of MFR-PNS/MFR, the melt flow index is not equal to zero.

In one aspect, the ethylene polymers described herein may have a Mw/Mn ratio, or polydispersity ratio, in the range of from about 3.5 to about 18, from about 4 to about 18, from about 4 to about 16, from about 6 to about 16, from about 5 to about 15, or from about 5 to about 12. In addition or alternatively, the ethylene polymer may have a Mz/Mw ratio in the range from about 3 .5 to about 10, about 5 to about 10, about 4 to about 9, about 5 to about 9, about 4 to about 8, or about 5 to about 8.

In one aspect, the ethylene polymers described herein may have a weight average molecular weight (Mw) in the range of from about 100,000 to about 400,000 g/mol, from about 100,000 to about 300,000 g/mol, from about 100,000 to about 200,000 g/mol, from about 150,000 to about 400,000 g/mol, or from about 150,000 to about 350,000 g/mol. In addition or alternatively, the ethylene polymer may have a number average molecular weight (Mn) in the range of from about 10,000 to about 100,000 g/mol, from about 10,000 to about 50,000 g/mol, from about 10,000 to about 40,000 g/mol, from about 10,000 to about 30,000 g/mol, from about 12,000 to about 40 000 g/mol or from about 12,000 to about 28,000 g/mol. In addition or alternatively, the ethylene polymer may have a z-weight average molecular weight (Mz) in the range of from about 500,000 to about 2,500,000 g/mol, from about 600,000 to about 2,000,000 g/mol, from about 750,000 to about 2,500,000 g/mol, from about 750,000 to about 1,750,000 g/mol, or from about 750,000 to about 1,500,000 g/mol.

Without being limited to these values, the ethylene polymers described herein may have a zero shear viscosity at 190°C in the range of from about 1x10 ⁵ to about 1x10 ¹⁷ Pa-s, from about 1x10 ⁶ to about 1x10 ¹⁶ Pa-s, or from about 1x10 ⁷ to about 1x10 ¹³ Pa-s. Further, said ethylene polymers may have a CY-a value of about 0.2 or less, such as about 0.02 to about 0.2, about 0.02 to about 0.18, about 0.02 to about 0.10, about 0.03 to about 0.2, about 0.03 to about 0.15, about 0.04 to about 0.16, or about 0.04 to about 0.12. The zero shear viscosity and the CY-a parameter are determined from the viscosity measured at 190° C. using the empirical Carro-Yasuda (CY) model as described herein.

The average number of long chain branches (LCBs) per 1000 carbon atoms in total in an ethylene polymer with a molecular weight in the range of 400,000 to 600,000 g/mol exceeds (by any amount described herein, for example, at least 50%, at least 75%, at least 100%, at least 200% or at least 400%, and often up to up to 1000-1500% or more) the average number of LCR per 1000 carbon atoms in general in the range of molecular weights from 4000000 to 6000000 g/mol. In some aspects, the average number of long chain branches (LCBs) per 1,000 total carbons in an ethylene polymer with a molecular weight in the range of 400,000 to 600,000 g/mol may be at least 50% greater (or at least 75% greater, or at least 100% greater, or at least 200% greater, or at least 400% greater, or at least 500% exceed and often even exceed by 1000-1500%) their number in the range of molecular weights from 4,000,000 to 6,000,000 g/mol. All averages for the number of LCBs described herein are number averages.

The average number of long chain branches (LCBs) per 1,000 total carbons in an ethylene polymer with a molecular weight in the range of 400,000 to 600,000 g/mol is not particularly limited, but often falls within the range of about 0.015 to about 0.085; alternatively, from about 0.02 to about 0.07; alternatively, from about 0.03 to about 0.07; alternatively, from about 0.02 to about 0.06; or, alternatively, from about 0.03 to about 0.06.

When considering the polymer as a whole (according to the Janzen-Colby model), ethylene polymers typically have long chain branching (LCB) levels ranging from about 0.01 to about 0.08 LCB, from about 0.01 to about 0.06 LCB, from about 0.02 to about 0.06 LCB, from about 0.02 to about 0.05, or from about 0.025 to about 0.045 LCR per 1000 carbons overall.

In addition, ethylene polymers tend to have an opposite distribution of short chain branches (SCB content increases with increasing molecular weight). This characteristic of SCBC is quantified herein by the average number of short chain branches (SCB) per 1000 carbon atoms in total in an ethylene polymer with a molecular weight in the range of 400,000 to 600,000 g/mol, which exceeds their number in the molecular weight range of 40,000 to 60,000 g/mol. In some aspects, the average number of short chain branches (SCC) per 1,000 total carbons in an ethylene polymer with a molecular weight in the range of 400,000 to 600,000 g/mol is at least 25% higher (or at least 50% higher, or at least 75% higher, or at least 100% higher, or at least 125% higher, or at least 150% exceeds and often exceeds by 250-500%) their number in the range of molecular weights from 40,000 to 60,000 g/mol. All average values of the number of CCRs described in this document are the average values.

Reverse RCBC can be further characterized by the number of short chain branches (SCBs) per 1000 carbons in total in an ethylene polymer of a particular weight average molecular weight (M _w ) which is greater than that of the same number average molecular weight (M _n ), and/or the number of SCBs per 1000 carbons in total in an ethylene polymer with a particular z-average molecular weight (M _z ) which is exceeds their number at the same M _w , and/or the number of SCRs per 1000 carbon atoms in general in an ethylene polymer with a particular M _z that exceeds their number at the same M _n .

In one aspect, the ethylene polymer described herein may be a reactor product (e.g., a single reactor product) and, e.g., a non-reactor mixture of two polymers, e.g., having different molecular weight characteristics. One of ordinary skill in the art will appreciate that physical mixtures of two different polymer resins can be made, but this requires additional processing and complexity that is not present in the case of a reactor product.

PRODUCTS AND PRODUCTS

Industrial products may be made from and/or may contain olefin polymers (eg, ethylene polymers) according to the present invention, and, accordingly, are included in this document. For example, articles that may contain the 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 article, fuel tank, geomembrane, household container, liner, molded product, medical device or material, outdoor storage product, outdoor play equipment, pipe, sheet or tape, toy or roadblock, etc. For the manufacture of these products can be used in different ways. Non-limiting examples of these methods include injection molding, blow molding, spin molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, etc. In addition, additives and modifiers are often added to these polymers to provide effective polymer processing or end product properties. These methods and materials are described in the Modern Plastics Encyclopedia , Mid-November 1995 Issue, Volume 72, No. 12; and Film Extrusion Manual - Pr Cess, Materials, Properties , TAPPI Press, 1992; the description of which is incorporated herein in its entirety by reference. According to some aspects of the invention, the article of manufacture may comprise any of the olefin polymers (or ethylene polymers) described herein, and the article of manufacture may be or may comprise a blown film, tube, or blow molded product.

This document also discusses a method of molding or manufacturing an industrial product containing any of the polymer described in this document. For example, the method may include (i) contacting the catalyst composition with an olefin monomer (e.g., ethylene) and an optional olefin comonomer under polymerization conditions in a polymerization reactor system to produce an olefin polymer (e.g., an ethylene polymer), wherein the catalyst composition may contain a catalyst component I, a catalyst component II, an activator (e.g., an activator-support containing a solid oxide treated with an electron withdrawing anion), and an optional cocatalyst (eg, an organoaluminum compound); and (ii) forming an industrial article containing an olefin polymer (or ethylene polymer). The molding step may include mixing, melt processing, extrusion, casting or thermoforming, etc., including combinations thereof.

Any suitable additives such as antioxidants, acid neutralizers, antiblocking agents, slip agents, colorants, fillers, processing aids, UV inhibitors, etc., and combinations thereof, may be combined with the polymer in the melt processing step (extrusion step).

CATALYTIC SYSTEMS AND POLYMERIZATION METHODS

In accordance with some aspects of the present invention, an olefin polymer (eg, an ethylene polymer) can be produced using a dual catalyst system. According to these aspects, the catalyst component I may comprise any suitable one-bridged or two-bridged carbon metallocene compound containing two indenyl groups or an indenyl group and a cyclopentadienyl group, or any one-bridged or two-bridged carbon metallocene compound containing two indenyl groups or an indenyl group and a cyclopentadienyl group described herein. Catalyst component II may contain any single-bridged metallocene compound containing a fluorenyl group and an alkenyl-substituted cyclopentadienyl group, or any single-bridged metallocene compound containing a fluorenyl group and an alkenyl-substituted cyclopentadienyl group described herein. The catalyst system may also contain any suitable activator or any activator described herein, and optionally any suitable cocatalyst or any cocatalyst described herein.

Let us first turn to the catalyst component II, which may contain a metallocene compound with one bridging atom containing a fluorenyl group and a cyclopentadienyl group with an alkenyl substituent. In one aspect, the fluorenyl group may be substituted, while in another aspect, the fluorenyl group may be unsubstituted. In addition, the bridged metallocene compound in the catalyst component II may contain zirconium, hafnium or titanium. In addition, the monatomic bridge may be one carbon atom or one silicon atom, although not limited to them. In some aspects, said bridging atom may have two substituents independently selected from H or any C ₁ -C ₁₈ hydrocarbyl group described herein (eg, one or both substituents may be a phenyl group). The alkenyl substituent on the cyclopentadienyl group may be any suitable alkenyl group such as a C ₃ -C ₁₈ alkenyl group or a C ₃ -C ₈ terminal alkenyl group.

The catalyst component II may contain, according to specific aspects of the present invention, a bridged metallocene compound having the formula ( II ):

In formula ( II ), M, Cp, R ^X , R ^Y , E and each X are independent elements of the bridged metallocene compound. Accordingly, a bridged metallocene compound having formula ( II) can be described using any combination of M, Cp, R ^X , R ^Y , E and X described herein.

In accordance with aspects of the present invention, the metal in formula ( II ), M, may be Ti, Zr or Hf. In one aspect, for example, M may be Zr or Hf, while in another aspect, M may be Ti; alternatively, M may be Zr; or, alternatively, M may be Hf.

Each X in the formula (II) can independently be a monoanionic ligand. In some aspects, suitable monoanionic ligands may include, but are not limited to, H (hydride), BH₄, halide, C₁-C₃₆ hydrocarbyl group, C₁-C₃₆ hydrocarboxy group, C₁-C₃₆ hydrocarbylaminyl group, C₁-C₃₆ hydrocarbylsilyl group, C₁-C₃₆ hydrocarbylaminylsilyl group, -OBR¹ ₂ or -OSO₂R¹, where R¹ represents C₁-C₃₆ hydrocarbyl group. It is assumed that every X may be either the same or a different monoanionic ligand. In addition to the typical variants of each X that are described herein, additional suitable hydrocarbyl groups, hydrocarboxy groups, hydrocarbylaminyl groups, hydrocarbylsilyl groups, and hydrocarbylaminylsilyl groups are described, for example, in US patent No. 9758600, the contents of which are incorporated herein in its entirety by reference.

In one aspect, each X can independently be H, BH₄, halide (e.g. F, Cl, Br, etc.), C₁-C₁₈ hydrocarbyl group, C₁-C₁₈ hydrocarboxy group, C₁-C₁₈ hydrocarbylaminyl group, C₁-C₁₈ hydrocarbylsilyl group or C₁-C₁₈ a hydrocarbylaminylsilyl group. Alternatively, every X may independently represent H, BH₄, halide, OBR¹ ₂ or OSO₂R¹, where R¹ represents C₁-C₁₈ hydrocarbyl group. According to another aspect, each X may independently represent H, BH₄, halide, C₁-C₁₂ hydrocarbyl group, C₁-C₁₂ hydrocarboxy group, C₁-C₁₂ hydrocarbylaminyl group, C₁-C₁₂ hydrocarbylsilyl group, C₁-C₁₂ hydrocarbylaminylsilyl group, OBR¹ ₂ or OSO₂R¹, where R¹ represents C₁-C₁₂ hydrocarbyl group. According to another aspect, each X may independently represent H, BH₄, halide, C₁-C₁₀ hydrocarbyl group, C₁-C₁₀ hydrocarboxy group, C₁-C₁₀ hydrocarbylaminyl group, C₁-C₁₀ hydrocarbylsilyl group, C₁-C₁₀ hydrocarbylaminylsilyl group, OBR¹ ₂ or OSO₂R¹, where R¹ represents C₁-C₁₀ hydrocarbyl group. In yet another aspect, each X can independently be H, BH₄, halide, C₁-C₈ hydrocarbyl group, C₁-C₈ hydrocarboxy group, C₁-C₈ hydrocarbylaminyl group, C₁-C₈ hydrocarbylsilyl group, C₁-C₈ hydrocarbylaminylsilyl group, OBR¹ ₂ or OSO₂R¹, where R¹ represents C₁-C₈ hydrocarbyl group. According to another aspect, each X independently may be halide or C₁-C₁₈ hydrocarbyl group. For example, each X may be Cl.

According to one aspect, each X may independently represent H, BH₄, halide, or C₁-C₃₆ a hydrocarbyl group, a hydrocarboxy group, a hydrocarbylaminyl group, a hydrocarbylsilyl group, or a hydrocarbylaminylsilyl group, wherein, in another aspect, each X may independently represent H, BH₄ or C₁-C₁₈ a hydrocarboxy group, a hydrocarbylaminyl group, a hydrocarbylsilyl group, or a hydrocarbylaminylsilyl group. In yet another aspect, each X may independently be a halide; alternatively, C₁-C₁₈ a hydrocarbyl group; alternatively, C₁-C₁₈ a hydrocarboxy group; alternatively, C₁-C₁₈ a hydrocarbylaminyl group; alternatively, C₁-C₁₈ a hydrocarbylsilyl group; or alternatively C₁-C₁₈ a hydrocarbylaminylsilyl group. According to another aspect, each X may be H; alternatively, F; alternatively, Cl; alternatively, Br; alternatively, I; alternatively, BH₄; alternatively, C₁-C₁₈ a hydrocarbyl group; alternatively, C₁-C₁₈ a hydrocarboxy group; alternatively, C₁-C₁₈ a hydrocarbylaminyl group; alternatively, C₁-C₁₈ a hydrocarbylsilyl group; or alternatively C₁-C₁₈ a hydrocarbylaminylsilyl group.

Every X independently may be, in some aspects, H, halide, methyl, phenyl, benzyl, alkoxy, aryloxy, acetylacetonate, formate, acetate, stearate, oleate, benzoate, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, or hydrocarbylaminylsilyl; alternatively, H, halide, methyl, phenyl or benzyl; alternatively, alkoxy, aryloxy or acetylacetonate; alternatively, alkylaminyl or dialkylaminyl; alternatively, trihydrocarbylsilyl or hydrocarbylaminylsilyl; alternatively, H or halide; alternatively, methyl, phenyl, benzyl, alkoxy, aryloxy, acetylacetonate, alkylaminyl or dialkylaminyl; alternatively, H; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively, benzyl; alternatively, alkoxy; alternatively, aryloxy; alternatively, acetylacetonate; alternatively, alkylaminyl; alternatively, dialkylaminyl; alternatively, trihydrocarbylsilyl; or, alternatively, hydrocarbylaminylsilyl. According to these and other aspects, alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl and hydrocarbylaminylsilyl can be C₁-C₃₆, C₁-C₁₈, C₁-C₁₂ or C₁-C₈alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl and hydrocarbylaminylsilyl.

In addition, every X may independently be, in certain aspects, a halide or C₁-C₁₈ a hydrocarbyl group; alternatively halide or C₁-C₈ a hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl or phenyl; alternatively, Cl, methyl, benzyl or phenyl; alternatively, C₁-C₁₈an alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl or hydrocarbylaminylsilyl group; alternatively, C₁-C₈an alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl or hydrocarbylaminylsilyl group; or alternatively methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, toluyl, benzyl, naphthyl, trimethylsilyl, triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In the formula (II) Cp may be a cyclopentadienyl group with an alkenyl substituent. In some aspects, Cp may not contain additional substituents other than the alkenyl substituent. In other aspects, Cp may be further substituted with one substituent, two substituents, and so on. If present, each additional substituent on Cp may independently be H, halide, C₁-C₃₆ hydrocarbyl group, C₁-C₃₆ halogenated hydrocarbyl group, C₁-C₃₆ hydrocarboxy or C₁-C₃₆ a hydrocarbylsilyl group. It is important to note that each additional substituent in Cp may be either the same or a different substituent group. In addition, each additional substituent may be located at any position of the cyclopentadienyl ring structure that satisfies the rules of chemical valency. In general, any additional substituent on Cp can independently be H or any halide, C₁-C₃₆ hydrocarbyl group, C₁-C₃₆ halogenated hydrocarbyl group, C₁-C₃₆ hydrocarboxy or C₁-C₃₆ a hydrocarbylsilyl group as described herein. In addition to the exemplary substituents described herein, additional suitable hydrocarbyl groups, halogenated hydrocarbyl groups, hydrocarboxy groups, and hydrocarbylsilyl groups are described, for example, in US Pat. No. 9,758,600, the contents of which are incorporated herein in their entirety by reference.

In one aspect, for example, each additional substituent on Cp can independently be a C ₁ -C ₁₂ hydrocarbyl group or a C ₁ -C ₁₂ hydrocarbylsilyl group. In another aspect, each additional substituent on Cp may independently be a C ₁ -C ₈ alkyl group or a C ₃ -C ₈ alkenyl group. In yet another aspect, each additional substituent on Cp can independently be H, Cl, CF ₃ , methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group a nonenyl group, a decenyl group, a phenyl group, a toluyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group.

Similarly, R ^X and R ^Y in formula ( II ) can independently be H or any halide, C ₁ -C ₃₆ hydrocarbyl group, C ₁ -C ₃₆ halogenated hydrocarbyl group, C ₁ -C ₃₆ hydrocarboxy group, or C ₁ -C ₃₆ hydrocarbylsilyl group described herein. In one aspect, for example, R ^X and R ^Y can independently represent an H or C ₁ -C ₁₂ hydrocarbyl group. According to another aspect, R ^X and R ^Y can independently represent a C ₁ -C ₁₀ hydrocarbyl group or, alternatively, a C ₁ -C ₆ alkyl group. In another aspect, R ^X and R ^Y can independently be H, Cl, CF ₃ , methyl group, ethyl group, propyl group, butyl group (e.g., t-Bu), pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a toluyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group, etc. In another aspect, R ^X and R ^Y can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group a ny group, a phenyl group, a toluyl group or a benzyl group.

The bridging group E in formula ( II ) may be a bridging group having the formula >E ^A R ^A R ^B where E ^A may be C, Si or Ge and R ^A and R ^B independently may be an H or C ₁ -C ₁₈ hydrocarbyl group. According to some aspects of the present invention, R ^A and R ^B can independently represent a C ₁ -C ₁₂ hydrocarbyl group; alternatively, R ^A and R ^B can independently represent a C ₁ -C ₈ hydrocarbyl group; alternatively, R ^A and R ^B may independently represent a phenyl group, a C ₁ -C ₈ alkyl group, or a C ₃ -C ₈ alkenyl group; alternatively, R ^A and R ^B independently may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decene an yl group, a phenyl group, a cyclohexylphenyl group, a naphthyl group, a toluyl group, or a benzyl group; or, alternatively, R ^A and R ^B independently may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a phenyl group, or a benzyl group. According to these and other aspects, R ^A and R ^B may be either the same or different.

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

etc., as well as their combinations.

Catalyst component II is not limited exclusively to bridged metallocene compounds such as those 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;

Catalyst component I may contain, according to specific aspects of the present invention, a metallocene compound with one bridging atom or two bridging carbon atoms containing two indenyl groups or an indenyl group and a cyclopentadienyl group. The cyclopentadienyl group and the indenyl group may independently be substituted or unsubstituted. Often, the catalyst component I contains zirconium or titanium, and more often, the catalyst component I may be a zirconium-based metallocene compound.

In one aspect, the catalyst component I contains two indenyl groups, such as two unsubstituted indenyl groups. If the metallocene compound is a metallocene compound with one bridging atom, then the bridging atom may be a carbon or silicon atom. Similar to the bridging group E in formula ( II ), the bridging carbon or silicon atom may have two substituents independently selected from H or C ₁ -C ₁₈ hydrocarbyl group or H or C ₁ -C ₈ hydrocarbyl group; alternatively, two substituents independently selected from a C ₁ -C ₆ alkyl group; or, alternatively, two substituents independently selected from methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl naphthyl group, phenyl group, cyclohexylphenyl group, naphthyl group, toluyl group or benzyl group. The two substituents may be either the same or different.

If the metallocene compound is a two-carbon bridged metallocene compound, then the two-carbon bridge may be substituted or unsubstituted. For example, the bridging group may have the formula -CR ^C R ^D -CR ^E R ^F - where R ^C , R ^D , R ^E and R ^F independently may be H or any C ₁ -C ₁₈ hydrocarbyl group described herein. For example, R ^C , R ^D , R ^E and R ^F can independently represent an H or C ₁ -C ₆ alkyl group, or alternatively H or a methyl group.

According to another aspect, the catalyst component I contains an indenyl group and a cyclopentadienyl group. The indenyl group and the cyclopentadienyl group may independently be substituted or unsubstituted. In some aspects, at least one of the indenyl group and the cyclopentadienyl group is substituted, and the substituent(s) may be any substituent described herein above as a Cp substituent in formula ( II ). Thus, each substituent may independently be a C ₁ -C ₁₂ hydrocarbyl group or a C ₁ -C ₁₂ hydrocarbylsilyl group, or alternatively a C ₁ -C ₈ alkyl group or a C ₃ -C ₈ alkenyl group.

As mentioned above, if one carbon or silicon atom is a bridging atom between an indenyl group and a cyclopentadienyl group, then the bridging carbon or silicon atom - analogously to the bridging group E in formula ( II ) - may contain two substituents independently selected from H or C ₁ -C ₁₈ hydrocarbyl group, two substituents independently selected from H or C ₁ -C ₈ hydrocarbyl group, or two substituents independently selected from C ₁ -C ₆ alkyl group. The two substituents may be either the same or different.

Illustrative and non-limiting examples of metallocene compounds suitable for use as catalyst component I may include the following compounds:

, , ,

etc., as well as their combinations.

Catalyst component I is not limited exclusively to bridged metallocene compounds such as those described above. Other suitable metallocene compounds are described in US Pat. Nos. 8,288,487 and 8,426,538, the contents of which are incorporated herein in their entirety by reference.

In one aspect of the present invention, the weight ratio of catalyst component I to catalyst component II in the catalyst composition may 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, from about 4:1 to about 1:4, from about 3:1 to about 1:3; about 2:1 to about 1:2, about 1.5:1 to about 1:1.5, about 1.25:1 to about 1:1.25, or about 1.1:1 to about 1:1.1. In another aspect, catalyst component I is a major component of the catalyst composition, and in said aspects, the weight ratio of catalyst component I to catalyst component II in the catalyst composition may be from about 10:1 to about 1:1, from about 8:1 to about 1.5:1, from about 5:1 to about 1.5:1, or from about 5:1 to about 2:1.

In addition, the dual catalyst system contains an activator. For example, the catalyst system may contain a support activator, an alumoxane compound, an organoboron or organoboron compound, an ionizing ionic compound, etc., or any combination thereof. The catalyst system may contain one or more than one activator.

In one aspect, the catalyst system may contain an alumoxane compound, an organoboron or organoboron compound, an ionizing ionic compound, etc., or a combination thereof. Examples of these activators are described in, for example, US Pat. According to another aspect, the catalyst system may contain an alumoxane compound. According to another aspect, the catalyst system may contain an organoboron or organoboron compound. According to another aspect, the catalyst system may contain an ionizing ionic compound.

In other aspects, the catalyst system may comprise a support activator, for example, a support activator comprising a solid oxide treated with an electron withdrawing anion. Examples of these materials are described in, for example, US Pat. For example, the activator-support may comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica -zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated-chlorinated silica coated alumina, fluorinated silica coated alumina, sulfated silica coated alumina or phosphated silica coated alumina, etc., and any combination thereof. In some aspects, the support activator may comprise a fluorinated solid oxide and/or a sulfated solid oxide.

Various methods can be used to obtain support activators suitable for the present invention. Methods for contacting a solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and addition amounts, impregnation with metals or metal ions (e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc., or combinations thereof) and various calcination methods and conditions are described, for example, in US Pat. No. 6107 230 6165929 6294494 6300271 6316553 6355594 6376415 6388017 6391816 6395666 6524987 6548441 6548442 613712, 6632894, 6667274, 6750302, 7294599, 7601665, 7884163 and 8309485, the contents of which are incorporated herein in their entirety by reference. Other suitable processes and methods for making support activators (eg, fluorinated solid oxides, sulfated solid oxides, etc.) are well known to those skilled in the art.

Catalyst compositions containing a catalyst component I, a catalyst component II, an activator (one or more than one) and optionally a co-catalyst can be used in the present invention. If present, the cocatalyst may include, but is not limited to, alkyl metal or organometallic cocatalysts, where the metal includes boron, aluminium, zinc, etc. Optionally, the catalyst systems provided herein may contain a co-catalyst or a combination of co-catalysts. For example, compounds based on alkylboron, alkylaluminum and alkylzinc can often be used as cocatalysts in these catalyst systems. Exemplary boron compounds may include, but are not limited to, tri-n-butylborane, tripropylborane, triethylborane, etc., 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., and any combination thereof. Examples of zinc compounds (e.g., organozinc compounds) that can be used as co-catalysts 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, according to one aspect of the present invention, the dual catalyst composition may comprise a catalyst component I, a catalyst component II, a support activator, and an organoaluminum compound (and/or an organozinc compound).

According to another aspect of the present invention, a catalyst composition is provided which comprises a catalyst component I, a catalyst component II, a support activator and an organoaluminum compound, wherein said catalyst composition is substantially free of alumoxanes, organoboron or organoboron compounds, ionizing ionic compounds and/or other similar materials; alternatively, essentially free of alumoxane; alternatively, essentially free of organoboron or organoboron compounds; or, alternatively, essentially free of ionizing ionic compounds. According to these aspects, the catalyst composition has the catalytic activity discussed in this document, and in the absence of these additional materials. For example, a catalyst composition according to the present invention may consist essentially of a catalyst component I, a catalyst component II, an activator-support, and an organoaluminum compound, where there are no other materials in the catalyst composition that could increase/decrease the activity of the catalyst composition by more than about 10% relative to the catalytic activity of the catalyst composition in the absence of these materials.

Catalyst compositions of the present invention generally have a catalytic activity of greater than about 250 grams of ethylene polymer (homopolymer and/or copolymer as required by context) per gram of support activator per hour (abbreviated as g/g/h). In another aspect, the catalytic activity may be greater than about 350, greater than about 450, or greater than about 550 g/g/hr. Also, in another aspect, the catalytic activity may be greater than about 700 g/g/h, greater than about 1000 g/g/h, or greater than about 2000 g/g/h, and often even 3500-6000 g/g/h. Illustrative and non-limiting ranges for catalytic activity include about 500 to about 5000, about 750 to about 4000, or about 1000 to about 3500 g/g/h, and so on. This activity is measured under slurry polymerization conditions using triisobutylaluminum as co-catalyst, isobutane as diluent, at a polymerization temperature of about 90° C. and a reactor pressure of about 400 psig (2.2 MPa g). Besides. in some aspects, the activator-support may comprise sulfated alumina, fluorinated silica-alumina, or fluorinated silica-coated alumina, although not limited to these materials.

The present invention further includes methods for preparing said catalyst compositions, such as, for example, bringing the respective catalyst components into contact in any order or sequence. According to one aspect, for example, the catalyst composition can be obtained by a method comprising bringing into contact in any order a catalyst component I, a catalyst component II and an activator, while, according to another aspect, a catalyst composition can be obtained by a method including bringing into contact in any order a catalyst component I, a catalyst component II, an activator and a co-catalyst.

Olefin polymers (eg, ethylene polymers) can be produced using the described catalyst systems by any suitable olefin polymerization process using different types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. One of these methods for polymerizing olefins to polymerize olefins in the presence of a catalyst composition of the present invention may include contacting the catalyst composition with an olefin monomer and optionally one or more olefin comonomers in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise, as described herein, a catalyst component I, a catalyst component II, an activator, and an optional co-catalyst. The present invention also includes any olefin polymers (eg, ethylene polymers) produced by any of the polymerization processes described herein.

As used herein, "polymerization reactor" includes any polymerization reactor in which olefin monomers and comonomers (one or more than one comonomer) can be polymerized (including oligomerization) to produce homopolymers, copolymers, terpolymers, etc. Various types of polymerization reactors include reactors which may be referred to as a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, etc., 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. The polymerization conditions for different 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 contain vertical or horizontal loops. High pressure reactors may include autoclave or tubular reactors. Different types of reactors may include batch or continuous processes. In continuous processes, intermittent or continuous discharge of the product may be used. Reactor systems and polymerization processes may also include some or all of the direct reuse of unreacted monomer, unreacted comonomer and/or diluent.

The polymerization reactor system may contain one reactor or several reactors (2 reactors, more than 2 reactors, etc.) of the same or different types. For example, the polymerization reactor system may comprise a slurry reactor, a gas phase reactor, a solution reactor, or a combination of two or more of these reactors. The production of polymers in multiple reactors may include multiple steps in at least two separate polymerization reactors connected to each other by a transfer device that allows the polymers produced in the first polymerization reactor to be transferred to the second reactor. The target polymerization conditions in one of the reactors may differ from the operating conditions in the other(s) reactor(s). Alternatively, multi-reactor polymerization may involve manually transferring polymer from one reactor to subsequent reactors to continue the polymerization. Multiple reactor systems can include any combination, including but not limited to multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with loop and/or gas phase reactors. Several reactors can be operated sequentially, simultaneously, or in both of these modes. Accordingly, the present invention includes polymerization reactor systems containing one reactor, containing two reactors, and containing more than two reactors. The polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, according to certain aspects of the present invention, as well as combinations of several of these reactors.

In one aspect, the polymerization reactor system may comprise at least one slurry loop reactor containing vertical or horizontal loops. The monomer, diluent, catalyst and comonomer can be continuously fed into the loop reactor in which the polymerization is carried out. In general, continuous processes may include continuously introducing the monomer/comonomer, catalyst and diluent into the polymerization reactor and continuously withdrawing the slurry containing the polymer particles and the diluent from said reactor. The reactor effluent may be flashed to remove solid polymer from liquid components that contain diluent, monomer and/or comonomer. Various technologies can be used for this separation step, including, but not limited to, flash evaporation, which can include any combination of heat input and pressure reduction, separation by cyclonic action in either a cyclone or a hydrocyclone, or separation by centrifugation.

An exemplary slurry polymerization process (also referred to as a polymer particle production process) is described, for example, in US Pat.

Suitable diluents for use in slurry polymerization include, but are not limited to, the polymerizable monomer and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop reactor polymerization reactions can be carried out in bulk when no diluent is used.

In yet another aspect, the polymerization reactor system may comprise at least one gas phase reactor (eg, a fluidized bed reactor). These reactor systems may employ a continuous recycle stream containing one or more monomers circulating continuously 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 back to the reactor. Simultaneously, it is possible to remove the polymer product from the reactor and add new or fresh monomer to replace the polymerized monomer. Said gas phase reactors may provide for a multi-stage gas phase olefin polymerization process in which olefins are polymerized in gas phase in at least two independent gas phase polymerization zones, wherein the polymer containing the catalyst formed in the first polymerization zone is fed into the second polymerization zone. Typical gas phase reactors are described in US Pat.

According to another aspect, the polymerization reactor system may comprise a high pressure polymerization reactor, for example, may comprise a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones to which fresh monomer, initiators or catalysts are added. The monomer may be entrained in the inert gas stream and introduced into one zone of the reactor. The initiators, catalysts and/or catalyst components may be entrained in the gas stream and introduced into another zone of the reactor. For polymerization, the gas streams can be mixed. Heat and pressure can be appropriately applied to ensure optimum polymerization reaction conditions.

In yet another aspect, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer/comonomer is brought into contact with the catalyst composition using suitable agitators or other means. A carrier containing an inert organic diluent or an excess of monomer may be used. If desired, the monomer/comonomer may be contacted in the vapor phase with the catalytic reaction product with or without the presence of liquid material. The polymerization zone can be maintained at a temperature and pressure that allows the formation of a polymer solution in the reaction medium. Agitation may be used to provide better temperature control and to maintain the uniformity of the polymerization mixtures in the polymerization zone. Appropriate means are used to dissipate the exothermic heat of the polymerization reaction.

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

The polymerization conditions that can be controlled to provide the efficiency and desired properties of the polymer may include temperature, pressure, and concentrations of various reactants. The polymerization temperature can affect catalyst performance, polymer molecular weight and molecular weight distribution. Different polymerization conditions can be maintained at a substantially constant level, for example, to obtain an olefin polymer (or ethylene polymer) of a particular class. A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the Gibbs free energy equation. As a rule, it includes a temperature from about 60°C to about 280°C, for example, 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 range from about 70°C to about 100°C, or from about 75°C to about 95°C.

Suitable pressure may also vary depending on the type of reactor and polymerization. Liquid phase polymerization pressure in a loop reactor is typically less than 1000 psig (6.9 MPa g). The pressure for gas phase polymerization is typically from about 200 to 500 psig (1.4 MPa to 3.4 MPa g). High pressure polymerization in tubular or autoclave reactors is generally carried out at pressures of from about 20,000 to 75,000 psig (138 to 517 MPa g). Polymerization reactors can also be operated in the supercritical region, corresponding generally to elevated temperature and pressure. Operation above the critical point in the pressure/temperature diagram (supercritical phase) can provide advantages to the polymerization reaction process.

Olefin monomers that can be used in conjunction with the catalyst compositions in the polymerization processes of the present invention may generally include olefin compounds having from 2 to 30 carbon atoms per molecule and at least one olefinic double bond, such as ethylene or propylene. According to one aspect, the olefin monomer may contain a C ₂ -C ₂₀ olefin; alternatively, C ₂ -C ₂₀ alpha-olefin; alternatively, a C ₂ -C ₁₀ olefin; alternatively, C ₂ -C ₁₀ alpha-olefin; alternatively, the olefin monomer may contain ethylene; or, alternatively, the olefin monomer may contain propylene (for example, to obtain a polypropylene homopolymer or a propylene-based copolymer).

If a copolymer (or alternatively a terpolymer) is desired, then the olefin monomer and the olefin comonomer may independently contain, for example, a C ₂ -C ₂₀ alpha olefin. In some aspects, the olefin monomer may comprise ethylene or propylene that is copolymerized with at least one comonomer (eg, C ₂ -C ₂₀ alpha olefin, C ₃ -C ₂₀ alpha olefin, etc.). According to one aspect of the present invention, the olefin monomer used in the polymerization process may contain ethylene. According to this aspect, the comonomer may contain a C ₃ -C ₁₀ alpha-olefin; alternatively, the comonomer may contain 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may contain 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may contain 1-butene; alternatively, the comonomer may contain 1-hexene; or, alternatively, the comonomer may contain 1-octene.

EXAMPLES

The invention is further illustrated in the following examples, which should not be considered as imposing any restrictions on the scope of the present invention. Various other aspects, implementations, modifications, and equivalents may be suggested by those of ordinary skill in the art after studying the description provided herein without departing from the spirit of the present invention or the scope of the appended claims.

Melt flow index (MFR, g/10 min) was determined according to ASTM D1238 at 190°C using a weight of 2160 grams, and Melt flow index at increased shear stress (MFR-MS, g/10 min) was determined according to ASTM D1238 at 190°C using a weight of 21600 grams. The density was determined in grams per cubic centimeter (g/cm ³ ) in a sample obtained by pressing in a form, cooled at a rate of 15°C per hour and aged for 40 hours at room temperature, in accordance with ASTM D1505 and ASTM D4703.

Molecular weight and molecular weight distributions were determined using a PL-GPC 220 system (Polymer Labs, Agilent Company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operated at 145°C. The flow rate of the mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 g/l of 2,6-di-tert-butyl-4-methylphenol (BHT) was set per 1 ml/min, the concentration of the polymer solution was 1.0-1.5 mg/ml depending on the molecular weight. Samples were prepared at 150°C nominally for 4 hours with occasional gentle agitation, after which the solutions were transferred to sample tubes for sample injection. The volume of the injected sample was approximately 200 µl. An internal calibration method was used to determine molecular weight and molecular weight distribution using Chevron Phillips Chemical Company HDPE polyethylene resin, ^MARLEX® BHB5003, as a standard. The cumulative table for the standard was previously determined in a separate SEC-MALS experiment. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z-average molecular weight, and Mp is the peak molecular weight (position on the molecular weight axis of the highest point on the molecular weight distribution curve).

The rheological properties of the melt were described as follows. Pulsating shear measurements of small strain (less than 10%) were performed on an Anton Paar MCR rheometer using parallel plate geometry. All rheological tests were carried out at 190°C. Then the data were substituted into the dependence curve of the complex viscosity |η * | on frequency (ω) using a modified three-parameter empirical Carro-Yasuda (CY) model to obtain zero shear viscosity, η0, characteristic viscous relaxation time, τη, and rheological width parameter, a (CY-a parameter). A simplified empirical Carro-Yasuda (CY) model is presented below.

,

where: |η * (ω) |=value of complex shear viscosity;

η0 = viscosity at zero shear rate;

τη = viscous relaxation time (tau(η));

a = parameter "rheological width" (parameter CY-a);

n =sets the final slope of the exponential function, given value 2/11; And

ω = angular frequency of deformation in oscillatory shear.

A detailed description of the significance and interpretation of the CY model and the parameters derived from it can be found in: C. A. Hieber and H. H. Chiang, Rheol. Acta 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci. 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd edition, John Wiley & Sons (1987); the contents of each of which are incorporated herein in their entirety by reference.

The number of long chain branches (LCBs) per 1000 carbon atoms in the polymer as a whole was calculated by the method of Janzen and Colby ( J. Mol. Struct ., 485/486, 569-584 (1999), the contents are incorporated herein in their entirety by reference) based on the values of viscosity at zero shear rate, η _o (defined in the Carro-Yasuda model, as described above herein) and measured values of M _w obtained using a multi-angle light scattering detector Dawn EOS (Wyatt). According to the Janzen-Colby method, the polymer according to example 41 contained 0.032 LCB per 1000 carbon atoms in total, which is a typical value for other ethylene polymers obtained in the examples. As expected, the number of LCBs in the proposed examples falls in the range of ~0.01-0.06 (the number of LCBs per 1000 carbon atoms in general).

LCB content and LCB distribution were determined according to the method proposed by Yu, et al (Yu, DesLauriers, Rohlfing, Polymer , 2015 , 46 , 5165-5192, the contents are incorporated herein in their entirety by reference). Briefly, the SEC-MALS system connected a DAWN EOS photometer (Wyatt Technology, Santa Barbara, CA) to a Waters 150-CV plus GPC/SEC system (Milford, MA) or a PL-210 GPC/SEC system (Polymer Labs, Agilent at time of filing) via a hot transfer line, temperature controlled at 145°C. Pumped degassed mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 wt.% BHT (butylated hydroxytoluene) through the built-in filter, and then passed through a series of SEC columns. The polymer solutions introduced into the system were moved through the columns using the mobile phase for fractionation. First, the fractionated polymers were eluted through a MALS photometer, in which light scattering signals were obtained, then they were passed through a differential refractive index detector (DRI) or an IR4 detector (Polymer Characterization SA, Spain), in which their concentration was quantified.

The DAWN EOS system was calibrated using pure toluene at room temperature to convert measured voltage values to scattered light intensity. During calibration, toluene was filtered through a 0.02 µm filter (Whatman) and passed directly through the flow cell in the EOS system. At room temperature, the Rayleigh ratio is 1.406×10 ^-5 cm ^-1 . A narrow distribution polystyrene (PS) standard (American Polymer Standards) with an MW of 30,000 g/mol at a concentration of about 5~10 mg/ml in TCB was used to normalize the system at 145°C. Under given chromatographic conditions, the estimated radius of gyration ( R _g ) of polystyrene (PS) was 5.6 nm. A differential refractive index detector (DRI) was calibrated using known amounts of the PE standard. Using the averaged values of the total area of the chromatographic peaks in the recorded chromatograms for at least five samples, the DRI constant (α _RI ) was calculated using the equation below (equation 1):

Equation 1

where I _RI is the signal intensity at the DRI detector, c is the polymer concentration, and dn/dc is the increment in the refractive index of the PE in the TCB at the measurement temperature.

With a flow rate set at 0.7 ml/min, the mobile phase was eluted through three (3) 7.5 mm x 300 mm, 20 µm Mixed-A columns (Polymer Labs, at time of filing, Agilent). Prepared solutions of PE with a nominal concentration of 1.5 mg/ml at 150°C for 4 hours. For each chromatographic fraction, both the absolute molecular weight ( M ) and the root mean square (RMS) radius, or radius of gyration, R _g , were determined based on Debye plots. As a control linear PE, CPChem Marlex™ HiD9640, a high density PE with a wide MWD, was used. The refractive index increment dn/dc in this study was 0.097 ml/g for PE dissolved in TCB at 135°C.

The Zimm-Stockmayer approach (Zimm, St°Ckmayer, J. Chem. Phys. 1949 , 17 , 1301, incorporated herein in its entirety by reference) was used to determine the number of LCBs in polyethylene resins. In the SEC-MALS analysis, both M and R _g were measured simultaneously for each fraction in the chromatogram. At one molecular weight, the Rg _of a branched polymer is less than that of a linear polymer. The branching index ( g _M ) is defined as the ratio of the rms radius of gyration of a branched polymer to the radius of a linear polymer of the same molecular weight using Equation 2,

Equation 2

where the subscripts b and l denote branched and linear polymer, respectively.

The weighted average number of LCRs per molecule ( B _3w ) was calculated using Equation 3 using proprietary software,

(3)

LCR frequency ( , the number of LCRs per 1000 carbon atoms in total) was calculated using Equation 4 using the value of B _3w obtained in Equation 3,

(4)

where M ₀ is the molecular weight of the polyethylene unit, M _i is the molecular weight ^{of the ith} fraction .

Since the presence of SCB in a polymer can affect the ratio R _g - MW, correction for SCB was performed before using Equations 3 and 4 to calculate LCB and distribution of LCB in PE copolymers. To correct for the effect of SCB on the branching index in MWD, two relationships must be determined: the first is the relationship between the correction factor for the branching index (Δ g _M ) and the SCB content ( x _SCB ), and the other is the relationship between the SCB content and the molecular weight, both of which were determined experimentally. Mathematically, the product of these two ratios determines the dependence of the correction factor of the branching index (Δg _M ) on MM, as shown in equation 5,

(5)

where x _SCB is the SCB content (ie the number of SCBs per 1000 total carbon atoms) in the copolymer in question.

To determine the relationship between Δ g _M and x _SCB , PE standards were used that met the following criteria: the standards were substantially free of LCB and had a flat SCB distribution and known SCB content. At least five PCR standards were used to correct for the effect of the PCR. The content of SCB in these SCB standards ranged from 0 to 34 SCB/1000 carbon atoms in total.

Short chain branch content and short chain branch distribution (SCC) in molecular weight distribution was determined on a GPC system with an IR5 detector (IR5-GPC), where the GPC system was a PL220 GPC/SEC system (Polymer Labs, Agilent) equipped with three Styragel HMW-6E columns (Waters, MA) for polymer separation. An IR5 MCT thermoelectrically cooled detector (IR5) (Polymer Char, Spain) was connected to the GPC columns via a hot transfer line. Chromatographic data was obtained from two output ports in the IR5 detector. First, the analog signal is passed from the analog output port to a digitizer before being connected to computer "A" for molecular weight determination using Cirrus software (Polymer Labs, at the time of filing by Agilent Company) and an internal calibration method using Marlex™ BHB5003 HDPE resin (Chevron Phillips Chemical) as the molecular weight standard. The digital signals, on the other hand, travel via a USB cable directly to Computer B, where they are collected using the LabView data acquisition software supplied by Polymer Char. Set the following chromatographic conditions: the temperature of the thermostat columns 145°C; flow rate 1 ml/min; sample volume 0.4 ml; and a polymer concentration of about 2 mg/ml depending on the molecular weight of the sample. The temperature of the hot transfer line and the measuring cell of the IR5 detector was set to 150°C, while the temperature of the electronics of the IR5 detector was set to 60°C. The content of short chain branches was determined by an in-house developed method using the ratio of signal intensity of CH ₃ (I _CH3 ) to CH ₂ (I _CH2 ) in combination with a calibration curve. The calibration curve was a plot of the SCB content (x _SCB ) versus the signal intensity ratio I _CH3 /I _CH2 . A set of polyethylene resins (at least 5) with an SCC level ranging from zero to about 32 SCC/1000 carbon atoms (SCC standards) was used to construct a calibration curve. All of these SCR standards had a known SCR level and a flat RCCC profile, which were determined previously by NMR and solvent gradient fractionation combined with NMR (SGF-NMR) methods. Using the PCR calibration curves constructed in this manner, the short chain branch distribution profile was determined by molecular weight distribution for the resins fractionated in the IR5-GPC system under exactly the same chromatography conditions as for the indicated PCR standards. Based on the relationship between signal intensity ratio and eluted volume, the dependence of SCR distribution on MWD was determined using a pre-built SCR calibration curve (i.e., _ICH3 / _ICH2 signal intensity ratio versus SCR content) and an MM calibration curve (i.e., molecular weight versus elution time) to convert the ratio of _ICH3 / _ICH2 signal intensity and elution time to SCR content and molecular weight, respectively.

Silica Coated Fluorinated Alumina Support Activators (FSCA) were prepared as follows. Got boehmite in W.R. Grace & Company called "Alumina A", which had a surface area of 300 m²/g, pore volume 1.3 ml/g and average particle size 100 microns. First, the alumina was calcined in dry air at about 600°C for about 6 hours, cooled to ambient temperature, and then brought into contact with tetraethylorthosilicate in isopropanol to achieve 25 wt. % SiO₂. After drying, the silica-coated alumina was calcined at 600°C within 3 hours. Silica coated fluorinated 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. Thereafter, the fluorinated silica coated alumina (FSCA) was collected and stored under a dry nitrogen atmosphere and used without access to the ambient atmosphere.

EXAMPLES 1-76

Comparative Example 76 was a commercially available chromium-catalyzed HDPE resin manufactured by Chevron-Phillips Chemical Company LP, where Examples 1-75 were prepared as follows. The polymerization experiments for Examples 1-75 were run for 30 minutes in a one gallon (3.8 L) stainless steel autoclave reactor containing two liters of isobutane as diluent and hydrogen added from a 325 cc auxiliary vessel. In general, solutions of the metallocene compounds were prepared by dissolving 20 mg of the respective catalyst component I and the metallocene catalyst component II in 20 ml of toluene. Under isobutane purging conditions, 1 ml of TIBA (25% in heptanes), about 100-400 mg of FSCA, and metallocene solutions were introduced into the cold reactor through the feed port. The reactor was closed and 2 L of isobutane was added. The reactor was quickly heated to a temperature within 5 degrees of the operating temperature, and then 1-hexene (if used), ethylene and hydrogen (if used) were introduced into the reactor. Ethylene was supplied as needed to maintain the target pressure. Maintained the target temperature in the reactor during the experiment using an automatic heating-cooling system. After the reactor was vented, purged and cooled, the resulting polymer product was dried at 60° C. under reduced pressure. The structures of the metallocene compounds used in Examples 1-75 are shown below (Ph=phenyl; t-Bu=t-butyl):

MET-1A MET-1B MET-2A

Table I and Table II summarize the specific polymerization conditions for Examples 1-66 and Examples 67-75, respectively. Similarly, Table III and Table IV summarize the different properties of polymers according to Examples 1-66 and Examples 67-75 and Comparative Example 76, respectively. A typical rheological curve (viscosity versus shear rate at 190° C.) for some of the polymers shown in Tables III-IV is shown in FIG. 1 , and a typical molecular weight distribution curve (dependence of the amount of polymer on the logarithm of molecular weight) for some of the polymers shown in tables III-IV is presented in FIG. 2 . FIG. 1 illustrates a graph of dynamic rheological properties for polymers according to examples 37-38, 41, 65 and 76, while in FIG. 2 illustrates the molecular weight distribution for polymers according to examples 37-38, 41, 65 and 76.

Exemplary molecular weight and long chain branch distribution curves for some of the polymers shown in Tables III-IV are shown in FIG. 3-5 and representative molecular weight and short chain branch distribution curves for some of the polymers shown in Tables III-IV are shown in FIG. 6-8 . FIG. 3 illustrates graphs for molecular weight distribution and distribution of long chain branches for the polymer according to example 41, while in FIG. 4 illustrates a plot for molecular weight distribution and distribution of long chain branches for the polymer according to example 60, and FIG. 5 illustrates a plot for molecular weight distribution and distribution of long chain branches for the polymer of Example 61. FIG. 6 illustrates plots for molecular weight distribution and distribution of short chain branches for the polymer according to example 41, while in FIG. 7 illustrates a plot for molecular weight distribution and distribution of short chain branches for the polymer according to example 60, and FIG. 8 illustrates a plot for molecular weight distribution and distribution of short chain branches for the polymer according to example 61. According to the data shown in FIG. 3-8 , Table V summarizes the SCB content and LCB content for the respective ethylene polymer in a specific molecular weight range.

Согласно указанным таблицам и фигурам становится очевидно, что были получены этиленовые полимеры (например, сополимеры этилена/1-гексена), имеющие широкий спектр свойств полимера, таких как показатель текучести расплава менее 1 г/10 мин (или менее 0,5 г/10 мин), отношение ПТР-ПНС/ПТР в диапазоне 10-45, плотность в диапазоне 0,93-0,965 г/см ³ (или в диапазоне 0,93-0,958 г/см ³ ), параметр CY-a менее 0,2 (или в диапазоне 0,03-0,15), вязкость при нулевой скорости сдвига при 190°C в диапазоне 1×10 ⁶ -1×10 ¹⁶ Па-с, отношение Mw/Mn в диапазоне 3,5-18 (или в диапазоне от 6 до 16), отношение Mz/Mw в диапазоне 3,5-10 (или в диапазоне 5-8), значение Mn в диапазоне 10000-60000 г/моль (или в диапазоне 10000-40000 г/моль), значение Mw в диапазоне 100000-400000 г/моль (или в диапазоне 100000-300000 г/моль), и значение Mz в диапазоне 500000-2500000 г/моль (или в диапазоне 750000-1500000 г/моль). In general, many of the polymers of Examples 1-75 have properties that can provide processing performance, shear thinning, melt strength, and sleeve stability comparable to or improved over the chromium-based polymer of Example 76.

The increasing distribution of comonomer in the proposed polymers according to examples 1-75 is illustrated in FIG. 6-8 , which show the molecular weight distribution and distribution of short chain branches for polymers according to example 41, example 60 and example 61, which are typical polymers according to examples 1-75 of the invention. In these figures, the relative number of short chain branches (SCB) at higher molecular weight is higher than at lower molecular weight (2 methyl chain ends (CE) are assumed, and the number of SCBs is given in terms of 1000 carbon atoms (TC) in the polymer as a whole). In particular, the average number of SCCs per 1000 carbon atoms in general in these polymers with a molecular weight in the range from 400,000 to 600,000 g/mol exceeded their number in the molecular weight in the range from 40,000 to 60,000 g/mol. The reverse is true for the chromium-based polymer of example 76: the average number of SCCs per 1000 carbon atoms in general in the molecular weight range from 400,000 to 600,000 g/mol is less than their number in the molecular weight range from 40,000 to 60,000 g/mol (decreasing comonomer distribution).

The number average number of SCR per 1000 carbon atoms in general in the respective polymers according to FIG. 6-8 with a molecular weight in the range of 400,000 to 600,000 g/mol and a molecular weight in the range of 40,000 to 60,000 g/mol can be calculated based on Equations 6 and 7, respectively, and are listed in Table V.

Equation 6

Equation 7

Where is the number average number of SCCs in the respective molecular weight range, and is the number of SCRs in fraction i .

As shown in Table V , the number average number of SCRs per 1000 carbon atoms in total in the polymers according to FIG. 6-8 at a molecular weight in the range from 400,000 to 600,000 g/mol is ~122-153% higher than their number at a molecular weight in the range from 40,000 to 60,000 g/mol.

The concentration of long chain branches in the high molecular weight fraction (but not the very high molecular weight tail) of the proposed polymers according to examples 1-75 is illustrated in FIG. 3-5 , which show the molecular weight distribution and distribution of long chain branches in polymers according to example 41, example 60 and example 61, which are typical polymers according to examples 1-75 of the invention. In these figures, the average number of LCRs per 1000 carbon atoms in general in polymers with a molecular weight in the range from 400,000 to 600,000 g/mol exceeded their number at a molecular weight in the range from 4,000,000 to 6,000,000 g/mol.

The number average number of LCRs per 1000 carbon atoms in general in the respective polymers according to FIG. 3-5 with a molecular weight in the range of 400,000 to 600,000 g/mol and a molecular weight in the range of 4,000,000 to 6,000,000 g/mol can be calculated based on Equations 8 and 9, respectively, and are listed in Table V.

Equation 8

Equation 9

Where is the number average number of LCBs in the respective molecular weight range, and represents LCB in fraction i .

As shown in Table V , the number average number of LCRs per 1000 carbons in total in the polymers according to FIG. 3-5 with a molecular weight in the range from 400,000 to 600,000 g/mol is at least 600% higher than their number with a molecular weight in the range from 4,000,000 to 6,000,000 g/mol. For the examples shown in Table V , the number average number of LCRs per 1000 carbons in general at a molecular weight in the range of 400,000 to 600,000 g/mol was in the range of ~0.03-0.06.

Table I. Examples 1-66 - Polymerization experiments. Example MET-2A
(mg) MET-1A
(mg) FSCA
(G) Pressure
(psig (MPa g)) 1-hexene
(G) _H2
(ppm) Temperature
(°C) Polymer
(G) 1 0.1 1 0.190 403 (2.78) 5 - 90 241 2 0.2 1 0.188 403 (2.78) 5 - 90 159 3 0.3 1 0.176 403 (2.78) 5 - 90 223 4 0.4 1 0.200 403 (2.78) 5 - 90 145 5 0.5 1 0.192 403 (2.78) 5 - 90 142 6 0.5 1 0.185 403 (2.78) 10 - 90 257 7 0.5 1 0.187 403 (2.78) 5 - 95 258 8 1 0.3 0.123 403 (2.78) 5 - 95 140 9 1 0.3 0.109 403 (2.78) 10 - 95 100 10 1 0.5 0.120 403 (2.78) 5 - 95 135 eleven 1 0.5 0.128 403 (2.78) 10 - 95 156 12 0.5 0.5 0.119 403 (2.78) 5 - 95 120 13 0.5 0.5 0.113 403 (2.78) 10 - 95 87 14 1 0.3 0.117 403 (2.78) 5 - 95 201 15 1 0.3 0.114 403 (2.78) 10 - 95 219 16 0.6 0.3 0.102 403 (2.78) 5 - 95 136 17 0.6 0.3 0.115 403 (2.78) 10 - 95 210 18 1 0.5 0.226 403 (2.78) 5 50 90 200 19 1 0.5 0.222 403 (2.78) 10 50 90 87 20 1 1 0.198 403 (2.78) 5 50 90 175 21 1 1 0.200 403 (2.78) 10 50 90 176 22 1 0.5 0.226 403 (2.78) 5 50 90 190 23 0.5 1 0.190 403 (2.78) 5 50 90 132 24 0.5 1 0.200 403 (2.78) 10 50 90 135 25 1 1 0.208 403 (2.78) 2 50 90 253 26 1 1 0.231 403 (2.78) 4 50 90 279 27 1.5 1 0.208 403 (2.78) 2 50 90 242 28 1.5 1 0.194 403 (2.78) 3 - 90 225 29 1.5 1 0.216 403 (2.78) 5 - 90 225 thirty 0.5 1.2 0.214 403 (2.78) 5 - 90 153 31 0.5 1.2 0.195 403 (2.78) 5 150 90 145 32 0.5 1.2 0.191 403 (2.78) 5 250 90 101 33 0.2 1 0.203 402 (2.77) 10 110 90 235 34 0.2 1 0.202 402 (2.77) 5 110 90 187 35 0.2 1 0.201 402 (2.77) 10 - 90 366 36 0.2 1 0.202 402 (2.77) 5 - 90 139 37 0.2 1 0.202 402 (2.77) 5 55 90 180 38 0.2 1 0.201 374 (2.58) 5 55 85 200 39 0.2 1 0.199 402 (2.77) 3 - 90 189 40 0.1 1 0.202 402 (2.77) 3 - 90 167 41 0.2 1 0.100 402 (2.77) 3 110 90 77 42 0.1 1 0.204 402 (2.77) 3 110 90 180 43 0.1 1 0.201 402 (2.77) 5 - 90 177 44 0.1 1 0.198 402 (2.77) 1 - 90 204 45 0.1 1 0.203 402 (2.77) 2 - 90 203 46 0.1 1 0.176 402 (2.77) 4 - 90 176 47 0.1 1 0.184 374 (2.58) 5 - 85 185 48 0.1 1 0.149 374 (2.58) 3 - 85 149 49 0.1 1 0.164 374 (2.58) 2 - 85 164 50 0.1 1 0.409 374 (2.58) 2 - 85 409 51 0.4 1 0.202 340 (2.34) 40 55 85 67 52 0.4 1 0.201 340 (2.34) 20 110 85 46 53 0.4 1 0.204 402 (2.77) 20 55 90 95 54 0.4 1 0.203 374 (2.58) 20 55 85 172 55 0.4 1 0.202 402 (2.77) 40 - 90 178 56 0.4 1 0.201 430 (2.96) thirty - 95 138 57 0.4 1 0.304 374 (2.58) 20 - 85 125 58 0.4 1 0.300 374 (2.58) 40 - 85 87 59 0.4 1 0.300 374 (2.58) 10 - 85 123 60 0.4 1 0.204 374 (2.58) 10 55 85 129 61 0.4 1 0.202 374 (2.58) 20 55 85 101 62 0.4 1 0.204 345 (2.38) 10 55 80 102 63 0.4 1 0.205 345 (2.38) 20 55 80 157 64 0.3 1 0.204 374 (2.58) 10 55 85 177 65 0.3 1 0.204 345 (2.38) 10 55 80 37 66 0.3 1 0.203 345 (2.38) 20 55 80 94

Table II. Examples 67-75 - Polymerization experiments. Example MET-2A
(mg) MET-1B (mg) FSCA
(G) Pressure (psig (MPa g)) 1-hexene (g) _H2
(ppm) Temperature (°C) Polymer
(G) 67 1.2 0.5 0.225 403 (2.78) 5 - 90 111 68 1.2 0.5 0.210 403 (2.78) 5 150 90 119 69 1.2 0.5 0.193 403 (2.78) 5 250 90 73 70 1.2 0.5 0.214 403 (2.78) 5 350 90 80 71 0.5 1 0.218 403 (2.78) 3 50 90 281 72 0.5 1 0.220 403 (2.78) 10 50 90 156 73 0.5 1 0.206 403 (2.78) 5 50 90 156 74 1 1 0.216 403 (2.78) 5 100 90 150 75 1 1 0.202 403 (2.78) 10 100 90 134

Table III. Examples 1-66 - Properties of polymers. Example PTR
(g/10 min) PTR-PNS
(g/10 min) Density
(g/cc) η ₀
(Pass) _τƞ
(With) CY-a 1 0.05 7.7 0.950 8.21E+06 3.03E-02 0.074 2 0.01 6.5 0.946 2.33E+10 2.62E+01 0.046 3 0.03 8.6 0.946 1.30E+09 1.63E+01 0.059 4 - 5.2 0.949 2.96E+12 1.89E+04 0.041 5 - 3.0 0.948 1.99E+12 1.32E+05 0.046 6 - 3.0 0.940 1.48E+13 7.54E+05 0.042 7 0.08 9.4 0.946 7.16E+11 1.51E+04 0.044 8 0.03 6.8 0.940 3.11E+14 2.72E+07 0.038 9 - 2.9 0.934 3.90E+20 5.62E+16 0.036 10 0.01 3.9 0.940 3.96E+13 6.11E+07 0.048 eleven 0.05 12 0.936 7.00E+08 7.01E+02 0.078 12 0 0 0.938 2.05E+09 2.77E+04 0.114 13 0 2.7 0.933 1.40E+11 4.26E+06 0.086 14 0.10 2.7 0.934 1.44E+06 6.80E+00 0.417 15 - - 0.928 1.24E+06 5.37E+00 0.474 16 - - 0.934 2.25E+06 9.05E+00 0.447 17 - 0.1 0.927 1.22E+06 4.89E+00 0.488 18 0.27 14 0.944 1.77E+11 2.47E+01 0.037 19 1.49 64 0.944 2.85E+05 1.90E-01 0.117 20 0.13 eleven 0.945 1.16E+12 4.85E+04 0.043 21 0.07 7.9 0.939 1.30E+09 2.31E+03 0.077 22 0.58 20 0.945 1.71E+09 1.13E-01 0.043 23 0.07 12 0.946 8.31E+05 1.11E+01 0.253 24 - 5.6 0.940 3.08E+06 3.95E+01 0.221 25 0.17 12 0.954 7.59E+11 3.01E+02 0.037 26 0.22 13 0.950 2.10E+10 9.51E-01 0.039 27 0.30 13 0.953 4.75E+07 4.49E-02 0.059 28 0.29 12 0.951 9.20E+07 8.72E-01 0.064 29 0.19 9.8 0.950 2.82E+08 1.53E+00 0.059 thirty - 1.0 0.944 7.71E+08 5.52E+03 0.118 31 0.66 55 0.960 2.30E+04 2.93E-01 0.417 32 2.20 124 0.963 4.51E+03 4.75E-02 0.518 35 0.21 29 0.939 - - - 36 0.12 36 0.940 - - - 37 0.06 20 0.951 2.88E+12 8.38E+04 0.041 38 0.30 37 0.948 - - - 39 0.16 37 0.942 - - - 40 0.10 10 0.942 2.38E+11 6.24E+01 0.038 41 0.14 35 0.951 3.35E+07 4.60E+01 0.090 42 3.13 135 - - - - 43 0.12 eleven 0.941 1.85E+10 2.30E+01 0.045 44 0.03 7.1 0.947 5.16E+19 3.93E+08 0.021 45 - 6.1 0.943 6.58E+16 5.81E+08 0.030 46 - 6.5 0.945 1.03E+16 2.95E+07 0.030 47 - 4.7 0.947 1.48E+11 1.85E+03 0.047 48 - 2.7 - - - - 49 - 3.0 0.943 3.17E+14 3.59E+07 0.039 50 - 22 0.950 1.21E+11 1.41E+00 0.035 51 5.28 212 - - - - 52 1.07 108 - - - - 53 0.62 79 - - - - 54 0.47 46 - - - - 56 3.40 143 - - - - 57 - 3.2 - 4.26E+14 1.96E+09 0.046 58 0.15 19 - - - - 59 0.01 3.6 - 9.30E+15 4.95E+09 0.037 60 0.20 thirty 0.945 2.80E+08 2.83E+02 0.075 61 0.20 thirty 0.933 3.95E+09 2.52E+03 0.061 62 0.11 26 - 1.50E+10 1.71E+04 0.059 63 0.38 114 - - - - 64 2.66 138 - - - - 65 0.07 19 0.952 3.00E+09 1.82E+04 0.078 66 7.74 396 - - - -

Table III. Examples 1-66 - Properties of polymers (continued). Example M _n /1000
(g/mol) M _w /1000
(g/mol) _Mz /1000
(g/mol) M _w /M _{n Mz} / _Mw 1 52 187 1118 3.62 5.97 2 49 198 1405 4.01 7.08 3 52 208 1107 3.98 5.32 4 52 269 1842 5.15 6.85 5 54 274 1768 5.03 6.46 6 57 316 1905 5.53 6.02 7 47 242 1450 5.14 5.99 8 46 260 1450 5.65 5.58 9 37 230 1071 6.15 4.65 10 45 275 1466 6.12 5.32 eleven 35 237 1367 6.83 5.77 12 48 388 1933 8.04 4.98 13 38 337 2012 8.77 5.97 14 59 363 939 6.11 2.59 15 62 350 856 5.67 2.45 16 63 400 972 6.37 2.43 17 58 379 1023 6.56 2.70 18 36 188 1187 5.23 6.31 19 20 117 690 5.85 5.87 20 34 225 1593 6.58 7.08 21 33 228 1342 6.79 5.89 22 thirty 152 1032 5.12 6.79 23 25 232 1340 9.23 5.78 24 32 264 1323 8.33 5.01 25 44 244 1716 5.57 7.02 26 44 217 1530 4.95 7.06 27 44 195 1218 4.39 6.24 28 44 221 1441 5.01 6.52 29 44 208 1226 4.74 5.90 thirty 57 436 2051 7.66 4.70 31 14 141 670 10.04 4.76 32 8 102 401 12.45 3.91 35 38 146 557 3.84 3.81 36 40 180 779 4.49 4.33 37 thirty 190 1317 6.34 6.93 38 22 151 876 6.73 5.80 39 37 174 983 4.67 5.63 40 40 189 1024 4.63 5.42 41 21 178 1227 8.55 6.90 42 - - - - - 43 39 194 1075 4.95 5.53 44 45 243 1514 5.45 6.22 45 41 228 1258 5.52 5.51 46 42 228 1270 5.44 5.56 47 53 236 1320 4.41 5.61 48 - - - - - 49 50 251 1310 5.05 5.23 50 37 138 486 3.68 3.53 51 - - - - - 52 - - - - - 53 - - - - - 54 - - - - - 56 - - - - - 57 26 239 1303 9.33 5.46 58 - - - - - 59 18 254 1397 13.76 5.50 60 10 151 901 14.41 5.97 61 eleven 152 911 13.29 5.98 62 12 160 1085 13.58 6.80 63 - - - - - 64 - - - - - 65 13 176 1220 13.52 6.94 66 - - - - -

Table IV. Examples 67-75 and Comparative Example 76 - Polymer Properties. Example PTR
(g/10 min) PTR-PNS
(g/10 min) Density
(g/cc) η ₀
(Pass) _τη
(With) CY-a 67 - - 0.937 2.64E+07 1.59E+02 0.560 68 0.86 25 0.953 1.62E+04 5.46E-02 0.321 69 5.8 127 0.961 2.14E+03 7.68E-03 0.356 70 12.4 273 0.961 8.14E+02 2.79E-03 0.393 71 - - 0.931 3.36E+17 3.61E+14 0.105 72 0.14 12 0.939 6.11E+05 3.00E+00 0.193 73 - 2.6 0.940 4.02E+06 2.28E+01 0.186 74 0.11 8.6 0.943 1.59E+06 6.97E+00 0.170 75 0.40 24 0.940 1.20E+05 4.17E-01 0.195 76 0.2 20 0.955 6.07E+05 1.67E+00 0.157

Table IV. Examples 67-75 and Comparative Example 76 - Properties of Polymers
(continuation). Example M _n /1000
(g/mol) M _w /1000
(g/mol) _Mz /1000
(g/mol) M _w /M _{n Mz} / _Mw 67 49 651 2518 13.16 3.87 68 17 128 416 7.4 3.25 69 12 82 260 6.55 3.19 70 9 67 207 7.06 3.14 71 77 258 1173 3.34 4.54 72 thirty 161 489 5.25 3.04 73 42 218 659 5.23 3.02 74 28 173 548 6.21 3.17 75 21 142 533 6.68 3.77 76 21 145 848 6.99 5.83

Table V. Average content of LCR and CCR in specific molecular weight ranges. Example
41 Example
60 Example
61 Average number of SCRs per 1000 carbons overall (a) range 400,000-600,000 g/mol 2.4 4.8 13.3 (b) range 40000-60000 g/mol 1.0 1.9 6.0 Ratio (a)/(b) in percent 240% 253% 222% Average number of LCBs per 1000 carbons overall (a) range 400,000-600,000 g/mol 0.0528 0.0410 0.0365 (b) range 4000000-6000000 g/mol 2.9E-7 0.0052 0.0049 Ratio (a)/(b) in percent very high 788% 745%

The invention has been described above with reference to numerous aspects and specific examples. Those skilled in the art will be able to offer many options in view of the above detailed description. All such obvious variations are included within the full intended scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following (aspects are described as "comprising", but, alternatively, may "consist essentially of" or "consist of"):

Aspect 1. An ethylene polymer having:

a melt flow rate of about 1 g/10 min or less;

density in the range from about 0.93 to about 0.965 g/cm ³ ;

a CY-a parameter at 190° C. of about 0.2 or less;

the average number of short chain branches (SCC) per 1000 carbon atoms in total in a polymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds (by any amount described herein, for example, at least 25%, at least 50%, at least 75%, at least 100%, at least 125%, etc. ) their number at a molecular weight in the range from 40,000 to 60,000 g/mol; And

the average number of long chain branches (LCBs) per 1000 carbon atoms in total in a polymer with a molecular weight in the range of 400,000 to 600,000 g/mol, which exceeds (by any amount described herein, for example, at least 50%, at least 75%, at least 100%, at least 200%, at least 400%, etc. .) their number at a molecular weight in the range from 4,000,000 to 6,000,000 g/mol.

Aspect 2 The polymer as defined in Aspect 1, wherein said ethylene polymer has a melt flow index (MFR) in any of the ranges described herein, such as about 0.7 g/10 min or less, about 0.5 g/10 min or less, about 0.35 g/10 min or less, about 0.25 g/10 min or less, etc.

Aspect 3. The polymer as defined in aspect 1 or 2, wherein said ethylene polymer has a high shear melt flow rate (MFR-SHF) in any of the ranges described herein, for example, from about 2 to about 50 g/10 min, from about 3 to about 40 g/10 min, from about 10 to about 45 g/10 min, from about 12 to about 35 g/1 0 min, etc.

Aspect 4 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an MFR-PNS/MFR in any of the ranges described herein, such as about 80 to about 400, about 90 to about 300, about 100 to about 250, etc.

Aspect 5. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a density in any of the ranges described herein, for example, from about 0.93 to about 0.962 g/cm ³ , from about 0.93 to about 0.958 g/cm 3 , from about 0.935 to about 0.965 g/cm ³ , from about 0.94 to about 0.9 58 g/ ^{cm 3 ,} about 0.95 to about 0.96 g/cm ³ , etc.

Aspect 6. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a CY-a parameter in any of the ranges described herein, for example, from about 0.02 to about 0.2, from about 0.02 to about 0.18, from about 0.02 to about 0.10, from about 0.03 to about 0.15, from about 0.04 to about 0.12, and t .d.

Aspect 7. The polymer as defined in any of the preceding aspects, characterized in that said ethylene polymer has a number of short chain branches (SCB) per 1000 carbon atoms in total in a polymer of a given Mz that exceeds their number at the same Mw, and/or a number of short chain branches (SCB) per 1000 carbon atoms in total in a polymer of a given Mw that exceeds their number at the same Mn, and/or the number of short chain branches kidney branches (KBR) per 1000 carbons overall in a polymer with a given Mz that exceeds their number at the same Mn (reverse distribution of short chain branches or increasing distribution of comonomer).

Aspect 8. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an average number of long chain branches (LCBs) per 1,000 carbon atoms overall in a polymer with a molecular weight in the range of 400,000 to 600,000 g/mol in any of the ranges described herein, for example, from about 0.015 to about 0.085, from about 0.02 to about 0.07, about 0.03 to about 0.06, etc.

Aspect 9. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer contains from about 0.01 to about 0.08 DSB, from about 0.01 to about 0.06 DSB, from about 0.02 to about 0.06 DSB, from about 0.02 to about 0.05 DSB, etc., per 1000 total carbon atoms.

Aspect 10 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a Mw/Mn ratio within any of the ranges described herein, e.g., about 3.5 to about 18, about 4 to about 16, about 5 to about 15, about 6 to about 16, etc.

Aspect 11 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an Mz/Mw ratio within any of the ranges described herein, e.g., about 3.5 to about 10, about 4 to about 9, about 5 to about 9, about 5 to about 8, etc.

Aspect 12 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an Mz in any of the ranges described herein, e.g., from about 500,000 to about 2,500,000 g/mol, from about 600,000 to about 2,000,000 g/mol, from about 750,000 to about 2,000,000 g/mol, from about 750,000 up to about 1,750,000 g/mol, from about 750,000 to about 1,500,000 g/mol, etc.

Aspect 13 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a Mw in any of the ranges described herein, e.g., from about 100,000 to about 400,000 g/mol, from about 100,000 to about 300,000 g/mol, from about 100,000 to about 200,000 g/mol, from about 150,000 to about 400000 g/mol, etc.

Aspect 14 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has Mn in any of the ranges described herein, e.g., from about 10,000 to about 100,000 g/mol, from about 10,000 to about 50,000 g/mol, from about 10,000 to about 40,000 g/mol, from about 10,000 to about 30,000 g /mol, etc.

Aspect 15. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a zero shear viscosity in any of the ranges described herein, for example, from about 1x10 ⁵ to about 1x10 ¹⁷ Pa-s, from about 1x10 ⁶ to about 1x10 ¹⁶ Pa-s, from about 1x10 ⁷ to about 1x10 ¹³ Pa-s, and t .d.

Aspect 16 A polymer as defined in any of the preceding aspects, characterized in that said ethylene polymer is the only product of the reactor, and, for example, a mixture of two polymers not obtained after removal from the reactor, for example, having different molecular weight characteristics.

Aspect 17 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer comprises an ethylene/α-olefin copolymer and/or an ethylene homopolymer.

Aspect 18 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, an ethylene homopolymer, or any combination thereof.

Aspect 19 A polymer as defined in any of the preceding aspects, wherein said ethylene polymer comprises an ethylene/1-hexene copolymer.

Aspect 20. An article containing an ethylene polymer as defined in any of Aspects 1-19.

Aspect 21. An article containing an ethylene polymer as defined in any one of aspects 1-19, wherein said article is an agricultural film, an automotive part, a bottle, a chemical container, a drum, fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, an insert, a molded product, a medical device or material, an outdoor storage product, an outdoor play equipment, a pipe , sheet or tape, toy or roadblock.

Aspect 22. Catalyst composition comprising:

Catalyst component I containing any metallocene compound with one bridging atom or two bridging carbon atoms described herein containing two indenyl groups or an indenyl group and a cyclopentadienyl group;

a catalyst component II containing any one-bridged metallocene compound described herein containing a fluorenyl group and an alkenyl-substituted cyclopentadienyl group;

any activator described herein; And

optionally any cocatalyst described herein.

Aspect 23 A composition as defined in aspect 22, wherein said activator comprises a support activator, an alumoxane compound, an organoboron or organoboron compound, an ionizing ionic compound, or any combination thereof.

Aspect 24. The composition defined in aspect 22, characterized in that said activator contains an alumoxane compound.

Aspect 25. The composition defined in aspect 22, characterized in that said activator contains an organoboron or organoboron compound.

Aspect 26. The composition defined in aspect 22, characterized in that said activator contains an ionizing ionic compound.

Aspect 27 The composition as defined in aspect 22, wherein said activator comprises a support activator, wherein said support activator comprises any solid oxide treated with any electron withdrawing anion described herein.

Aspect 28. The composition defined in aspect 22, characterized in that said activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulphated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulphated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated silica-coated alumina, fluorinated-chlorinated silica-coated alumina, sulfated-silica-coated alumina, phosphated-silica-coated alumina, or any combination thereof.

Aspect 29 The composition as defined in aspect 22, wherein said activator comprises fluorinated alumina, sulphated alumina, fluorinated silica-alumina, sulphated silica-alumina, fluorinated silica-coated alumina, fluorinated-chlorinated silica-coated alumina, sulphated silica-coated alumina, or any combination thereof.

Aspect 30 The composition as defined in aspect 22, wherein said activator comprises a fluorinated solid oxide and/or a sulfated solid oxide.

Aspect 31 A composition as defined in any of aspects 27-30, wherein said activator further comprises any metal or metal ion described herein, such as zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, or any combination thereof.

Aspect 32 A composition as defined in any of aspects 22-31, wherein said catalyst composition contains a cocatalyst, for example any suitable cocatalyst.

Aspect 33 A composition as defined in any of aspects 22-32 wherein said cocatalyst comprises any of the organoaluminum compounds described herein.

Aspect 34 The composition as defined in aspect 33, wherein said organoaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.

Aspect 35 A composition as defined in any one of aspects 27-34, wherein said catalyst composition comprises a catalyst component I, a catalyst component II, an electron withdrawing anion treated solid oxide, and an organoaluminum compound.

Aspect 36 A composition as defined in any of aspects 22-35, wherein said catalyst component I contains two unsubstituted indenyl groups.

Aspect 37 A composition as defined in any of aspects 22-36 wherein said catalyst component I contains one bridging carbon or silicon atom.

Aspect 38 A composition as defined in aspect 37 wherein said bridging carbon or silicon atom has two substituents independently selected from H or a C ₁ -C ₁₈ hydrocarbyl group, eg a C ₁ -C ₆ alkyl group.

Aspect 39 A composition as defined in any of aspects 22-36, wherein said catalyst component I contains a bridge of two carbon atoms.

Aspect 40 A composition as defined in any one of aspects 22-35, wherein said catalyst component I contains an indenyl group and a cyclopentadienyl group.

Aspect 41 The composition as defined in aspect 40, wherein said catalyst component I contains one bridging carbon or silicon atom.

Aspect 42 A composition as defined in aspect 41 wherein said bridging carbon or silicon atom contains two substituents independently selected from H or a C ₁ -C ₁₈ hydrocarbyl group, eg a C ₁ -C ₆ alkyl group.

Aspect 43 A composition as defined in any one of aspects 40-42, wherein at least one of said indenyl group and cyclopentadienyl group is substituted.

Aspect 44 A composition as defined in any of aspects 22-43, wherein said catalyst component I contains zirconium or titanium.

Aspect 45 A composition as defined in any one of aspects 22-44, wherein said catalyst component II contains one bridging carbon or silicon atom.

Aspect 46 A composition as defined in aspect 45 wherein said bridging carbon or silicon atom contains two substituents independently selected from H or C ₁ -C ₁₈ hydrocarbyl group, eg phenyl group.

Aspect 47 A composition as defined in any of aspects 22-46 wherein said fluorenyl group is substituted.

Aspect 48 A composition as defined in any of aspects 22-47 wherein said alkenyl substituent is a C ₃ -C ₁₈ alkenyl group, eg a C ₃ -C ₈ terminal alkenyl group.

Aspect 49 A composition as defined in any one of aspects 22-48, wherein said catalyst component II contains zirconium, hafnium, or titanium.

Aspect 50 A composition as defined in any of aspects 27-49, wherein said catalyst composition is substantially free of alumoxane compounds, organoboron or organoboron compounds, ionizing ionic compounds, or combinations thereof.

Aspect 51. A composition as defined in any of aspects 22-50, wherein the weight ratio of catalyst component I to catalyst component II in said catalyst composition is within any of the ranges described herein, for example, from about 10:1 to about 1:10, from about 10:1 to about 1:1, from about 5:1 to about 1:5, from about 5:1 to about 2:1, from about 2:1 up to about 1:2, etc.

Aspect 52 The composition as defined in any one of aspects 22-51, wherein said catalyst composition is prepared by a process comprising bringing into contact, in any order, a catalyst component I, a catalyst component II, and an activator.

Aspect 53 The composition as defined in any one of aspects 22-51, wherein said catalyst composition is prepared by a process comprising contacting, in any order, a catalyst component I, a catalyst component II, an activator, and a co-catalyst.

Aspect 54. A composition as defined in any of aspects 22-53, wherein said catalyst composition has a catalytic activity within any of the ranges described herein, such as about 500 to about 5000, about 750 to about 4000, about 1000 to about 3500 grams, etc., of ethylene polymer per gram of activator-support per hour under slurry polymer conditions. polymerization using triisobutylaluminum as cocatalyst, isobutane as diluent, and at a polymerization temperature of 90°C and a reactor pressure of 400 psig (2.2 MPa g).

Aspect 55. A process for polymerizing olefins, comprising contacting the catalyst composition defined in any of aspects 22-54 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

Aspect 56 The method as defined in aspect 55, wherein said olefin monomer comprises any olefin monomer described herein, for example, any C ₂ -C ₂₀ olefin.

Aspect 57 The method as defined in aspect 55 or 56 wherein said olefin monomer and olefin comonomer independently contain a C ₂ -C ₂₀ alpha olefin.

Aspect 58 A process as defined in any of aspects 55-57, wherein said olefin monomer contains ethylene.

Aspect 59 A process as defined in any of aspects 55-58, wherein said catalyst composition is contacted with ethylene and an olefin comonomer containing a C ₃ -C ₁₀ alpha olefin.

Aspect 60. The process as defined in any of aspects 55-59, wherein said catalyst composition is contacted with ethylene and an olefin comonomer containing 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 61 A process as defined in any one of aspects 55-57, wherein said olefin monomer contains propylene.

Aspect 62. The method as defined in any of aspects 55-61, wherein said 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 63. The method as defined in any of aspects 55-62, wherein said polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

Aspect 64. The method as defined in any one of aspects 55-63, wherein said polymerization reactor system comprises a loop slurry reactor.

Aspect 65. The method defined in any one of aspects 55-64, wherein said polymerization reactor system comprises a single reactor.

Aspect 66 A process as defined in any of aspects 55-64, wherein said polymerization reactor system comprises 2 reactors.

Aspect 67 The method as defined in any of aspects 55-64, wherein said polymerization reactor system comprises more than 2 reactors.

Aspect 68 The method as defined in any of aspects 55-67 wherein said olefin polymer comprises any of the olefin polymers described herein.

Aspect 69 A process as defined in any of aspects 55-60 and 62-68, wherein said olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

Aspect 70 The method as defined in any of aspects 55-60 and 62-68, wherein said olefin polymer comprises an ethylene/1-hexene copolymer.

Aspect 71 The method as defined in any of aspects 55-57 and 61-68, wherein said olefin polymer comprises a polypropylene homopolymer or a propylene-based copolymer.

Aspect 72. The method as defined in any of aspects 55-71, wherein said 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 psig (about 1.4 to about 6.9 MPa g).

Aspect 73 A process as defined in any one of aspects 55-72, wherein said polymerization conditions are substantially constant, eg, for a particular class of polymer.

Aspect 74 A process as defined in any of aspects 55-73, wherein no hydrogen is added to said polymerization reactor system.

Aspect 75 The process as defined in any one of aspects 55-73, wherein hydrogen is added to said polymerization reactor system.

Aspect 76 A process as defined in any of aspects 55-75, wherein said olefin polymer produced is as defined in any of aspects 1-19.

Aspect 77 An olefin polymer obtained from an olefin polymerization process as defined in any of Aspects 55-75.

Aspect 78 An ethylene polymer as defined in any of aspects 1-19, prepared by a method as defined in any of aspects 55-75.

Aspect 79 An article containing a polymer as defined in any of Aspects 77-78.

Aspect 80. A method of forming or making an industrial article containing an olefin polymer, comprising (i) carrying out the process for polymerizing olefins defined in any of aspects 55-75 to obtain an olefin polymer (e.g., an ethylene polymer according to any of aspects 1-19), and (ii) forming an industrial article containing an olefin polymer, for example, by any of the methods described herein.

Claims (64)

1. Copolymer of ethylene with an alpha-olefin, where the alpha-olefin is selected from 1-butene, 1-hexene, 1-octene, or a combination thereof, and this ethylene copolymer has: melt flow index 1 g/10 min or less; density in the range from 0.93 to 0.965 g/cm ³ ; a CY-a parameter at 190° C. of 0.2 or less; an average number of short chain branches (SCC) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number at a molecular weight in the range from 40,000 to 60,000 g/mol; And the average number of long chain branches (LCB) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number with a molecular weight in the range from 4,000,000 to 6,000,000 g/mol, wherein said ethylene copolymer has an average number of DSBs in the range of 0.015 to 0.085 DSBs per 1000 atoms of all carbon atoms at a molecular weight in the range of 400,000 to 600,000 g/mol. 2. An industrial product containing an ethylene copolymer according to claim 1. 3. Ethylene copolymer according to claim 1, characterized in that: the average number of CCRs per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol is at least 50% higher than their number with a molecular weight in the range from 40,000 to 60,000 g/mol; And the average number of LCRs per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol is at least 100% higher than their number with a molecular weight in the range from 4,000,000 to 6,000,000 g/mol. 4. Ethylene copolymer according to claim 1, characterized in that: the melt flow rate is 0.5 g/10 min or less; the density is from 0.93 to 0.958 g/cm ³ ; And the parameter CY-a at 190°C is from 0.03 to 0.15. 5. Ethylene copolymer according to claim 1, characterized in that said ethylene polymer has an MFR-RNS in the range of 10 to 45 g/10 min. 6. Ethylene copolymer according to claim 1, characterized in that said ethylene copolymer has: the ratio of M _w /M _n in the range from 3.5 to 18; And ratio M _z /M _w in the range from 3.5 to 10. 7. Ethylene copolymer according to claim 1, characterized in that said ethylene copolymer has: M _n in the range from 10000 to 100000 g/mol; M _w in the range from 100,000 to 400,000 g/mol; And M _z in the range from 500,000 to 2,500,000 g/mol. 8. Ethylene copolymer according to claim 1, characterized in that said ethylene copolymer contains from 0.01 to 0.06 DCR per 1000 atoms of all carbon atoms. 9. Ethylene copolymer according to claim 1, characterized in that said ethylene copolymer has a viscosity at zero shear rate in the range from 1×10 ⁶ to 1×10 ¹⁶ Pa-s at 190°C. 10. An ethylene copolymer according to claim 1, characterized in that said ethylene copolymer has: the ratio of M _w /M _n in the range from 6 to 16; And ratio M _z /M _w in the range from 5 to 8. 11. An ethylene copolymer according to claim 1, characterized in that said ethylene copolymer has: M _n in the range from 10000 to 40000 g/mol; M _w in the range from 100,000 to 300,000 g/mol; M _z in the range from 750,000 to 1,500,000 g/mol. 12. An industrial product containing an ethylene copolymer according to claim 11. 13. Ethylene copolymer according to claim 1, characterized in that: the average number of CCRs per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol is at least 75% higher than their number with a molecular weight in the range from 40,000 to 60,000 g/mol; And the average number of LCRs per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol is at least 200% higher than their number with a molecular weight in the range from 4,000,000 to 6,000,000 g/mol. 14. Copolymer of ethylene with an alpha-olefin, where the alpha-olefin is selected from 1-butene, 1-hexene, 1-octene, or a combination thereof, and this ethylene copolymer has: melt flow index 1 g/10 min or less; density in the range from 0.93 to 0.965 g/cm ³ ; a CY-a parameter at 190° C. of 0.2 or less; from 0.01 to 0.06 long chain branches (LCB) per 1000 atoms of all carbon atoms; an average number of short chain branches (SCC) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number at a molecular weight in the range from 40,000 to 60,000 g/mol; And the average number of long chain branches (LCB) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number at a molecular weight in the range from 4,000,000 to 6,000,000 g/mol. 15. Ethylene copolymer according to claim 14, characterized in that: the density is from 0.93 to 0.958 g/cm ³ ; And said ethylene copolymer contains from 0.02 to 0.06 LCB per 1000 atoms of all carbon atoms. 16. An industrial product containing an ethylene copolymer according to claim 15. 17. Copolymer of ethylene with an alpha-olefin, where the alpha-olefin is selected from 1-butene, 1-hexene, 1-octene, or a combination thereof, and this ethylene copolymer has: melt flow index 1 g/10 min or less; density in the range from 0.93 to 0.965 g/cm ³ ; a CY-a parameter at 190° C. of 0.2 or less; M _n in the range from 10000 to 40000 g/mol; M _w in the range from 100,000 to 300,000 g/mol; M _z in the range from 750,000 to 1,500,000 g/mol; an average number of short chain branches (SCC) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number at a molecular weight in the range from 40,000 to 60,000 g/mol; And the average number of long chain branches (LCB) per 1000 atoms of all carbon atoms in an ethylene copolymer with a molecular weight in the range from 400,000 to 600,000 g/mol, which exceeds their number with a molecular weight in the range from 4,000,000 to 6,000,000 g/mol, moreover, the average number of DSBs has a value in the range from 0.02 to 0.07 DSBs per 1000 atoms of all carbon atoms at a molecular weight in the range from 400,000 to 600,000 g/mol, and said ethylene copolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof. 18. An industrial product containing an ethylene copolymer according to claim 17. 19. Ethylene copolymer according to claim 17, characterized in that: the flow index is 0.7 g/10 min or less; the density is from 0.93 to 0.958 g/cm ³ ; And the parameter CY-a at 190°C is from 0.02 to 0.18. 20. Ethylene copolymer according to claim 19, characterized in that said ethylene copolymer has an MFR-RNS in the range of 10 to 45 g/10 min.

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