ISOLATED TOPOLOGICAL VARIATION POLYETHYLENE HOMOPOLYMER AND METHOD OF DOING THE SAME

专利摘要:
COMPOSITION COMPRISING A POLYETHYLENE, COMPOSITION, ISOLATED TOPOLOGICAL VARIATION POLYETHYLENE HOMOPOLYMER HAVING A LONG CHAIN BRANCHING FREQUENCY OF MORE THAN 0.5 LONG CHAIN BRANCHES PER 1000 TOTAL CARBONS, METHOD, MODIFIER MODIFIER MODIFIER AND POLYMER FRACTION FLUID FLOW, METHOD FOR THE PRODUCTION OF POLYOLEFINS OF TOPOLOGICAL VARIATION, POLYOLEFIN AND METHOD. A composition comprising a polyethylene wherein the composition is enriched in topologically varying polymer molecules by an enrichment factor and wherein the composition exhibits a long chain branching frequency of more than about 0.5 long chain branches per 1000 carbon atoms in total. A composition, comprising an insulated Ziegler catalyzed polyethylene having a long chain branching frequency of more than about 0.5 long chain branches per 1000 carbon atoms in total at the high molecular weight end.
公开号:BR112014004831B1
申请号:R112014004831-2
申请日:2012-08-30
公开日:2021-08-03
发明作者:Youlu Yu；Chung C. Tso；David C. Rohlfing；Paul J. Deslauriers；Melvin Hildebrand；Max P. Mcdaniel；Qing Yang
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present disclosure refers to new polymer compositions and methods to produce and use the same. More specifically, the present disclosure relates to topologically varying polymer compositions. FUNDAMENTALS OF THE INVENTION
[002] Polymeric compositions, such as polyethylene compositions, are used to produce a wide variety of articles. The use of a specific polymer composition in a specific application will depend on the type of physical and/or mechanical properties exhibited by the polymer. Thus, there is a constant need to develop polymers that exhibit new physical and/or mechanical properties and methods for producing these polymers. BRIEF SUMMARY
[003] It is disclosed in this document a composition comprising polyethylene in which the composition is enriched in polymer molecules, having topological variations by an enrichment factor and in which the composition exhibits a long chain branching frequency greater than 0.5 of long chain branches per 1000 carbon atoms in total.
[004] Disclosed herein is a composition comprising an isolated Ziegler-catalyzed polyethylene having a long chain branching frequency of greater than 0.5 long chain branches per 1000 carbon atoms in total at the high molecular weight end.
[005] It is disclosed in this document an isolated topologically varying polyethylene homopolymer with a long chain branching frequency greater than around 0.5 long chain branches per 1000 total carbons in which the homopolymer is isolated from a catalyzed polyethylene by Ziegler
[006] Also disclosed in this document is a method comprising contacting a Ziegler catalyzed with an ethylene monomer under conditions suitable for forming an ethylene polymer; recovering an ethylene polymer; fractionating the ethylene polymer into polymer fractions by solvent gradient fractionation; identifying topologically varying ethylene polymer fractions having radius of spin values smaller than that of a linear polymer of identical weight average molecular weight; and recovering polymer fractions having radius of rotation values smaller than that of a linear polymer of identical weight average molecular weight and a topologically varying ethylene polymer fraction produced by this method.
[007] Also disclosed in this document is a fluid flow modifier, comprising the topologically varying ethylene polymer produced by the methods disclosed in this document.
[008] Also disclosed in this document is a method for the production of topologically varying polyolefins comprising contacting a Ziegler catalyst in the presence of a polar aprotic solvent with an olefin under conditions suitable for the production of a polyolefin wherein the polyolefins produced in the presence of the Polar aprotic solvents have an increased amount of topologically varying polyolefins as compared to a polyolefin produced under control conditions in the absence of a polar aprotic solvent.
[009] Also disclosed herein is a method comprising contacting an olefin monomer with a catalyst under a first set of conditions suitable for forming a first olefin polymer, wherein the first olefin polymer comprises an amount (x) of molecules of topologically varying olefin polymer; adjusting the first set of conditions to produce a second set of conditions; and contacting an olefin monomer with a catalyst under the second set of conditions suitable for forming a second olefin polymer, wherein the second olefin polymer comprises an amount (y) of topologically varying olefin polymer molecules, in where y is greater than x and where the second set of conditions comprises a nonpolar protic solvent. BRIEF DESCRIPTION OF THE ILLUSTRATIONS
[0010] Figure 1 displays raw chromatograms for samples from table I. Raw chromatograms for selected polyethylene polymers listed in table I with the dots and lines representing the 90° of scattering and light concentration chromatograms, respectively.
[0011] Figure 2 is a graph of the relationship between molecular weight and elution volume (MW-VE) for samples from Table 1.
[0012] Figure 3 is a graph of the relationship between the radius of rotation and elution volume for the samples in Example 1.
[0013] Figure 4 is a graph of the relationship between the radius of rotation and molecular weight for samples from Example 1. The dashed line in the figure represents the radius of rotation R g - extended M and molecular weight ratio for the linear control.
[0014] Figure 5 is a graph of the relationship between radius of rotation and molecular weight of samples from Example 1 measured at varying concentrations.
[0015] Figure 6 is a graph of the relationship between radius of rotation and molecular weight for a polymer of PE and SGF fractions.
[0016] Figure 7 is a graph of the molecular weight distribution profile for an SGF fraction from example 1.
[0017] Figure 8 is a graph of the relationship between radius of rotation and molecular weight samples from Example 1.
[0018] Figure 9 depicts raw chromatograms for samples from Example 1.
[0019] Figure 10 is a graph of the distribution of long chain branching across the molecular weight distribution profile for a sample from Example 1.
[0020] Figure 11 is a graph of melt zero shear viscosity as a function of weight-average molecular weight for the samples from Example 1.
[0021] Figure 12 is a graph of the relationship between molecular weight and elution volume for the samples from Example 1.
[0022] Figure 13 depicts a simulated relationship between zero shear viscosity and long chain branching frequency using Janzen-Colby model with the following parameters: MW = 663 kg/mol; B = 6; K = 1.42x10-5; and MC = 3800. The solid line represents the branched polymer and the dashed line the linear polymer of the same molecular weight.
[0023] Figure 14 is a plot of dynamic melt viscosity versus frequency and (b) the van Gurp-Palment plots for selected samples from Example 1.
[0024] Figures 15-18 are graphs of the molecular weight distribution for the samples from Example 2.
[0025] Figures 19-22 are graphs of radius of rotation versus molecular weight for the samples from Example 2. DETAILED DESCRIPTION
[0026] Disclosed herein are one or more source polymers, one or more polymer fractions isolated from a source polymer (a polymer isolate fraction) and methods of making and using the same. In this document, polymer may refer to a material collected as the product of a polymerization reaction (eg, a polymer "base" or reactor that is substantially free of one or more additional components, such as additives), a polymeric composition ( for example, a base polymer and one or more additional components, such as additives), or both. In one embodiment the source polymer is a Ziegler catalyzed olefin polymer, alternatively a Ziegler catalyzed polyethylene homopolymer. In this document, a homopolymer may contain small amounts of comonomer that do not materially alter the basic characteristics of the source polymers (or the polymer fractions isolated from it). Despite the potential presence of small amounts of the comonomer, such a polymer is generally referred to in this document as a homopolymer.
[0027] In one embodiment, a source polymer of the type disclosed herein is a mixture of polymer subpopulations that can be isolated (eg, separated or fractionated) from the source polymer and recovered as one or more isolated polymer fractions. The subpopulations of the source polymer (and likewise one or more isolated polymer fractions corresponding to them) may vary in polymer architecture, such that subpopulations can be distinguished based on factors such as the subpopulation's molecular weight distribution and the type of the extent of the branch within the subpopulation. In one embodiment, a source polymer of the type disclosed herein is subject to fractionation based on molecular size to produce a plurality of isolated polymer fractions. In one embodiment at least one of the isolated polymer fractions exhibits a polymer architecture that is characterized by a high frequency of topological variations, resulting in the formation of compact structures. In one embodiment, the topological variations comprise a high frequency of long-chain branching that results in rheological characteristics of the type disclosed herein.
[0028] In one embodiment, the source polymer is an olefin polymer (eg, ethylene, propylene, 1-butene) catalyzed by Ziegler that is subjected to a size separation technique (eg, solvent gradient fractionation) which yields one or more isolated polymer fractions having topological variations of the type described herein. Hereinafter, the disclosure will refer to the source polymer as a Ziegler catalyzed polyethylene polymer which is designated Z-SP while isolated polymer fractions having topological variations of the type disclosed in this document are referred to as a topologically varying polymer fraction, catalyzed by Ziegler and designated TVZ-IPF. In one embodiment, the polymer (eg, Z-SP or TVZ-IPF) is a homopolymer. Alternatively, the polymer (eg Z-SP or TVZ-IPF) is a copolymer.
[0029] To more clearly define the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in the disclosure but is not specifically defined herein, the definition of the IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997) may apply, provided that definition does not conflict with any other type of disclosure or definition applied in this document, or sue indefinitely or not entitled to any claim for that definition to apply. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with definition or use of controls in this document provided.
[0030] Table element groups are indicated using the numbering scheme indicated in the version of the periodic table of elements, published in Chemical and Engineering News, 63(5), 27, 1985. In some cases a group of elements may be indicated using a common name assigned to the group; for example, alkaline earth metals (or alkali metals) for Group 1 elements, alkaline earth metals (or alkali metals) for Group 2 elements, transition metals for Group 3-12 elements, and halogens for Group 17 elements.
[0031] A chemical "group" is described according to how that group is formally derived from a reference or "precursor" compound, for example, by the number of hydrogen atoms formally removed from the parent compound to generate the group, even if this group is not literally synthesized in this way. These groups can be used as substituents or coordinated or attached to metal atoms. By way of example, an "alkyl group" can be formally derived by removing one hydrogen atom from an alkane, while an "alkylene group" can be formally derived by removing two hydrogen atoms from an alkane. In addition, a more general term can be used to encompass a variety of groups that are formally obtained by removing any number ("one or more") of hydrogen atoms from the compound, a precursor which in this example can be described as a "alkane group", and which encompasses an "alkyl group," an "alkylene group", and the materials have three or more hydrogen atoms, as needed for the situation, taken from the alkane. Fully, the disclosure that a substituent, linker, or other chemical moiety may constitute a particular "group" implies that well-known rules of chemical structure and bonding are followed when that group is employed as described. When describing a group as being "derived by", "derived from", "formed by", or "formed from", such terms are used in a formal sense and are not intended to reflect any specific synthetic methods or procedure , unless otherwise specified or the context requires otherwise.
[0032] The term "substituted" when used to describe a group, for example when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen radical that formally replaces a hydrogen in that group and is intended to not be limiting. A group or groups may also be referred to herein as "substituted" or by equivalent terms such as "unsubstituted" which refer to the original group, in which a non-hydrogen radical does not replace a hydrogen within that group. "Substituted" is intended to be non-limiting and include inorganic or organic substituents.
[0033] Unless otherwise specified, any carbon-containing group for which the number of carbon atoms is not specified may have, in accordance with proper chemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 atoms of carbon, or any range or combination of ranges between these values. For example, unless otherwise specified, any carbon-containing group can have 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, of 1 to 10 carbon atoms or 1 to 5 carbon atoms and the like. In addition, other identifiers or qualifying terms may be used to indicate the presence or absence of a particular substituent, a particular regiochemistry and/or stereochemistry, or the presence or absence of an underlying branched structure or backbone.
[0034] Within this disclosure the normal rules of organic naming will prevail. For example, when referencing substituted compounds or groups, references to substitution patterns are taken so that the indicated group(s) is (are) located in the indicated position and that all other non-indicated positions are hydrogen . For example, reference to a 4-substituted phenyl group indicates that there is a non-hydrogen substituent located at the 4 position and hydrogens located at the 2, 3, 5, and 6 positions. By way of another example, reference to a substituted naphth-2-yl at 3 indicates that there is a non-hydrogen substituent located at position 3 and hydrogens located at positions 1, 4, 5, 6, 7 and 8. Reference to compounds or groups having substitutions at positions other than the indicated position will be reference using comprising or some other alternative language. For example, a reference to a phenyl group comprising a substituent at position 4 refers to a group having a non-hydrogen atom at position 4 and hydrogen or any non-hydrogen group at positions 2, 3, 5 and 6.
[0035] Modalities disclosed in this document which may provide the materials listed as suitable to satisfy a particular characteristic of the modality delimited by the term "or". For example, a particular feature of the disclosed subject may be disclosed as follows: Feature X can be A, B, or C. It is also provided that for each feature of the statement it can also be formulated as a list of alternatives such that the statement " Feature X is A, alternatively B, or alternatively C" is also an embodiment of the present disclosure whether the statement is explicitly recited or not.
[0036] In one embodiment, a Z-SP of the type described in this document can be prepared by any appropriate methodology, for example, employing one or more catalyst systems, in one or more reactors, in solution, in slurry or in gas phase , and/or varying the monomer concentration in the polymerization reaction and/or changing all of the materials, parameters, and/or reactor conditions involved in the production of the Z-SPs, as will be described in more detail here.
[0037] The Z-SPs of the present disclosure can be produced using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce Z-SP of the type disclosed herein. Homopolymers and/or copolymers produced in the reactor can be referred to as resin and/or polymers. The various types of reactors include, but are not limited to what may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, autoclave, or other reactor and/or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Mud reactors can comprise vertical and/or horizontal cycles. High pressure reactors can comprise autoclave and/or tubular reactors. Reactor types can include batch and/or continuous processes. Continuous processes may use intermittent and/or continuous product transfer or discharge. Processes can also include direct partial or complete recycling of unreacted monomer, unreacted comonomer, catalyst and/or co-catalysts, diluents, and/or other materials from the polymerization process.
[0038] Polymerization reactor systems of the present disclosure may include one type of reactor in a system or multiple reactors of the same or different type, operated in any suitable configuration. Polymer production in multiple reactors can include several stages in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor into the second reactor. Alternatively, polymerization in multiple reactors may include the transfer, whether manual or automatic, of polymer from one reactor to the subsequent reactor or further polymerization reactors. Alternatively, multi-stage or multi-step polymerization can take place in a single reactor, where the conditions are changed so that a different polymerization reaction takes place.
[0039] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the entire polymer production process of the present disclosure. Multiple reactor systems can include any combination that includes, but is not limited to multiple cycle reactors, multiple gas phase reactors, a combination of gas phase and cycle reactors, high pressure multiple reactors, or a high pressure combination. pressure with cycle and/or gas reactors. Multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and/or any combination of reactors can be employed to produce the polymer of the present disclosure.
[0040] According to an embodiment, the polymerization reactor system may comprise at least one cycle slurry reactor. These reactors are common and can comprise vertical or horizontal cycles. Monomer, diluent, catalyst system and optionally any comonomer can be continuously fed to a slurry loop reactor, where polymerization takes place. Generally, continuous processes can comprise continuously introducing a monomer, a catalyst, and/or a diluent into a polymerization reactor and continuously removing this reactor from a suspension comprising the polymer particles and the diluent. Reactor effluent may be flash evaporated to remove liquids comprising the solid polymer 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 addition and pressure reduction; separation by cyclonic action, whether in a cyclone or hydrocyclone; centrifugal separation; or other appropriate method of separation.
[0041] Typical slurry polymerization processes (also known as particle form processes) are disclosed in Patent Nos. US3,248,179, US4,501,885, US5,565,175, US5,575,979, US6,239,235, US6,262,191 and US6,833,415, for example; each of which is incorporated herein by reference in their entirety.
[0042] Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, Neopentane and n-hexane. Some cycle polymerization reactions can take place under bulk conditions where no diluent is used. One example is the polymerization of propylene monomer as disclosed in Patent No. US5,455,314, which is incorporated herein by reference in its entirety.
[0043] According to yet another embodiment, the polymerization reactor may comprise at least one gas-phase reactor. Such systems can employ a continuous recycle stream that contains one or more monomers continuously recycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be taken from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas-phase reactors may comprise a process for a gas-phase, multi-step polymerization of olefins, in which olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones, while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in Patent Nos. US4,588,790, US5,352,749, and US5,436,304, each of which are incorporated herein by reference in their entirety.
[0044] According to yet another embodiment, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have multiple zones where fresh monomer, initiators or catalysts are added. Monomer can be entrained in an inert gaseous stream and introduced into a reactor zone. Initiators, catalysts and/or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas streams can be interleaved for polymerization. Heat and pressure can be appropriately employed to obtain optimal polymerization reaction conditions.
[0045] According to yet another embodiment the polymerization reactor may comprise a solution polymerization reactor, wherein the monomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an organic diluent or monomer in excess of may be employed. If desired, the monomer can be brought into vapor-phase contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in the reaction medium. Agitation can be employed to obtain the best temperature control and maintain uniform polymerization mixtures throughout the entire polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[0046] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one raw material feed system, at least one feed system for the catalyst or catalyst components, and/or at least one feed system. polymer recovery. Reactor systems suitable for the present invention may additionally comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis and control of process.
[0047] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and amount of catalyst or co-catalyst, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperatures below the depolymerization temperature, in accordance with the Gibbs Free Energy Equation. Typically this includes around 60 °C to around 280 °C, for example, and/or around 70 °C to around 110 °C, depending on the type of polymerization reactor and/or process. polymerization.
[0048] Appropriate pressures will also vary according to the reactor and polymerization process. Pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). Pressure for gas phase polymerization is generally around 200 - 500 psig (1.38 - 3.45 MPa). High pressure polymerization in tubular or autoclave reactors is generally performed at around 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region generally taking place at higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.
[0049] The concentration of various reactants can be controlled to produce polymers with certain physical and mechanical properties. The proposed end use product that will be formed by the polymer and the method of forming that product can be varied to determine the properties of the desired end product. Mechanical properties include, but are not limited to tensile strength, flexural modulus, impact strength, creep, stress relaxation and hardness testing. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, short chain branching, branching long-chain and rheological measurements.
[0050] Concentrations of monomer, comonomer (if present), hydrogen, cocatalyst, modifiers and electron donors are generally important in producing specific polymer properties. Hydrogen can be used to control product molecular weight. Cocatalysts can be used to alkylate, eliminate toxics and/or control molecular weight. The concentration of toxics can be minimized, as toxics can affect reactions and/or affect polymer product properties in other ways. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
[0051] The Z-SP can comprise additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, anti-adherent agents, tacifiers, polymer processing aids and combinations thereof. In one embodiment, the Z-SP comprises carbon black. Such additives can be used singly or in combination and can be included in the polymer before, during, or after the preparation of Z-SP as described herein. Such additives can be added by any suitable technique, for example, during an extrusion or compounding step such as during pelleting or subsequent processing into an end-use article. Z-SPs as described in this document can be formed into various articles, including, but not limited to, household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes, and linings.
[0052] In one embodiment, a method of preparing a polymer comprises contacting an ethylene monomer with a catalyst system under conditions suitable for forming a polymer of the type described herein. In one embodiment, the catalyst system comprises a transition metal complex. The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like do not depend on the actual product resulting from the contact or reaction of the components of the mixtures, the nature of the catalytic active site, or the fate of the cocatalyst, the catalyst, any olefin monomer used to prepare a pre-contacted mixture, or the activator support, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system" and so on can include both heterogeneous and homogeneous compositions.
[0053] In one embodiment, a catalyst system suitable for preparing a Z-SP comprises a Ziegler-Natta catalyst. In one embodiment, the Ziegler-Natta catalyst comprises a Group 4, Group 5, or Group 6 transition metal salt. The transition metal salt may comprise an oxide, alkoxide or halide of a Group 4, Group 4 transition metal. 5 or Group 6. In addition, the catalyst system may optionally comprise a magnesium compound, internal or external magnesium donors, and support materials such as Group 13 or Group 14 inorganic oxides. In one embodiment, the Ziegler-Natta catalyst comprises a halide (e.g., chloride) salt of a Group 4, Group 5, or Group 6 transition metal. Non-limiting examples of Ziegler-Natta catalysts suitable for non-limiting use with the methods of this disclosure include TiCl4, TiBr4, Ti(OC2H5 )3Cl, Ti(OC3H7)2Cl2, Ti(OC6H13)2Cl2, Ti(OC2H5)2Br2, Ti(OC12H25)Cl2, TiCl3, VOCl3, VCl4, ZrCl4, MoO2Cl2, CrCl3, VO(OC3H7)2, or their combinations.
[0054] The catalyst system may additionally include one or more electron donors, such as inner electron donors and/or outer electron donors. Internal electron donors can include without limitation amines, amides, esters, ketones, nitriles, ethers, phosphines, diethers, succinates, phthalates, dialkoxybenzenes or combinations thereof. External electron donors can include, without limitation, monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, organosilicon compounds or combinations thereof. In one embodiment, the external donor can include, without limitation, diphenyldimethoxysilane (DPMS), cyclohexylmethyldimethoxysilane (CDMS), diisopropyldimethoxysilane, dicyclopentyldimethoxysilane (CPDS) or combinations thereof. The outer donor can be the same or different from the inner electron donor used.
[0055] In one embodiment, the catalyst system optionally comprises a metal hydride and/or a metal alkyl that can function as a cocatalyst. Generally, the metal alkyl compound that can be used in the catalyst disclosure system can be any heteroplectic or homopletic metal alkyl compound. In one embodiment, the metal alkyl may comprise, consisting essentially of, or consisting of, an alkyl metal halide, an alkyl metal halide, or any combination thereof; alternatively, an alkyl metal halide; or, alternatively, an alkyl metal halide.
[0056] In one embodiment, the metal of the metal alkyl may comprise, consist essentially of, or consist of, a group 1, 2, 11, 12, 13 or 14 metal; or alternatively a group 13 or 14 metal; or, alternatively, a group 13 metal. In some embodiments, the metal alkyl metal (not alkyl metal halide or alkyl metal halide) may be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminum or tin; alternatively lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum or tin; alternatively lithium, sodium or potassium; alternatively, magnesium, calcium; alternatively lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively, zinc; alternatively, boron; alternatively, aluminum; or alternatively tin. In some embodiments, the metal alkyl (not metal alkyl halide or metal alkyl halide) may comprise, consist essentially of, or consist of, a lithium alkyl, a sodium alkyl, a magnesium alkyl, a boron alkyl, a zinc alkyl, or an aluminum alkyl. In some embodiments, the metal alkyl (not an alkyl metal halide or an alkyl metal halide) can comprise, consist essentially of, or consist of an aluminum alkyl.
[0057] In one embodiment, the aluminum alkyl can be an aluminum trialkyl, an alkyl aluminum halide, an alkyl aluminum alkoxide, an aluminoxane, or any combination thereof. In some embodiments, the aluminum alkyl can be an aluminum trialkyl, an alkyl aluminum halide, an aluminoxane, or any combination thereof; or, alternatively, an aluminum trialkyl, an aluminoxane or any combination thereof. In other embodiments, the aluminum alkyl can be a trialkylaluminum; alternatively, an alkylaluminum halide; alternatively, an alkylaluminum alkoxide; or alternatively an aluminoxane.
[0058] In a non-limiting modality, the aluminoxane may have a repeating unit characterized by formula I: Formula I
where R' is a linear or branched alkyl group. Alkyl groups for metal alkyls have been independently described herein and can be used without limitation to describe aluminoxanes having Formula I. Generally, n of Formula I is greater than 1; or, alternatively, greater than 2. In one embodiment, n can range from 2 to 15; or alternatively, range from 3 to 10.
[0059] In one aspect, each halide of any alkyl metal halide disclosed herein may independently be fluoride, chloride, bromide or iodide; alternatively, chloride, bromide or iodide. In one embodiment, each halide of any alkyl metal halide disclosed herein can be fluorine; alternatively, chloride; alternatively, bromide; or alternatively, iodide.
[0060] In one aspect, each alkyl group of any metal alkyl disclosed herein (not metal alkyl halide or metal alkyl halide) independently may be a C1 to C20 alkyl group; alternatively, an alkyl group from C1 to C10 alkyl group; or, alternatively, a to C6 C1 alkyl group. In one embodiment, each alkyl group(s), independently, can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group; alternatively a methyl group, an ethyl group, a butyl group, a hexyl group or an octyl group. In some embodiments, the alkyl group can independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group, or an n-group. -octyl; alternatively, a methyl group, an ethyl group, an n-butyl group or an iso-butyl group; alternatively a methyl group; alternatively, an ethyl group; alternatively an n-propyl group; alternatively an n-butyl group; alternatively, an iso-butyl group; alternatively, an n-hexyl group; or, alternatively, an n-octyl group.
[0061] In one aspect, each alkyl group of any metal alkyl disclosed herein (not alkyl metal halide or alkyl metal halide) independently may be a C1 to C20 alkyl group; alternatively, an alkyl group from C1 to C10 alkyl group; or, alternatively, a C1 alkyl group from to C6. In one embodiment, each alkoxide group of any metal alkyl alkoxide disclosed herein can independently be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a hydroxy group. heptoxy or an octoxy group; alternatively a methoxy group, an ethoxy group, a butoxy group, a hexoxy group or an octoxy group. In some embodiments, each alkoxide group of any metal alkyl alkoxide disclosed herein can independently be a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an iso-butoxy group, an n-hexoxy group or an n-octoxy group; alternatively, a methoxy group, an ethoxy group, an n-butoxy group or an iso-butoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an n-butoxy group; alternatively, an iso-butoxy group; Alternatively, an n-hexoxy group; or, alternatively, an n-octoxy group.
[0062] In a non-limiting embodiment, useful metal alkyls may include lithium-methyl, n-butyl lithium, sec-butyl lithium, lithium-tert-butyl, diethyl magnesium, di-n-butylmagnesium, ethylmagnesium chloride, n chloride - butylmagnesium and diethyl zinc.
[0063] In a non-limiting embodiment, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum or mixtures thereof. In some non-limiting embodiments, trialkylaluminum compounds can include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum or mixtures thereof; alternatively triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octlaluminum or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds can include trimethylaluminum; alternatively triethylaluminum; alternatively tripropylaluminium; alternatively tri-n-butylaluminum; alternatively, triisobutylaluminum; alternatively trihexylaluminum; or, alternatively, tri-n-octylaluminum.
[0064] In a non-limiting embodiment, useful alkylaluminum halides may include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride and mixtures thereof. In other non-limiting embodiments, alkylaluminum halides can include diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively, ethyl aluminum sesquichloride.
[0065] In a non-limiting embodiment, useful aluminoxanes may include methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylxaluminoxane , 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane or mixtures thereof; in some non-limiting embodiments, useful aluminoxanes may include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutyl aluminoxane, t-butyl aluminoxane or mixtures thereof. In other non-limiting embodiments, useful aluminoxanes can include methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively iso-propylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, iso-pentylaluminoxane; or alternatively, neopentylaluminoxane.
[0066] In one embodiment, the catalyst composition comprises a support. Ziegler-Natta catalysts can generally be supplied on an inorganic support, eg deposited on a crystalline solid support. The support can be an inert solid, which is chemically non-reactive with any of the components of the Ziegler-Natta catalyst system, or which can influence catalyst performance. In one embodiment, the support is a magnesium compound. Examples of magnesium compounds that are suitable for use in the catalyst compositions of this disclosure include, but are not limited to, magnesium halides, dialkoxymagnesium, alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylates. magnesium or combinations thereof.
[0067] Z-SPs of the type disclosed herein comprise a plurality of polymer subpopulations that are distinguishable based on the polymer architecture of the individual subpopulation. Here "polymer architecture" refers to polymer microstructure and is a function of a number of variables including for example, polymer molecular weight, polymer chain length, and degree of polymer chain branching. In this document, the properties disclosed for a Z-SP refer to the composition as a whole and reflect the contributions of all individual polymer subpopulations present in the Z-SP, unless otherwise indicated.
[0068] In one embodiment, a Z-SP of the type described in this document is characterized by a density of approximately 0.90 g/cm3 up to around 0.97 g/cm3, as an alternative of approximately 0.92 g/cm3 up to around 0.97 g/cm3, or alternatively around 0.93 g/cm3 to approximately 0.96 g/cm3, determined in accordance with ASTM D1505.
[0069] In one embodiment, a Z-SP of the type described in this document can be characterized by a weighted average molecular weight (MW) around 20 kg/mol to around 2,000 kg/mol, alternatively around 50 kg/mol up to around 800 kg/mol; or, alternatively, around 50 kg/mol to around 500 kg/mol; an average molecular weight (Mn) around 5 kg/mol to around 500 kg/mol, alternatively around 10 kg/mol to around 200 kg/mol; or, alternatively, around 20 kg/mol to around 125 kg/mol; and a z-average molecular weight (Mz) around 40 kg/mol to around 4000 kg/mol, alternatively around 100 g/mol to over 1600 kg/mol; or alternatively around 150 kg/mol to about 1,000 kg/mol. Weight average molecular weight describes the molecular weight distribution of a polymer and is calculated according to equation 1:

[0070] where Ni is the number of molecules of molecular weight Mi. All molecular weight averages are expressed in grams per mol (g/mol) or Daltons (Da). The number average molecular weight is the common average of the molecular weights of the individual polymers calculated by measuring the molecular weight of polymer molecules Mi deNi, adding the points, and dividing by the number of polymer molecules, according to equation 2:

[0071] The z-average molecular weight is a higher order molecular weight that is calculated according to equation 3:
where Ni is the number of molecules of molecular weight Mi.Mi.
[0072] The molecular weight distribution (MWD) of the Z-SP can be characterized by the ratio of weighted average molecular weight (MW) to the number average molecular weight (Mn), which is also referred to as the polydispersity index ( PDI) or more simply as polydispersity. A Z-SP of the type disclosed in this document may have a PDI around 3 to around 100, alternatively around 3.5 to around 50, or alternatively around 3.5 to 10.
[0073] A Z-SP of the type described in this document can be a multimodal polymer. In some embodiments, Z-SP is a unimodal polymer. In this document, the "modality" of a polymer resin here refers to the shape of its molecular weight distribution curve, i.e. the appearance of the graph of the polymer weight fraction as a function of its molecular weight. Polymer weight fraction refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak may be referred to as a unimodal polymer, a polymer having a curve showing two distinct peaks may be referred to as a bimodal polymer, a polymer having a curve showing three distinct peaks may be referred to as trimodal polymer etc. Polymers having molecular weight distribution curves showing more than one peak may collectively be referred to as multimodal polymers. For example, a bimodal polymer can have a first component that can generally be characterized as a component of higher molecular weight polymers and a second component that can be generally characterized as a component of lower molecular weight polymers (eg, the second component with a molecular weight lower than the first component). A trimodal polymer can have a molecular weight distribution profile showing three distinct peaks corresponding to three individual polymer components.
[0074] In one embodiment, a Z-SP of the type described in this document can be characterized by a shear response in the range around 15 to around 150, alternatively around 18 to around 100, or, alternatively, around 22 to around 50. Shear response refers to the ratio of melt index high load to melt index (HLMI/MI).
[0075] In one modality, a Z-SP of the type described in this document can be characterized by a Carreau Yasuda parameter 'a' in the range around 0.10 to around 0.70, alternatively around 0.15 a around 0.60, or alternatively around 0.20 to around 0.55. The Carreau Yasuda parameter 'a' (CY-a) is defined as the rheological amplitude parameter. Rheological amplitude refers to the amplitude of the transition region between Newtonian and power law shear rate for a polymer or to the frequency dependence of the polymer's viscosity. Rheological amplitude is a function of a polymer's relaxation time distribution, which in turn is a function of the polymer's molecular structure or architecture. The CY-a parameter can be obtained by assuming the Cox-Merz rule and calculated by fitting the flow curves generated in linear viscoelastic dynamic oscillatory frequency sweep experiments with a modified Carreau-Yasuda (CY) model, which is represented by equation 4:
on what
= magnitude of complex shear viscosity (Pa^s) h0= zero shear viscosity (Pa • s) [defines Newtonian plateau] w = angular frequency of oscillatory shear strain (ie, shear rate (1/s) ) a = rheological amplitude parameter th = viscous relaxation time (s) [describes location instead of transition region] n = power law constant [defines final slope of high shear rate region].
[0076] To facilitate model fit, the power law constant n is kept at a constant value (i.e., 2/11). Dynamic shear viscosity can be measured experimentally, and the data can be fitted to the values of the 4CY equation to determine ^o values and other rheological parameters. Details of the meaning and interpretation of the CY model and derived parameters can be found in: C.A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R.B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd edition, John Wiley & Sons (1987), each of which is incorporated by reference herein in its entirety.
[0077] In one embodiment, a Z-SP of the type described in this document can be characterized by a zero shear viscosity (^), defined by equation 4, in the range around 5.0 E + 01 Pa.s to em around 2.0 E + 09 Pa.s, alternatively around 5.0 E + Pa.s 02 to around 1.0 E + 07 Pa.s, or, alternatively, around 2.0 E + 03 Pa.s to around 2.0 E + 06 Pa.s. Zero shear viscosity refers to the viscosity of the polymer at a zero shear rate and is indicative of the material's molecular structure.
[0078] In one embodiment, a Z-SP of the type described in this document can be characterized by a rheological behavior that can be described as in obedience to Arnett's 3.4 power laws. Arnett's power law 3.4 (equation 5)
where h = zero shear viscosity (Pa • s) [defines Newtonian plateau] k = Arnett law constant MW = weighted average molecular weight (Da) represent the expected dependence of zero shear viscosity for linear polymers when plotted as a function of the weighted average molecular weight. For example, a Z-SP of the type disclosed in this document cannot exhibit any significant deviation of (qo) zero shear viscosity from the 3.4 power law of Arnett using a molecular weight determined by the conventional GPC method together with the broad calibration.
[0079] In one embodiment, a Z-SP of the type described in this document can be characterized by a peak of LCB content is determined as the number of LCBs, per 1000 carbon atoms, which is designated X. In one embodiment, X is greater than about 0.10 LCB per 1000 carbon atoms (LCB/103 carbons), alternatively greater than about 0.25 LCB/103 carbons, or alternatively greater than 0.50 LCB/103 carbons. In this document, peak LCB content refers to the maximum concentration of LCB as a function of molecular weight. The number of LCBs per 103 total carbons is calculated using the formula 1,000 * M0* B/M, where B is the number of LCBs per chain, M0 is the molecular weight of the repeating unit (ie, the methylene group , -CH2 -, for polyethylene); and M is the molecular mass of an SEC slice where all macromolecules in the same SEC slice are assumed to have the same molecular weight. B is calculated according to equation 6:
where g is defined as the ratio of the radius of rotation of a branched polymer to that of a linear polymer of the same molecular weight. Both the radius of rotation and the molecular weight can be determined using SEC-MALS. In one embodiment, a Z-SP of the type disclosed in this document has an LCB content peak which is determined as the number of LCBs per chain ((B.). In one embodiment, for a Z-SP of the type disclosed in this document B it is greater than around 10 LCB/chain, alternatively greater than around 35 LCB/chain, or alternatively greater than around 100 LCB/chain.
[0080] In one embodiment, a Z-SP of the type disclosed in this document is subject to exclusion chromatography (SEC). SEC involves chromatographic separation of materials based on their hydrodynamic volumes or size. Typically in SEC, molecules larger than the pore size cannot enter the pores and elute along with the first peak in the chromatogram. Molecules that are smaller than the pore size can enter the pores, resulting in the longest residence time in the column and elution as the last peak in the chromatogram. Thus, the time required for a material to elute from an SEC column depends on the extent to which the material can enter and traverse the pores present in the chromatographic material. An indicator of molecular size and shape is the radius of rotation, Rg, which is defined as the radius of the root mean square of the molecule. For linear polymers, typical SEC elution behavior can be characterized as follows: polymer molecules with a large molecular weight and a large Rg will elute in small volumes, followed by polymer molecules with a lower molecular weight and a lower Rg than elute in large volumes. In this document, a linear polymer or linear polymer substantially refers to a polymer having less than about 0.005 LCB/1000 carbons. The Z-SPs of this disclosure can be characterized by an atypical SEC elution behavior in which high MW, co-elution of large Rg components with low lowMw, small Rg components. In one embodiment, for Z-SPs of the type disclosed herein, the coil shrink factor, g, with a molecular weight of 5.0E + 06 g/mol is less than about 0.75, alternatively less than about 0.50, or alternatively less than 0.15; with a molecular weight of 1.0 E + 07 g/mol, the g factor is less than approximately 0.50, alternatively less around 0.15, or alternatively less than 0.05. The coil reduction factor is defined by the ratio of the square of the radius of rotation of a branched polymer to that of a linear one with the same molecular weight and can be determined according to Equation 7
where subscribed and bel represents the branched and linear polymer, respectively.
[0081] Z-SPs of the type disclosed in this document may exhibit atypical SEC elution behavior such that when the molecular weight of the Z-SP component decreases the Rg of the polymers gradually go from less than, equal to, and possibly much greater, of the polymer linear with the same or similar molecular weight. In this document, a linear polymer, having a molecular weight "equalized similar" to the weight of that of the described Z-SP components has a molecular weight that is within about ± 20%, 15%, 10% or 5% of that of the Z-SP component. In one embodiment, a Z-SP of the type disclosed herein can be characterized by a plot of Rg versus molecular weight, exhibiting a "C"-shaped curve (e.g., an end hook or Shepard hook shape ). In one embodiment, a Z-SP of the type disclosed in this document can be characterized by a graph of Rg versus molecular weight, being substantially similar to the graph shown in Figure 4.
[0082] In one embodiment, a Z-SP of the type described in this document may be subjected to separation into one or more polymer populations (and one or more polymer fractions resulting from recovered isolates) using any appropriate methodology. In one embodiment, a Z-SP of the type disclosed herein is subject to solvent gradient fractionation (SGF). SGF is a chromatographic technique, employing as a chromatographic material an inert packaging material (eg stainless steel), which is applied to a polymer composition (eg Z-SP of the type disclosed in this document). The Z-SP is then subjected to a solvent gradient that breaks down the polymer into nearly monodisperse molecular weight distributions. The absence of interactions between the packaging material and the polymer allows for fractionation based almost exclusively on the molecular weight characteristics of the individual polymer populations of a Z-SP. In one embodiment, a Z-SP of the type disclosed herein when subjected to SGF is fractionated into a plurality of polymer populations of different molecular weight distributions, and one or more resulting isolated polymer fractions is recovered. In the following, the polymer populations obtained by SGF (and corresponding to one or more resulting isolated polymer fractions thus recovered) from the Z-SP are called SGF-isolated polymer fractions.
[0083] In one embodiment, the individual isolated SGF-polymer fractions can be subjected to size exclusion chromatography (SEC), also known as gel permeation chromatography (GPC). In one embodiment, at least some of the individual isolated SGF-polymer fractions when subjected to SEC exhibit atypical SEC elution behavior in which the residence time of SGF-polymer fractions in an SEC column is equal to or greater than that of a polymer linear with the same or similar molecular weight. In one embodiment, one or more isolated polymer-SGF fractions that exhibit atypical SEC elution behavior comprise the Ziegler-catalyzed (i.e., TVZ-IPF) polymer isolated fraction of topological variation. In one embodiment, an isolated polymer-SGF fraction that exhibits atypical SEC elution behavior is a TVZ-IPF. In one embodiment the TVZ-IPFs represent a subpopulation of Ziegler-catalyzed polymers (eg, Z-SP of the type disclosed herein) that can be isolated and identified using any appropriate methodology (eg, SGF and SEC). In one embodiment, a Z-SP of the type disclosed herein comprises from about 0.1 weight percent (wt%) to about 30% wt% of a TVZ-IPF based on the total weight of to Z-SP, alternatively from about 0.5% by weight to around 20% by weight, alternatively from % by weight around 0.15 to around 15% by weight, or alternatively by around 1% by weight to around 10% by weight. In one embodiment, the TVZ-IPF can be located in the high molecular weight of the SP-Z such that the polymer molecules within the TVZ-IPF have weight average molecular masses of more than around 75,000 g/mol, alternatively higher than in around 150,000 g/mol, or alternatively greater than around 300,000 g/mol. As will be understood by one of skill in the art, the distribution of topologically varying polymer molecules within a source polymer composition will depend on a variety of factors. As such, the weight weight average molecular weight of these topologically varying polymer molecules can be changed and thus the location of these topologically varying polymer molecules in different molecular weight ranges (e.g., at the lower end of molecular weight) is also covered.
[0084] In one embodiment, the TVZ-IPF comprises a polymer population that is isolated from a Z-SP of the type disclosed herein and exhibits characteristics also of the type disclosed in this document (e.g., SEC elution behavior atypical). The TVZ-IPF disclosed herein may comprise polymer molecules (eg, polyethylene) having one or more topological variations that result in the observed atypical SEC elution behavior. It is anticipated that polymer molecules may contain any topological variation or polymer microstructure that results in the observed atypical SEC behavior. For example, TVZ-IPF may exhibit high branching frequency, differences in branch length and/or differences in branch nature when compared to polymer fractions that exhibit typical SEC elution behavior. In one embodiment, TVZ-IPFs comprise highly branched polymer molecules, where the branches emanate from a central linear polymer structure. In one embodiment the branching is dendritic in nature, in other embodiments the branching is irregular and/or random in nature.
[0085] The TVZ-IPF of the type disclosed in this document when submitted to SEC may exhibit a radius of rotation (Rg) ranging from around 35 nm to around 75 nm, alternatively around 39 nm to around from 65 nm or alternatively around 43 nm to around 50 nm for a molecular weight of 5 E + 06 g/mol; ranging from around 45 nm to around 110 nm, alternatively around 50 nm to around 90 nm or alternatively around 55 nm to around 70 nm for a molecular weight of 1.0 E + 07 g/mol as determined by SEC-MALS.
[0086] In one modality, a TVZ-IPF of the type described in this document is characterized by a density of approximately 0.90 g/cm3 up to around 0.965 g/cm3, as an alternative of approximately 0.92 g/cm3 up to around 0.965 g/cm3, or alternatively around 0.93 g/cm3 to approximately 0.96 g/cm3, determined in accordance with ASTM D1505.
[0087] In one embodiment, a TVZ-IPF of the type disclosed in this document can be characterized by a peak of LCB content is determined as the number of LCBs per 1000 carbon atoms, which is designated X. In one embodiment, X is greater than around 0.1 LCB per 1000 carbon atoms (LCB/103 carbons), alternatively larger than around 0.25 LCB/103 carbons, or alternatively larger than 0.5 LCB/103 carbons.
[0088] In one embodiment, a TVZ-IPF of the type disclosed in this document has an LCB peak content which is determined as the number of LCBs per chain (B). In one embodiment, for a TVZ-IPF of the type disclosed in this document B it is greater than around 10 LCB/chain, alternatively greater than around 25, or alternatively greater than around 50 at a molecular weight of 5.0E + 06 g/mol.
[0089] In one embodiment, a TVZ-IPF of the type described in this document can be characterized by a weighted average molecular weight (MW) around 50 kg/mol to around 2,000 kg/mol, alternative around 75 kg /mol to around 1000 kg/mol; alternatively, around 150 kg/mol to around 1000 kg/mol; or alternatively from around 100 kg/mol to around 500 kg/mol; or alternatively from around 25 kg/mol to around 200 kg/mol; and z-average molecular weight (Mz) from around 50 kg/mol to around 4,000 kg/mol, alternatively around 100 kg/mol; or alternatively from around 200 g/mol to around 1000 kg/mol.
[0090] A TVZ-IPF of the type disclosed in this document may have a PDI around 3 to around 100, alternatively around 3.2 to around 50, or alternatively around 1.2 to around 15, or alternatively from around 3.5 to around 25.
[0091] In one embodiment, a TVZ-IPF of the type described in this document can be characterized by a Carreau Yasuda 'a' parameter in the range around 0.05 to around 0.70, alternatively around 0.10 at about 0.55, alternatively around 0.15 to around 0.50, or alternatively around 0.15 to around 0.45.
[0092] In one embodiment, a TVZ-IPF of the type described in this document can be characterized by a zero shear viscosity (^), defined by equation 4, in the range around 5.0 E + 02 Pa.s to em around 1.0 E + 07 Pa.s, alternatively around 2.0 E + 03 Pa.s up to around 1.0 E and + 06 Pa.s, or alternatively around 1.0 E + 04 Pa.s to around 5.0 E + 05 Pa.s.
[0093] In one embodiment, a TVZ-IPF of the type described in this document can be characterized by its rheological behavior which can be described as negatively deviating from the power law of Arnett 3.4. For example, a TVZ-IPF of the type disclosed herein may exhibit a negatively shifted zero shear viscosity compared to a polymer of the same weight average molecular weight. In one embodiment, a TVZ-IPF of the type described in this document may have a zero shear viscosity (^), defined by equation 4, to be around 20% up to 500 times, alternatively around 2 to 200 times, or alternately around 5 times to 100 times smaller than a linear polymer of the same weight average molecular weight. In this document, the weight average molecular weight is that determined by SEC-MALS.
[0094] In one embodiment, a TVZ-IPF of the type disclosed in this document exhibits elasticity. In this document, the elasticity is reflected by the loss angle, δ, being less than 90° as a complex shear modulus, |G * |, is reduced to around 1.0 E + 02 Pa, alternatively up to around 1.0 E + 01 Pa. In some cases, "S"-shaped van Gurp-Palm graphs are observed. In one embodiment, a TVZ-IPF of the type disclosed in this document has a van Gurp-Palmen (vG-P) plot of the loss angle δ (δ = tan-1(G'7G')) against the corresponding magnitude of the modulus of complex shear, of |G*|, which plateaus at angles less than around 90° and decreases as the modulus complex, of |G*|, decreases. The vG-P approach is a qualitative means to extract information about the nature of LCB in polymers with designed LCB architectures.
[0095] In one embodiment, a TVZ-IPF is isolated as a subpopulation of a Z-SP (eg, polyethylene) in which it may be present in amounts disclosed herein. In such embodiments, the TVZ-IPF may undergo one or more techniques to isolate the source polymer subpopulation (i.e., Z-SP) such that the amount of source polymer does not exhibit behavior characteristic of a TVZ-IPF remaining in the TVZ-IPF (ie the medium from which it was isolated) is present in an amount of minus around 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1%, based on the total weight of the TVZ-IPF. In some embodiments, a TVZ-IPF of the type disclosed in this document is present in an effective amount to perform or be used in any user and/or application of a desired process and in such embodiments, the amount of e/the source polymer or amount of others polymer populations present that do not show the characteristics of TVZ-IPF (eg SEC atypical behaviors, high level of branching, etc...) may be greater than around 10%, alternatively greater than around 15%, alternatively greater than around 20%, or alternatively less than over 100%.
[0096] In one embodiment, a TVZ-IPF of the type disclosed in this document is isolated as a subpopulation of Z-SP (eg, PE homopolymer). As will be understood by one of skill in the art the properties of a TVZ-IPF of the type disclosed herein are affected by a variety of factors such as degree of branching, inter-dot chain length and molecular weight distribution. Thus, the TVZ-IPF can be modified to meet any process objective and/or in any way compatible with the components of the TVZ-IPF. For example, TVZ-IPF can be augmented by oxidation; surface modified by undergoing materials for corona treatment, plasma treatment, photochemical treatment, chemical treatment (eg, halogenation, phosphate, epoxy treatment); chemical grafting (eg grafting surface by redox initiators); polar modifications and the like. These treatments can be used to change one or more characteristics of the TVZ-IPF (polarity, hydrophilicity, etc...). In one embodiment the TVZ-IPFs of this disclosure can be modified by (i) end capping with short chains or organic molecules; (ii) end grafting through live polymerization; (iii) blending with polymer components; and/or (iv) crosslinking the polymer chains. As will be understood by one of skill in the art, end capping refers to the positioning of functional groups at chain ends while live polymerization refers to the form of addition polymerization, in which the ability of a growing polymer chain to terminate has been removed.
[0097] In one embodiment, TVZ-IPFs of the type disclosed in this document is obtained by fractionating the size of a Z-SP (eg, homopolymer polyethylene) also of the type disclosed in this document. TVZ-IPF can be characterized by an atypical SEC elution behavior, a high frequency of topological variations (eg high levels of long chain branching), a g of R that is equal to or less than that of a linear polymer. , having the same weight-average molecular weight, a negative deviation from the Arnett power law line 3.4 or combinations.
[0098] In one embodiment, the TVZ-IPF has a frequency branch of greater than about 0.5 long chain branches per 1000 total carbons and is isolated from a Ziegler-Natta catalyzed polyethylene homopolymer catalyzed by size exclusion chromatography.
[0099] In one embodiment, a method for producing topologically varying polyolefins comprises contacting a catalyst (eg Ziegler) in the presence of a polar aprotic solvent with an olefin under conditions suitable for producing a polyolefin in which the polyolefins produced in the presence of the polar aprotic solvent have an increased amount of topological variation of polyolefins as compared to a polyolefin produced under control conditions in the absence of a polar aprotic solvent. In this document, control conditions refer to conditions similar to those used to produce the first polyolefin, in which variables that can affect the collected data are monitored and held constant.
[00100] TVZ-IPFs of the type disclosed in this document may be used in any suitable application. For example, TVZ-IPFs of the type disclosed herein may find utility in non-linear optics, nanomaterials for host-guest encapsulation, in the manufacture of inorganic-organic hybrids, paints, lubricants, adhesives, compatibilizers, rheology modifiers, curing additives , dye carrier, dispersants, flow drag eductor, supports for controlled drug release and the like.
[00101] TVZ-IPFs of the type disclosed herein represent a fraction of the molecules within a Ziegler-catalyzed olefin polymer (eg, polyethylene). These polymer molecules can contain the majority (eg greater than about 90%) of the topological variations and resulting compact structures within the composition as a whole. In one embodiment, polymer molecules comprising TVZ-IPF are molecules substantially responsible for the characteristics of the Z-SP that are incompatible with the behavior of a linear polymer (eg, Rg values, atypical SEC elution behaviors, negative deviation of the Arnett's power law 3.4). The methodologies disclosed in this document can result in fractionation of the source polymer composition (i.e., Z-SP) into a plurality or fractions in which at least one fraction is enriched with polymer molecules containing topological variations. In one embodiment, the methodologies disclosed in this document can result in fractionation of the Z-SP into at least two fractions where one fraction contains more than about 75%, 80%, 85%, 90% or 95% of the polymer molecules containing topological variations based on the total number of polymer molecules containing topological variations. In such an embodiment, at least two fractions are obtained, a fraction enriched in polymer molecules, having topological and impoverished variations, and a fraction of polymer molecules, having topological variations. The depleted fraction of polymer molecules, having topological variations may, to the extent that it is depleted of such polymers, exhibit behavior characteristic of a linear polymer. The fraction enriched in polymer molecules, having topological variations may, insofar as it is enriched in such polymers, exhibit behavior characteristics of a branched or hyper-branched polymers, e.g. behavior of the type disclosed in this document for a TVZ-IPF . In one embodiment, the fraction enriched in polymer molecules having topological variations is enriched by a factor, termed CO enrichment factor, when compared to the fraction depleted of such polymers. In a modality ro can be calculated by equation 7b:

[00102] Where Z-SP is the weight of the source polymers before fractionation; TVZ(Z-SP) is the weight of polymers having topological variations; TV-IPF is the weight of polymer molecules having topological variations in the enriched fraction and IPF is the total weight of the enriched polymer fraction.
[00103] In such modalities, the properties exhibited by the fraction enriched in polymer molecules, having topological variations have values that increase by enriching the ro factor. In one modality, the enrichment factor is greater than around 2, alternatively greater than 10, alternatively greater than around 20, alternatively greater than around 50, or alternatively greater than around 200.
[00104] The following enumerated embodiments are provided as non-limiting examples: 1. An isolated hyper-branched ethylene polymer wherein the hyper-branched ethylene polymer is isolated from a transition metal catalyzed ethylene polymer. 2. The isolated hyper-branched ethylene polymer of embodiment 1 having a long chain branch frequency greater than 0.5 long chain branches per 1000 total carbon atoms at the high molecular weight end. 3. The hyperbranched ethylene polymer isolated from modalities 1 or 2 polymer wherein the Ziegler-Natta catalyzed transition metal ethylene polymer. 4. The isolated hyperbranched ethylene polymer of embodiments 1, 2 or 3 wherein the transition metal catalyzed ethylene polymer is a homopolymer. 5. The isolated hyperbranched ethylene polymer of embodiments 1, 2, 3 or 4 with a zero shear viscosity that is less than the zero shear viscosity calculated from the Arnett power law line 3.4. 6. The isolated hyperbranched ethylene polymer of embodiments 1, 2, 3 or 4 or 5 having a zero shear viscosity less than the zero shear viscosity of a polyethylene polymer of the same weight average molecular weight. 7. A polymer composition, having a major component and a minor component, wherein the major component comprises more than about 50% of the total polymer composition and wherein the minor component comprises the hyperbranched ethylene polymer isolated to from claims 1, 2, 3, 4, 5 or 6. The composition of claim 7 wherein the composition exhibits increased shear thinning as compared to a composition of polyethylene or the like, having less than about 0.5 branches long chain by 1000 total carbon atoms at the high molecular weight end. The composition of claims 7 or 8 wherein the composition exhibits increased shear thinning when compared to an otherwise or similar polyethylene composition having less than about 0.5 long chain branches per 1000 carbon atoms in total at the high molecular weight end. 10. A fluid flow modifier, comprising the isolated hyper-branched ethylene polymer or polymer composition of any preceding claim. 11. An ethylene polymer composition comprising more than about 10% by weight of a hyperbranched ethylene homopolymer wherein the hyperbranched ethylene homopolymer has greater than about 0.5 long chain branches per 1000 atoms of carbon in total at the high molecular weight end. 12. An ethylene polymer composition comprising more than about 20% by weight of a hyperbranched ethylene homopolymer wherein the hyperbranched ethylene homopolymer has more than about 0.5 long chain branches per 1000 atoms of carbon in total at the high molecular weight end. 13. An ethylene polymer composition comprising more than about 30% by weight of a hyperbranched ethylene homopolymer wherein the hyperbranched ethylene homopolymer has more than about 0.5 long chain branches per 1000 carbon atoms in total at the high molecular weight end. 14. An ethylene polymer composition comprising more than about 50% by weight of a hyperbranched ethylene homopolymer wherein the hyperbranched ethylene homopolymer has more than about 0.5 long chain branches per 1000 atoms of carbon in total at the high molecular weight end. 15. The ethylene polymer composition of embodiments 11, 12, 13 or 14 wherein the ethylene polymer composition is produced by contacting an ethylene monomer with a transition metal catalyst under conditions suitable for forming the ethylene polymer composition. 16. A hyper-branched ethylene homopolymer isolated from compositions of embodiments 11, 12, 13 or 14. 17. A method which includes contacting a transition metal catalyst composition with an ethylene monomer under conditions suitable for the formation of an ethylene homopolymer and recovering an ethylene homopolymer, wherein the ethylene homopolymer comprises greater than about 20% by weight of a hyper-branched ethylene homopolymer and wherein the hyper-branched ethylene homopolymer has greater than about branches long chain 0.5 per 1000 carbon atoms in total to the high molecular weight end. 18. Incorporation method 17 under which conditions suitable for forming an ethylene homopolymer exclude free radicals. 19. An isolated hyperbranched ethylene polymer composition having a higher molecular weight component and a lower molecular weight component. 20. The isolated hyperbranched ethylene polymer composition of embodiment 19 having a long chain branch of greater than 0.5 long chain branches per 1000 total carbon lasts in the high molecular weight end weight. 21. The hyperbranched ethylene polymer composition of modality 19 wherein the higher molecular weight component co-elutes in a size exclusion chromatograph with linear, low molecular weight components. 22. The isolated hyperbranched ethylene polymer composition of embodiments 19, 20 or 21, wherein the radius of rotation is reduced as compared to linear having the same molecular weight. 23. The method of embodiment 5 further comprising isolating the hyperbranched ethylene homopolymer from the ethylene homopolymer. 24. A method for producing topologically varying polyolefins comprising contacting a Ziegler catalyst with an olefin under conditions suitable for producing a polyolefin wherein the conditions suitable for producing the topologically varying polyolefins comprise a polar aprotic solvent. 25. The composition comprising a polyethylene wherein the composition is enriched in polymer molecules having topological variations by an enrichment factor and in which the composition exhibits a long chain branching higher frequency over long chain branches 0.5 per 1000 atoms of carbon in total. 26. The composition of embodiment 25 wherein the polyethylene is a Ziegler catalyzed polyethylene. 27. The composition of embodiments 25 or 26 wherein o is greater than about 2. 28. The composition comprises an isolated Ziegler catalyzed polyethylene having a long chain branch of more than about 0.5 chain branches long by 1000 carbon atoms in total at the high molecular weight end. 29. The composition of embodiment 28, wherein the insulated Ziegler-catalyzed polyethylene has a smaller radius of rotation than a linear polymer of the same weight average molecular weight. 30. The composition of modality 28 or 29, wherein the isolated Ziegler-catalyzed polyethylene has a rotation radius of around 35 nm to around 75 nm at the average molecular weight of 5 x 106 g/mol and around 45 nm to around 110 nm at a weighted average molecular weight around 1 X 107 g/mol. 31. A topologically varying polyethylene isolated homopolymer having a long chain branch frequency of more than 0.5 long chain branches per 1000 total carbons wherein the homopolymer is isolated from a homopolymer is isolated from Ziegler catalyzed polyethylene homopolymer by solvent gradient fractionation and where the radius of rotation of the homopolymer of topological variation is smaller than that of a linear polymer of identical molecular weight. 32. The topologically varying polyethylene homopolymer of embodiment 31 having a zero shear viscosity that negatively deviates from the Arnett 3.4 power law. 33. The topologically varying polyethylene homopolymer of modality 31 or 32 having a zero shear viscosity ranging from about 5.0E + 02 Pa.s to about 1.0E + 07 Pa.s. 34. The topologically varying polyethylene homopolymer of embodiment 31, 32 or 33 having a zero shear viscosity that is about 20% to about 500 times less than a similar linear polymer of otherwise the same molecular weight. 35. The topologically varying polyethylene homopolymer of embodiment 31, 32, 33 or 34 having a density of approximately 0.90 g/cm3 to up to 0.965 g/cm3 . 36. The topologically varying polyethylene homopolymer of embodiment 31, 32, 33 or 34, having a density weighted average molecular weight from about 50 kg/mol to about 2000 kg/mol. 37. The topologically varying polyethylene homopolymer of modality 31, 32, 33, 34, 35 or 36 having a CY-a parameter from around 0.05 to up to around 0.70. 38. The topologically variable polyethylene homopolymer of embodiment 31, 32, 33, 34, 35, 36 or 37, having a polydispersity index of about 3 to about 100. 39. The topologically variable polyethylene homopolymer of embodiments 31, 32, 33, 34, 35, 36 or 37, wherein the topologically varying polyethylene homopolymer is present in the Ziegler-Natta polyethylene homopolymer in the amount of 0.1% by weight to around 30% by weight. Weight. 40. Homopolymer modalities of topological variation 31, 32, 33, 34, 35, 36, 37 or 38 in which a van Gurp-Palmen (vG-P) plot of loss angle against the corresponding magnitude of the shear modulus of the complex, from |G * |, plateaus at angles smaller than around 90° and decreasing as the complex's shear modulus, |G * |, decreases. 41. A method comprising: contacting a Ziegler catalyst with a monomer under conditions suitable for forming an ethylene polymer; recovering an ethylene polymer; fractionating the ethylene polymer into polymer fractions by solvent gradient fractionation; identify topologically varying ethylene polymer fractions having spin radius values smaller than that of a polymer of identical average molecular molecular weight; and recovering polymer fractions having generation radii values less than that of that identical weight weight average molecular weight linear polymer. 42. The method of embodiment 41 wherein polymer fractions having radius of rotation values less than that of a linear polymer of the same weight average molecular weight has a long chain branch of more than about 0.5 branches of long chain per 1000 carbon atoms in total. 43. The method of embodiment 41 or 42 wherein the polymer fractions having radius of rotation values less than that of a linear polymer of the same weight average molecular weight having a zero shear viscosity that negatively deviates from the power line law of Arnett 3.4. 44. The method of embodiment 41, 42 or 43 wherein the polymer fractions having radius of rotation values smaller than that of a linear polymer of the same weight average molecular weight having a zero shear viscosity ranging around 5.0 E +02 Pa.sa to around 1.0 E+07 Pa.s. 45. The fraction method of embodiment 41, 42, 43 or 44 further comprising modifying polymer fractions having radius values of values less than that of the linear polymer of identical weight average molecular weight. 46. The method of modality 45 wherein the modification comprises oxidation, surface modification, corona treatment, plasma treatment, photochemical treatment, chemical treatment chemical grafting, end capping with short chains or organic molecules, end grafting by means of live polymerization, crosslinking of polymer chains or combinations thereof. 47. A topologically varying ethylene polymer fraction produced by the method of embodiments 41, 42, 43, 44, 45 or 46. 48. A fluid flow modifier comprising the topologically varying ethylene polymer of embodiment 47. A method for producing topologically varying polyolefins comprising contacting a Ziegler catalyst in the presence of a polar aprotic solvent with an olefin under conditions suitable for the production of a polyolefin wherein the polyolefins in the presence of the polar aprotic solvent has an increased amount of polyolefins as compared to polyolefin produced under control conditions in the absence of a polar aprotic solvent. 50. The polyolefin produced in accordance with embodiment 49. 51. A method comprising: contacting an olefin monomer with a catalyst under a first set of conditions suitable for forming an olefin polymer wherein the first olefin polymer comprises a amount (x) of topologically varying olefin polymer molecules; adjust the first set of conditions to produce a second set of conditions; and contacting an olefin monomer with a catalyst under the second set of conditions suitable for forming a second olefin polymer wherein the second olefin polymer comprises an amount (y) of topologically varying olefin polymer molecules, wherein y is greater than x and where the second set of conditions comprises a nonpolar protic solvent. EXAMPLES
[00105] The following determinations were made as follows:
[00106] SEC-MALS. SEC-MALS, a combined size exclusion chromatography (SEC) method, also known as gel permeation chromatography (GPC), with multi-angle light (MALS), was performed on the polymer samples using the following procedure:
[00107] A DAWN EOS multi-angle light scattering photometer (Wyatt Technology, CA) was attached to a Waters 150-CV plus GPC system (Waters Inc., MA) via a thermally controlled transfer line at 145 °C . At a rate of 0.7 mL/min, mobile phase 1, 2,4-trichlorobenzene (TCB) containing 0.5 g/L of 2,6-di-tert-butyl-1,4-methylphenol (BHT) was eluted through three 3 Φ 7.5 mm x 300 mm 20 μm mixed A-LS columns (Polimer Labs, now an Agilent Company). Z-SP solutions with nominal concentrations of 1.0 mg/mL were prepared at 150 °C for 3-4 h before being transferred to SEC injection vials sitting on a carousel heated to 145 °C. In addition to a concentration chromatogram, seventeen (17) chromatograms of light scattering at different angles of scattering were acquired for each injection. On each chromatography slice, both the absolute molecular weight (M) and the root-mean square radius, commonly known as the radius of rotation, Rg, were obtained from a Debye plot. The linear PE polymer reference used in this study was a high density polyethylene (HDPE) with a molecular weight distribution (MWD) (CPChem Marlex ™ 9640) made with a Cr-based catalyst. Detailed SEC-MALS method can be found in Polymer, 2005, 46, 5165-5182.
[00108] Rheology. Samples for melt viscosity measurement were compression molded at 182 °C for a total of three minutes. The samples were allowed to melt at relatively low pressure for one minute and then subjected to pressure for an additional two minutes. The molded samples were then quenched in a cold press (room temperature), disks with a diameter of 2 mm x 25.4 mm were removed from the mold of the molded slabs for rheological characterization. The fluff samples were stabilized with 0.1% by weight BHT dispersed in acetone and vacuum dried prior to molding.
[00109] Small-stem oscillatory measurements were performed on an ARES rheometer (Rheometrics Inc., now TA Instruments) using parallel plate geometry. The rheometer test chamber was covered in nitrogen in order to minimize polymer degradation. Upon sample loading after oven thermal equilibration, the species were pressed against the plates with a thickness of 1.6 mm and the excess was reduced. Dynamic shear viscosities were measured over an angular frequency range of 0.03 - 100 rad/s. These data were fitted into the Carreau-Yasuda equation (C-Y) to determine the zero-scissor shear viscosity (qo) and other rheological parameters.
[00110] Fractionation. (a) Solvent-gradient fractionation (SGF). General SGF fractionation procedures were followed. Briefly, 15 g of each PE sample (eg the Z-SP) was dissolved in 800 ml TCB solvent containing 0.1 wt% BHT at 140°C to ca. 14 h in an Erlenmeyer flask, before loading onto an SGF column packed with 60 mesh stainless steel balls and thermostatically regulated at 140 °C. The column was then slowly cooled at a rate of 1.5 °C/h until the temperature reached 40 °C. After rinsing with pure n-butyl cellosolve (BCS, a non-solvent for polyethylene) to twice the column dead volume to replace TCB, the column temperature was brought to 110°C and kept there overnight. At a constant temperature of 110°C, the column was washed with a binary solvent mixture of BCS and TCB with a gradual increase in TCB content, starting with a low TCB content. For each solvent composition, two washes were done to ensure complete separation. The combined eluent from the two washes was quickly poured into a container containing twice the volume of eluent acetone. For the last fraction, however, the column was washed twice with pure TCB at 140 °C to elute all the polymers that were left on the column. This fraction is also called the z-fraction. Acetone precipitated polymers on the ship were filtered, washed with acetone and vacuum dried at 40°C until the weights remained constant.
[00111] (b) SEC Fractionation Column. SEC column fractionation was conducted by collecting the SEC eluent from the PE sample from the 16 to 20 mL range and from the 20 to 27 mL range, respectively, using three 3 Φ 7.5 mm x 300 mm 20 μm mixed A-LS columns (Polimer Labs, now a Varian Company). According to the elution profile of the Z-SP polymer, the complete polymer must be separated into two fractions with the low MW fraction that supposedly do not contain any high MW components (see below) if the separation follows the separation mechanism of exclusion by size. Eluents from multiple SEC injections collected at the same interval elution intervals were then combined and precipitated with acetone at least twice the eluent volume before being filtered, dried and redissolved in TCB for SEC-MALS analysis.
[00112] The polymer samples (ie Z-SPs) used in the examples were made using Ti-based Ziegler-Natta Catalyst, Lynx ® 100, under hydrogen pressure in Chevron-Phillips slurry cycle reactors, at least that indicated otherwise and are all PE homopolymers. The characteristics of the Z-SP polymers are listed in Table I. Polymer fractions used in this study (ie, TVZ-IPFs) were obtained via a gradient fractionation solvent using the procedures described in this document. Example 1


[00113] One of the interesting features of these chromatograms is that there is a huge light scattering peak associated with very weak concentration differential refractive index (DRI) detector signals for low elution volumes. A bimodality feature can be clearly seen in these light scattering chromatograms. Beside low volume elution (corresponding to high MW), the MW of these polymers is significantly higher, sometimes by more than an order of magnitude, than the linear control for the same elution volume (Figure 2). Another interesting feature of these chromatograms is that light scattering signals do not return to baseline even after the time concentration signal has reached baseline (Figure 1). As a consequence, the conventional trend of decreasing MW and Rg with increasing elution volume is often followed by increasing MW and Rg values with increasing elution volume (figures 2-3). This SEC elution behavior of these Z-SPs is obviously against the conventional size-exclusion separation mechanism, macromolecules are separated according to their hydrodynamic volumes in the SEC columns. Results shown in Figures 1-3 provide clear chromatographic evidence suggesting that some species in the Z-SP solutions do not follow the normal SEC separation mechanism, in which some high MW components appeared to have an elution delay, of co-elution with components. low MW at higher elution volumes.
[00114] In Figure 4, Rg is plotted as a function of molecular weight (MW) for the same polymers as shown in Figure 1. Compared to the Rg-M ratio of the linear polymer PR, a striking feature of these Zn-SPs is that their Rg at the high molecular weight end is drastically smaller than the control linear for the same MWs. As MW increases, the Rg of these Z-SPs gradually goes from less than, equal to, and eventually much greater than, the linear control of the same MW. Consequently, for low MW, two corresponding Rg values are found for eachM, resulting in a graph -Rg-M formatted in general "C". This new phenomenon is somewhat unexpected because, in principle, the size of a linear polymer must have the highest Rg for the same type polymer with the same molecular weight, given polymers are separated by the normal SEC mechanism, ie, separated by volumes hydrodynamics.
[00115] SEC-MALS of Fractionated PE polymers (eg isolated polymer fractions). In order to further study the nature of the topologically varying components (eg strongly branched) in the Z-SP polymers, HZNP-1 (an example of a slurry cycle PE homopolymer) was subjected to solvent gradient fractionation . The Rg-MW ratios of the two largest MW fractions (HZNP-f1 and f2-HZNP) of HZNP-1 are depicted in Figure 6. As expected, the higher molecular weight fraction, HZNP-f2 or the z-fraction, is actually intended to have a concentrated population of these topological variations (eg, strongly branched structures), which is evidenced by the negative deviation of Rg from the linear control. The MWD profile of this z-fraction is given in Figure 7. Also, the above mentioned SEC elution anomaly is shown in which the Rg-MW curve and ”C” shape was observed. In contrast, its lower adjacent MW fraction, HZNP-f1 was found to be essentially linear. This fraction shows no sign of SEC anomaly as seen in the complete polymer or in the z-fraction. This fractionated polymer, with no SEC anomaly (ie, atypical SEC elution behavior) is assigned to a topologically homogeneous polymer fraction (THPF).The Rg-MW of the THPF is in superposition with the linear PE control.It seems evident that all compact structured species are located at the high MW end of the Z-SP. SEC-MALS analysis analysis was also performed on the SEC column fractional fractions (SEC fractions) and the results are shown in Figure 8. Contrary to the SEC-MALS results of the SGF fractions shown in Figure 6, the SEC-MALS results of these fractions second indicate that not only does the high MW fraction (HZNPSEC-f1) contain compact-structured components, the low MW fraction (HZNPSEC-f2) does as well. Furthermore, both higher molecular weight (HMW) and lower molecular weight (LMWH) SEC fractions show the aforementioned elution anomaly, viz the HMW and compact structured macromolecules co-elute with the LMW molecules in volumes of large elution. According to the Z-SP raw chromatogram as shown in Figure 9, however, the smallest MW fraction would not contain any of the components in its high MW tail if the fractionation in the SEC column had followed the exclusion separation mechanism by normal size.
[00116] Long Chain Branching Frequencies. The Zimm-Stockmayer approach was used to calculate the LCB content, comparing the Rg-MW relationships between the Z-SP and the linear PE control. As defined by Zimm and Stockmayer the branching index, gM, is a relationship between the radius of rotation (Rg) of a branched polymer to a linear one with the same molecular weight (M.),

[00117] in which the subscript bel represent the branched and linear polymers, respectively. At a given gM, the average weight number of LCB per molecule (B3w) equation 9:
where the LCB is assumed to be trifunctional (or Y-shaped) and polydispersed. LCB frequency, l(# LCB /1 000 Carbons) , in Meu can be calculated using equation 10:
where Mo is the molecular weight of the repeating unit of the polymer in question. For polyethylene, M0 is equal to 14,027.
[00118] Since HZNG-1, a gas phase PE homopolymer, is the only one of the group that did not show the aforementioned abnormal elution (Figure 4), it was chosen as an example to demonstrate the LCB content and distribution of LCB via MWD (LCBD) for the Z-SP listed in Table I. As can be seen in Figure 4, at the low MW end, Rg of HZNG-1 is superposable with that of the linear PE control until it reaches molecular weight ca. . 200,000 g/mol, from that point onwards the Rg of HZNG-1 becomes less than the linear PE control of the same molecular weight. Drastically smaller Rg values can be seen by components in the HMW tail of this Z-SP. LCB distribution profiles deduced using Eqs. 7, 9 and 10 are shown in Figure 10. While polymers of MW less than 200,000 g/mol in HZNG-1 MW are essentially linear, LCB was found to increase with increasing MW at the edge of higher MW. In the polymer head tail, the number of LCBs per molecule and frequency of LCBs are greater than 100 LCB/molecule and 0.5 LCB/1000 carbons, respectively. Furthermore, the LCB population appears to be exclusively concentrated at the HMW end. Similar quantitative LCB calculation, however, has not been tested for other Z-SP polymers listed in Table I simply because of their anomalous elution behavior.
[00119] Rheological property. Zero shear viscosity. Because rheology is a sensitive means to detect sparsely populated LCB in HDPE, it was used for further study of the Z-SPs listed in Table I. The relationship between the ^o and MW for the Z-SP, whose MW spans a wide range, is represented in Figure 11. For comparison, graphical representations in this figure also include a high density polyethylene polymer (HDPE-1), made with Cr Phillips catalyst. Note that the solid line in Figure 11 is the power law line 3.4. As can be seen from this figure, the zero shear viscosities of all these Z-SPs, although with a slight downward variation, seem to follow the 3.4 power law reasonably even though even after all, they have all been verified. for containing compact structures, as discussed above. In contrast to Zn-Sps, this HDPE polymer is clearly in line with the 3.4 power law above. Its melt zero shear viscosity is more than an order of magnitude greater than that of a linear polymer of the same M even though this polymer contains only a very low level of long chain branching (ca. 0.003 LCB/1,000 carbons). In fact, the LCB level in this HDPE is below the SEC-MALS detection limit as evidenced by its Rg - Mw graph, being virtually in superposition with the linear PE control, Marlex ™ 9640.
[00120] As shown in Figure 11, using the Mw minus the relative method using a broad MWD PE as the standard, the zero shear viscosity of HZNP-f2 is slightly below (ie, negatively deviated from) the power law line 3.4 (the filled diamond), meaning that the zero shear viscosity of this fraction is not greater, but preferably slightly less than that of a linear of the same MW. Using the absolute Mw value, this negative deviation from the 3.4 law power line becomes pronounced. From Figure 12, it can be understood that the absolute MW of this SGF fraction (ie a TVZ-IPF), HZNP-f2, as determined by SEC-MALS would be much higher than deduced from the relative method. Specifically, the SEC-MALS determined Mw for this fraction is 6.63E + 05 g/mol, while the one deduced from the relative method is 1.83E + 05 g/mol (Table I). The ratio of ^0 and that of absolute Mw for this SGF fraction is also represented in Figure 11 (open diamond in dashed circle). Quite clearly, this data point is further down from the 3.4 power law line.
[00121] The van Gurp-Palmen graphs. Dynamic rheology curves of these Z-SPs look mostly normal. As shown in Figure 14a, all data points can be equipped with the CY equation very well except for the first two points at the lowest frequency with the z-fraction HZHP-f2 (ie TVZ-IPF) which has a curvature for up. This "S-shaped" curve suggests the presence of an elastic component in this z-fraction SGF (ie, TVZ-IPF). Figure 14b is a van Gurp-Palmen (vG-P) plot of the loss angle δ (δ = tan-1(G'7G')) against the corresponding magnitude of the complex shear modulus, of |G * |, for the same samples shown in figure 14a. The vG-P approach is a qualitative means to extract information about the nature of LCB in polymers with designed LCB architectures. For linear polymers, at very high |G * |, the loss angle δ starts from a low value. Decrease of |G * | results in the loss angle δ to increase monotonically until it stabilizes at 90°. However, it was found that the loss angle δ of these Z-SP levels at an angle less than 90° and goes down as the complex shear modulus, |G * |, decreases further (figure 14b). This is especially pronounced HZNP-f2, whose loss angle levels at 83°, instead of 90° at low |G * | as you would expect for linear polymer. This rheological behavior suggests that this sample has some elasticity, which is likely a result of the presence of LCB in it. Predictive Characterization of a TVZ-IPF
[00122] NMR will be performed on a sample of a TVZ-IPF isolated from a PE homopolymer catalyzed by Ziegler-Natta to determine the primary polymer structure, branching content and the nature of the branching. NMR experiments can be performed with a Varian Unity Inova-500 system running at 13C frequency 125.7 MHz. For example, TVZ-IPF can be solubilized in solvents containing 90% TCB and 10% 1.4- dichlorobenzene-d4 (DCB-d4) and placed in a 10mm NALORAC probe whose temperature will be controlled at 125 °C. The sampler slew rate can be 15 Hz and at least 6000 transients can be acquired by each solution with the following conditions: 5 s acquisition time, 10 s delay time and 90° pulse angle.
[00123] Differential Scanning Calorimetry (DSC) DSC will be performed on a sample of a TVZ-IPF isolated from a PE homopolymer catalyzed by Ziegler-Natta catalyzed to determine the polymer melting behavior.
[00124] Density. The density of a TVZ-IPF will be determined in accordance with ASTM D-1505.
[00125] Brookfield Viscometry will be performed on a sample of a TVZ-IPF isolated from a homopolymer catalyzed by Ziegler-Natta to determine the potential of the polymer as a viscosity modifier.
[00126] A non-Ziegler catalyst will be used to polymerize an olefin monomer under conditions suitable for the formation of a polymer and the presence of topological variations in the polymer will be evaluated. Example 2.
[00127] Four catalysts/running recipes were used to produce source polymers, which was then analyzed by SEC-MALS. The degree of unusual deviation from linearity was taken as a qualitative indication of the amount of any topologically varying component/subpopulation (eg hyper-branched) contained in the yield of source polymers. Polymerization Process
[00128] Polymerization operations were carried out in a 2.2 liter steel reactor equipped with a marine agitator rotating at 400 rpm. The reactor was surrounded by a steel jacket through which a mixture of steam and cold water was continuously injected. By controlling the proportion of steam and water, the temperature inside the reactor could be precisely adjusted to within 0.5°C with the help of electronic control instruments. A small amount (0.1 to 3 grams typically) of the solid catalyst was first charged under nitrogen to the dry reactor. About 1.0 liter of liquid isobutane was charged and the reactor, along with 1 ml of 1M triethylaluminum cocatalyst and, if indicated, 1 ml of dichloromethane cocatalyst. The mixer was activated and the reactor contents were heated to 95 °C, and the desired amount of hydrogen was added. Finally ethylene was added to the reactor at a fixed equal pressure, either 300 psig (2.1 MPa) or 400 psig (2.76 MPa), as indicated. Ethylene was supplied continuously on demand to maintain the desired pressure throughout the experiment.
[00129] After the desired amount of source polymer is obtained, usually within 0.5 to 3 hours, the flow of ethylene was stopped and the reactor slowly depressurized and cooled and then opened to recover a granular polymer powder. In all cases, the reactor was cleaned without any indication of any wall scale, coating or other forms of fouling. The source polymer powder was then removed and weighed. Activity was specified as grams of polymer produced per gram of solid catalyst loaded per hour. Catalyst and Source Polymer Preparation
[00130] Recipe A: A silica was obtained from Philidelphia Quartz Company under the name EP10X, having a surface area of 300 m2/g and a pore volume of 1.6 ml/g. A 12.5 g sample was dried for three hours at 300 °C in a fluidized bed of nitrogen. After three hours, 3.0 mL of liquid TiCl4 was injected and evaporated in the nitrogen stream, used to fluidize the sample at 0.1 ft/s (0.03 m/s). Vapor passes through the sample bed, a reaction with silica and surface saturation with titanium chloride species. The Ti-treated sample was then stored chilled under dry nitrogen.
[00131] A1 (23B): A 2.159 gram sample of this catalyst was loaded into the reactor along with 25 psi (172 KPa) hydrogen and 400 psi (2.76 MPa) ethylene. Dichloromethane was not used. In 26 minutes, the reaction was stopped and 268 g of polyethylene were obtained.
[00132] Recipe B: The recipe above, recipe A, was repeated, except that VOCl3 was injected instead of TiCl4. A sample of 11.85 grams of silica was calcined in flowing nitrogen for three hours and then after 2.3 mL of VOCl3 was vaporized in the nitrogen stream and carried through a fluidizing silica bed in which it reacted with the sample. The V-treated sample was then stored chilled under dry nitrogen.
[00133] B1 (24B): A 0.77 gram sample of this catalyst was charged into the reactor along with 25 psi (172 KPa) hydrogen and 400 psi (2.76 MPa) ethylene. Dichloromethane was not used. In 166 minutes, the reaction was stopped and 134g of polyethylene was recovered.
[00134] B2 (32A): A 2.2834 gram sample of this catalyst was charged into the reactor along with 100 psi (690 KPa) of hydrogen and 400 psi (2.76 MPa) of ethylene. Dichloromethane was not used. In 45 minutes, the reaction was stopped and 207 g of polyethylene was recovered.
[00135] B3 (34A): A 1.7588 gram sample of this catalyst was charged into the reactor along with 100 psi (690 KPa) of hydrogen and only 300 psi (2.1 MPa) of ethylene. Dichloromethane was not used. In 240 minutes, the reaction was stopped and 210 g of polyethylene was recovered.
[00136] Recipe C: The same catalyst as described under Recipe B that was used in Recipe C, except that dichloromethane was also added to the reactor.
[00137] CI (24A): A 2.3795 gram sample of this catalyst was charged into the reactor along with 25 psi (172 KPa) of hydrogen, 400 psi (2.76 MPa) of ethylene, and 1.0 mL of dichloromethane . In just 10 minutes, the reaction was stopped and 136 g of polyethylene was recovered.
[00138] C2 (25A): A 0.9118 gram sample of catalyst was charged into the reactor along with 25 psi (172 KPa) of hydrogen, 400 psi (2.76 MPa) of ethylene, and 1 mL of dichloromethane. In 38 minutes, the reaction was stopped and 267 g of polyethylene was recovered.
[00139] Recipe D: A 16.95 g sample of the same silica used above was fluidized in dry nitrogen for three hours at 600 °C. It was then slurried in dry heptane with dibutylmagnesium added at a charge of 2.0% Mg on silica. TiCl4 was then injected into heptane at which a charge of 1.1 mols of Ti per Mg mol. The heptane was then evaporated under flowing nitrogen to produce a dry brown catalyst.
[00140] D1 (32B): A 0.0766 gram sample of this catalyst was charged into the reactor along with 100 psi (689 KPa) hydrogen and 400 psi (2.76 MPa) ethylene. Dichloromethane was not used. In 78 minutes the reaction was stopped and 18 g of polyethylene were recovered.
[00141] D2 (33B): A 2.264 gram sample of this catalyst was charged into the reactor along with 100 psi (689 KPa) of hydrogen and 300 psi (2.1 MPa) of ethylene. Dichloromethane was not used. In 211 minutes the reaction was stopped and 321 g of polyethylene was recovered. SEC-MALS Analysis of Source Polymers
[00142] The Z-SPs obtained by polymerization with the catalysts produced by Recipe A, B, C or D were analyzed by SEC-MALS. Figures 15, 16, 17 and 18 are graphs of the molecular weight distributions obtained by the samples. They ranged from wide to quite narrow; however, there was no obvious connection with the presence of topological variation (eg hyper-branched) component/subpopulation.
[00143] The radius of rotation (Rg) as a function of molecular weight for these polymers is plotted in Figures 19, 20, 21 and 22. The amount of topologically varying component (eg hyper-branched) component contained in each polymer source can be measured by the starting degree of the control line, which is marked as "Not Branching" on each graph. The positive deviation at low MW is particularly indicative of high levels of branching.
[00144] Figure 19 shows that the polymer produced using recipe A produces only a small deviation from linearity. That is, little of the topological variation component (eg hyper-branched) was produced. Similarly, in Figure 20, polymer produced using recipe B also exhibited little component of topological variation (eg, hyper-branched). Note, however, that polymer produced using recipe B2, made with 100 psi (689 KPa) of H2, exhibits a greater match than Z-SP produced using recipe B1, made with only 25 psi (172 KPa) of H2. This indicates that the presence of H2 is useful in producing a topological variation component (eg hyper-branched).
[00145] Both polymers in Figure 21 exhibit a high degree of starting from the reference line line, even though both were made with only 25 psi (172 KPa) of H2. These polymers produced using recipe C were actually made with the same vanadium catalyst as was used in recipe B. However, recipe C added dichloromethane to the reactor. The main difference between polymer produced using recipes B and C indicate that dichloromethane is a major contributor to topological variation component formation (eg hyper-branched). In fact, polymer produced using recipe C1, made with only 25 psi (172 KPa) of H2, exhibited more extreme Rg behavior than polymer produced using recipe B2 made with 100 psi (689 KPa) H2.
[00146] Figure 22 shows the most extreme behavior of a polymer produced using recipe D. Both source polymers D1 and D2 were made with 100 psi (689 KPa) of H2. However, the latter was made with 300 psi (2.1 MPa) of ethylene instead of the usual 400 psi (2.76 MPa). Interestingly, the catalyst in recipe D, like the recipe in A, was based on titanium chloride. Yet recipe A seems to produce little component of topological variation (eg hyper-branched), whereas recipe D produces the most observed in these tests. In recipe D, the Ti sites are thought to be in a lower state and possibly more acidic. The normal Lewis base donor ligands commonly used in the preparation of titanium catalysts were omitted from Preparation D, and this may explain the difference. The results demonstrate that source polymers having different degrees of linearity can be obtained using the methodologies disclosed in this document.
[00147] While the various modalities have been shown and described, modifications to them may be made without deviating from the scope and teachings of the disclosure. The modalities described in this document are exemplary only and are not intended to be limiting. Many variations and modifications of the subject matter disclosed in this document are possible and are within the scope of the disclosure. Where numerical ranges or limitations are expressly indicated, such express ranges or limitations shall be understood to include iterative ranges or limitations of similar magnitude that fall within the expressly stated ranges or limitations (eg, from around 1 to around 10 includes 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term "optionally" in relation to any element of a claim is intended to mean that the subject matter is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms, such as, understand, include, having, etc. is to be understood as providing support for the more restricted terms, such as, consisting of, consisting essentially of, consisting substantially of etc.
[00148] In this sense, the scope of protection is not limited by the description defined above, but is limited only by the following claims, this scope includes all equivalents of the subject matter of the claims. Each and every claim is incorporated in the specification as an embodiment of the present disclosure. Thus, the claims are a further description and are in addition to the embodiments of the present disclosure. The discussion of a reference in the disclosure is not an admission that it is prior art of the present disclosure, especially any reference may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited in this document are incorporated by reference, insofar as
[00149] They provide exemplary, procedural details or complementary to those set forth herein.

权利要求:
Claims (14)
[0001]
1. Isolated topologically varying polyethylene homopolymer having a long chain branching frequency of more than 0.5 long chain branches per 1000 total carbons, characterized in that the homopolymer is isolated from a polyethylene homopolymer catalyzed by Ziegler by solvent gradient fractionation and wherein the radius of rotation of the homopolymer of topological variation is smaller than that of a linear polymer of identical molecular weight and wherein the topological variation comprises a long chain branch.
[0002]
2. Polyethylene homopolymer of topological variation according to claim 1, characterized in that it has a zero shear viscosity that negatively deviates from the Arnett 3.4 power law.
[0003]
3. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a zero shear viscosity ranging from 5.0E + 02 Pa.s to about 1.0 E + 07 Pa.s.
[0004]
4. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a zero shear viscosity that is 20% to 500 times lower than a linear polymer of the same molecular weight.
[0005]
5. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a density of 0.90 g/cm3 to 0.965 g/cm3.
[0006]
6. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a weighted average molecular weight of 50 kg/mol to 2,000 kg/mol.
[0007]
7. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a CY-a parameter from 0.05 to 0.70.
[0008]
8. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that it has a polydispersity index from 3 to 100.
[0009]
9. Polyethylene homopolymer of topological variation, according to claim 1, characterized in that the polyethylene homopolymer of topological variation is present in the Ziegler-Natta polyethylene homopolymer in the amount of 0.1% by weight to 30% by weight.
[0010]
10. Method, characterized in that it comprises: -contacting a Ziegler catalyst with an ethylene monomer under conditions suitable for the formation of an ethylene polymer; - recovering an ethylene polymer; - fractionating the ethylene polymer into polymer fractions by solvent gradient fractionation; - identify topologically varying ethylene polymer fractions having spin radius values smaller than that of a polymer of identical weight average molecular weight; and - recovering the polymer fractions as defined in claim 1 having generation radius values less than that linear polymer of identical weight average molecular weight, and wherein the polymer fractions exhibit a zero shear viscosity that negatively deviates from the law of Arnett power 3.4.
[0011]
11. Method according to claim 10, characterized in that the polymer fractions having a radius of rotation values smaller than that of a linear polymer with the same weighted average molecular weight have a long chain branch greater than 0 .5 long chain branches per 1000 carbon atoms in total.
[0012]
12. Method according to claim 10, characterized in that the polymer fractions having radius of rotation values smaller than that of a linear polymer of the same weighted average molecular weight having a zero shear viscosity ranging from 5.0E +02 Pa.s to 1.0E+07 Pa.s.
[0013]
13. Method according to claim 10, characterized in that it additionally comprises modifying the polymer fractions having radius values of values smaller than that of the linear polymer of identical weight average molecular weight.
[0014]
14. Method according to claim 13, characterized in that it comprises oxidation, surface modification, corona treatment, plasma treatment, photochemical treatment, chemical grafting, chemical treatment, end capping with short chains or organic molecules, end grafts by live polymerization, blending with other polymer components, crosslinking polymer chains or combinations thereof.

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同族专利:

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EP2751190B1|2020-02-26|

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EP2751190A1|2014-07-09|

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CN103764749B|2016-10-26|

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KR20140059212A|2014-05-15|

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CA2846637A1|2013-03-07|

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WO2013033328A1|2013-03-07|

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SG11201400246SA|2014-03-28|

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CN103764749A|2014-04-30|

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BR112014004831A2|2017-04-04|

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US8933175B2|2015-01-13|

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法律状态:
2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-21| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161528996P| true| 2011-08-30|2011-08-30|

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US61/528,996|2011-08-30|

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PCT/US2012/053041|WO2013033328A1|2011-08-30|2012-08-30|Hyperbranched polymers and methods of making and using same|

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