Bimodal polyethylene

Bimodal polyethylene technology field

[0001] The embodiments of the present disclosure relate to a polymer, and more specifically, the embodiments relate to bimodal polyethylene.

Background technique

[0002] Polymers can be used in many products, including membranes and pipes. Polymers can be formed by reacting one or more types of monomers in a polymerization reaction. The industry has been working to develop new and improved materials and/or methods that can be used to form polymers for existing and new products.

[0003] New and improved polymers and/or methods are developed for pipelines used in thermal fluid applications. Polymer pipes used for thermal fluid applications must withstand the strain associated with the thermal fluid moving under pressure, usually hot water. According to the standard DIN 16833, hot water pipes must meet the requirement of being effective for at least 165 hours at 95°C and 3.6MPa pressure.

[0004] Examples of polymers suitable for such hot water applications include high temperature resistant polyethylene (PE-RT). This is a polyethylene polymer used for hot and cold water and industrial piping applications. These materials have unique molecular structures and crystalline microstructures, which provide excellent long-term hydrostatic strength at high temperatures without the need for cross-linking materials. The application of PE-RT includes industrial applications, and its temperature resistance can prevent traditional polyethylene and metal materials from being corroded frequently. Therefore, despite the progress made in PE-RT, there is still a need to improve the hydrostatic strength of PE-RT at high temperatures and the production technology of this PE-RT material.

Summary of the invention

[0005] As provided herein, the present disclosure provides improvements in PE-RT in terms of the improvement of the hydrostatic strength of PE-RT at high temperatures and the production technology of PE-RT of the present disclosure. Specifically, the present disclosure provides a bimodal polyethylene, which has a density of 0.930 to 0.950 grams per cubic centimeter (g/ccm); a melt index (I2) of 0.1 to 1.0 g/10 minutes; a melt of 20 to 90 Volume flow ratio (I21/I2); wherein the bimodal polyethylene comprises a high weight average molecular weight (HMW) polyethylene component and a low weight average molecular weight (LMW) polyethylene component, characterized in that the bimodal polyethylene has The chromatogram of gel permeation chromatography (GPC) shows a clear bimodal weight average molecular weight distribution, and its local minimum between the peak representing the HMW polyethylene component and the peak representing the LMW polyethylene component is at log (Molecular weight) Within the range of 3.5 to 5.5.

Description of the drawings

[0006] FIG. 1 is a graph showing a molecular weight distribution (MWD) curve of bimodal polyethylene using the SEC technique (GPC method) described herein according to an embodiment of the present disclosure. DWf as used in Figure 1 is the change in weight fraction, and dLogM (also called dLog (MW)) is the change in the logarithm of the molecular weight.

Detailed ways

[0007] For convenience, various specific test procedures have been identified to determine properties such as average molecular weight, extrapolated stress, polydispersity index (PDI), flow index (FI), and melt flow ratio (MFR). However, when a person of ordinary skill reads this patent and wants to determine whether a polymer has a specific property defined in the claims, he can follow any public or recognized method or test procedure to determine that property (although the specific determination procedure is Preferred, and any procedure specified in the claims is mandatory rather than just preferred).

[0008] The term "polyethylene" refers to units derived from at least 50% ethylene, preferably units derived from at least 70% ethylene, more preferably units derived from at least 80% ethylene, or units derived from 90% ethylene, or 95% % Ethylene-derived units or even 100% ethylene-derived units made of polymers. Therefore, polyethylene can be a homopolymer or a copolymer, including terpolymers with other monomer units. The polyethylene described herein may, for example, comprise units derived from the following comonomers, which are preferably ά olefins, for example, propylene, 1-butene, 1-pentene, 1-hexene or mixture. Other embodiments may include diene, ethacrylate, or methacrylate.

[0009] When used herein to describe bimodal polyethylene, the term "bimodal" refers to "bimodal molecular weight distribution", as reflected in one or more printed publications or issued patents, the term It is understood to be the broadest definition of that term given by those in the relevant field. At least one example of the bimodal polyethylene of the present invention is shown in FIG. 1, in which the horizontal axis is expressed as the logarithm of the molecular weight (Log MW). For example, the bimodal polyethylene seen in Figure 1 contains a higher molecular weight distribution peak and a lower molecular weight distribution peak, for example, representing the two peaks of the term "bimodal" polyethylene as used herein (as shown in Figure 1 display). As described herein, high temperature gel permeation chromatography is used to determine weight average molecular weight and number average molecular weight

[0010] A material with more than two peaks of different molecular weight distribution will be considered as the term "bimodal" as used herein, although the material may also be referred to as "multimodal", for example, three peaks or even four peaks. Peak and so on. As described below, various different types of methods and reactor configurations can be used to produce the bimodal polyethylene of the present invention, including melt blending, series reactors (ie, reactors configured in sequence), and the use of bimodal catalyst systems. Single reactor. Any polyethylene considered to be a "multimodal" composition in U.S. Patent No. 6,579,922 is considered to fall within the broad meaning of the term "bimodal polyethylene" herein, although the bimodal polyethylene claimed herein is not There are important differences between the bimodal compositions disclosed in that patent.

[0011] The term "bimodal catalyst system" includes any of the following compositions, mixtures or systems, which comprise at least two different catalyst compounds, each catalyst compound having the same or different metal groups but usually different ligands or catalysts Structure, including "dual catalyst". Alternatively, each different catalyst compound of the bimodal catalyst system is present on a single support particle, for example, in this case, the dual catalyst is considered a supported catalyst. However, the term bimodal catalyst system also broadly encompasses systems or mixtures in which one of the catalysts is present on one set of carrier particles, and the other catalyst is present on another set of carrier particles. Preferably, in that latter case, the two supported catalysts are introduced into a single reactor simultaneously or sequentially, and the polymerization is carried out in the presence of two groups of supported catalysts. Alternatively, the bimodal catalyst system comprises a mixture of unsupported catalysts in the form of a slurry.

[0012] The term flow index "FI" as used herein refers to I21, which is measured at 190C according to ASTM-1238, Condition E. The term melt flow ratio "MFRQ21/I2)" as used herein means the ratio of 121 (also referred to as FI) to I2, and both I21 and I2 are measured at 190C according to ASTM-1238, condition E. Density is the physical property of the composition, which is measured according to ASTM-D1505 and expressed as grams per cubic centimeter (or grams per milliliter).

[0013] The term "high temperature resistance" as used herein broadly refers to any one or more of the group of mechanical properties, for example, properties related to strength, for example, to characterize the properties of resins used to make pipes, In particular, the resins that meet the hot and cold water pipes and distribution system components are manufactured in a standard size ratio and are intended to be used for water supply of 100 psig (6.9 bar) with a maximum operating temperature of up to and including 180°F ( 82°C). Preferably, the bimodal polyethylene of the present disclosure is characterized by the high temperature resistance measured on a compression molded plate formed by the bimodal polyethylene, wherein the measurement is based on ASTM F276914 at a stress of 2.4 MPa and a temperature of 90° C. According to the requirements of ASTM F 1473PENT test. A further feature of the bimodal polyethylene of the present disclosure may be its high temperature resistance as a PE-RT II type material, when evaluated according to ISO 9080 or equivalent and its internal pressure test is performed according to ISO 1167-1 and ISO 1167-2 When, in the temperature and internal pressure range as provided in ISO 22391, the bimodal polyethylene meets the requirements of ISO 24033 for PE-RT type II materials

The 4-parameter model. As such, the bimodal polyethylene of the present invention may also be referred to herein as a high-temperature resistant bimodal polyethylene.

[0014] As described below, certain properties or characteristics of the composition, polymer, pipeline, or catalyst system are expressed with respect to a lower limit (e.g., X or greater) or an upper limit (e.g., Y or less). It should be understood that any lower limit can be combined with any upper limit to provide various alternative ranges.

[0015] The bimodal polyethylene of the present invention comprises a high weight average molecular weight (HMW) polyethylene component and a low weight average molecular weight (LMW) polyethylene component. The HMW polyethylene component as used herein means the polyethylene component in bimodal polyethylene whose weight average molecular weight is higher than the weight average molecular weight of at least one other polyethylene component in the same composition. Preferably, the HMW polyethylene component has identifiable peaks, for example, as shown in FIG. 1. In certain embodiments, the HMW polyethylene component is a component that forms part of the bimodal polyethylene and has a weight average molecular weight (Mw) of 10,000 to 1,000,000. In different specific embodiments, the weight average molecular weight of the HMW polyethylene component can range from a low point of 20,000, or 50,000, or 100,000, or 150,000, or 200,000, or 250,000 or 300,000 to a high point of 1,000,000, or 900,000, or 800,000. , Or 700,000, or 600,000 or any combination of the above upper and lower limits.

[0016] The LMW polyethylene component as used herein means the polyethylene component in bimodal polyethylene whose weight average molecular weight is lower than the weight average molecular weight of at least one other polyethylene component in the same bimodal polyethylene . Preferably, the LMW polyethylene component has identifiable peaks, for example, as shown in FIG. 1. In certain embodiments, the LMW polyethylene component is a component that forms part of the bimodal polyethylene and has a weight average molecular weight (Mw) of 1,000 to 100,000. In different specific embodiments, the weight average molecular weight of the LMW polyethylene component can range from a low point of 3,000, or 5,000, or 8,000, or 10,000, or 12,000, or 15,000 or 20,000 to a high point of 100,000, or 50,000, or 40,000. , Or 35,000, or 30,000 or any combination of the above upper and lower limits.

[0017] The term "weight average molecular weight" is used to describe the bimodal polyethylene described herein, or a term used to describe a high molecular weight polyethylene component and a low molecular weight polyethylene component. In either case, the term "average molecular weight" broadly refers to any weight average molecular weight (Mw) measured or calculated according to any published method that incorporates ASTM D 3536-91 (1991) and ASTM D 5296 -92 (1992) procedures, equipment and conditions.

[0018] The weight average molecular weight of the specific polyethylene component described in the claims, for example, the HMW component and the LMW component can also be determined by any published method, including those mentioned in the above paragraph; however, it is preferred The method is to use any published deconvolution procedure, for example, any disclosed technique for elucidating the molecular information of each individual component polymer in a bimodal polymer. A particularly preferred technique is a technique using Flory deconvolution, including but not limited to the Flory program shown in US Patent No. 6,534,604, which is incorporated herein by reference in its entirety.

[0019] FIG. 1 provides a chromatogram of gel permeation chromatography (GPC) of an example of bimodal polyethylene according to the present disclosure. As can be seen, Figure 1 shows a clear bimodal molecular weight distribution with a local minimum between the peak representing the HMW polyethylene component and the peak representing the LMW polyethylene component in the range of 10 g (molecular weight) 3.5 to 5.5 Inside. The chromatogram seen in Figure 1 also shows a bimodal polyethylene in which the ratio of the height of the peak representing the HMW polyethylene component on the chromatogram of the bimodal polyethylene to the local minimum is 1.2 to 3.0 ( Peak height/local minimum of the HMW polyethylene component). Regarding the LMW polyethylene component, the ratio of the height of the peak representing the LMW polyethylene component on the chromatogram of the bimodal polyethylene seen in Figure 1 to the local minimum is 1.2 to 3.0 (the peak of the LMW polyethylene component) High/local minimum). The height of the peak representing the LMW polyethylene component on the chromatogram of the bimodal polyethylene and the height of the peak representing the HMW polyethylene component on the bimodal polyethylene The ratio of the height on the chromatogram is 0.5 to 2.5 (the height of the LMW polyethylene component/the height of the HMW polyethylene component).

[0020] The term "portion" is defined herein as the weight percentage of the high molecular weight component in the bimodal composition. Therefore, its

The relative amount of the high molecular weight component to the low molecular weight component in the bimodal polyethylene is described, including any bimodal polyethylene described herein. The weight percentage of each component can also be expressed by the area of each molecular weight distribution curve seen after the deconvolution of the entire molecular weight distribution curve.

[0021] The term "spread" as used herein means the ratio of the weight average molecular weight of the high molecular weight polyethylene component (sometimes referred to as Mwhmw) to the weight average molecular weight of the low molecular weight polyethylene component (sometimes referred to as Mwlmw)" "Dispersion" can also be expressed as the ratio Mwhmw:Mwlmw.

[0022] As used herein, the term "PDI" means polydispersity index, and means the same thing as "MWD" (Molecular Weight Distribution), as reflected in one or more printed publications or issued patents The term is understood to be the broadest definition given to that term by persons in the relevant field. PDI (MWD) is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), that is, Mw/Mn.

[0023] In any bimodal polyethylene described above or elsewhere herein, the lower limit of density is 0.930 grams per cubic centimeter (g/ccm) or 0.935 g/ccm, and the upper limit is 0.950 g/ccm, or 0.945 g /ccm, or 0.940g/ccm, or any combination of the above upper and lower limits. For example, in one embodiment, the density of the bimodal polyethylene is 0.930 g/ccm to 0.950 g/ccm. In any of the bimodal polyethylenes described above or elsewhere herein, the weight average molecular weight (Mw) of the low molecular weight polyethylene component can be, for example, 1,000 to 100,000, or somewhere in between as disclosed elsewhere herein. Any range between the lower limit and the upper limit. In any of the bimodal polyethylenes described above or elsewhere herein, the weight average molecular weight (Mw) of the high molecular weight polyethylene component can be, for example, 10,000 to 1,000,000, or somewhere in between as disclosed elsewhere herein. Any range between the lower limit and the upper limit.

[0024] In any of the bimodal polyethylenes described above or elsewhere herein, the high molecular weight polyethylene component may comprise polyethylene, which comprises comonomers, namely butene, hexene and mixtures thereof, wherein the copolymerized monomer The body is present in a content of 1.0 weight percent (wt.%) of polyethylene, or preferably more than 2.0 wt.% of polyethylene, or more preferably more than 3.0 wt.% of polyethylene. In any of the bimodal polyethylenes described above or elsewhere herein, the low-molecular-weight polyethylene component may comprise polyethylene, which contains comonomers, namely butene, hexene, and mixtures thereof, wherein the comonomers are The ethylene is present in a content of 3.0 wt.%, or preferably less than 2.0 wt.% of polyethylene, or more preferably less than 1.0 wt.% of polyethylene.

[0025] In one or more of the bimodal polyethylene disclosed herein, the high weight average molecular weight polyethylene component is present in the following amount: wherein the lower limit is 40wt.%, 45wt.% based on the total weight of the bimodal polyethylene Or 50wt.% and the upper limit is 75wt.%, 70wt.%, or 65wt.% based on the total weight of the bimodal polyethylene, or any combination of the above upper and lower limits. These weight percentages are also referred to as "parts" as described above. In one embodiment, the high weight average molecular weight polyethylene component is present in an amount of 40 to 75 weight percent based on the total weight of the bimodal polyethylene.

[0026] In one or more of the bimodal polyethylene disclosed herein, the low weight average molecular weight polyethylene component is present in the following amount: the lower limit is 25wt.%, 30wt based on the total weight of the bimodal polyethylene. % Or 35wt.% and the upper limit is 60wt.%, 55wt.% or 50wt.% based on the total weight of the bimodal polyethylene. Therefore, in one embodiment, the low weight average molecular weight polyethylene component is present in an amount of 25 to 60 weight percent based on the total weight of the bimodal polyethylene.

[0027] In one or more of the bimodal polyethylenes disclosed herein, the lower limit of the ratio Mwhmw:Mwlmw as defined above may be 20:1, 25:1, 30:1, or 35:1, and The upper limit can be 100:1, 90:1, 80:1, or 70:1, or it can be any combination of the above upper and lower limits. For example, the ratio of the high weight average molecular weight component (Mwhmw) to the low weight average molecular weight component (Mwlmw) of bimodal polyethylene is 20:1 to 100:1.

[0028] In one or more of the bimodal polyethylene disclosed herein, the FI (121) of the bimodal polyethylene may be 10 to 20 grams/10 minutes (g/10 minutes). In an alternative embodiment, FI may be expressed as having any one of multiple ranges, for example

For example, the lower limit is 10g/10 minutes or more, or 11g/10 minutes or more, or 12g/10 minutes or more, or 13g/10 minutes or more, or 14g/10 minutes or more; and the upper limit is 20g/10 minutes Or less, or 19 g/10 minutes or less, or 18 g/10 minutes or less, or 17 g/10 minutes or less, or 16 g/10 minutes or less, or expressed as any combination of the above upper and lower limits.

[0029] In one or more of the bimodal polyethylene disclosed herein, the FI (I2) of the bimodal polyethylene may be 0.1 to 10 g/10 minutes. In alternative embodiments, FI may be expressed as having any one of a number of ranges, for example, the lower limit is 0.1 g/10 minutes or more, or 0.2 g/10 minutes or more, or 0.3 g/10 minutes or more Or 0.4g/10 minutes; and the upper limit is 1.0g/10 minutes or less, or 0.9g/10 minutes or less, or 0.8g/10 minutes or less, or 0.7g/10 minutes or less, or 0.6g/10 Minutes or less, or any combination of the above upper and lower limits. In one embodiment, the FI (I2) of the bimodal polyethylene is 0.1 to 1.0 g/10 minutes.

[0030] In one or more of the bimodal polyethylene disclosed herein, MFRQ21/I2) may be 20 to 90. In alternative embodiments, MFR can be expressed as having any of a number of ranges, for example, the lower limit is 20, or 25, or 30, or 35 or 40; and the upper limit is 90, or 85, or 80, or 75, or 70, or 65, or 60, or 55 or expressed as any combination of the above upper and lower limits.

[0031] In one or more of the bimodal polyethylene disclosed herein, the PDI of the entire bimodal polyethylene may be expressed as having any one of a plurality of ranges, for example, the lower limit is 12 or 15; and the upper limit It is 30 or less, or 25 or less, or 20 or less, or expressed as any combination of the above upper and lower limits. In some embodiments, the PDI may be 12 to 30, or 12 to 25, or 15 to 25.

[0032] In one or more of the bimodal polyethylenes disclosed herein, the high-molecular-weight and low-molecular-weight polyethylene components are the reaction products of a polymerization process performed in a single reactor. Examples of such reactors are disclosed in more detail elsewhere herein. In one or more of the bimodal polyethylenes disclosed herein, the high-molecular-weight and low-molecular-weight polyethylene components are the reaction products of the polymerization method performed in the gas phase polymerization method. The details of available gas phase polymerization methods are described elsewhere herein.

[0033] A bimodal catalyst system is used to form the bimodal polyethylene of the present invention. Generally, bimodal polyethylene is formed from the complex I catalysts and non-metallocene catalysts. For example, a polymerization catalyst comprising a zoxocene of Formula I can be used in a single reactor to form the bimodal polyethylene of the present disclosure.

[0034] The chalcocene catalyst is a metallocene catalyst. The metallocene catalyst compound may comprise a "semi-sandwich" and/or "full-sandwich" compound, which has one or more Cp ligands (e.g., cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom And a ligand that is isobaric with cyclopentadienyl) and one or more groups bound to at least one metal atom. As used herein, unless reference is made to the previous IUPAC table in Roman numerals (which also appears in the same table) or unless otherwise specified, all references to the Periodic Table and its groups refer to the "Holy Concise Chemistry" Dictionary (HAWLEY' S CONDENSED CHEMICAL DICTIONARY), thirteenth edition, John Wiley & Sons, Inc., (1997) published new notes (reproduced here with permission from IUPAC).

[0035] A Cp ligand is one or more rings or ring systems, at least a part of which includes a π-bonded system such as cyclodienyl ligands and heterocyclic analogs. The ring or ring system generally contains atoms selected from the group consisting of atoms of groups 13 to 16, and in certain exemplary embodiments, the atoms constituting the Cp ligand are selected from the group consisting of carbon, nitrogen, oxygen, silicon , Sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, wherein carbon constitutes at least 50% of the ring member. In a more specific exemplary embodiment, the Cp ligand is selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands that are isobaric with cyclopentadienyl, which is not limited Examples include cyclopentadienyl, indenyl, fluorenyl, and other structures. Other non-limiting examples of such ligands include loops

Pentadienyl, cyclopentyl phenanthryl, indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentadienyl dodecenyl, phenanthryl indenyl, 3 ,4-Benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopentyl[a] acenaphthylene, 7-H-dibenzofluorenyl, indeno[1,2-9]anthracene , Thioindenyl, thienofluorenyl, its hydrogenated form (for example, 4,5,6,7-tetrahydroindenyl or "H4lnd"), and its substituted form (as discussed and described in more detail below) And its heterocyclic form.

[0036] In an exemplary embodiment, the metal atom "M" of the metallocene catalyst compound may be selected from group 3 to 12 atoms and lanthanide atoms; and in a more specific exemplary embodiment, selected from the group Group 3 to 10 atoms, and in a more specific exemplary embodiment, selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni; and in a more specific exemplary embodiment, selected from the group consisting of group 4, 5, and 6 atoms, and in a more specific exemplary embodiment, selected from Ti , Zr, Hf atoms, and in yet more specific exemplary embodiments, are selected from Hf. In an exemplary embodiment, the oxidation state of the metal atom "M" may be in the range of 0 to +7; and in a more specific exemplary embodiment, it may be +1, +2, +3, +4 Or +5; and in a more specific exemplary embodiment, it may be +2, +3, or +4. Unless otherwise specified, the group bound to the metal atom "M" makes the compound and structure described in the following formulae neutral. The Cp ligand forms at least one chemical bond with the metal atom M to form a "metallocene catalyst compound. The Cp ligand is different from the leaving group bound to the catalyst compound because it is not very sensitive to substitution/extraction reactions.

[0037] As used herein, the phrase "catalyst system" or "bimodal catalyst system" includes at least one "catalyst component" and at least one "activator", both of which are further described herein. The catalyst system may also include other components, such as supports, etc., and is not limited to individual catalyst components and/or activators or combinations thereof. The catalyst system can include any number of catalyst components in any combination as described herein, and any activator in any combination as described herein.

[0038] As used herein, the phrase "catalyst compound" includes any compound capable of catalyzing the polymerization or oligomerization of olefins once properly activated.

[0039] As used herein, the phrase "leaving group" refers to one or more chemical moieties bound to the metal center of the catalyst component, which can be extracted from the catalyst component by an activator to produce paraolefin A species that is active in polymerization or oligomerization reactions. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, ethylenic, and aromatic groups (ie, hydrocarbyl), which includes hydrogen and carbon lacking one hydrogen. The "hydrocarbylene" lacks two hydrogens. As used herein, "alkyl" includes straight, branched, and cyclic alkanyl groups lacking one hydrogen. Thus, for example, a CH3 group ("methyl") and a CH3CH2 group ("ethyl") are examples of alkyl groups. As used herein, "alkenyl" includes straight chain, branched chain, and cyclic alkenyl groups lacking one hydrogen; hexyl includes straight chain, branched chain, and cyclic ethylenyl groups lacking one hydrogen group. As used herein, the "aryl" group includes phenyl, zeyl, pyridyl, and other groups, and its molecules have the ring structure characteristics of benzene, naphthylene, phenanthrene, anthracene, and the like. It should be understood that the "aryl" group can be a C6 to C20 aryl group. For example, C6H5-aromatic structure is "phenyl" and C6H4-aromatic structure is "phenylene". An "arylalkyl" group is an alkyl group having an aryl group pendant from it. It should be understood that the "aralkyl" group can be a C7 to C20 aralkyl group. "Alkylaryl" is an aryl group having one or more alkyl groups pendant from it. As used in this article, "Alkylene" includes straight, branched and cyclic hydrocarbon groups lacking two hydrogens. Thus, one CH2 one ("methylene") and one CH2CH2 one ("ethylene") are examples of alkylene groups. Other groups lacking two hydrogen groups include "arylene" and "alkenylene". As used herein, the phrase "heteroatom" includes any atom other than carbon and hydrogen, which can be bonded to carbon, and in one embodiment, is selected from B, Al, Si, Ge, N, P, O And S group. A "heteroatom-containing group" is a hydrocarbon group that contains a heteroatom and may contain one or more of the same or different heteroatoms, and in a specific embodiment, contains 1 to 3 heteroatoms. Non-limiting examples of heteroatom-containing groups include imines, amines, oxides, ethers, ethers, ketones, oxazoline heterocycles, oxazoline

CN 110012669 A Groups such as management and sulfuric acid. As used herein, "alkyl carboxylate", "aryl carboxylate" and "alkylaryl carboxylate" are alkyl, aryl, and alkylaryl groups having a carboxyl group at any position, respectively. . Examples include C6H5cH2c (0) 0One,CH₃C (0) 0 first class. As used herein, an aralkyl group is defined as a substituted aryl group. As used herein, the term "substituted" means that the group following this term has at least one part in place of one or more hydrogens at any position, the part being selected from halogen groups (especially Cl, F, Br ), hydroxyl, valkynyl, carboxyl, amine, instantaneous, alkoxy, phenyl, Q to C20 alkyl, C2 to Cio alkenyl, and combinations thereof. Examples of substituted alkyl and aryl groups include, but are not limited to, acyl, alkylamino, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbyl, aryloxycarbyl, amino Formyl, alkyl and dialkylcarbamoyl, acyloxy, amido, arylamino, and combinations thereof.

[0040] The embodiments of the present disclosure include a polymerization catalyst of Formula I:

<img file="CN110012669A_D0001.tif" />

(Formula I)

[0042] wherein each of * to Ri° is independently Q to C20 alkyl, aryl or aralkyl or hydrogen, wherein M is the first

Group 4 metal, and wherein each X is independently a halide, Q to C20 alkyl, aralkyl, or hydrogen.

[0043] Embodiments of the present disclosure may also include a polymerization catalyst of Formula I:

<img file="CN110012669A_D0002.tif" />

(Formula Π)

[0045] wherein each of * to R6 is independently Q to C20 alkyl, aryl or aralkyl or hydrogen, wherein M is a Group 4 metal, and wherein each X is independently a halide, Q to C20 alkyl, aralkyl or hydrogen.

The embodiments of the present disclosure further include a polymerization catalyst of formula m:

[0046]

[0047]

<img file="CN110012669A_D0003.tif" />

[00481 (Formula III) wherein each of R1 to R12 is independently a C1 to C20 alkyl, aryl or aralkyl group or hydrogen, wherein at least one of R4 to R7 is not hydrogen, wherein μ is the fourth Group metal, and wherein each X is independently a halide, Q to C20 alkyl, aralkyl, or hydrogen. In various embodiments, each of R9, R10, and R11 and R12 of Formula I may be hydrogen. further,

CN 110012669 A In formula HI (and formula IV, VI, VI, VΠ, VΠI, IX), it should be understood that the "bottom" Cp ligand (ie, the "CP1" mentioned in Table 1) includes R8 to The "top" Cp ligand (ie, "CP2") contains R1 to R3 as shown in formula IVTX.

[0049] In various embodiments, each of RXrRrII and O of Formula I may be hydrogen. For example, in some embodiments, the polymerization catalyst of Formula I may further include the following zoxocene catalyst:

[0050]

<img file="CN110012669A_D0004.tif" />

(Formula VIII); (Formula IX)

[0052] That is, in various embodiments, the polymerization catalyst of Formula I may include the polymerization catalyst of Formula IV, V, VI, Vn, Vin, IX, or a combination thereof. But the present disclosure is not limited to this. On the contrary, various components of formula IV, V, VI, VΠ, VΠI, IX can be added, removed, and/or changed. For example, although formulas IV, V, VI, VΠ, VΠI, and IX each show M as a wrong atom, it should be understood that X can be changed, for example, can be changed to be selected from the group 3 to 12 atoms and indium elements Different compounds of atoms and other possible atoms. As shown in the formula Ν pine, gui a11a111 and combination, in various embodiments, each of Jia, 1~2, and 1~3 may be hydrogen.

[0053] In some embodiments, adjacent R- groups may be combined to form a ring. For example, R5 and R6 of formula I can form a cycloalkyl group together, such as cyclohexyl-1,1,4,4-tetramethyl, and other possible combinations of adjacent R1 to R12 of formula I and/or other possibilities Type of ring.

[0054] In some embodiments, each of R7 and R4 may independently be a C1 to C20 alkyl group. For example, R8 is C1 to C20 alkyl and/or C1 to C3 alkyl and other possible groups.

[0055] In some embodiments, each of R, R2, R3 of Formula III is hydrogen. Similarly, in some embodiments, each of R5 and R6 of Formula III is hydrogen. As mentioned above, in some embodiments, the metallocene catalyst of Formula I may be titanium, aluminum, or aluminum.

[0056] As mentioned above, the polymerization catalyst of Formula I may be included in a bimodal polymerization catalyst system, which further includes a non-metallocene catalyst. The non-metallocene olefin polymerization catalyst may be a catalyst compound containing a group 15 metal. That is, the bimodal polymerization catalyst system may include one or more Group 15 metal-containing catalyst compounds. As used herein, these are referred to as non-metallocene fluorinated polymerization catalyst compounds. The group 15 metal-containing compound usually contains a group 3 to 14 metal atom, a group 3 to 7 or a group 4 to 6 metal atom. In many embodiments, the Group 15 metal-containing compound comprises a Group 4 metal atom bonded to at least one leaving group and also bonded to at least two Group 15 atoms, at least one of which is also bonded through another group To the 15th or 16th group of atoms.

[0057] In one or more embodiments, at least one of the 15th group atoms is also bonded to the 15th or 16th group atoms through another group, and the other group may be a Q to C20 Huang group, containing Heteroatomic groups, silicon, aluminum, tin, lead, or phosphorus, where the group 15 or 16 atom may not be bonded to any substance or bonded to hydrogen, group 14 atom-containing group, halogen or heteroatom-containing group And each of the two Group 15 atoms is also bound to a cyclic group, and may optionally be bound to hydrogen, halogen, heteroatom or phosphorous or heteroatom-containing groups.

[0058] Compounds containing Group 15 metals can be more specifically described by structure (X) or (XI):

R¹-Y, \

[0059] _R3-"------MⁿX_n+m^R3One bite\ /M^Xn+E |\zI'

R5 (X) R⁵(XI)

[0060] Wherein M is a transition metal of Groups 3 to 12 or a Group 13 or 14 main group metal, a Group 4, 5 or 6 metal. In many embodiments, M is a Group 4 metal such as aluminum, titanium or aluminum. Each X is independently a leaving group such as an anionic leaving group. The leaving group can contain hydrogen, alkyl, heteroatom, halogen or alkyl; y is. Or 1 (when y is ., the group L'does not exist). The term'η' is the oxidation state of M. In various embodiments, n is +3, +4, or +5. In many embodiments, n is +4. The term m represents the formal charge of the YZL or YZL' ligand, and in various embodiments is 0, -1, -2, or -3. In many embodiments, m is -2°L is a group 15 or 16 element such as nitrogen or oxygen; L'is a group containing a group 15 or 16 element or group 14 such as carbon, silicon or aluminum . Y is a group 15 element such as nitrogen or phosphorus. In many embodiments, Y is nitrogen. Z is a group 15 element such as nitrogen or phosphorus. In many embodiments, Z is nitrogen. R1 and Rz are independently a C1 to C20 yellow group, a heteroatom-containing group containing up to twenty carbon atoms, silicon, aluminum, tin, lead, or phosphorus. In many embodiments, R1 and R2 are C2 to C20 alkyl, aryl or aralkyl groups, such as linear, branched or cyclic C2 to C20 alkyl groups or C2 to C6 yellow groups. R1 and R2 can also be interconnected. R3 can be absent, or can be a phosgene, hydrogen, halogen, heterogeneous A group of atoms. In many embodiments, for example, if L is oxygen, or hydrogen, or a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, then R3 is not present. R4 and R5 are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a polycyclic ring system, It usually has up to 20 carbon atoms. In many embodiments, R4 and R5 have between 3 and 10 carbon atoms, or are C1 to C20 yellow, C1 to C20 aryl, or C1 to C20 aralkyl or heteroatom-containing groups. R4 and R5 can be interconnected. R6 and R7 are independently absent and are hydrogen, alkyl, halogen, heteroatom or alkyl, such as linear, cyclic or branched alkyl having 1 to 20 carbon atoms. In many embodiments, R6 and R7 are not present. R* may be absent, or may be hydrogen, a group containing a group 14 atom, a halogen, or a group containing a heteroatom.

[0061] "The formal charge of the YZL or YZL' ligand" means the charge of the entire ligand without the metal and the leaving group X. "R1 and R2 can also be interconnected" means that R1 and R2 can be directly bonded to each other or can be bonded to each other through other groups "R4 and R5 can also be interconnected" means that R4 and R5 can be directly bonded to each other or can be bonded to each other through Other groups are bonded to each other.

[0062] In one or more embodiments, R4 and R5 are independently groups represented by the following structure (XII).

R^,z

[0063]

<img file="CN110012669A_D0005.tif" />

Bound to Z or Υ (χ_Π)

[0064] When R4 and R5 are independently alkyl, aryl, substituted aryl, cyclic alkyl, substituted cyclic alkyl, cyclic aralkyl, substituted cyclic aralkyl or Polycyclic systems usually have up to 20 carbon atoms. In many embodiments, R4 and R5 have between 3 and 10 carbon atoms, or are C1 to C20 yellow, C1 to C20 aryl, or C1 to C20 aralkyl or heteroatom-containing groups. R4 and R5 can be interconnected, and R8 to R8 are each independently hydrogen, C1 to C40 alkyl, halide, heteroatom, heteroatom-containing group containing up to 40 carbon atoms. In many embodiments, R8 to R12 are C1 to C20 linear or branched alkyl groups such as methyl, ethyl, propyl or butyl. Any two of the R groups may form a cyclic group and/or a heterocyclic group. The cyclic group may be aromatic. In one embodiment, R9, R1°, and R12 are independently methyl, ethyl, propyl, or butyl (including all isomers). In another embodiment, R9, R1°, and R12 are methyl, and R8 and R11 are hydrogen.

[0065] In one or more embodiments, both R4 and R5 are groups represented by the following structure (XIII).

[0066]

<img file="CN110012669A_D0006.tif" />

[0067] (XIII) When R4 and R5 follow the structure (XIII), M is a Group 4 metal such as aluminum, titanium or aluminum. In many embodiments, M is wrong. Each of L, Y, and Z may be nitrogen. Each of Ri and R2 may be -CH2-CH2-0R3 may be hydrogen, and R6 and R7 may not be present.

[0068] The bimodal polymerization catalyst system may include a catalyst component in a slurry, which may have an initial catalyst compound and an added solution catalyst component added to the slurry. Generally, depending on the solubility, the non-metallocene polymerization catalyst will be supported in the initial slurry. However, in some embodiments, the initial catalyst component slurry may contain no catalyst but may have an activator or support. In this case, two or more solution catalysts may be added to the slurry so that each solution catalyst is supported.

[0069] Any number of combinations of catalyst components can be used in the embodiments. For example, the catalyst component slurry may include an activator and a carrier or supported activator. In addition, in addition to the activator and the support, the slurry may contain a catalyst compound. As stated, the catalyst compound in the slurry can be supported.

[0070] The slurry may contain one or more activators and supports and one or more catalyst compounds. For example, the slurry may include two or more activators (such as aluminoxane and modified aluminoxane) and a catalyst compound, or the slurry may include a supported activator and more than one catalyst compound. In one embodiment, the slurry includes a support, an activator, and two catalyst compounds. In another embodiment, the slurry contains a support, an activator, and two different catalyst compounds

It can be added to the slurry alone or in combination. The slurry containing silica and aluminoxane can be contacted with a catalyst compound, allowed to react, and thereafter the slurry can be contacted with another catalyst compound, for example, in a fine-tuning system.

[0071] The molar ratio of the metal in the activator to the metal in the catalyst compound in the slurry may be 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. The slurry can include a support material, which can be any inert particulate support material known in the art, including but not limited to silica, fumed silica, alumina, clay, talc, or other support materials such as those described above. In one embodiment, the slurry contains silica and an activator, such as methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), as discussed further below.

[0072] One or more diluents or carriers can be used to promote the combination of any two or more components of the catalyst system in the slurry or in the fine-tuned catalyst solution. For example, a single-site catalyst compound and activator can be combined in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture to provide a catalyst mixture. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. The dry or mixed with toluene support can then be added to the catalyst mixture, or the catalyst/activator mixture can be added to the support.

[0073] The catalyst is not limited to a slurry arrangement, as the mixed catalyst system can be made on a support and dried. The dried catalyst system can then be added to the reactor through a dry feed system.

[0074] As used herein, the terms "support" and "support" are used interchangeably and refer to any support material, including porous support materials such as talc, inorganic oxides, and inorganic chlorides. One or more single-site catalyst compounds of the slurry can be supported on the same or a separate support together with the activator, or the activator can be used in an unsupported form, or can be deposited on a carrier different from the single-site catalyst compound Above or any combination thereof. This can be achieved by any technique commonly used in the art. Various other methods exist in the art for supporting single-site catalyst compounds. The single-site catalyst compound of the slurry can be spray dried. The support used with the single-site catalyst compound can be functionalized, or at least one substituent or leaving group can be selected. The carrier material can be any conventional carrier material.

[0075] Preferably, the support material is a porous support material, such as talc, inorganic oxide or inorganic chloride. Other carrier materials include resin carrier materials (for example, polystyrene), functionalized or cross-linked organic carriers, such as polystyrene, divinylbenzene, polyolefin or polymer compounds, zeolite, clay, or any other organic or inorganic carrier materials, etc. , Or a mixture thereof.

[0076] The preferred support material is an inorganic oxide containing a Group 2, 3, 4, 5, 13 or 14 metal oxide. Preferred supports include silica, fumed silica, alumina (WO 99/60033), silica-alumina and mixtures thereof. Other useful supports include magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride (US Patent No. 5,965,477), montmorillonite (European Patent EP-Bl 0 5 11 665), phyllosilicate, zeolite, talc, clay (US Patent No. 6,034,187) etc. Moreover, a combination of these support materials, for example, silica-magnet, silica-alumina, silica-titania, and the like can be used. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 Bl.

[0077] Other carrier materials include nanocomposites as described in PCT WO 99/47598, aerogels as described in WO 99/48605, spherulites as described in U.S. Patent No. 5,972,510, and as described in WO 99/ The polymer beads described in 50311. An example of a suitable carrier is available under the trade name Cabosi1^TM Fumed silica obtained from TS-610, or other TS or TG series carriers available from Cabot Corporation. Fumed silica is usually silica with particles of 7 to 30 nanometers in size, which has been treated with dimethylsilyl dichloride (ie, dichlorodimethylsilane) so that most of the surface hydroxyl groups are sealed end.

[0078] It is generally preferred that the support material, preferably the inorganic oxide, has a surface area of 10 to 700 meters per gram (m/g) and a pore volume of 0.1 to 4.0 cm.³/g, and the average particle size is in the range of 5 to 500um. More preferably, the surface of the carrier material

The product is in the range of 50 to 500m/g, and the pore volume is 0.5 to 3.5cm³/g, and the average particle size is 10 to 200um. Most preferably, the surface area of the support material is in the range of 100 to 400 m/g, and the pore volume is 0.8 to 3.0 cm³/g, and the average particle size is 5 to 100um.

[0079] The support material can be chemically treated, for example with a fluoride compound as described in WO 00/12565. Other supported activators are described in, for example, WO 00/13792, which relates to supported boron-containing solid acid complexes.

[0080] In the method of forming the components of the supported catalyst composition, the amount of liquid in which the activator is present is less than four times the pore volume of the support material, more preferably less than three times, even more preferably less than two times; preferably The range is a range of 1.1 times to 3.5 times, and most preferably, a range of 1.2 to 3 times. In another embodiment, the amount of liquid in which the activator is present is one to less than one time the pore volume of the support material used to form the supported activator. Procedures for measuring the total pore volume of porous supports are well known in the art.

[0081] As used herein, the term "activator" can refer to any compound or combination of compounds, supported or unsupported, which can activate a single-site catalyst compound or component, such as by generating a cationic species of the catalyst component . For example, this may include extracting at least one leaving group (the "X" group in the single-site catalyst compound described herein) from the metal center of the single-site catalyst compound/component. The activator may also be referred to as a "co-catalyst."

[0082] For example, the activator may include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or any other compound including a Lewis base, an aluminum alkyl, and/or a conventional cocatalyst. In addition to the methylaluminoxane ("MAO") and modified methylaluminoxane ("MMAO) mentioned above, illustrative activators may include, but are not limited to, aluminoxane or modified aluminoxane , And/or ionizing compounds, neutral particles or ions, such as tris (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, trisperfluorophenyl boron non-metallic precursors, trisperfluoro zeyl boron non-metallic precursors Body or any combination thereof.

[0083] Aluminoxanes can be described as oligomeric aluminum compounds having -Al(R)-O-subunits, where R is an alkyl group. Examples of aluminoxanes include, but are not limited to, MAO, MMAO, ethyl aluminoxane, isobutyl aluminoxane, or a combination thereof. Aluminoxanes can be produced by the hydrolysis of the corresponding trialkylaluminum compounds. MMAO can be produced by the hydrolysis of trimethylaluminum and higher trialkylaluminum such as triisobutylaluminum. MMAO is generally more soluble in aliphatic solvents and more stable during storage. There are various methods for preparing aluminoxanes and modified aluminoxanes.

[0084] As described above, one or more organoaluminum compounds such as one or more alkyl aluminum compounds may be used in combination with aluminoxane. For example, aluminum alkyl materials that can be used are diethyl aluminum ethoxide, diethyl aluminum chloride and/or diisobutyl aluminum hydride. Examples of trialkyl aluminum compounds include, but are not limited to, trimethyl aluminum, triethyl aluminum ("TEAL"), triisobutyl aluminum (TiBAl"), tri-n-hexyl aluminum, tri-n-octyl aluminum, tripropyl Aluminum, tributyl aluminum, etc.

[0085] The bimodal catalyst system may include only a catalyst compound such as a chalcocene, or may include an activator in addition to the catalyst compound. The bimodal catalyst system used in the fine-tuning process can be prepared by dissolving the catalyst compound and optional activator in a liquid solvent. The liquid solvent may be an alkane such as a C5 to C30 alkane, or a C5 to C10 alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene can also be used. In addition, mineral oil is used as a solvent. The solution used should be liquid under the conditions of the feed to the polymerization reactor and relatively inert. In one embodiment, the liquid used in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid used in the catalyst compound solution is the same as the diluent used in the bimodal catalyst system.

[0086] If the bimodal catalyst system includes both an activator and a catalyst compound, the ratio of the metal in the activator to the metal in the catalyst compound in the solution may be 1000:1 to 0.5:1, 300:1 to 1: 1 or 150:1 to 1:1. In various embodiments, based on the weight of the solvent and activator or catalyst compound, the activator and catalyst compound are present in the solution as follows: up to 90wt.%, up to 50wt.%, up to 20wt.%, more Up to 10wt.%, up to 5wt.%, less than

Iwt.% or between 100ppm and Iwt.%.

[0087] The catalyst component solution may include any of the soluble catalyst compounds described in the catalyst section herein. When the catalyst is dissolved in the solution, higher solubility can be expected. Therefore, the catalyst compound in the catalyst component solution may generally contain a metallocene which may have a higher solubility than other catalysts.

[0088] In the polymerization method described below, any of the above-mentioned catalyst component-containing solutions may be combined with any of the above-mentioned catalyst component-containing slurry (slurry/slurries). In addition, more than one catalyst component solution can be used.

[0089] In gas phase polyethylene production methods, it may be desirable to use one or more static control agents to help regulate the level of static in the reactor. As used herein, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can affect or drive the static charge (negative, positive, or zero) in the fluidized bed. The specific static control agent used may depend on the nature of the static charge, and the choice of non-destatic control agent may vary according to the polymer produced and the single-site catalyst compound used.

[0090] Control agents such as aluminum stearate can be used. The static control agent used can be selected because it can receive static electricity in the fluidized bed without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and antistatic compositions, such as those provided by Innospec Inc. under the trade name OCTASTAT. For example, OCTASTAT 2000 is a mixture of polyblock copolymers, polymerized polyamines and oil-soluble sulfonic acids.

[0091] The above-mentioned control agent and other control agents can be used alone or in combination as a control agent. For example, a metal carboxylate salt can be combined with an amine-containing control agent (e.g., a metal carboxylate salt and belongs to KEMAMINE® (available from Crompton Corporation) or ATMER® (available from ICI Americas Inc. (ICI Americas Inc.) ) To obtain) any series member) combination of the product series.

[0092] Other useful continuity additives include ethyleneimine additives useful in the embodiments disclosed herein, which may include polyethyleneimine having the following general formula:

[0093]-(CH2-CH2-NH) plant, where n can be 10 to 10,000. Polyethyleneimine can be linear, branched, or hyperbranched (for example, forming a dendritic or dendritic polymer structure). It may be a homopolymer or copolymer of ethyleneimine or a mixture thereof (hereinafter referred to as polyethyleneimine). Although linear polymers represented by the chemical formula -[CH2YH2-NH]- can be used as polyethyleneimine, materials having primary, secondary, and tertiary branches can also be used. Commercial polyethyleneimine may be a compound having a branched chain of an ethyleneimine polymer.

[0094] Suitable polyethyleneimine is commercially available from BASF Corporation (BASF Corporation) under the trade name Lupasol. These compounds can be prepared in various molecular weights and product activities. Examples of commercial polyethyleneimines sold by BASF suitable for use in the present invention include, but are not limited to, Lupasol FG and Lupasol WF.

[0095] Another useful continuity additive may comprise a mixture of aluminum distearate and an ethoxylated amine compound, for example, IRGASTAT available from Huntsman (previously Ciba Specialty Chemicals) AS-990. The mixture of aluminum distearate and ethoxylated amine compounds can be slurried in mineral oil, for example, Hydrobrite 380. For example, a mixture of aluminum distearate and ethoxylated amine compounds can be slurried in mineral oil to have a total slurry concentration in the following range: 5wt.% to 50wt.%, or 10wt.% to 40wt. % Or 15wt.% to 30wt. %. Other static control agents and additives are also suitable.

[0096] One or more continuity additives or one or more static control agents may be added to the reactor in an amount of 0.05 to 200 Ppm based on the weight of all the feeds entering the reactor without recycling. In some embodiments, the continuity additive may be added in an amount of 2 to 100 ppm or in an amount of 4 to 50 Ppm.

[0097] One or more of the bimodal polyethylene disclosed herein can be carried out in the presence of a bimodal catalyst system.

Prepared by polymerization, the bimodal catalyst system contains bis(2-(2,4,6-trimethylphenylamido)ethyl)amine diphenyl aluminum. In one or more of the bimodal polyethylenes disclosed herein, the high-molecular-weight and low-molecular-weight polyethylene components may be formed by polymerization in the presence of a bimodal catalyst system, the bimodal catalyst system comprising bis(2 -(Pentamethylphenylamido)ethyl)amine diphenyl aluminum. In one or more of the bimodal polyethylenes disclosed herein, the high-molecular-weight and low-molecular-weight polyethylene components may be formed by polymerization in the presence of a bimodal catalyst system comprising (Five Cyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride or (pentamethylcyclopentadienyl) (n-propylcyclopentadienyl) dimethyl zirconium. In one or more of the bimodal polyethylenes disclosed herein, the high-molecular-weight and low-molecular-weight polyethylene components may be formed by polymerization in the presence of a bimodal catalyst system that contains bimodal Butylcyclopentadienyl) zirconium dichloride or bis(n-butylcyclopentadienyl) dimethyl zirconium.

[0098] One or more of the bimodal polyethylenes disclosed herein can also be prepared by polymerization in the presence of a bimodal catalyst system, the bimodal catalyst system comprising a molar ratio of 3.0:1 bis(2- (Pentamethyl phenyl amido) ethyl) amine diphenyl zirconium and (tetramethyl cyclopentadienyl) (n-propyl cyclopentadienyl) zirconium dichloride or (tetramethyl cyclopentadienyl) Alkenyl) (n-propyl cyclopentadienyl) dimethyl zirconium and (tetramethyl cyclopentadienyl) (n-propyl cyclopentadienyl) dimethyl zirconium fine-tuning catalyst. (Tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) dimethylzinc trimming catalyst may be present in an alkane solvent, which is added to the alkane solvent to adjust the melt flow ratio of the bimodal polyethylene. The bimodal polyethylene formed using this combination of catalysts can be formed using a single reactor as provided herein. Alkane solvents have 3 to 7 carbon atoms and may be branched or straight chain. Examples of the alkane solvent include hexane, isopentane, and isobutane.

[0099] The polymerization method used to form any bimodal polyethylene described herein can be carried out using any suitable method, for example, high pressure, solution, slurry and gas phase methods using known equipment and reaction conditions, and is not limited to any A specific type of aggregation system. Generally, the polymerization temperature can be 0 to 300C under atmospheric pressure, subatmospheric pressure or superatmospheric pressure. Specifically, the slurry or solution polymerization system can adopt sub-atmospheric or super-atmospheric pressure, and the temperature range is 40 to 300C.

[0100] The present disclosure is not limited to any particular type of fluidization or gas phase polymerization reaction, and can be performed in a single reactor or multiple reactors, such as two or more reactors in series. In the embodiments, the present invention can be carried out in a fluidized bed polymerization (which can be mechanical stirring and/or gas fluidization), or with those utilizing gas phase similar to those described herein. In addition to the well-known conventional gas-phase polymerization method, the "condensation mode" including the "induced condensation mode" of the gas-phase polymerization and the "liquid monomer" operation may be used, which is also within the scope of the present invention.

[0101] Embodiments may employ condensation mode polymerization, as disclosed in U.S. Patent Nos. 4,543,399; 4,588,790; 4,994,534; 5,352,749; 5,462,999; and 6,489,408. The condensing mode method can be used to achieve higher cooling capacity and therefore higher reactor productivity. In addition to the condensable fluid of the polymerization process itself, other condensable fluids that are inert to polymerization can be introduced to initiate condensation mode operation, such as by the method described in US Patent No. 5,43,6,304.

[0102] In some embodiments, liquid phase polymerization systems can be used, such as those described in US Patent No. 3,324,095. The liquid phase polymerization system generally includes a reactor to which the olefin monomer and the catalyst composition are fed. The reactor contains a liquid reaction medium, which can dissolve or suspend the polyolefin product. The liquid reaction medium may include inert liquid hydrocarbons, bulk liquid monomers, or mixtures thereof that do not react under the polymerization conditions used. Although this inert liquid hydrocarbon may not serve as a solvent for the catalyst composition or the polymer obtained by this method, it usually serves as a solvent for the monomer used in the polymerization. Inert liquid hydrocarbons suitable for this purpose may include isobutane, isopentane, hexane, cyclohexane, isohexane, heptane, octane, benzene, toluene, and mixtures and isomers thereof. The reactive contact between the olefin monomer and the catalyst composition can be maintained by continuous stirring or stirring. The liquid reaction medium containing the olefin polymer product and unreacted olefin monomer is continuously removed from

Take it out of the reactor. The olefin polymer product is separated, and the unreacted olefin monomer and liquid reaction medium are generally recycled and fed back into the reactor.

[0103] Some embodiments of the present disclosure may be particularly applicable to gas phase polymerization systems at the following superatmospheric pressure and temperature: the superatmospheric pressure is in the range of 0.07 to 68.9 bar (1 to 1000 sig), in some embodiments 3.45 to 27.6 bar (50 to 400 sig), in other embodiments 6.89 to 24.1 bar (100 to 350 psig), and the temperature is in the range of 30 to 130°C, or 65 to 110°C, in other embodiments The range of 75 to 120°C or the range of 80 to 120°C in other embodiments. In some embodiments, the operating temperature may be lower than 112C. Stirred or fluidized bed gas phase polymerization systems can be used in the examples.

[0104] Bimodal polyethylene can be made using a gas phase polymerization method, for example, using a fluidized bed reactor. This type of reactor and the equipment used to operate the reactor are well known and fully described in the following, for example, U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541, 270; EP -A-0 802 202 and Belgian patent number 839,380. These patents disclose gas phase polymerization methods in which the polymerization medium is mechanically stirred or fluidized by continuous flow of gaseous monomer and diluent.

[0105] Other contemplated gas phase processes include series or multi-stage polymerization processes. Examples include U.S. Patent Nos. 5,627,242, 5,665,818, and 5,677,375 and European publications EP-A-0 794 200, EP-B 1-0 649 992, EP-A-0 802 202, and EP-B-634421.

[0106] The polymerization method can be performed as a continuous gas phase method such as a fluidized bed method. The fluidized bed reactor may include a reaction zone and a so-called velocity reduction zone. The reaction zone may include a bed of growing polymer particles, formed polymer particles, and a small amount of catalyst particles that are fluidized by continuous flow of gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, some of the recycled gas may be cooled and compressed to form a liquid, which increases the heat removal capacity of the recycled gas stream when it enters the reaction zone again. The appropriate gas flow rate can be easily determined through simple experiments. The rate of replenishing gaseous monomer into the circulating gas stream is equal to the rate at which the particulate polymer product and related monomers are removed from the reactor, and the composition of the gas passing through the reactor is adjusted to maintain a substantially steady state in the reaction zone Gaseous composition. The gas leaving the reaction zone passes through the velocity reduction zone where entrained particles are removed. Optionally, finer entrained particles and dust can be removed in a cyclone and/or fine filter. The gas is passed through a heat exchanger where the heat of polymerization is removed, compressed in a compressor, and then returned to the reaction zone.

[0107] The reactor temperature of the fluidized bed method herein is preferably 30°C or 40°C or 50°C to 90°C or 100°C or 110C or 120C. Generally, considering the sintering temperature of the bimodal polyethylene product in the reactor, the reactor temperature is operated at the highest possible temperature. Regardless of the method used to make the bimodal polyethylene of the present invention, the polymerization temperature or reaction temperature should be lower than the melting or "sintering" temperature of the bimodal polyethylene to be formed. Therefore, in one embodiment, the upper temperature limit is the melting temperature of the bimodal polyethylene produced in the reactor.

[0108] Slurry polymerization methods can also be used. Slurry polymerization methods generally use pressures ranging from 1 to 50 atmospheres or even higher and temperatures ranging from 0°C to 120C, and more specifically 30°C to 100C. In slurry polymerization, a suspension of solid particulate polymer is a reaction product formed in a liquid polymerization diluent medium to which ethylene and comonomer are added, and hydrogen and a catalyst are usually added. The suspension containing the diluent is removed from the reactor intermittently or continuously, wherein the volatile components are separated from the polymer and optionally recycled to the reactor after distillation. The liquid diluent used in the polymerization medium is usually an alkane having 3 to 7 carbon atoms, and in one embodiment is a branched chain alkane. The medium used should be liquid and relatively inert under the polymerization conditions. When using a propane medium, the method must be operated above the critical temperature and pressure of the reactive diluent. In one embodiment, a hexane, isopentane or isobutane medium is used.

[0109] Particle form polymerization is also useful, which is a method in which the temperature is kept below the temperature at which the bimodal polyethylene enters the solution. Other slurry methods include those using loop reactors and those using multiple stirred reactors in series, parallel, or a combination thereof. Non-limiting examples of slurry methods include continuous loop or stirred tank methods. Also, other examples of the slurry process are described in U.S. Patent Nos. 4,613,484 and 2 metallocene-based polyolefin 322-332 (2000).

[0110] These methods can be used to produce bimodal polyethylene. Preferably, the olefin is ethylene, and optionally, a comonomer comprising 3 to 7 carbon atoms. Particularly preferred is polyethylene. This polyethylene is preferably a homopolymer of ethylene and a copolymer of ethylene and at least one alpha olefin, wherein the ethylene content is at least about 50% by weight of the total monomers involved. Exemplary olefins useful herein are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and the like. Polyenes such as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, and olefins formed in situ in the polymerization medium can also be used herein. When olefins are formed in situ in the polymerization medium, the formation of polyolefins containing long chain branching may occur.

[0111] In the production of bimodal polyethylene, comonomers may be present in the polymerization reactor. When present, the comonomer can be present with the ethylene monomer at any level that will achieve the desired weight percentage of the comonomer incorporated into the bimodal polyethylene. In one embodiment of bimodal polyethylene, the molar ratio of comonomer and ethylene is in the range of 0.0001 (comonomer: ethylene) to 50, and in another embodiment, 0.0001 to 5, and in another In one embodiment, it is 0.0005 to 1.0, and in yet another embodiment, it is 0.001 to 0.5. Expressed in absolute values, when making bimodal polyethylene, the range of the amount of ethylene present in the polymerization reactor can be up to 1000 atmospheres in one embodiment, and up to 500 atmospheres in another embodiment, and Up to 200 atmospheres in yet another implementation, and up to 100 atmospheres in yet another implementation, and up to 50 atmospheres in yet another embodiment.

[0112] Hydrogen is generally used in olefin polymerization to control the final properties of polyolefins, as described in "Polypropylene Handbook", 76-78 (Hanser Publishers, 1996). With certain catalyst systems, increasing the concentration (partial pressure) of hydrogen can increase the melt flow rate (MFR) (also referred to herein as melt index (MI)) of the produced polyolefin. Therefore, MFR or MI may be affected by the concentration of hydrogen. The amount of hydrogen in the polymerization can be expressed as a molar ratio relative to the total polymerizable monomers, for example, ethylene, or a blend of ethylene and hexene, propylene, pentene, and mixtures thereof. The amount of hydrogen used in the polymerization method of the present invention is the amount required to achieve the desired MFR or MI of the final polyolefin resin. In one embodiment, the molar ratio of hydrogen to total monomers (H2 monomers) is greater than 0.0001 in one embodiment, and greater than 0.0005 in another embodiment, and greater than 0.001 in yet another implementation, and In yet another embodiment, less than 10, and in yet another embodiment, less than 5, and in yet another embodiment, less than 3, and in yet another embodiment, less than 0.10, where the desired range may include this Any combination of the upper limit of any molar ratio and the lower limit of any molar ratio. In other words, the amount of hydrogen in the reactor at any time can be In the following range: up to 5000Pm, and up to 4000Pm in another embodiment, and up to 3000Pm in yet another embodiment, and between 50Pm and 5000Pm in yet another embodiment, and in yet another embodiment In another embodiment, it is between 500Pm and 2000Pm.

[0113] The pressure of one or more reactors (single reactor or two or more reactors) in the gas phase process can be: from 100 sig (690 kPa) to 500 sig (3448 kPa), and in another embodiment The range of 200Psig (1379kPa) to 400Psig (2759kPa), and in yet another embodiment is in the range of 250Psig (1724kPa) to 350Psig (2414kPa).

[0114] A gas phase reactor employing the catalyst system described herein can produce polymers in the following yields: 500 lbs (227Kg/hr) per hour to 00,000 lbs/hr (90,900Kg/hr), and in another example Is greater than 1000lbs/hr (455Kg/hr), and in yet another embodiment is greater than 10,000lbs/hr (4540Kg/hr), and in yet another

More than 25,000 lbs/hr (11,300Kg/hr) in an embodiment, and in yet another embodiment more than 35,000 lbs/hr (15,900Kg/hr), and in yet another embodiment, more than 50,000 lbs/hr (22,700 Kg/hr), and in yet another embodiment, from 65,000 lbs/hr (29,000 Kg/hr) to U100,000 lbs/hr (45,500 Kg/hr).

[0115] The methods disclosed herein may optionally use inert particulate materials as fluidization aids. These inert particulate materials may include carbon black, silica, talc and clay, and inert polymer materials. For example, the primary particle size of carbon black is 10 to 100 nanometers, the average size of aggregates is 0.1 to 30 microns, and the specific surface area is 30 to 1500 m.²/g. The primary particle size of silica is 5 to 50 nanometers, the average size of aggregates is 0.1 to 30 microns, and the specific surface area is 50 to 500 m²/ g. The average particle size of clay, talc and polymer materials is 0.01 to 10 microns, and the specific surface area is 3 to 30m²/g. The amount of these inert particulate materials can be 0.3% to 80% or 5% to 50% based on the weight of the final product.

[0116] Chain transfer agents, accelerators, scavengers, and other additives can and are commonly used in the polymerization methods disclosed herein. Chain transfer agents are commonly used to control polymer molecular weight. Examples of these compounds are hydrogen and metal alkyls with the general formula MxRy, where M is a metal from groups 3 to 12, and x is the oxidation state of the metal, usually 1, 2, 3, 4, 5 or 6, each R Is independently an alkyl group or an aryl group, and y is 0, 1, 2, 3, 4, 5, or 6. In some embodiments, alkyl zinc such as diethyl zinc is used. Typical accelerators may include halogenated hydrocarbons such as CHC13, CFC13, CH3-CC13, CF2C1CC13, and ethyl trichloroacetate. Such promoters are well known to those skilled in the art, and are disclosed in, for example, U.S. Patent No. 4,988,783. Other organometallic compounds, such as scavengers for poisons, can also be used to increase catalyst activity. Examples of these compounds include metal alkyls such as aluminum alkyls, for example, triisobutyl aluminum. Some compounds can be used to neutralize static electricity in fluidized bed reactors, and other compounds called drivers rather than antistatic agents can always force static electricity from positive to negative or from negative to positive. The use of these additives is completely within the skill of those skilled in the art. If these additives are solid, they can be added to the circulation loop, riser and/or descender alone or independently of the liquid catalyst, or as part of the catalyst, as long as they do not interfere The desired atomization. In order to be part of the bimodal catalyst system, the additives should be liquid or capable of being dissolved in the bimodal catalyst system.

[0117] The slurry or gas phase process can be carried out in the presence of a metallocene-type catalyst system, and is not present or substantially free of such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylaluminum and two Any scavengers such as ethyl aluminum chloride, dibutyl zinc, etc. are "essentially free" meaning that these compounds are not intentionally added to the reactor or any reactor components, and if present, the content in the reactor is less than 1 ppm.

[0118] As described in the examples herein, the appropriate selection of the bimodal catalyst system and the ratio of the catalyst used can be used to adjust the molecular weight distribution of the HMW and LMW components of the bimodal polyethylene of the present invention. The HMW and LMW components can be controlled by combining catalysts that have a suitable weight average molecular weight (Mw) and combine to form a comonomer under polymerization conditions. This can be adjusted during the formation of the bimodal catalyst, for example, by supporting both catalysts on a single support. In some embodiments, the relative amount of the catalyst can be adjusted by adding one of the components to the polymerization catalyst and/or the catalyst mixture, such as the bimodal polymerization catalyst on the way into the reactor in a process called "fine tuning" system. Feedback of polymer property data can be used to control the amount of catalyst added.

[0119] Using multiple catalysts co-supported on a single carrier mixed with an activator, such as silica methylaluminoxane (SMAO), to produce products in one reactor instead of multiple reactors can also provide cost advantages . Further, the use of a single support also facilitates the intimate mixing of polymers, and provides improved operability relative to preparing a mixture of polymers of different Mw and density in a single reactor independent of multiple catalysts.

[0120] The properties of the bimodal polyethylene of the present disclosure can be adjusted by adjusting the mixing time, temperature, and concentration of the solution, slurry, and any optionally added materials (nucleating agent, catalyst compound, activator, etc.) as described above. And order to control. Molecular weight

The distribution, melt index, relative amount of polymer produced by each catalyst, and other properties of the polymer produced can also be changed by manipulating process parameters. Any number of process parameters can be adjusted, including manipulating the hydrogen concentration in the polymerization system, changing the amount of the first catalyst in the polymerization system, and/or changing the amount of the second catalyst of the bimodal catalyst system in the polymerization system. Other process parameters that can be adjusted include changing the relative ratio of the catalysts of the bimodal catalyst system during the polymerization process (and optionally adjusting their respective feed rates to maintain a stable or constant polymer production rate). The concentration of reactants in the reactor can be adjusted by: changing the amount of liquid or gas extracted or removed from the process, changing the amount and/or composition of the recovered liquid and/or recovered gas returned to the polymerization process, where the recovered Liquid or recovered gas can be recovered from the polymer discharged during the polymerization process. Further concentration parameters that can be adjusted include changing the polymerization temperature, changing the partial pressure of ethylene during the polymerization, changing the ratio of ethylene to comonomer during the polymerization, and changing the ratio of activator to transition metal in the activation sequence. Time-related parameters can be adjusted, such as changing the relative feed rate of the slurry or solution, online changing the mixing time, temperature and/or mixing degree of the slurry and solution, and adding different types of activator compounds to the polymerization process and in the polymerization process Add oxygen or fluorobenzene or other catalyst poisons. Any combination of these adjustments can be used to control The properties of the final bimodal polyethylene product.

[0121] In one embodiment, the molecular weight distribution of the bimodal polyethylene is measured at regular intervals, and if necessary, one of the above-mentioned process parameters is changed to make the composition reach the desired level, such as temperature, catalyst compound feed rate , The ratio of two or more catalysts to each other, the ratio of comonomer to monomer, monomer partial pressure and/or hydrogen concentration. The molecular weight distribution can be measured by size exclusion chromatography (SEC), for example, gel permeation chromatography (GPC) and other techniques.

[0122] In one embodiment, the bimodal polyethylene product properties are measured online, and in response, the ratio of the combined catalyst is changed. The measured product properties can include dynamic shear viscosity, flow index melt index, density, molecular weight distribution, comonomer content, and combinations thereof. In another embodiment, when the ratio of the catalyst compound is changed, the introduction rate of the catalyst composition into the reactor or other process parameters are changed to maintain the desired production rate.

[0123] As mentioned herein, the weight average molecular weight (Mw), number average molecular weight (Mn), and Mw/Mn are determined by using high temperature gel permeation chromatography (Polymer Laboratories). The high temperature gel permeation chromatography is equipped with a differential refractive index detector (DRI). A Polymer Laboratories PLgel 10 μπι Mixed-B column was used. The nominal flow rate is 1.0mL/min, and the nominal injection volume is 300UL. Various transmission lines, columns and differential refractometers (DRI detectors) are contained in an oven maintained at 160C. . The solvent used for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent 1, 2, and 4 grades of trichlorobenzene (TCB). Then the TCB mixture is passed through 0. Um Teflon filter filter. Then use an online degasser to degas the TCB before entering the GPC instrument. By placing the dried polymer in a glass vial, add the desired amount of TCB, then at 160. . . Under continuous heating and shaking for about 2 hours to prepare a polymer solution. All quantities are measured by gravimetric method. The injection concentration is 0.5 to 2. Lower concentration is used for higher molecular weight samples. Before running each sample, clean the DRI detector. The flow rate in the device was then increased to 1.0 ml/min, and the DRI was allowed to stabilize for 8 hours before injecting the first sample. The molecular weight is determined by combining a general calibration relationship with column calibration with a series of monodisperse polystyrene (PS) standards. MW is calculated using the following formula at each elution volume:

-log( K_x / K_PA a" +11 ,,

[0124] log M r = ^Ύ + log M PS αχ +1 +ι

[0125] The variable with the subscript "X" represents the test sample, and the variable with the subscript "PS" represents the PS. In this method, aps = 0.67 and Kps = 0.000175, while ax and Κχ are obtained from published literature. Specifically, for PE, a/K = 0.695/0.000579, and for PP, 0.705/0.0002288.

[0126] The concentration c of each point in the chromatogram is calculated by subtracting the baseline DRI signal IDRI using the following equation: c =

KDRIIDRI/(dn/dc), where KDRI is a constant determined by calibrating DRI, and (dn/dc) is the refractive index increment of the system. Specifically, for polyethylene, dn/dc = 0.109.

[0127] The mass recovery is calculated from the ratio of the integrated area of the concentration chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection ring volume.

[0128] Unless otherwise stated, all molecular weights are reported in g/mol. If there is a conflict between the GPC-DRI program and "Fast GPC", the above GPC-DRI program should be used. Further details on the method of determining Mw, Mn, MWD are described in US 2006/0173123, pages 24 to 25, paragraphs [0334] to [0341]. The catalyst productivity (ie, Cat Prod) (gram polymer/gram catalyst-hour) can be determined as the ratio of the amount of polymer produced to the amount of catalyst added to the reactor. The melting temperature (ie, Tm) can be determined by differential scanning calorimetry in accordance with ASTM D 3418-08. For example, use a scan rate of 10 °C/min for a 10 mg sample and use a second heating cycle.

[0129] Bimodal polyethylene is suitable for products such as films, fibers, non-woven and/or woven fabrics, extruded products and/or molded products. Examples of films include blown or cast films formed by single-layer extrusion, co-extrusion or lamination, which can be used as shrink films, cling films, stretch films, and sealing films in food contact and non-food contact applications , Oriented film, snack packaging, heavy bags, grocery bags, baked and frozen food packaging, medical packaging, industrial linings, diaphragms, etc., agricultural films and sheets. Examples of fibers include melt spinning, solution spinning, and meltblown fiber operations, used in woven or non-woven form to make filters, diaper fabrics, sanitary products, medical clothing, geotextiles, and the like. Examples of extruded products include pipes, medical pipes, wire and cable coatings, pipes, geomembranes, and pond liners. Examples of molded articles include single-layer and multi-layer structures by injection molding or rotational molding or blow molding methods in the form of bottles, cans, large hollow products, rigid food containers, toys, and the like.

[0130] All numerical values are the values indicated by "about" or "approximately", and take into account experimental errors and variations that can be expected by those of ordinary skill in the art.

[0131] Examples

[0132] Some embodiments of the present disclosure will now be described in detail in the following embodiments. Unless otherwise stated, all materials used herein were purchased from Sigma Aldrich.

[0133] In the example, the following test procedure was used. The density is measured according to ASTM-D-1505. For the melt flow ratio (MFR, (I21/I2), I2 and I21 are measured according to ASTM-1238, condition E at 190°C. The tensile yield is measured according to ASTM D638-14. The flexural modulus is measured according to ASTM D790. Use DSC to measure oxidation-induction time (OIT), which provides a measure of degradation over time in an oxygen environment at a constant temperature. As described in the above specific embodiments, measure the weight average molecular weight (Mw), number average molecular weight (Mn) ) And Mw/Mn. Measure the Pennsylvania Notch Test (PENT) according to ASTM F1473-94.

[0134] Preparation of Bimodal Catalyst System

[0135] The following bimodal catalyst system was used to prepare the bimodal polyethylene of Example 1. Example 1 was produced using gas phase polymerization in a single reactor system, where the spray-dried catalyst system contained bis(2-pentamethylphenylamido)ethyl)amine diphenyl zirconium in a molar ratio of 3.0:1 and (Tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) zirconium dichloride. This catalyst system is commercially available from Univation Technologies Co., Ltd. (Univation Technologies, LLC) (Houston, Texas) and is sold as PRODIGY^tm Sold by Bimodal Catalysts. The reactor was also fed with a second catalyst, which was prepared by mixing 69 g (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) dimethyl zirconium in 99.8 ml of isopentane . A second catalyst is added as a catalyst fine-tuning feed during the polymerization process to adjust the flow index properties of the bimodal polyethylene. "Dry mode" is used, which means that the material is introduced in the form of dry powder (granules).

[0136] Polymerization method

[0137] The bimodal polyethylene of Example 1 was produced in a single gas phase polymerization reactor. The gas phase reactor used is a pilot

The production capacity of a large-scale continuous fluidized bed reactor is 10 to 501bs resin per hour. For the experimental run, before starting, the inside of the reactor is preloaded with a seedbed of granular resin. First, the reactor with the seedbed was dried with high-purity nitrogen under a moisture of less than 5Ppm. The reaction gas is then introduced into the reactor to establish gas phase conditions. At the same time, the reactor is heated to the desired temperature. The reactor was charged with hydrogen sufficient to produce a hydrogen to ethylene ratio of 0.006 mole ratio under the reaction conditions and hexene to produce a hexene to ethylene ratio of 0.011 mole ratio under the reaction conditions. Pressurize the reactor with ethylene (total pressure = 220 psi) and maintain the temperature at 105°C. Once the conditions are reached, the slurry catalyst is injected into the reactor. At the same time, before entering the reactor at different molar ratios ranging from 1.5 to U2.0 (Zr eight/Ziw, mol/mol), another catalyst fine-tuning feed is mixed with the main catalyst stream to fine-tune the flow index and melting Index to the target. Use about three bed inversions to achieve steady-state production of bimodal polyethylene.

[0138] Table 1 and Table 2 provide Example 1 of the bimodal polyethylene and the properties of the three commercially available polymer compositions. QHM 22F is a PERT I single reactor product available from Qilu Petrochemicals (Shandong, China). XRT70 is a high-density PERT II type polyethylene manufactured using To tai's double-ring technology, and is available from Total Petrochemicals &amp; Refining SA. Hostalen 4731B is PERT Π type polyethylene, which is available from Lyondell Basell Industries, Rotterdam, the Netherlands.

[0139] Table 1-Properties of Example 1 and Comparative Examples

[0140]

<td>sample</td><td>density</td><td>Melt Index</td><td>MFR</td><td>Tensile yield</td><td>Flexural teaching</td><td>OIT @ 210°C</td><td>PENT</td><td>PENT</td>

<td></td><td>^cm³</td><td>h</td><td>hi/h</td><td>MPa</td><td>2% second MPa</td><td>minute</td><td>@80 Ό2.4MPa Hr</td><td>@90 °C 2.4 MPa hours</td>

<td>Comparative example AC22F)</td><td>0.9383</td><td>0.68</td><td>18</td><td>18Ό5</td><td>635</td><td>683</td><td>338</td><td>197</td>

<td>Comparative example B CXRT-70)</td><td>0.948</td><td>0J3</td><td>92</td><td>23J2</td><td>856</td><td>7926</td><td>&gt;2000</td><td>&gt;2000</td>

<td>Comparative example CtHostalen 4731B)</td><td>0.9482</td><td>0J4</td><td>64</td><td>2L4</td><td>850</td><td>7431</td><td>1312</td><td>339</td>

<td>Example 1</td><td>0,9478</td><td>024</td><td>70</td><td>252</td><td>862</td><td>58</td><td>&gt;2000</td><td>&gt;2000</td>

[0141] Table 2-Molecular Weight of Example 1 and Comparative Example

<td></td><td>Mn</td><td>Mw</td><td>Mz</td><td>Mw/Mn</td>

<td>Comparative example A (22F)</td><td>39,815</td><td>134,242</td><td>287,230</td><td>3.37</td>

<td>Comparative example B (XRT70)</td><td>12,930</td><td>255,929</td><td>1,717,486</td><td>19.79</td>

<td>Comparative example C (Hostalen 4731B)</td><td>11,555</td><td>245,962</td><td>1,478,745</td><td>21.29</td>

<td>Example 1</td><td>8,347</td><td>204,720</td><td>1,322,827</td><td>24.53</td>

[0143] As seen in Table 1 and Table 2, the bimodal polyethylene of Example 1 showed excellent slow crack growth resistance as indicated by PENT, despite being produced in a single reactor. Example 1 shows a higher Mw/Mn ratio, which indicates that a wider molecular weight distribution leads to better processability and higher throughput when processed into tubes.

[0144] Regarding PENT, specific size specimens of the Pennsylvania Notch Test (PENT) were prepared for the polymers of Example 1 and Comparative Examples A to C. PENT is a laboratory-scale screening test that uses small samples to predict the resistance to slow crack growth in pipes. The sample in the form of particles of each of Example 1 and Comparative Examples A to C was compression molded to make according to ASTM standards

PENT's board. Cut three rectangular samples from the board, cut them and place them on the PENT test bench. The test is carried out at 80°C and 2.4MPa and 90°C and 2.4MPa. The results are shown in Table 1 above. PENT is a general method for predicting the life of polyethylene structures that fail due to slow crack growth. A higher PENT hour indicates a longer life of the polyethylene pipe. As can be seen from the data of Example 1 in Table 1, PENT at 80°C and 90°C exceeds 2000 hours, which is significantly higher than 90°C for PE-RT pipe resin. . And the ASTM requirement of 500 hours under 2.4MPa.

[0145] In addition, FIG. 1 shows the molecular weight distribution (MWD) curves of the bimodal polyethylene (Example 1) and Comparative Examples A to C using the SEC technique (GPC method) described herein. As shown, the curve of Example 1 shows two peaks, one of which corresponds to a relatively low molecular weight component and the other corresponds to a high molecular weight component. In contrast, each curve of Comparative Examples A to C shows an overall wide peak whose width is approximately equal to the total width of the two peaks that define Example 1.

[0146] The GPC of Example 1 uses nine Schulz-Flory distributions for deconvolution, and allocates the lowest four to the LMW part and the highest four to the HMW part. The results are as follows: Wt.% of the HMW component is equal to 59%, the number average molecular weight (Mwn) of the LMW component is 3,499, the Mwn of the HMW component is 69,214, the weight average molecular weight (Mww) of the LMW component is 9,214 and the HMW component The Mww of minutes is 333,144.

[0147] Pipeline short-term hydraulic strength test

[0148] The standardized internal pressure test of plastic pipes is listed in ISO 1167, which is titled "Thermoplastic pipes used for transporting fluids-internal pressure resistance-test method". The test specifies a method for determining the resistance to constant internal pressure at a constant temperature. The test requires that the sample be stored in an environment at a specific temperature, which can be water ("water in water" test), another liquid ("liquid in water") or air ("water in air" test).

[0149] As described in ISO 22391-2, the high temperature resistant bimodal polyethylene of Example 1 was subjected to a hydraulic pressure test following ISO 24033:2009. This test is a short-term screening hydrostatic pressure test and is carried out under three specific hydrostatic pressure conditions. The test was performed on a SDR 11 pipe with a diameter of 1 inch (25.4 mm) and a thickness of 0.12 inch (3 mm) as a "water-in-water" test. In terms of pipe length, the standard requires at least six times the outer diameter. In our example, the length of the pipe is 18 inches (457mm). [0150] The tube sample was formed of the high temperature resistant bimodal polyethylene of Example 1. The tube sample undergoes three internal pressure conditions at two temperatures. Table 3 shows the test results of the short-term hydrostatic strength test of the tube sample made of the high temperature resistant bimodal polyethylene of Example 1. In all cases, the high temperature resistant bimodal polyethylene of Example 1 far exceeds the failure time standards of PE-RT specified in ISO 22391 -2 and ISO 24033.

[0151] Table 3-Static Water Pipeline Test

[0152]

<td>temperature</td><td>Hoop stress</td><td>ISO model requirements for ductile failure</td><td>Example 1</td>

<td>°C</td><td>MPa</td><td>Hr</td><td>Toughness failure time</td>

<td>90Ό</td><td>4.75</td><td>0.3</td><td>81.42</td>

<td>90C</td><td>4.65</td><td>0.9</td><td>402.43</td>

<td>90C</td><td>4.6</td><td>1.4</td><td>523.1</td>

<td>23C</td><td>10.5</td><td>2</td><td>1121</td>

<td>23C</td><td>10.4</td><td>4.5</td><td>2493</td>

<td>23C</td><td>10.3</td><td>10.1</td><td>2493</td>