Catalyst compositions comprising fluoride-ated supports and methods of using the same

Abstract

The present invention relates to catalyst compositions comprising a fluorided support and methods of using the same. The present invention relates to catalyst systems comprising a fluorided silica, an alkylaluminoxane activator, and a bridged monocyclopentadienyl Group 4 transition metal compound, wherein the fluorided support has not been calcined at a temperature of 400°C or greater, and the catalyst system is preferably prepared using a wet-mix method, particularly an aqueous method.

Description

[0001] This application is a divisional application of Chinese patent application No. 201680028584.0, filed on March 10, 2016, entitled "Catalyst Composition Containing a Fluorinated Support and Method of Using the Same Thereof".

[0002] Priority requirements

[0003] This application claims priority to U.S. Provisional Application Serial No. 62 / 149,814, filed April 20, 2015, and European Application No. 15173732.7, filed June 25, 2015, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0004] This invention relates to novel catalyst compositions comprising a monocyclopentadienyl transition metal compound, a fluorinated support, and optionally an activator, and their uses. Background Technology

[0005] Olefin polymerization catalysts have enormous industrial applications. Therefore, there is interest in finding new catalyst systems that improve the commercial availability of catalysts and allow for the production of polymers with improved performance. Catalysts for olefin polymerization are typically based on cyclopentadienyl transition metal compounds as catalyst precursors, which are activated with aluminoxanes or activators containing noncoordinate anions.

[0006] A typical metallocene catalyst system comprises a metallocene catalyst, a support, and an activator. Supported catalyst systems are used in many polymerization processes, often in slurry or gas-phase polymerization. For example, US 6,846,770 and US 6,664,348 disclose catalyst compositions containing at least one metallocene, at least one activator, and a support fluorinated with a fluorinated compound. See also WO 05 / 075525; US 2002 / 007023; WO 2003 / 025027; US 2005 / 0288461; and US 2014 / 0031504.

[0007] Metallocenes are often combined with other catalysts, or even other metallocenes, to attempt to modify polymer properties. See, for example, US 8,088,867. Similarly, US 5,516,848 discloses the use of transition metal compounds based on two different cyclopentadienyl groups activated with aluminoxanes or noncoordinate anions. Specifically, this example discloses catalyst compounds combined with, for example, Me2Si(Me4C5)(NcC) activated with an activator. 12 H 23 TiCl2 and rac-Me2Si(H4Ind)ZrCl2, or Me2Si(Me4C5)(NcC 12H 23TiCl2 and Me2Si(Ind2)HfMe2, (Ind = indyl), the activator being such as methylaluminoxane or N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, thereby producing polypropylene with a bimodal molecular weight distribution (Mw / Mn), varying amounts of isotactic regularity (12 to 52% by weight in the products of Examples 2, 3 and 4), weight-average molecular weights exceeding 100,000 and some even up to 1.2 million, used as thermoplastics. See also US 4,701,432; US 5,077,255; US 7,141,632; US 6,207,606; US 8,598,061; Hong et al., Immobilized Me2Si(C5Me4)(Nt-Bu)TiCl2 / (nBuCp)2ZrCl2 Hybrid Metallocene Catalyst System for the Production of Poly(ethylene-co-hexene) with Psuedo-bimodal Molecular Weight and Inverse Co Monomer Distribution, (Polymer Engineering and Science-2007, DOI 10.1002 / pen, pp. 131-139, published online at Wiley InterScience (www.interscience.wiley.com) 2007 Society of Plastics Engineers); US 2012 / 0130032; US 7,192,902; US 8,110,518; US 7,355,058; US 5,382,630; US 5,382,631; US ​​8,575,284, US 6,069,213; Kim, JD et al., J. Polym. Sci. Part A: Polym Chem., 38, 1427 (2000); Iedema, PD et al., Ind. Eng. Chem. Res., 43, 36 (2004); US 6,656,866; US 8,815,357; US 2004 / 259722; US2014 / 0031504; US 5,135,526; US 7,385,015;WO 2007 / 080365;WO 2012 / 006272; WO 2014 / 0242314; WO 00 / 12565; WO 02 / 060957; WO 2004 / 046214; WO 2009 / 146167; and EP 2 374 822A.

[0008] There remains a need in the field for new and improved catalyst systems for olefin polymerization to achieve enhanced activity or specific polymer properties, such as high melting point, high molecular weight, to improve conversion or comonomer incorporation, or to alter the comonomer distribution without compromising the properties of the resulting polymer. Summary of the Invention

[0009] This invention relates to a catalyst system comprising fluorinated silica, an alkylaluminoxane activator, and a bridged monocyclopentadienyl group 4 transition metal compound, wherein the fluorinated support is not calcined at 400°C or higher.

[0010] The present invention also relates to a method for producing ethylene polymers, comprising: i) reacting ethylene and C3-C in a gas phase or a slurry phase. 20 The comonomer is contacted with a catalyst system comprising a fluorinated support, an alkylaluminoxane activator, and a bridged monocyclopentadienyl group 4 transition metal compound, wherein the fluorinated support is not calcined at 400°C or higher, and ii) a polymer comprising at least 50 mol% ethylene is obtained.

[0011] This invention also relates to a catalyst system comprising a fluorinated support, an alkylaluminoxane activator, and a metallocene catalyst compound, wherein the metallocene is represented by the following formula:

[0012] T y Cp m MG n X q

[0013] Each Cp independently represents a substituted or unsubstituted cyclopentadienyl group (e.g., cyclopentadiene, indene, or fluorene), M is a Group 4 transition metal, such as titanium, zirconium, or hafnium, G is a heteroatom-containing group bonded to M, and optionally, T is a group of formula JR*. z This indicates that J represents N, P, O, or S, and R* represents C1-C. 20 The hydrocarbon group, z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group (such as a halogen group, hydrogen group, alkyl group, alkenyl group or alkylaryl group), and m = 1, n = 1, 2 or 3, q ​​= 1, 2 or 3, and the sum of m + n + q is equal to the oxidation state of the transition metal; wherein preferably, m = 1, n = 1, and y = 1. Attached Figure Description

[0014] Figure 1 GPC of LLDPE produced using catalyst A supported in Example 2.

[0015] Figure 2GPC of LLDPE produced using catalyst B supported in Example 2.

[0016] Figure 3 GPC of LLDPE produced using catalyst C supported in Example 2.

[0017] Figure 4 TREF of LLDPE produced using catalyst B supported in Example 2.

[0018] Figure 5 TREF of LLDPE produced using catalyst C supported in Example 2. Invention Details

[0020] For the purposes of this invention and its claims, a new numbering scheme for the periodic table of elements as described in Chemical and Engineering News, 63(5), pg.27, (1985) is used, for example, “Group 4 metals” for elements in Group 4 of the periodic table, such as Hf, Ti or Zr.

[0021] "Olefin" or "alkene" is a straight-chain, branched, or cyclic compound containing carbon and hydrogen with at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in the polymer or copolymer is in a polymeric form of an olefin. For example, when a copolymer is described as containing 35% to 55% wt% "ethylene," it should be understood that the polymeric units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are present in 35% to 55% wt% based on the weight of the copolymer. A "polymer" has two or more identical or different polymeric units. A "homopolymer" is a polymer having identical polymeric units. A "copolymer" is a polymer having two or more polymeric units that are different from each other. A "ternary polymer" is a polymer having three polymeric units that are different from each other. "Different" as used to describe polymeric units means that the polymeric units are at least one atom different from each other or are isomerically different. Therefore, the definition of copolymer used herein includes ternary polymers, etc. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, and so on.

[0022] For the purposes of this invention, ethylene should be considered as an α-olefin.

[0023] For the purposes of this invention and its claims, the term "substituted" means that a hydrogen group is replaced by a heteroatom or a heteroatom-containing group. For example, a "substituted hydrocarbon group" is a group consisting of carbon and hydrogen, wherein at least one carbon is replaced by a heteroatom or at least one hydrogen is replaced by a heteroatom-containing group, wherein each heteroatom is independently selected from Groups 13-16, excluding carbon, and preferably selected from B, Al, Si, Ge, N, P, O, S, and Se.

[0024] Here, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight. wt% is the weight percentage, and mol% is the molar percentage. Molecular weight distribution (MWD), also known as polydispersity, is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol. The following abbreviations are used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, Ind is cycloyl, Flu is fluorenyl, and MAO is methylaluminoxane.

[0025] For the purposes of this invention and its claims, a "catalyst system" is a combination of at least one catalyst compound, at least one activator, optionally a co-activator, and a fluorinated support material. For the purposes of this invention and its claims, when a catalyst system is described as comprising a neutral, stable form of a component, those skilled in the art will understand that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer.

[0026] In this description, metallocene catalysts may be described as catalyst precursors, precatalyst compounds, metallocene catalyst compounds, or transition metal compounds; these terms are used interchangeably.

[0027] Metallocene catalysts are defined as organometallic transition metal compounds having at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) bound to a transition metal.

[0028] For the purposes of this invention and the claims relating to metallocene catalyst compounds, the term "substituted" means that a hydrogen group is replaced by a hydrocarbon group, a halohydrocarbon group, a halogenated group, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0029] For the purposes of this invention and its claims, "alkoxide" includes those in which the alkyl group is a C1-C10 hydrocarbon group. The alkyl group may be straight-chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may contain at least one aromatic group.

[0030] This invention relates to a catalyst system comprising a fluorinated support, an alkylaluminoxane activator, and at least one metallocene catalyst compound, wherein the metallocene is a bridged monocyclopentadienyl group 4 transition metal compound, preferably represented by the following formula:

[0031] T y Cp m MG n X q

[0032] Where Cp is a cyclopentadienyl group (such as cyclopentadiene, indene, or fluorene) that may or may not be substituted, M is a group 4 transition metal, such as titanium, zirconium, or hafnium, and G is a metal of formula JR*. z The heteroatomic groups are represented, where J is N, P, O, or S, and R* is C1-C. 20 The hydrocarbon group, z is 1 or 2, T is a bridging group, y is 0 or 1, X is a leaving group (e.g., halogen group, hydrogen group, alkyl group, alkenyl group or alkylaryl group), m = 1, n = 1, 2 or 3, q ​​= 1, 2 or 3, and the sum of m + n + q is equal to the oxidation state of the transition metal (e.g. 2, 3, 4, preferably 4); wherein preferably, m = 1, n = 1 and y = 1.

[0033] The catalyst compound is present on the support as a catalyst supported at a concentration of 1-100 μmol / g, preferably 20-60 μmol / g.

[0034] The present invention also relates to metallocene catalyst compositions comprising reaction products of at least three components: (1) one or more bridging metallocenes having a cyclopentadienyl group; (2) one or more alkylaluminoxane activators; and (3) one or more fluorinated support compositions, wherein the fluorinated support compositions are not calcined at 400°C or higher, preferably, the fluorinated support compositions are calcined at a temperature of 100°C-395°C, or 125°C-350°C, or 150°C-300°C.

[0035] Typically, the fluorinated supports described herein are prepared by combining a solution of a polar solvent (e.g., water) and a fluorinating agent (e.g., SiF4 or (NH4)2SiF6) with a support slurry (e.g., a toluene slurry of silica), drying until it is free-flowing, and optionally calcining (typically at a temperature above 100°C for at least 1 hour). The support is then combined (separately or together) with an activator and a catalyst compound.

[0036] Fluorinated carrier

[0037] As used herein, the phrases "fluorinated support" and "fluorinated support composition" refer to a support, preferably particulate and porous, that has been treated with at least one inorganic fluorinated compound. For example, a fluorinated support composition may be a silica support in which a portion of the silica hydroxyl groups are replaced by fluorine or a fluorinated compound. Similarly, the term "support composition" refers to a support, preferably particulate and porous, that has been treated with at least one fluorinated compound. Suitable fluorinated compounds include, but are not limited to, inorganic fluorinated compounds and / or organic fluorinated compounds.

[0038] The carriers suitable for use in this invention are typically porous materials and may include organic materials, inorganic materials, and inorganic oxides. Desiredly, carriers suitable for use in this invention include talc, clay, silica, alumina, magnesium oxide, zirconium oxide, iron oxide, boron oxide, zinc oxide, barium oxide, thorium oxide, aluminum phosphate gel, polyvinyl chloride, and substituted polystyrene, and mixtures thereof. Other useful carrier materials include zeolites, clay, organoclay, or any other organic or inorganic carrier materials, or mixtures thereof.

[0039] Preferably, the support material is a finely divided inorganic oxide. Suitable inorganic oxide materials for the catalyst systems described herein include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina include magnesium oxide, titanium dioxide, zirconium oxide, etc. However, other suitable support materials can also be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, succinate, zeolite, talc, clay, etc. In addition, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. Preferred support materials include Al2O3, ZrO2, SiO2, and combinations thereof, more preferably SiO2, Al2O3, or SiO2 / Al2O3. In a preferred embodiment of the invention, the support is silica.

[0040] Preferably, the carrier material, preferably an inorganic oxide, and more preferably silicon dioxide, has a surface area ranging from about 10 to about 800 m². 2 / g (or approximately 10-700mg) 2 The pore volume ranges from about 0.1 to about 4.0 cc / g, and the average particle size ranges from about 5 to about 500 μm. More preferably, the surface area of ​​the carrier material ranges from about 50 to about 500 m². 2 The pore volume is approximately 0.5–3.5 cc / g, and the average particle size is approximately 10–200 μm. Most preferably, the surface area of ​​the carrier material ranges from approximately 100–400 m². 2 / g, pore volume approximately 0.8-3.0 cc / g and average particle size approximately 5-100 μm. The average pore size range of the carrier material that can be used in this invention is within the range of Preferably, 50-approximately And most preferably, 75-approximately In some implementations, the carrier material is high-surface-area amorphous silica (surface area = 300 m²). 2 / gm; pore volume is 1.65cm³. 3 / gm). Useful silica is marketed under the trade name DAVISON. TM 952, DAVISON TM 948 or DAVISON TM 955 is sold by the Davison Chemical Division of WRGrace and Company. Total surface area, also known as "surface area," and total pore volume, also known as "pore volume," and average pore diameter were determined using the Brunauer-Emmett-Teller (BET) method with nitrogen absorption and desorption (liquid nitrogen temperature, 77 K) on a Micromeritics Tristar II 3020 instrument after degassing the powder at 350 °C for four hours. More information on this method can be found, for example, "Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density," S. Lowell et al., Springer, 2004. Average particle size, also known as "particle size" or "particle diameter," was determined using Mastersizer, available from Malvern Instruments, Ltd., Worcestershire, UK. TM 3000 (range 1-3500 μm) was measured.

[0041] In a particularly useful embodiment, the carrier is silica, which is desirablely porous and has a surface area ranging from about 10 to about 800 μm. 2 The total pore volume ranges from about 0.1 to about 4.0 cc / g, and the average particle size ranges from about 10 to about 500 μm. More preferably, the surface area ranges from about 50 to about 500 m². 2 The pore volume ranges from about 0.5 to about 3.5 cc / g, and the average particle size ranges from about 15 to about 150 μm. Most preferably, the surface area ranges from about 100 to about 400 m². 2 The pore volume ranges from about 0.8 to about 3.0 cc / g, and the average particle size ranges from about 20 to about 100 μm. Typical porous silica support materials have an average pore diameter ranging from about 10 to about 100 μm. Ideally, the average pore diameter of the carrier material is approximately 50-100 mm. And most expected about 75-

[0042] The fluorine compounds suitable for providing fluorine to the support can be organic or inorganic fluorine compounds, and preferably inorganic fluorine-containing compounds. Such inorganic fluorine-containing compounds can be any compound containing fluorine atoms, provided they do not contain carbon atoms. Particularly desirable are inorganic fluorine-containing compounds selected from NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, and NH4HF2. Among these, ammonium hexafluorosilicate, SiF4, and ammonium tetrafluoroborate are particularly useful. Combinations of two or more inorganic fluorine-containing compounds can also be used.

[0043] Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluorinated compounds are typically solid particles, such as silica supports. A useful method of treating the support with fluorinated compounds is to simply dry-mix the two components at concentrations of 0.01-10.0 mmol F / g support, preferably in the range of 0.05-6.0 mmol F / g support, and most preferably in the range of 0.1-3.0 mmol F / g support. The fluorinated compound can be dry-mixed with the support before or after adding it to a container for dehydration or calcination. Therefore, the fluorine concentration present on the support preferably ranges from 0.1-25 wt%, or 0.19-19 wt%, or 0.6-3.5 wt%, based on the weight of the support.

[0044] Another method of treating the support with fluorine compounds is to dissolve the fluorine compound in a solvent, such as water, and then contact the support (dry or combined with water or a hydrocarbon solvent) with the solution containing the fluorine compound. When using water and silica as the support, it is desirable to use an amount of water less than the total pore volume of the support.

[0045] A typical drawback of the dry-mixing method is that the fluorinating agent (such as ammonium hexafluorosilicate - density approximately 2.1 g / cm³)... 3 ) and silica (e.g., Davison) TM 948 - Density approximately 0.7 g / cm³ 3 The density difference between the silica carrier and the fluorinated silica makes it difficult to distribute the fluorinating agent uniformly / uniformly. This density difference also causes ammonium hexafluorosilicate to precipitate in the fluorinated silica derived from the dry-mixing method. The concentration of ammonium hexafluorosilicate in the fluorinated silica (prepared via the dry-mixing method) stored in bottles was observed over a two-week period. Such precipitation can lead to operational problems on a commercial scale.

[0046] To overcome these problems, an alternative method (wet mixing) has been developed. The wet mixing method uses a minimal amount of a polar solvent (e.g., water or methanol, ethanol, isopropanol, any solvent capable of dissolving fluoride compounds (e.g., ammonium hexafluorosilicate) to dissolve the fluorinating agent (e.g., ammonium hexafluorosilicate). The fluoride compound solution (e.g., ammonium hexafluorosilicate solution) is then added to a silica slurry in a nonpolar solvent (e.g., toluene or benzene, chloroform, etc.), and the resulting mixture is vigorously stirred. The polar / hydrophilic nature of the fluoride compound (e.g., ammonium hexafluorosilicate) causes it to adsorb onto the hydrophilic silica surface. When the nonpolar solvent is removed (by filtration), silica with a uniformly distributed fluorinating agent (e.g., ammonium hexafluorosilicate) is obtained and ready for subsequent drying and calcination steps. The wet mixing method (especially the aqueous form of the wet method) also provides simplified post-processing and rapid drying. Calcination can be carried out in a shorter time based on the small amount of water or other polar solvents used.

[0047] This method reduces or eliminates the non-uniform distribution of fluorinating agents in silica associated with other methods. Furthermore, fluorinated silica prepared by wet methods exhibits excellent operability, while fluorinated silica prepared by dry mixing methods often suffers from poor operability due to frequent blockages in the catalyst feed line.

[0048] The dehydration or calcination of silica does not necessarily need to be carried out before the reaction with fluorine compounds, but may be carried out if necessary. Ideally, the reaction between silica and fluorine compounds is carried out at temperatures of about 100°C to about 400°C, and more preferably about 150°C to about 350°C for two to eight hours.

[0049] In one embodiment, the fluorinated support composition can be generally represented by the formula: Sup-F, where "Sup" is the support and "F" is a fluorine atom bound to the support. The fluorine atom can be bound to the support directly or indirectly, chemically or physically. Examples of chemical or physical bonding are covalent and ionic bonding, respectively.

[0050] In another embodiment, the fluorinated support composition is represented by the following formula: Sup-LF n Wherein “Sup” is a carrier, preferably selected from talc, clay, silica, alumina, magnesium oxide, zirconium oxide, iron oxide, boron oxide, calcium oxide, zinc oxide, barium oxide, thorium oxide, aluminum phosphate gel, polyvinyl chloride, and substituted polystyrene; “L” is a first member selected from (i) bonds sufficient to bind F to Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr that bind to Sup and to F; and (iii) O that binds to Sup and to a second member selected from B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, Al, or Zr that binds to F; “F” is a fluorine atom; and “n” is a number from 1 to 7.

[0051] Examples of bonds sufficient to bind F to Sup are chemical or physical bonds, such as, for example, covalent and ionic bonds.

[0052] The fluorinated support material is then typically slurried in a nonpolar solvent, and the resulting slurry is contacted with a solution of a metallocene compound and an activator. In some embodiments, the slurry of the fluorinated support material is first contacted with the activator for a period ranging from about 0.5 hours to about 24 hours, from about 1 hour to about 16 hours, or from about 2 hours to about 8 hours. The solution of the metallocene compound is then contacted with the separated fluorinated support / activator. In some embodiments, the supported catalyst system is generated in situ. In alternative embodiments, the slurry of the fluorinated support material is first contacted with the catalyst compound for a period ranging from about 0.5 hours to about 24 hours, from about 1 hour (or 2 hours) to about 16 hours, or from about 2 hours (or 4 hours) to about 8 hours. The slurry of the supported metallocene compound is then contacted with the activator solution.

[0053] The mixture of metallocene, activator, and fluorinated support can be heated to about 0°C to about 70°C, preferably about 23°C to about 60°C, and preferably at room temperature. The contact time typically ranges from about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0054] In a preferred embodiment of the invention, the fluorinated support material is slurried in a nonpolar solvent, and the resulting slurry is contacted with a solution of methylaluminoxane (typically 30 wt% MAO in toluene). The fluorinated support / MAO mixture is then heated to an elevated temperature (30°C-120°C, preferably 80-100°C) and vigorously stirred for a period of time (0.1-24 hours, preferably 1-3 hours). The support / activator is separated by filtration, washed with a nonpolar solvent (e.g., toluene, pentane, hexane, etc.), and dried. The separated support / activator is then slurried in a nonpolar solvent (e.g., toluene), and a solution of the metal compound / compound is contacted with the support / activator slurry. Vigorous stirring may then be applied.

[0055] In a preferred embodiment of the invention, the fluorinated carrier material is slowly added in solid form to a solution of MAO in a nonpolar solvent (e.g., toluene) under vigorous stirring (typically at room temperature). This order of addition, i.e., the slow and gradual addition of fluorinated silica to the MAO solution, is referred to as “reverse addition.” After the addition of fluorinated silica is complete, the fluorinated carrier / MAO mixture is then heated to an elevated temperature (30°C-120°C, preferably 80-100°C) under vigorous stirring for a period of time (0.1-24 hours, preferably 1-3 hours). The carrier / activator is separated by filtration, washed with a nonpolar solvent (e.g., toluene, pentane, hexane, etc.), and dried. The separated carrier / activator is then slurried in a nonpolar solvent (e.g., toluene), and then one or more metallocene compounds are contacted with the carrier / activator slurry. Vigorous stirring may be applied.

[0056] Under otherwise identical conditions, the “reverse addition” method of immobilizing MAO on the surface of fluorinated silica provides higher polymerization activity for many catalysts compared to the “conventional addition” method, in which MAO solution is added to a slurry of fluorinated silica in a nonpolar solvent.

[0057] A suitable nonpolar solvent is one in which all reactants used herein—the activator and the metallocene compound—are at least partially soluble and are liquid at the reaction temperature. Preferred nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other materials, including cycloalkanes such as cyclohexane, and aromatics such as benzene, toluene, and ethylbenzene, may also be used.

[0058] In a preferred embodiment of the invention, the fluorinated support described herein is prepared by combining a solution of a polar solvent and a fluorinating agent (e.g., (NH4)2SiF6) with a slurry of the support (e.g., a toluene slurry of silica), drying until free-flowing, optionally calcining (typically at a temperature of 100°C–400°C for at least 1 hour), and then combining an activator and a catalyst compound (the activator and catalyst compound may be added to the support separately or together).

[0059] In another embodiment of the invention, the ratio of water to solvent (by weight) is 1:10 to 1:1000, preferably 1:20 to 1:50.

[0060] In another embodiment of the invention, the fluorinated silica support is capable of immobilizing greater than 5.0 mmol "Al" per gram of silica, and preferably greater than 6.0 mmol "Al" / gram of silica. The "Al" (from alkylaluminoxanes, such as MAO) immobilized on 1 gram of fluorinated silica can be determined by aluminum titration. The titration is performed at 100°C under ambient pressure, allowing the aluminoxane (15 mmol Al) and 1 gram of fluorinated silica to react for 3 hours. Afterward, the silica is washed with toluene (10 ml, 3 times) and then with pentane (10 ml, 3 times). The solid is then collected and vacuum dried for 8 hours until the solvent is removed. The sample is then weighed, and the weight difference is divided by the Mw of the aluminum compound (Mw as reported in Chemical and Engineering News, 63(5), page 27, (1985)). Methylaluminoxane is defined as Me-Al-O. In the following examples, "Silica-1" has an Al absorption of approximately 5.5 mmol / g, while "Silica-2" has an Al absorption of approximately 6.8 mmol / g. Higher Al absorption (or loading) is often desirable and is expected because it is thought to provide higher polymerization activity, provided that the silica and catalyst precursor remain constant. In a useful embodiment of the invention, the catalyst system comprising a fluorinated silica support has a fixed Al content of greater than 5.0 mmol / g silica, and preferably greater than 6.0 mmol / g silica.

[0061] Alternatively, the fluorinated silica support preferably contains less than 0.05 mmol / g of fluorinating agent (e.g., (NH4)2SiF6), preferably less than 0.02 mmol / g of fluorinating agent, through... 1 Measured by H NMR.

[0062] Alternatively, the surface area of ​​the fluorinated silica support is greater than 200 m². 2 / g, preferably, greater than 250m 2 / g, determined by BET. Alternatively, the combined fluorinated silica support and activator (e.g., MAO) have a surface area greater than 250m². 2 / g, preferably greater than 350m 2 / g, determined by BET.

[0063] In embodiments where SiF4 and / or (NH4)2SiF6 are fluorinating agents, immediately after the alkylaluminoxane is combined with the fluorinated support, the combined product preferably contains less than 0.04 mmol per gram of tetraalkylsilane per gram of support (preferably less than 0.02 mmol, more preferably less than 0.01 mmol), as by means of... 1 H NMR determination (where the alkyl group is derived from alkylaluminoxane).

[0064] In a useful embodiment, the ratio of fluorine mmol per gram of silica in the fluorinated carrier is 0.1-1.5, preferably 0.2-1.2, and more preferably 0.4-1.0.

[0065] For fluorinated silica prepared using (NH4)2SiF6, the amount of residual (NH4)2SiF6 in the silica should be equal to or less than 0.04 mmol (NH4)2SiF6 / g silica, preferably equal to or less than 0.02 mmol (NH4)2SiF6 / g silica, and more preferably equal to or less than 0.01 mmol (NH4)2SiF6 / g silica.

[0066] Catalyst compounds

[0067] Useful catalysts include compounds represented by the following formula:

[0068] T y Cp m MG n X q

[0069] Where Cp is a substituted or unsubstituted cyclopentadienyl group (e.g., cyclopentadiene, indene, or fluorene), M is a Group 4 transition metal, such as titanium, zirconium, or hafnium, and G is a cyclopentadienyl group of formula JR*. zThe heteroatomic groups are represented as follows: J is a group 15 or 16 element, preferably N, P, O or S; R* is a straight-chain, branched or cyclic hydrocarbon group having 1-20 carbon atoms; z is 1 or 2; T is a bridging group; and y is 0 or 1; each X independently represents a leaving group, or two X are connected and bonded to a metal atom to form a metal ring or two X are connected to form a chelate ligand, diene ligand or alkylene ligand; and m = 1, n = 1, 2 or 3, q ​​= 1, 2 or 3, and the sum of m + n + q is equal to the oxidation state of the transition metal (preferably 2, 3 or 4, preferably 4).

[0070] In a preferred embodiment of the invention, M is a Group 4 transition metal (preferably Hf, Ti, and / or Zr, preferably Ti).

[0071] In a preferred embodiment, M is 1, n is 1, y is 1, each X is independently a monovalent anionic ligand, q is 2, and the transition metal is in an oxidation state of +4.

[0072] Typically, each G is independently represented as JR* z The heteroatomic group represents J, which is a group 15 or 16 element, preferably N, P, O or S (preferably N or O, preferably N), and R* is C1-C. 20 Hydrocarbon group and z is 1 or 2.

[0073] In one embodiment of the present invention, R* is C1-C 20 Alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or their isomers, including straight-chain, branched, or C3-C) 20 Cyclic isomers, and combinations thereof, such as tert-butyl, neopentyl, cyclododecyl, cyclodecyl, cyclooctyl, cyclohexyl, cyclohexylmethyl, etc.

[0074] In one embodiment of the present invention, R* is C1-C containing a multi-ring structure. 20 Hydrocarbon groups (such as bicyclo[2.2.1]heptyl (norbornyl), bicyclo[2.2.2]octyl, spiro[4.5]decyl, octahydrocyclopentadienyl, adamantyl, etc.).

[0075] In one implementation, when M is 1, n is preferably 1, and G is of formula JR*. z The heteroatomic group represents J, which is a group 15 or 16 element, preferably N, P, O or S (preferably N or O, preferably N), and R* is C1-C. 20 The hydrocarbon group, and z is 1 or 2, preferably JR*z is cyclododecylamino, tert-butylamino, and / or adamantane-1-ylamino.

[0076] In one embodiment, each X may independently be a halogen group, a hydrogen group, an alkyl group, an alkenyl group, or an arylalkyl group.

[0077] Alternatively, each X is independently selected from hydrocarbon groups, aryl groups, hydrogen groups, amino groups, alkoxide groups, thio groups, phosphoro groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof having 1-20 carbon atoms (two Xs may form a fused ring or part of a ring system). Preferably, each X is independently selected from halogen groups, aryl groups, alkylaryl groups (such as benzyl), and C1-C5 alkyl groups. Preferably, each X is benzyl, methyl, ethyl, propyl, butyl, pentyl, or chlorinated.

[0078] Typically, each Cp group independently represents a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, or a substituted or unsubstituted fluorene.

[0079] Each Cp group can be independently substituted by a combination of substituent groups R, wherein each R is independently an R group, such as hydrogen or a hydrocarbon group or a substituted hydrocarbon group. Non-limiting examples of substituent groups R include one or more selected from: hydrogen or straight-chain, branched alkyl, or alkenyl, alkynyl, cycloalkyl or aryl, acyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkylcarbamoyl or dialkylcarbamoyl, acyloxy, amide, arylamide, straight-chain, branched or cyclic alkylene, or combinations thereof. In a preferred embodiment, the substituent groups R have up to 50 non-hydrogen atoms, preferably 1-30 carbon atoms, and they can also be substituted by halogens or heteroatoms, etc. Non-limiting examples of substituent groups R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl groups, including all their isomers, such as tert-butyl, isopropyl, etc. Other groups that can be used as R include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbon-substituted organometallic groups, including trimethylsilyl, trimethylmethyl, methyldiethylsilyl, etc.; further groups that can be used as R include: 1) halocarbon-substituted organometallic groups including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylmethylalkyl, etc.; 2) disubstituted boron groups, including, for example, dimethylboron; 3) disubstituted nitrogen groups, including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; 4) thio groups, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide. Furthermore, at least two R groups, preferably two identical R groups, can be linked to form a ring structure having 3-20 non-hydrogen atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof.

[0080] In one embodiment of the Cp group, the substituent R is independently a hydrocarbon group, a halocarbonyl group, a halogen, or a heteroatom-containing group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof, N, O, S, P, or a C1-C group substituted with N, O, S, and / or P heteroatoms or containing heteroatoms (typically having up to 12 atoms, including the N, O, S, and P heteroatoms). 20 Hydrocarbon group.

[0081] Non-limiting examples of Cp groups include cyclopentadienyl ligands, cyclopentanandrolone ligands, indene ligands, indacenyl ligands, benzo[a]indene ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenyl ligands, cyclopentanedodecene ligands, azuleyl ligands, chamomile ligands, cyclopentadienyl ligands, phosphoryl ligands, phosphonamide ligands (WO 99 / 40125), pyrrole ligands, pyrazolyl ligands, carbazole ligands, boronbenzene ligands, etc., including their hydrogenated forms, such as tetrahydroindene ligands. In another embodiment, each Cp may independently contain one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, which combine with carbon atoms to form an open form, a ring, or preferably a fused ring or cyclic system, such as a heterocyclopentadienyl auxiliary ligand. Other Cp ligands include, but are not limited to, porphyrins, phthalocyanines, corrins, and other polyazine macrocycles. Particularly useful Cp groups include cyclopentadiene, indene, fluorene, and their substituted forms.

[0082] Preferably, T is present and is a bridging group containing at least one element from Group 13, 14, 15, or 16, specifically boron or an element from Group 14, 15, or 16. Examples of suitable bridging groups include P(=S)R', P(=Se)R', P(=O)R', R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R'2SiSiR'2, R' 2SiOSiR'2, R'2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2G eCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2, R'B, R'2C-BR', R'2C-BR'-CR'2, R'2C-O-CR'2, R'2CR'2C-O-CR'2CR' 2. R'2C-O-CR'2CR'2, R'2C-O-CR'=CR', R'2C-S-CR'2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR' =CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR'2CR'2, R'2C-Se-CR'=CR', R'2C-N=CR', R'2C-NR'- CR'2, R'2C-NR'-CR'2CR'2, R'2C-NR'-CR'=CR', R'2CR'2C-NR'-CR'2CR'2, R'2C-P=CR', R'2C-PR'-CR'2, O, S, Se, Te, NR', PR', AsR', SbR', OO, SS, R'N-NR', R'P-PR', OS, O-NR', O-PR', S-NR', S-PR', and R'N-PR', where R' is hydrogen or C1-C 20The bridging group T may be a substituted hydrocarbon group, a substituted carboalkyl group, a substituted carboalkyl group, a silylcarboalkyl group, or a germanylcarboalkyl group, and optionally, two or more adjacent R' may be linked to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic, or polycyclic substituent. Preferred examples of the bridging group T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NET, NPr, NBu, PEt, PPr, and PBu.

[0083] In a preferred embodiment of the invention, in any embodiment of any of the formulas described herein, T is represented by the formula Ra2J or (Ra2J)2, where J is C, Si, or Ge, and each Ra is independently hydrogen, halogen, C1-C20 hydrocarbon (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or C1-C 20 The substituted hydrocarbon group and two Ra can form cyclic structures, including aromatic, partially saturated or saturated cyclic or fused cyclic systems.

[0084] Preferably, T is a bridging group containing carbon or silicon dioxide, such as dialkylsilyl, and preferably, T is selected from CH2, CH2CH2, C(CH3)2, SiMe2, SiPh2, SiMePh, silylcyclobutyl (Si(CH2)3), (Ph)2C, (p-(Et)3SiPh)2C, and cyclopentamethylsilane (Si(CH2)4).

[0085] Useful bridging metallocene compounds having a cyclopentadienyl ring include those represented by the following formula:

[0086]

[0087] in

[0088] M is titanium, zirconium, or hafnium, preferably titanium;

[0089] Z is a substituted or unsubstituted Cp group (a useful Z group is represented by the following formula: (C5H) 4-d S* d ), where d is 1, 2, 3, or 4, S* is a hydrocarbon group, a heteroatom, a heteroatom-containing group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof, N, O, S, P, or C1-C substituted with N, O, S, and / or P heteroatoms or heteroatom-containing groups (typically having up to 12 atoms, including N, O, S, and P heteroatoms). 20The hydrocarbon group, the two S* can form a cyclic or polycyclic group, preferably, Z is a tetramethylcyclopentadienyl group;

[0090] T is the bridging group as described above, which is bonded to Z and Q, and y is 1;

[0091] Q is a heteroatom of Group 15 of the periodic table with a coordination number of 3 or a heteroatom of Group 16 with a coordination number of 2, such as N, O, S or P. Preferably, Q is nitrogen.

[0092] R is selected from C3-C 100 Substituted or unsubstituted monocyclic or polycyclic substituents that are partially unsaturated, unsaturated, or aromatic; or C2-C 100 Substituted or unsubstituted, unsaturated or partially unsaturated, straight-chain or branched alicyclic hydrocarbon substituents; or C1-C 100 Substituted or unsubstituted saturated hydrocarbon groups (preferably, R" is selected from methyl, ethyl, all propyl isomers, all butyl isomers, phenyl, benzyl, phenethyl, 1-adamantyl, cyclododecyl, cyclohexyl and norbornyl);

[0093] t represents the coordination number of the heteroatom Q, where "t-1-y" indicates the number of R substituents bonded to Q; and

[0094] Each X independently represents a leaving group (such as a monovalent anionic ligand) or two Xs linked together and bonded to a metal atom to form a metal ring or two Xs linked together to form a chelate ligand, diene ligand, or alkylene ligand.

[0095] Illustrative, non-limiting examples of preferred monocyclopentadienyl metallocene catalyst compositions for use in the present invention include:

[0096] Dimethylsilylene(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium,

[0097] Dimethylsilylene(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride

[0098] Dimethylsilylene(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0099] Dimethylsilylene(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride

[0100] μ-(CH3)2Si(cyclopentadienyl)(adamantane-1-ylamino)M(R)2;

[0101] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(adamantane-1-ylamino)M(R)2;

[0102] μ-(CH3)2(tetramethylcyclopentadienyl)(adamantane-1-ylamino)M(R)2;

[0103] μ-(CH3)2Si(tetramethylcyclopentadienyl)(adamantane-1-ylamino)M(R)2;

[0104] μ-(CH3)2C(tetramethylcyclopentadienyl)(adamantane-1-ylamino)M(R)2;

[0105] μ-(CH3)2Si(tetramethylcyclopentadienyl)(tert-butylamino)M(R)2;

[0106] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2;

[0107] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0108] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0109] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2;

[0110] Wherein M is selected from Ti, Zr, and Hf, and R is selected from halogens or C1-C5 alkyl groups, preferably, R is a methyl group. In a preferred embodiment, M is Ti, and R is Cl, Br, or Me.

[0111] In alternative embodiments, two or more different monocyclopentadienyl compounds may be used herein. For the purposes of this invention, one metallocene catalyst compound is considered different from another if they differ by at least one atom. For example, “bisindenylzirconium chloride” is different from (indenyl)(2-methylindenyl)zirconium chloride, which is different from “(indenyl)(2-methylindenyl)hafnium chloride”. For the purposes of this invention, catalyst compounds that differ only in isomerism are considered identical; for example, rac-dimethylsilylbis(2-methyl4-phenyl)dimethylhafnium is considered identical to meso-dimethylsilylbis(2-methyl4-phenyl)dimethylhafnium.

[0112] In a preferred embodiment, a monocyclopentadienyl compound is used in the catalyst system.

[0113] The synthesis of monocyclopentadienyl complexes is known in the art and is disclosed, for example, in WO93 / 19103, US 5,096,867 and US 5,264,405.

[0114] Activator

[0115] The terms "co-catalyst" and "activator" are used interchangeably herein and are defined as any compound capable of activating any of the catalyst compounds described above by converting a neutral catalyst compound into a catalytically active cationic compound. Non-limiting activators, for example, include aluminoxanes, alkylaluminums, ionized activators (which may be neutral or ionic), and conventional types of co-catalysts. Preferred activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that attract reactive σ-bonded metal ligands to prepare metal complex cations and provide charge-balanced non-coordinated or weakly coordinated anions.

[0116] Aluminoxane activator

[0117] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes typically contain -Al(R) 1 Oligomeric compounds of the )-O- subunit, wherein R 1 Alkyl groups are used. Examples of aluminum oxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkyl aluminum oxanes and modified aluminum oxanes are suitable as catalyst activators, especially when the ligands they attract are alkyl, halogen, alkanol, or amino. Mixtures of different aluminum oxanes and modified aluminum oxanes can also be used. Visually clear methylaluminoxanes are preferred. Turbid or gelled aluminum oxanes can be filtered to produce a clear solution or clear aluminum oxanes can be decanted from a turbid solution. A usable aluminum oxane is type 3A modified methylaluminoxane (MMAO) cocatalyst (commercially available under the trade name type 3A modified methylaluminoxane from Akzo Chemicals, Inc., protected under US 5,041,584).

[0118] Noncoordinate anionic activators

[0119] In alternative embodiments, alkylaluminoxanes can be used in combination with noncoordinate anionic activators. The term "noncoordinate anion" (NCA) refers to an anion that is not coordinated with a cation or is only weakly coordinated with a cation, thus remaining sufficiently readily decomposable to be replaced by a neutral Lewis base. "Compatible" noncoordinate anions are those that do not degrade to neutrality when the initially formed complex decomposes. Furthermore, this anion does not transfer anionic substituents or fragments to the cation, thereby forming neutral transition metal compounds and neutral byproducts. Noncoordinate anions that can be used according to the invention are compatible, stabilizing the transition metal cation in the sense of +1 by balancing their ionic charge, and still maintaining sufficient readily decomposability to allow replacement during polymerization.

[0120] The use of ionized or stoichiometric activators (neutral or ionic) is within the scope of this invention, such as tris(n-butylammonium tetra(pentafluorophenyl)borate, triperfluorophenylboron metal precursors or triperfluoronaphthylboron metal precursors, polyhalogenated heteroborane anions (WO98 / 43983), boric acid (US 5,942,459), in combination with aluminoxane or modified aluminoxane activators. The use of neutral or ionic activators in combination with aluminoxane or modified aluminoxane activators is also within the scope of this invention.

[0121] Preferred activators include N,N-dimethylphenylamine tetra(perfluoronaphthyl)borate, N,N-dimethylphenylamine tetra(perfluorobiphenyl)borate, N,N-dimethylphenylamine tetra(perfluorophenyl)borate, N,N-dimethylphenylamine tetra(3,5-bis(trifluoromethyl)-phenyl)borate, triphenylcarbazide tetra(perfluoronaphthyl)borate, triphenylcarbazide tetra(perfluorobiphenyl)borate, triphenylcarbazide tetra(3,5-bis(trifluoromethyl)-phenyl)borate, triphenylcarbazide tetra(perfluorophenyl)borate, [Ph3C + ][B(C6F5)4 - ], [Me3NH + ][B(C6F5)4 - ]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)-pyrrolidine; and tetra(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0122] In a preferred embodiment, the activator includes triarylcarbamates (such as triphenylcarbamate tetraphenylborate, triphenylcarbamate tetra(pentafluorophenyl)borate, triphenylcarbamate tetra-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbamate tetra(perfluoronaphthyl)borate, triphenylcarbamate tetra(perfluorobiphenyl)borate, and triphenylcarbamate tetra(3,5-bis(trifluoromethyl)phenyl)borate).

[0123] In another embodiment, the activator comprises one or more trialkylammonium tetra(pentafluorophenyl)borate, N,N-dialkylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylphenylammonium)tetra(pentafluorophenyl)borate, trialkylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylphenylammonium tetra(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetra(perfluoronaphthyl)borate, and N,N-dialkylphenylammonium tetra(perfluoronaphthyl)borate. Trialkylammonium tetra(perfluoro-biphenyl)borate, N,N-dialkylphenylammonium tetra(perfluoro-biphenyl)borate, trialkylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylphenylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylphenylammonium)tetra(3,5-bis(trifluoromethyl)phenyl)borate, di(isopropyl)ammonium tetra(pentafluorophenyl)borate (wherein the alkyl group is methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl).

[0124] Optional cleaning agents or activators

[0125] In addition to activator compounds, scavengers, chain transfer agents, or co-activators may also be used. Alkyl aluminum or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc.

[0126] Also useful chain transfer agents here are typically compounds represented by the formula AlR3, ZnR2 (where each R independently represents a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0127] Preparation of supported catalysts

[0128] In one embodiment, the present invention describes the preparation of fluorinated supports (e.g., silica) by adding a solution of a polar solvent (e.g., water) and a fluorinated compound (e.g., (NH4)2SiF6) to a support slurry (e.g., silica-toluene slurry). Such a preparation method facilitates a uniform distribution of the fluorinated compound (e.g., (NH4)2SiF6) on the support surface (e.g., the silica surface), in contrast to the less uniform distribution observed when a solid salt is combined with solid silica, as described in US 2002 / 0123582 A1. Metallocenes loaded on fluorinated supports from such preparations exhibit comparable or higher activity compared to metallocenes loaded on fluorinated supports prepared by solid / solid mixing.

[0129] In one embodiment, an aqueous solution of a fluorinating agent (such as (NH4)2SiF6) is added to a carrier slurry (such as a toluene slurry of silica). The mixture is vigorously stirred to allow the dissolved fluorine compound (in water) to be uniformly absorbed onto the surface of the hydrophilic carrier. After filtration, the wet carrier is allowed to air dry until it is free-flowing, and then it can be calcined (typically at a temperature above 100°C for at least 1 hour).

[0130] In one embodiment, a solution of a polar solvent and a fluorinating agent (such as (NH4)2SiF6) is added to a carrier slurry (such as a toluene slurry of silica). The mixture is vigorously stirred to allow the dissolved fluorine compound (in water) to be uniformly absorbed onto the surface of the hydrophilic carrier. After filtration, the wet carrier is allowed to air dry until it is free-flowing, and then it can be calcined (typically at a temperature above 100°C for at least 1 hour).

[0131] Polymerization process

[0132] In the embodiments described herein, the present invention relates to a polymerization method in which a monomer (e.g., ethylene) and optionally a comonomer (e.g., hexene) are contacted with a catalyst system comprising a combination of the aforementioned activator, fluorinated support, and metallocene compound. The catalyst compound, support, and activator can be combined in any order and are typically combined prior to contact with the monomer.

[0133] Useful monomers here include substituted or unsubstituted C2-C. 40 α-olefin, preferably, C2-C 20 α-olefin, preferably, C2-C 12 α-olefins, preferably ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, and their isomers. In a preferred embodiment of the invention, the monomer comprises ethylene, and optionally the comonomer comprises one or more C3-C... 40 Olefins, preferably C4-C 20 Olefins, or preferably, C6-C 12 Alkenes. C3-C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C3-C) 40 Cyclic alkenes may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0134] Example C3-C 40The comonomers include propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers, preferably hexene, heptenene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologues and derivatives.

[0135] In a preferred embodiment, one or more dienes present in the polymer produced herein are at most 10 wt%, preferably 0.00001-1.0 wt%, preferably 0.002-0.5 wt%, and even more preferably 0.003-0.2 wt%, based on the total weight of the composition. In some embodiments, 500 ppm or less of dienes are added to the polymerization, preferably 400 ppm or less, preferably 300 ppm or less. In other embodiments, at least 50 ppm of dienes are added to the polymerization, or 100 ppm or more, or 150 ppm or more.

[0136] Preferred diene monomers that can be used in this invention comprise any hydrocarbon structure having at least two unsaturated bonds, preferably C4-C. 30 In this process, at least two of the unsaturated bonds readily bind to the polymer via stereospecific or non-stereospecific catalysts. More preferably, the diene monomer is selected from α,ω-diene monomers (i.e., divinyl monomers). More preferably, the diene monomer is a linear divinyl monomer, most preferably those containing 4-30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecadiene, icosacene, icosacene, icosacene, icosacene, icosacene, icosacene, icosacene, triadecadiene, and triadecadiene. Particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tetadecanadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (Mw less than 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornene, ethimidenorbornene, divinylbenzene, dicyclopentadiene, or dienes containing more cyclopentadienyl groups, which may or may not have substituents at each ring position.

[0137] In a particularly preferred embodiment, the method of the present invention relates to the polymerization of ethylene and at least one comonomer having 3-8 carbon atoms, preferably 4-8 carbon atoms. Specifically, the comonomer is propylene, butene-1, 4-methyl-pentene-1, 3-methyl-pentene-1, hexene-1, and octene-1, with hexene-1, butene-1, and octene-1 being the most preferred.

[0138] The polymerization method of the present invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization method known in the art can be used. Such methods can be operated in batch, semi-batch, or continuous modes. Gas-phase polymerization and slurry methods are preferred. (A homogeneous polymerization method is defined as a method in which at least 90 wt% of the product is soluble in the reaction medium.) A bulk homogeneous method is particularly preferred. (A bulk method is defined as a method in which the monomer concentration in all feed to the reactor is 70 vol% or higher.) Alternatively, no solvent or diluent is present or added to the reaction medium (except for small amounts used as a carrier for the catalyst system or other additives, or amounts typically present in the monomer; for example, propane in propylene). In another embodiment, the method is a slurry method. The term "slurry polymerization method" as used herein refers to a polymerization method in which a supported catalyst is employed and the monomer is polymerized on supported catalyst particles. At least 95 wt% of the polymer product derived from the supported catalyst is in granular form as solid particles (insoluble in diluent).

[0139] Suitable diluents / solvents for polymerization include noncoordinate, inert liquids. Examples include straight-chain and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those commercially available (Isopar). TM Perhalogenated hydrocarbons, such as perfluorinated carbon (PFH); 4-10Alkanes, chlorobenzenes, and aromatic compounds and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that can be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably, the aromatic component is present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt%, based on the weight of the solvent.

[0140] In a preferred embodiment, the feed concentration of the monomers and comonomers used for polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, based on the total volume of the feed. Preferably, the polymerization is carried out using a bulk method.

[0141] Preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Typical temperatures and / or pressures include temperatures ranging from about 0°C to about 300°C, preferably from about 20°C to about 200°C, preferably from about 35°C to about 150°C, preferably from about 40°C to about 120°C, preferably from about 45°C to about 80°C; and pressures ranging from about 0.35 MPa to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.

[0142] In typical polymerization, the reaction run time is up to 300 minutes, preferably in the range of about 5-250 minutes, or preferably about 10-120 minutes.

[0143] In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of 0.001-50 psig (0.007-345 kPa), preferably 0.01-25 psig (0.07-172 kPa), and more preferably 0.1-10 psig (0.7-70 kPa).

[0144] In an alternative embodiment, the catalyst activity is at least 800 g polymer / g supported catalyst / hour, preferably 1,000 or higher g polymer / g supported catalyst / hour, preferably 100 or higher g polymer / g supported catalyst / hour, and preferably 1,600 or higher g polymer / g supported catalyst / hour.

[0145] In a preferred embodiment, little or no scavenging agent is used in the method to produce ethylene polymers. Preferably, the scavenging agent (e.g., trialkylaluminum) is present at 0 mol%, or the scavenging agent is present at a molar ratio of scavenging agent metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, and preferably less than 10:1.

[0146] In a preferred embodiment, polymerization is carried out: 1) at a temperature of 0-300°C (preferably 25-150°C, more preferably 40-120°C, more preferably 45-80°C); 2) at a pressure of atmospheric pressure to 10 MPa (preferably 0.35-10 MPa, more preferably 0.45-6 MPa, more preferably 0.5-4 MPa); 3) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane). The polymerization reaction is carried out in a solvent at a concentration of less than 1 wt%, preferably less than 0.5 wt%, preferably 0 wt%, based on the weight of the solvent; 4) the polymerization is preferably carried out in a reaction zone; and 5) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001-50 psig (0.007-345 kPa) (preferably 0.01-25 psig (0.07-172 kPa), more preferably 0.1-10 psig (0.7-70 kPa)).

[0147] The "reaction zone," also known as the "polymerization zone," is the container in which polymerization occurs, such as in a batch reactor. When multiple reactors are used in series or parallel configurations, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, polymerization takes place in a single reaction zone. The room temperature is 23°C, unless otherwise specified.

[0148] Gas phase polymerization

[0149] Typically, in fluidized bed processes for producing polymers, a gas stream containing one or more monomers is continuously circulated through a fluidized bed under reaction conditions and in the presence of a catalyst. The gaseous stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is removed from the reactor, and fresh monomers are added to replace the monomers polymerized. (See, for example, US Patents 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference in their entirety.)

[0150] Slurry phase aggregation

[0151] Slurry polymerization is typically operated at pressures ranging from 1 to about 50 atmospheres (15 psi to 735 psi, 103 kPa to 5068 kPa) or even higher, and at temperatures ranging from 0°C to about 120°C. In slurry polymerization, a suspension of solid particulate polymer is formed in a liquid polymerization diluent medium in which monomers and comonomers are added together with a catalyst. The suspension is removed from the reactor intermittently or continuously, volatile components are separated from the polymer in the reactor, and optionally recycled back to the reactor after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3-7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under polymerization conditions. When propane is used as the medium, the method must be operated above the critical temperature and pressure of the reaction diluent. Hexane or isobutane is preferably used as the medium.

[0152] In one embodiment, the preferred polymerization technique used in this invention is referred to as particulate polymerization or a slurry process, wherein the temperature is maintained below the temperature at which the polymer enters the solution. This technique is well known in the art, for example, as described in US 3,248,179, the entire contents of which are incorporated herein by reference. A preferred temperature range in the particulate process is about 85°C to about 110°C. Two preferred polymerization methods for the slurry process are those employing a loop reactor and those employing a stirred reactor with multiple reactors connected in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Furthermore, other examples of slurry processes are described in US 4,613,484, the entire contents of which are incorporated herein by reference.

[0153] In another embodiment, the slurry process is carried out continuously in a loop reactor. A catalyst, either as a slurry in isobutane or as a dry, free-flowing powder, is periodically injected into the reactor loop, which itself is filled with a circulating slurry of polymer particles grown in an isobutane diluent containing monomers and comonomers. Hydrogen, optionally, may be added in a molecular weight controlled manner. (In one embodiment, 500 ppm or less of hydrogen is added, or 400 ppm or less, or 300 ppm or less. In other embodiments, at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more.)

[0154] Depending on the desired polymer melting characteristics, the reactor can be maintained at pressures ranging from 3620 kPa to 4309 kPa and temperatures ranging from approximately 60°C to approximately 104°C. Because most of the reactor is in a double-walled configuration, the heat of reaction is removed through the annular tube walls. The slurry is exited from the reactor at regular intervals or continuously, sequentially through a heated low-pressure flash vessel, a rotary dryer, and a nitrogen purging column to remove isobutane diluent and all unreacted monomers and comonomers. The resulting hydrocarbon-free powder is then formulated for various applications.

[0155] Other additives may also be used in the polymerization as needed, such as one or more scavengers, accelerators, modifiers, chain transfer agents (such as diethylzinc), reducing agents, oxidizing agents, hydrogen, alkylaluminum or silanes.

[0156] Useful chain transfer agents are typically alkylaluminoxanes, compounds represented by the formula AlR3, ZnR2 (where each R independently represents a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0157] Polyolefin products

[0158] The present invention also relates to compositions of substances produced by the methods described herein.

[0159] In a preferred embodiment, the method described herein produces ethylene homopolymers or ethylene copolymers, such as ethylene-α-olefins (preferably C3-C4). 20 ) copolymers (such as ethylene-butene copolymers, ethylene-hexene and / or ethylene-octene copolymers) having: Mw / Mn greater than 1-4 (preferably greater than 1-3).

[0160] Similarly, the method of the present invention produces ethylene copolymers. In a preferred embodiment, the copolymer produced herein has 0-25 mol% (or 0.5-20 mol%, or 1-15 mol%, preferably 3-10 mol%) of one or more C3-C4 groups. 20 Olefin comonomer (preferably C3-C) 12 α-olefins, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene.

[0161] In a preferred embodiment, the monomer is ethylene, and the comonomer is hexene, preferably 1-15 mol% hexene, or 1-10 mol%.

[0162] Typically, the polymers produced here have a Mw of 5,000-1,000,000 g / mol (preferably 25,000-750,000 g / mol, more preferably 50,000-500,000 g / mol), and / or an Mw / Mn greater than 1-40 (or 1.2-20, or 1.3-10, or 1.4-5, 1.5-4, or 1.5-3).

[0163] In a preferred embodiment, the polymer produced herein has a single-peak or multi-peak molecular weight distribution (GPC) determined by gel permeation chromatography. "Single-peak" means the GPC trajectory has one peak or inflection point. "Multi-peak" means the GPC trajectory has at least two peaks or inflection points. An inflection point is the point where the sign of the second derivative of the curve changes (e.g., from negative to positive or vice versa).

[0164] Unless otherwise stated, Mw, Mn, and MWD are determined by GPC as described in the experimental section below.

[0165] In a preferred embodiment, the compositional distribution width index (CDBI) of the polymer produced herein is 50% or higher, preferably 60% or higher, and most preferably 70% or higher. CDBI is a measure of the monomer compositional distribution within the polymer chain, measured by the process described in PCT Publication WO 93 / 03093, published February 18, 1993, specifically columns 7 and 8, and in Wild et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982), and US 5,008,204, including ignoring fractions with a weight-average molecular weight (Mw) below 15,000 when determining the CDBI.

[0166] In another embodiment, the polymer produced herein exhibits two peaks in a TREF measurement (see below). The two peaks in the TREF measurement used in this specification and the appended claims refer to two distinct normalized ELS (evaporated mass light scattering) response peaks in a graph of the normalized ELS response (vertical axis or y-axis) versus elution temperature (horizontal axis or x-axis, with temperature increasing from left to right) when using the TREF method described below. In this context, a "peak" refers to a point where the overall slope of the graph changes from positive to negative as temperature increases. Between the two peaks is a local minimum, where the overall slope of the graph changes from negative to positive as temperature increases. The "overall trend" of the graph is intended to exclude multiple local minima and maxima that can occur at intervals of 2°C or less. Preferably, the two distinct peaks are separated by at least 3°C, more preferably by at least 4°C, and even more preferably by at least 5°C. Additionally, the two distinct peaks appear on the graph at temperatures above 20°C and below 120°C, where the elution temperature is run to 0°C or lower. This limitation avoids confusion with apparent peaks formed at low temperatures due to the material's continued solubility at the lowest elution temperatures. Two peaks on such a graph represent a bimodal composition distribution (CD). The bimodal CD can also be determined by other methods known to those skilled in the art. If the above methods do not show two peaks, an alternative method for TREF measurement can be used, disclosed in B. Monrabal, "Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Polyolefins," Journal of Applied Polymer Science, Vol. 52, 491-499, (1994).

[0167] TREF method

[0168] Temperature elution fractionation (TREF) analysis was performed using a CRYSTAF-TREF 200+ instrument from Polymer Char, SA, Valencia, Spain. A general description of the principles of TREF analysis and the specific equipment used is given below: Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem. 2011, 399, 1557. Figure 3 This is a suitable schematic diagram of the specific device used; however, with Figure 3The connection of the six-way valve shown differs from that of the device used in practice in that the line connected to the 11 o'clock port is connected to the 9 o'clock port, and the line connected to the 9 o'clock port is connected to the 11 o'clock port. Details regarding the analytical methods and characteristics of the equipment used are as follows.

[0169] Sample solutions and elutions were prepared using 1,2-dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene). The sample to be analyzed (approximately 25 mg, but less than approximately 10 mg) was dissolved in ODCB (25 mL, measured at ambient temperature) by stirring at 150 °C for 60 minutes. A small amount (0.5 ml) of solution was introduced into a column (15 cm long × 3 / 8” outer diameter) packed with an inert support (stainless steel balls) at 150 °C, and the column temperature was stabilized at 140 °C for 45 min. The temperature was then lowered to 30 °C at a cooling rate of 1 °C / min, allowing the sample volume to crystallize within the column. The column was held at 30 °C for 15 min, and then an ODCB flow (1 ml / min) was injected into the column for 10 min to elute, and the polymer without crystallization (soluble fraction) was measured. An infrared detector (Polymer Char IR4) was used to generate an absorbance signal proportional to the concentration of the polymer in the eluent. A complete TREF curve was then generated by increasing the column temperature from 30 °C to 140 °C at a rate of 2 °C / min while maintaining an ODCB flow rate of 1 ml / min to elute and measure the dissolved polymer.

[0170] blends

[0171] In another embodiment, the polymer produced herein (preferably an ethylene-hexene copolymer) is combined with one or more other polymers and then molded into films, molded parts, or other articles. Other useful polymers include polyethylene, isotactic polypropylene, high-isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene with ethylene and / or butene and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate, or any other polymer that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamino, polycarbonate, PET resin, cross-linked polyethylene, ethylene and vinyl alcohol copolymers (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0172] In a preferred embodiment, the polymer (preferably, polyethylene produced herein) is present in the above blend at 10-99 wt%, preferably 20-95 wt%, even more preferably at least 30-90 wt%, even more preferably at least 40-90 wt%, even more preferably at least 50-90 wt%, even more preferably at least 60-90 wt%, even more preferably at least 70-90 wt%, based on the weight of the polymer in the blend.

[0173] The above-described blends can be produced by mixing the polymer of the present invention with one or more polymers (as described above), by connecting reactors in series to prepare reactor blends, or by using more than one catalyst in the same reactor to produce multiple polymers. The polymers can be mixed together and then fed into an extruder, or they can be mixed in an extruder.

[0174] Blends can be formed using conventional equipment and methods, such as by drying the individual components and then melt-blending them in a mixer, or by directly mixing the components together in a mixer, such as a Banbury mixer, Haake mixer, Brabender internal mixer, or a single-screw or twin-screw extruder. This can include compounding extruders and side-arm extruders used directly downstream of the polymerization process, which may include blending resin powder or granules on the hopper of a film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and / or in the product (e.g., a film) formed from the blend, as needed. Such additives are known in the art and may include, for example, fillers; antioxidants (e.g., hindered phenols, such as IRGANOX). TM 1010 or IRGANOX TM 1076 (available from Ciba-Geigy); phosphites (e.g., IRGAFOS) TM 168 (available from Ciba-Geigy); anti-adhesion additives; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and glyceryl stearate, and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-sticking agents; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc, etc.

[0175] membrane

[0176] Specifically, any of the aforementioned polymers, such as the aforementioned ethylene copolymers or blends thereof, can be used in a variety of end-use applications. These applications include, for example, single-layer or multi-layer blown, extruded, and / or shrink films. These films can be formed by many well-known extrusion or co-extrusion techniques, such as blown film processing techniques, wherein the composition can be extruded through an annular die in a molten state, then expanded into a uniaxially or biaxially oriented melt, then cooled to form a tubular blown film, which can then be axially cut and unfolded to form a flat film. The film can subsequently be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more layers of the film can be oriented laterally and / or longitudinally to the same or different degrees. Uniaxial orientation can be accomplished using typical cold-drawing or hot-drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a twin-bubble process, and can be performed before or after the individual layers are polymerized together. For example, a polyethylene layer can be extruded, coated, or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be co-extruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and then, optionally, the combination can be further oriented. Typically, the film orientation is at most 15% in the machine direction (MD), preferably 5 to 7%, and at most 15% in the transverse direction (TD), preferably 7 to 9%. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions.

[0177] The thickness of the membrane varies depending on the intended application; however, membranes with a thickness of 1–50 μm are generally suitable. Membranes used for packaging are typically 10–50 μm thick. The thickness of the sealing layer is typically 0.2–50 μm. The sealing layer can be present on both the inner and outer surfaces of the membrane, or it can be present only on the inner or outer surface.

[0178] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave modification. In a preferred embodiment, one or both surface layers are modified by corona treatment. Detailed Implementation

[0179] experiment

[0180] The room temperature is 23°C, unless otherwise stated.

[0181] MAO is methylaluminoxane (30 wt%, in toluene), obtained from Albemarle.

[0182] Gel permeation chromatography with three detectors (GPC-3D)

[0183] Mw, Mn, and Mw / Mn were determined using high-temperature gel permeation chromatography (Agilent PL-220) equipped with three online detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details (including detector calibration) are described in: T. Sun, P. Brant, R.R. Chance, and W.W. Graessley, Macromolecules, Vol. 34, No. 19, pp. 6812-6820, (2001) and references therein. Three Agilent PLgel 10 μm mixed B LS columns were used. The nominal flow rate was 0.5 mL / min, and the nominal injection volume was 300 μL. All transfer lines, columns, viscometers, and differential refractive index detectors (DRI detectors) were kept in an oven maintained at 145 °C. The solvent used in this experiment was prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an online degasser before entering the GPC-3D. The polymer solution was prepared as follows: dried polymer was placed in a glass container, the desired amount of TCB was added, and the mixture was heated at 160 °C with continuous shaking for approximately 2 hours. All quantities were measured by gravimetric analysis. The TCB density used for the polymer concentration, expressed in mass / volume units, was 1.463 g / mL at room temperature and 1.284 g / mL at 145 °C. Injection concentrations were 0.5–2.0 mg / mL, with lower concentrations used for higher molecular weight samples. The DRI detector and viscometer were purged before each sample run. The flow rate in the apparatus was then increased to 0.5 mL / min, and the DRI was stabilized for 8 hours before injecting the first sample. The LS laser was turned on for at least 1–1.5 hours before sample run. The concentration c at each point in the chromatogram is the DRI signal I minus the baseline. DRI The following equation is used for calculation:

[0184] c = K DRI I DRI / (dn / dc)

[0185] Where K DRI This is a constant determined by DRI correction, and (dn / dc) is the refractive index increment of the system. At 145 °C and λ = 690 nm, the refractive index of TCB is n = 1.500. In such descriptions of the GPC-3D method, the parameters are expressed in units of concentration (g / cm³). 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity is expressed in dL / g.

[0186] The LS detector was a Wyatt Technology high-temperature DAWN HELEOS. The molecular weight M at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971).

[0187]

[0188] Where ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by DRI analysis, A2 is the second virial coefficient, P(θ) is the waveform factor used for monodisperse random coils, and K... o It is the system's optical constant:

[0189]

[0190] Where N A dn / dc is Avogadro's constant, and (dn / dc) is the refractive index increment of the system, which takes the same value obtained from the DRI method. The TCB refractive index at 145℃ and λ = 657 nm is n = 1.500.

[0191] A high-temperature Viscotek Corporation viscometer (featuring four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors) is used to determine specific viscosity. One sensor measures the total pressure drop along the detector, while the other sensor is located between the two sides of the bridge and measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is... s It is calculated from their output. The intrinsic viscosity [η] at each point in the chromatogram is calculated by the following equation:

[0192] η s = c[η] + 0.3(c[η]) 2

[0193] Where c is the concentration, which is measured by DRI output.

[0194] Branching index g' vis Also abbreviated as g', it is calculated using the output of the GPC-DRI-LS-VIS method as follows: The average intrinsic viscosity of the sample [η]. avg It is calculated using the following formula:

[0195]

[0196] The summation occurs on chromatographic segment i between the integration limits.

[0197] Branching index g' vis Defined as:

[0198]

[0199] Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis. Z is the branching index (g'). Zave Use the slice i at the polymer peak multiplied by the slice quality Mi. 2 Ci is calculated based on polymer concentration.

[0200] All molecular weights are weight average unless otherwise stated. All molecular weights are reported in g / mol unless otherwise stated.

[0201] Molecular weight and comonomer composition were determined using polymer Char GPC-IR.

[0202] The distribution and timing of molecular weights (Mw, Mn, Mw / Mn, etc.) and comonomer contents (C2, C3, C6, etc.) were determined using high-temperature gel permeation chromatography (PolymerChar GPC-IR) equipped with an infrared detector array IR5 based on a multi-channel bandpass filter, with one broadband channel for measuring polymer concentration and two narrow-band channels for characterizing the composition. Polymer separation was performed using three Agilent PLgel 10 μm Mix-B LS columns. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) containing 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm PTFE filter and degassed using an online degasser before entering the GPC instrument. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 μL. The entire system, including the transfer circuit, column, and detector, was kept in an oven maintained at 145 °C. Weigh a given amount of polymer sample and seal it in a standard vial containing 10 μL of flow marker (heptane). After loading the vial into the autosampler, the polymer automatically dissolves in the instrument containing 8 mL of TCB solvent. The polymer dissolves at 160 °C with continuous shaking, approximately 1 hour for most PE samples or 2 hours for PP samples. The TCB density used for concentration calculation is 1.463 g / mL at room temperature and 1.284 g / mL at 145 °C. Sample solution concentrations range from 0.2 to 2.0 mg / mL, with lower concentrations used for higher molecular weight samples.

[0203] The concentration c at each point in the chromatogram is calculated using the following formula from the broadband IR5 signal I minus the baseline:

[0204] c=αI

[0205] Where α is a mass constant determined using PE or PP standards. Mass recovery is calculated by the ratio of the integral area of ​​the concentration chromatography over the elution volume to the injected mass equal to the predetermined concentration multiplied by the injection loop volume.

[0206] Molecular weight was determined by combining a universal correction relation with column corrections based on a series of monodisperse polystyrene (PS) standards. MW was calculated for each elution volume according to the following equation.

[0207]

[0208] The variable with the subscript "X" represents the test sample, while the variable with the subscript "PS" represents PS. In this method, a PS =0.67, K PS =0.000175, while a X and K X Obtained from published literature. Specifically, for PE, a / K = 0.695 / 0.000579, and for PP, it is 0.705 / 0.0002288.

[0209] The comonomer composition is determined by the ratio of the IR detector intensities corresponding to the CH2 and CH3 channels, which are calibrated using a series of PE and PP homopolymer / polymer standards whose nominal values ​​are pre-determined by NMR or FTIR.

[0210] CRC was performed using the following procedure: Cross-fractional chromatography (CFC) analysis was conducted using the CFC-2 instrument, manufactured by PolymerChar, SA, Valencia, Spain. A general description of the principles of CFC analysis and the specific apparatus used is found in the following articles: Ortin, A.; Monrabal, B.; Sancho-Tello, J. Macromol. Symp. 2007, 257, 13. Figure 1 A suitable schematic diagram of the specific apparatus used is provided. Details of the analytical method and characteristics of the apparatus used are as follows.

[0211] Sample solutions and elutions were prepared using 1,2-dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxymethylbenzene). The sample to be analyzed (approximately 50 mg) was dissolved in ODCB (25 mL, measured at ambient temperature) by stirring at 150 °C (200 rpm) for 75 minutes. A small amount (0.5 ml) of solution was introduced into a TREF column (stainless steel; 3 / 8” outer diameter; 15 cm length; filled with non-porous stainless steel microspheres) at 150 °C. The column temperature was stabilized at 120–125 °C for 30 min, approximately 20 °C higher than the highest temperature fraction included in the GPC analysis obtained in the final bivariate distribution. The temperature was then lowered to 30 °C at a cooling rate of 0.2 °C / min to allow such a sample amount to crystallize in the column. This low temperature was maintained for 10 min, and then a solvent stream (1 ml / min) was injected into the TREF column to elute the soluble fraction (SF) to the GPC column (3x PLgel 10 μm mixed-B). 300x7.5mm (Varian, Inc.); The GPC column oven was maintained at a high temperature (140°C). SF was eluted from the TREF column for 5 minutes, then the injection valve was placed in the "load" position for 40 minutes to completely wash away all SF through the GPC column (standard GPC injection). All subsequent higher temperature fractions were analyzed using overlapping GPC injections, where the polymer was allowed to dissolve for at least 16 minutes at each temperature step, followed by injection from the TREF column into the GPC column for 3 minutes. Absorbance signals were generated using an IR4 (PolymerChar) infrared detector, which were proportional to the concentration of the polymer in the eluent.

[0212] A universal calibration method was used to determine the molecular weight distribution (MWD) and molecular weight average (Mn, Mw, etc.) of eluted polymer fractions. Universal calibration curves were generated using 13 narrow molecular weight distribution polystyrene standards (obtained from PolymerLabs, UK) in the range of 1.5–8200 kg / mol. Mark-Houwink parameters were obtained from Annex I of Mori, S.; Barth, HGSize Exclusion Chromatography; Springer, 1999. The following values ​​were used: K = 1.38 x 10⁻⁴ dl / g and α = 0.7 for polystyrene; and K = 5.05 x 10⁻⁴ dl / g and α = 0.693 for polyethylene. For polymer fractions eluted at temperature steps with a weight percentage (wt% recovery) below 0.5%, MWD and molecular weight average were not calculated; furthermore, such polymer fractions were not included in the calculation of cumulative MWD and molecular weight average for fractions.

[0213] Example 1

[0214] Synthesis of bridged monocyclopentadienyl titanium transition metal compounds.

[0215]

[0216] Complex A can be prepared according to US RE 37,788. Complex B can be prepared according to US 5,955,625. Complex C can be purchased from Austin Chemical Company Inc., Buffalo Grove, IL, or prepared by a known literature route. Complex D is prepared as follows:

[0217] 2-Bromo-2-methylpropionyl bromide (Aldrich), AlCl3 (Merck), NaBH4 (Aldrich), TsOH (Aldrich), dichlorodimethylsilane (Merck), tert-butylamine (Merck), 2.5M n BuLi in hexane (Chemetall GmbH), MeMgBr in ether (Aldrich), TiCl4(THF)2 (Aldrich), 2-methylindan-1-one (Aldrich), methyl bromide (Acros), K2CO3 (Merck), Na2SO4 (Akzo Nobel), hydrazine hydrate (Merck), ethylene glycol (Merck), KOH (Merck), 37% hydrochloric acid (Merck), potassium tert-butoxide (Acros), methanol (Merck), dichloromethane (Merck), hexane (Merck), toluene (Merck), silica gel 60 (40-63 μm; Merck), and CDCl3 (Deutero GmbH) were used as is. THF and diethyl ether (Merck; ether), freshly distilled from carbonyl benzophenone, were used for organometallic synthesis and catalysis.

[0218] Synthesis of pre-catalyst D

[0219]

[0220] Add 176 g (1.21 mol) of 2-methylindan-1-one and 205 g (1.44 mol, 1.2 eq.) of MeI in 200 mL of THF dropwise to a solution cooled to 0 °C. tThe solution was prepared in 1200 ml THF for 4 hours. The reaction mixture was stirred overnight at room temperature and then poured into 2 liters of water. The crude product was extracted with 300 ml hexane and then with 2 × 300 ml dichloromethane. The combined organic extracts were dried over K₂CO₃, passed through a short pad of silica gel 60 (40-63 μm), and the eluent was evaporated to dryness to give a red oil. The oil was then vacuum distilled to give 185 g (96%) of 2,2-dimethyl-1-one as a pale yellow oil, which crystallized at room temperature to a boiling point of 76-78 °C / 5 mm Hg.

[0221] For C 11 H 12 Analysis and calculation of O: C, 82.46; H, 7.55. Actual measurement: C, 82.24; H, 7.61.

[0222] 1 H NMR (CDCl3): δ7.76 (d, 1H, J=7.6Hz), 7.59 (dt, 1H, J=7.6, 1.2Hz), 7.44-7.35 (m, 2H), 3.00 (s, 2H), 1.24 (s, 6H). 13 C{ 1 H} NMR (CDCl3): δ211.38, 152.18, 135.30, 134.77, 127.37, 126.59, 124.40, 45.43, 42.81, 25.22.

[0223]

[0224] A mixture of 129 g (approximately 2.3 mol) KOH, 182.5 g (1.14 mol) 2,2-dimethylindan-1-one, and 144 mL of hydrazine hydrate was refluxed in 850 mL of ethylene glycol for 5 hours. Then, a Claisen distillation head with a condenser was used instead of a reflux condenser to remove H₂O, NH₂, NH₂, the product, and the mixture of ethylene glycol until the distillation temperature reached 195 °C. The residue was then cooled to room temperature, and 300 mL of ethylene glycol, a second portion of 2,2-dimethylindan-1-one (182.5 g, 1.139 mol), and hydrazine hydrate (144 mL) were added, and the reduction procedure was repeated as described above. The upper layer of the combined distillate (from two consecutive reductions) was separated, and the aqueous phase was diluted with 1,000 mL of water. The crude product was extracted with 3 × 300 mL of dichloromethane. The combined organic extracts were washed with 1M HCl, dried with K2CO3, passed through a silica gel 60 short pad (40-63 μm), and the eluent was evaporated to dryness. The residue was vacuum distilled to give 290 g (87%) of a colorless liquid of 2,2-dimethylaminomethylene, boiling point 73.5 °C / 20 mm Hg.

[0225] For C 11 H 14 Calculated values: C, 90.35; H, 9.65. Measured values: C, 90.50; H, 9.73.

[0226] 1 H NMR (CDCl3): δ7.19-7.08 (m, 4H, Ar- H ), 2.72(s, 4H, 2x CH2 In indene), 1.15 (s, 6H, 2x) CH3 In Indame (in Indame). 13 C{ 1 H} NMR (CDCl3): δ143.51, 125.93, 124.70, 47.70, 40.05, 28.77.

[0227]

[0228] A suspension of 420 g (3.15 mol, 2.66 eq.) AlCl3 cooled to -40 °C in 400 mL of dichloromethane was followed by the addition of a solution of 273 g (1.19 mol) 2-bromo-2-methylpropionyl bromide and 173.5 g (1.19 mol) 2,2-dimethylindene in 300 mL of dichloromethane for 30 minutes. The cooling bath was then removed, and the solution was stirred overnight at room temperature. The reaction mixture was poured into 2 kg of crushed ice, the organic phase was separated, and the aqueous phase was extracted with 3 × 500 mL of dichloromethane. The combined organic extracts were washed with aqueous K₂CO₃, then with dry anhydrous K₂CO₃, passed through a silica gel 60 short pad (40-63 μm), and the eluent was evaporated to dryness to give a yellow oil. The oily substance was distilled under vacuum to give 245 g (96%) of 2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indane-1(2H)-one (based on NMR spectroscopy evidence, the oily substance contained approximately 85-90% of the desired product) as a pale yellow oily substance that rapidly crystallized at room temperature to a boiling point of 153-165 °C / 1 mm Hg. The crude product was then recrystallized from 700 ml of hot hexane. The crystals precipitated in this solution were collected and dried under vacuum at +5 °C for one week. This process yielded 191 g (75%) of pure 2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indane-1(2H)-one as a white crystalline solid. Evaporation and drying of the mother liquor gave 52.4 g of a mixture of approximately 1:1 isomers of linear and angled indane ones.

[0229] For C 15 H 18Analysis and calculation of O: C, 84.07; H, 8.47. Measured values: C, 84.42; H, 8.60.

[0230] 1 H NMR (CDCl3): δ7.52 (s, 1H, Ar- H ), 7.21(s, 1H, Ar- H ), 3.32 (dd, 1H, J = 16.5 Hz, J = 7.1 Hz, 3-H in indan-1-one), 2.75, 2.73 (2xs, 4H, 2x CH2 In indene), 2.77-2.58 (m, 2H, 2, 3'-H in Indan-1-one), 1.29 (d, 3H, J = 7.3 Hz, 2- Me In indan-1-one), 1.15 (s, 6H, 2x) CH3 In Indame (in Indame). 13 C{ 1 H} NMR (CDCl3): δ208.99, 152.64, 152.40, 143.51, 135.08, 122.43, 119.65, 47.78, 46.77, 42.28, 40.65, 34.74, 28.44, 16.44.

[0231]

[0232] To a solution of 99.1 g (463 mmol) of 2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one cooled to 5 °C in 450 mL of THF, 26.3 g (695 mmol) of NaBH4 was added. Then, 225 mL of methanol was added dropwise over approximately 5 h at 5 °C with vigorous stirring. The resulting mixture was stirred at room temperature for 3 h and then evaporated to dryness. The residue was separated into layers between 500 mL of dichloromethane and 500 mL of 2 M HCl. The organic layer was separated, and the aqueous layer was extracted with 100 mL of dichloromethane. The combined organic extracts were evaporated to dryness to give a colorless oil. To a solution of this oil in 1000 mL of toluene, 1 g of TsOH was added, and the mixture was refluxed with a Dean-Stark head for 20 min, then cooled to room temperature using a water bath. The solution was washed with 10% aqueous Na2CO3. The organic layer was separated, and the aqueous layer was extracted with 2 × 100 mL of dichloromethane. The combined organic extracts were dried with K₂CO₃ and then passed through a silica gel 60 short pad (40-63 μm). The silica gel pad was further washed with 100 mL of dichloromethane. The combined organic eluents were evaporated and dried to give a pale yellow liquid. The crude product was vacuum distilled to give 77.7 g (85%) of 2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indane as a pale yellow oil, which crystallized rapidly at room temperature to a boiling point of 144-148 °C / 10 mm Hg.

[0233] For C 15 H 18 Calculated values: C, 90.85; H, 9.15. Measured values: C, 90.60; H, 9.04.

[0234] 1 H NMR (CDCl3): δ7.14 (s, 1H, Ar- H ), 7.03 (s, 1H, Ar- H ), 6.41 (bs, 1H, Cp- of vinyl H In indenyl), 3.21(s, 2H, benzyl C) H2 In indene), 2.70 (s, 4H, 2x) CH2 In indene), 2.11(s, 3H, 2-Me in indene), 1.14(s, 6H, 2x) CH3 In Indame (in Indame). 13 C{ 1 H} NMR (CDCl3): δ144.83, 144.22, 141.58, 141.35, 138.85, 127.08, 119.94, 116.08, 47.58, 47.53, 42.22, 40.25, 28.88, 16.79.

[0235]

[0236] To a solution of 9.92 g (50.0 mmol) of 2,2,6-trimethyl-1,2,3,5-tetrahydro-s-indole in 200 mL of toluene at room temperature, 20.0 mL (50.0 mmol) of 2.5 M hexane was added. n BuLi. The viscous solution was stirred for 3 hours, and then 20 ml of THF was added. The suspension was stirred at 60 °C for 1 hour, then cooled to -30 °C, and 20 ml (21.4 g, 166 mmol, 3.3 eq.) of dichlorodimethylsilane was added in one go. The resulting solution was refluxed for 1 hour and then filtered through a glass sieve (G3). The precipitate was washed separately with 50 ml of toluene. The combined filtrates were evaporated to dryness to give 14.7 g (about 100%) of dichloro(dimethyl)(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)silane as a viscous, pale yellow oil, which was used further without further purification.

[0237] For C 17 H 23 Analytical calculation of ClSi: C, 70.19; H, 7.97. Measured: C, 70.44; H, 8.20.

[0238] 1 H NMR (CDCl3): δ7.25 (s, 1H, Ar- H ), 7.12(s, 1H, Ar- H ), 6.56(s, 1H, Cp- of vinyl H In indenyl), 3.49 (s, 1H, benzyl Cp-) H In indene), 2.85-2.65 (m, 4H, C5) H4 Me2), 2.26 (s, 3H, 2-Me), 1.19, 1.14 (2xs, 2x3H, C5H4 Me2 ), 0.40, 0.15 (2xs, 2x3H, Si Me2 Cl). 13 C{ 1 H} NMR (CDCl3): δ144.41, 143.72, 141.26, 140.71, 138.70, 127.40, 119.94, 116.26, 49.33, 47.64, 47.55, 40.40, 28.85, 17.57, 1.07, -0.62.

[0239]

[0240] Add 20 ml (50 mmol) of 2.5 M hexane to a solution of 6.30 ml (4.39 g, 60 mmol, 1.2 eq.) tert-butylamine in 150 ml of ether cooled to -50 °C. n BuLi. The reaction mixture was stirred at room temperature for 4 hours, and the resulting suspension was cooled to -78°C. A solution of 14.7 g (50 mmol) of dichloro(2,6,6-trimethyl-1,5,6,7-tetrahydro-S-indarsen-1-yl)silane in 150 mL of ether was added. The mixture was warmed to room temperature and stirred overnight. It was then evaporated to dryness, and the residue was dissolved in 250 mL of toluene. The solution was filtered through a glass sieve (G3), and the precipitate was washed separately with 50 mL of toluene. The filtrate was concentrated under vacuum to give a viscous, pale yellow oil (15.6 g, 95%). Based on NMR spectroscopy, the oily substance was found to consist of two isomers: N-(tert-butyl)-1,1-dimethyl-1-(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)silaneamine (allyl isomer, approximately 70%) and N-(tert-butyl)-1,1-dimethyl-1-(2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indarsen-1-yl)silaneamine (vinyl isomer, approximately 30%).

[0241] For C 21 H 33 Analytical calculation of NSi: C, 77.00; H, 10.15; N, 4.28. Measured values: C, 77.29; H, 10.40; N, 4.01.

[0242] N-(tert-butyl)-1,1-dimethyl-1-(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)silaneamine (allyl isomer): 1 H NMR (CDCl3): δ7.32 (s, 1H, Ar- H ), 7.19(s, 1H, Ar- H ), 6.58 (s, 1H, Cp- of vinyl group H In indene), 3.39 (s, 1H, Cp- of benzyl) H In indene), 2.95-2.75 (m, 4H, C5) H4 Me2), 2.35(s, 3H, 2-Me), 1.35-1.21(m, 15H, t This +C5H4 Me2 ), 0.68 (bs, 1H, N) H ), 0.24, 0.04 (2xs, 2x3H, Si Me2 ).

[0243] N-(tert-butyl)-1,1-dimethyl-1-(2,6,6-trimethyl-3,5,6,7-tetrahydro-s-indarsen-1-yl)silaneamine (vinyl isomer): 1 H NMR (CDCl3): δ7.54 (s, 1H, Ar- H ), 7.27(s, 1H, Ar- H ), 3.40 (s, 2H, benzyl Cp- H In indene), 2.95-2.75 (m, 4H, C5) H4 Me2), 2.36(s, 3H, 2-Me), 1.35-1.21(m, 15H, t This +C5H4 Me2 ), 0.89 (bs, 1H, N) H ), 0.54 (s, 6H, Si) Me2 ).

[0244]

[0245] A solution of 15.6 g (47.6 mmol) of N-(tert-butyl)-1,1-dimethyl-1-(2,6,6-trimethyl-tetrahydro-s-indarsen-1-yl)silane (prepared as described above) in 200 ml of ether was added in a single batch at -78 °C to 40.0 ml (100 mmol) of 2.5 M hexane. n BuLi. The mixture was stirred at room temperature for 4 hours, and the slightly reddish solution was cooled to -78°C. 16.7 g (50.0 mmol) of TiCl4(THF)2 was added in one go. The resulting mixture was stirred at room temperature for 24 hours and then evaporated to dryness. The residue was extracted with 200 mL of warm toluene and filtered through a glass sieve (G3) to form a hot suspension. The precipitate was washed separately with 2 x 50 mL of hot toluene. The combined filtrates were evaporated to dryness, and the residue was extracted with 4 x 100 mL of warm hexane. The combined organic extracts were evaporated to about 250 mL. The crystals precipitated overnight from this solution at room temperature were collected, washed with 10 mL of hexane, and dried under vacuum. This process yielded 8.39 g (40%) of Me2Si(η). 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)(η 1 -N t Bu)TiCl2. The mother liquor was concentrated to approximately 100 ml. The crystals precipitated from this solution overnight at room temperature were collected again, washed with 10 ml of hexane, and dried under vacuum. This process yielded 2.71 g (13%) of the target complex. Therefore, Me2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)(η1 -N t The overall yield of Bu)TiCl2 was 53%.

[0246] For C 21 H 31 Analytical calculation of Cl2NSiTi: C, 56.76; H, 7.03; N, 3.15. Measured values: C, 56.90; H, 7.18; N, 2.97.

[0247] 1 H NMR (CDCl3): δ7.46 (s, 1H, Ar- H ), 7.40 (s, 1H, Ar- H ), 7.02 (s, 1H, Cp- H In indene), 2.85-2.67 (m, 4H, C5) H4 Me2), 2.34(s, 3H, 2-Me), 1.38(s, 9H, t This ), 1.145, 1.138 (2xs, 2x3H, C5H4 Me2 ), 0.90, 0.76 (2xs, 2x3H, Si Me2 ).

[0248]

[0249] 8.39 g (35.9 mmol) of Me₂Si(η) cooled to -30 °C 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)(η 1 -N t A suspension of Bu)TiCl2 in 150 ml of ether was added in a single batch to 28 ml (59.1 mmol, 3.1 eq.) of 2.11 M MeMgBr in ether. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was extracted with 4 × 50 ml of warm hexane. The combined extracts were evaporated to about 30 ml and then filtered through a glass sieve (G3). Crystals precipitated from the filtrate overnight at -30 °C were collected, washed with 2 × 10 ml of cold (-30 °C) hexane, and dried under vacuum. This process yielded 4.53 g (11.2 mmol, 60%) of Me2Si(η). 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)-(η 1 -N tBu)TiMe2. The mother liquor was concentrated to approximately 10 ml. Crystals precipitated overnight from the filtrate at -30°C were collected, washed with 10 ml of cold (-30°C) hexane, and dried under vacuum. This process yielded 1.45 g (19%) of the target complex. Therefore, Me2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsen-1-yl)(η 1 -N t The overall yield of Bu)TiMe2 was 79%.

[0250] For C 23 H 37 Analytical calculation of NSiTi: C, 68.46; H, 9.24; N, 3.47. Measured values: C, 68.19; H, 9.36; N, 3.41.

[0251] 1 H NMR (CDCl3): δ7.42 (s, 1H, Ar- H ), 7.22(s, 1H, Ar- H ), 6.94 (s, 1H, Cp- H In indene), 2.75 (s, 2H, C5) H4 Me2), 2.69 (d, 1H, J=15.47, C5 H4 Me2), 2.625 (d, 1H, J=15.47, C5 H4 Me2), 2.13(s, 3H, 2-Me), 1.50(s, 9H, t This ), 1.13, 1.11 (2xs, 2x3H, C5H4 Me2 ), 0.65, 0.56 (2xs, 2x3H, Si Me2 ), 0.5, -0.52 (2xs, 2x3H, Ti Me2 ).

[0252] Preparation of fluorinated silicon dioxide.

[0253] a) Preparation of fluorinated silica-1 by dry mixing.

[0254] 50g Grace Davison D948 TMSilica and 2.3 g of (NH4)2SiF6 (12.9 mmol, 1.55 mmol F / g silica) were combined in a plastic bottle. The mixture was tumbled together for 1 hour. The solid mixture was transferred to a tube furnace and heated to 200 °C under a constant nitrogen flow (temperature program: 25 °C / hr to 150 °C; hold at 150 °C for 4 hours; 50 °C / hr to 200 °C; hold at 200 °C for 4 hours; cool to room temperature). 47 g of fluorinated silica-1 was collected after calcination.

[0255] b) Preparation of fluorinated silica-2 by wet mixing.

[0256] Dissolve 2.41 g of (NH₄)₂SiF₆ (13.5 mmol, 1.62 mmol F / g silicon dioxide) in 14.7 g of water in a 20 ml glass vial. 50 g of Grace Davison D948 TM Silica and 200g of toluene in 250ml WheatonCELSTIR TM The aqueous feed solution of (NH4)2SiF6 was added to a toluene slurry of silica via a syringe under vigorous stirring. The mixture was stirred at room temperature for 16 hours. The slurry was then transferred through 250 ml of Optichem... TM The sample was filtered through a disposable polyethylene sieve, washed twice with 150 ml of pentane, and then air-dried overnight to obtain a white, free-flowing solid. The solid was transferred to a tube furnace and heated under a constant nitrogen flow (temperature program: 25 °C / hr to 150 °C; hold at 150 °C for 4 hours; 50 °C / hr to 200 °C; hold at 200 °C for 4 hours; cool to room temperature). 47.2 g of fluorinated silica-2 was collected after calcination.

[0257] c) Preparation of fluorinated silica-3 by wet mixing.

[0258] Dissolve 1.18 g of (NH4)2SiF6 (6.6 mmol, 0.79 mmol F / g silica) in 7.00 g of water in a 20 ml glass vial. Add 50 g of Grace Davison D948. TM Silica ("D948") and 200g of toluene in 250ml Wheaton CELSTIR TM The aqueous feed solution of (NH4)2SiF6 was added to a toluene slurry of silica via a syringe under vigorous stirring. The mixture was stirred at room temperature for 16 hours. The slurry was then passed through 110 ml Opt ichem. TMThe sample was filtered through a disposable polyethylene sieve, washed three times with 200 g of pentane, and then air-dried overnight to obtain a white, free-flowing solid. The solid was transferred to a tube furnace and heated under a constant nitrogen flow (temperature program: 25 °C / hr to 150 °C; hold at 150 °C for 4 hours; 50 °C / hr to 200 °C; hold at 200 °C for 4 hours; cool to room temperature). 46 g of fluorinated silica-2 was collected after calcination.

[0259] d) Preparation of fluorinated silica-4 by wet mixing.

[0260] Dissolve 1.18 g of (NH4)2SiF6 (6.6 mmol, 0.79 mmol F / g silica) in 7.00 g of water in a 20 ml glass vial. Add 50 g of Grace Davison D948. TM Silica and 200g of toluene in 250ml WheatonCELSTIR TM The aqueous feed solution of (NH4)2SiF6 was added to a toluene slurry of silica via a syringe under vigorous stirring. The mixture was stirred at room temperature for 16 hours. The slurry was then transferred through 110 ml of Optichem... TM The sample was filtered through a disposable polyethylene sieve, washed three times with 200 g of pentane, and then air-dried overnight to obtain a white, free-flowing solid. The solid was transferred to a tube furnace and heated under a constant nitrogen flow (temperature program: 100 °C / hr to 200 °C; hold at 200 °C for 2 hours; 100 °C / hr to 600 °C; hold at 600 °C for 6 hours; cool to room temperature).

[0261] e) Preparation of fluorinated silica-5 by wet mixing.

[0262] Dissolve 0.59 g of (NH4)2SiF6 (3.3 mmol, 0.40 mmol F / g silica) in 3.5 g of water in a 20 ml glass vial. Add 50 g of Grace Davison D948. TM Silica and 200g of toluene in 250ml WheatonCELSTIR TM The aqueous feed solution of (NH4)2SiF6 was added to a toluene slurry of silica via a syringe under vigorous stirring. The mixture was stirred at room temperature for 16 hours. The slurry was then transferred through 110 ml of Optichem... TMThe sample was filtered through a disposable polyethylene sieve, washed three times with 200 g of pentane, and then air-dried overnight to obtain a white, free-flowing solid. The solid was transferred to a tube furnace and heated under a constant nitrogen flow (temperature program: 25 °C / hr to 150 °C; hold at 150 °C for 4 hours; 50 °C / hr to 200 °C; hold at 200 °C for 4 hours; cool to room temperature).

[0263] Preparation of MAO (sMAO) supported on silica.

[0264] a) sMAO of silica-1.

[0265] In a glove box, 36g of MAO toluene solution (Albermarle, 13.6wt% Al) and 68g of anhydrous toluene were mixed in 125ml of Wheaton CELSTIR solution. TM Combine the ingredients. Set the stirring speed to 450 rpm. Every 5 minutes, slowly add 5g of silica-1 to CELSTIR. TM Add 26g of silica-1 over 30 minutes. Stir the slurry at room temperature for 15 minutes. Then apply CELSTIR. TM The slurry was placed in a sand bath heated to 100°C. The slurry was heated at 100°C for an additional 3 hours with a stirring rate of 215 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene sieve. The solids collected in the sieve were first washed twice with 30 g toluene, then three times with 30 g pentane. The solids were vacuum dried for 3 hours to obtain 34.9 g of sMAO-silica-1.

[0266] b) sMAO of silica-2

[0267] In a glove box, 10.6 g of MAO toluene solution (Albermarle, 13.6 wt% Al) and 40 g of anhydrous toluene were mixed in 100 ml of Wheaton Celsius solution. TM Combine the ingredients. Set the stirring speed to 450 rpm. Slowly add 10.0 g of silica-2 to CELSTIR. TM Stir the slurry at room temperature for 15 minutes. Then CELSTIR TM The slurry was placed in a sand bath heated to 100°C. The slurry was heated at 100°C for an additional 3 hours with a stirring rate of 250 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene sieve. The solids collected in the sieve were first washed three times with 40 g toluene, then three times with 40 g pentane. The solids were vacuum dried for 16 hours to obtain 12.9 g of sMAO silica-2.

[0268] c) sMAO of silica-3

[0269] In a glove box, 45.1 g of MAO toluene solution (Albermarle, 13.6 wt% Al) and 120 g of anhydrous toluene were mixed in 250 ml of Wheaton CELSTIR solution. TM Combine the ingredients. Set the stirring speed to 500 rpm. Slowly add 36.0 g of silica-3 to CELSTIR in increments of 5 g. TM Stir the slurry at room temperature for 15 minutes. Then CELSTIR TM The slurry was placed in a sand bath heated to 100°C. The slurry was heated at 100°C for an additional 3 hours with a stirring rate of 200 rpm. The final slurry was filtered through a 110 ml Optichem disposable polyethylene sieve. The solids collected in the sieve were first washed with 120 g of toluene, then twice with 80 g of pentane. The solids were vacuum dried for 16 hours. 49.7 g of sMAO-silica-3 was obtained.

[0270] d) sMAO of silica-4

[0271] In a glove box, mix 2.0 g of silica-4 and 8.0 g of anhydrous toluene in 25 ml of Wheaton CELSTIR. TM Combine the ingredients. Set the stirring speed to 500 rpm. Slowly add 2.4 g of MAO toluene solution (Albermarle, 13.6 wt% Al) to CELSTIR. TM Stir the slurry at room temperature for 15 minutes. Then CELSTIR TM Place in a sand bath heated to 80°C. Heat the slurry at 80°C for another hour with a stirring rate of 300 rpm. Filter the final slurry through a 25 ml Optichem disposable polyethylene sieve. The solids collected in the sieve are first washed three times with 6 g toluene, then three times with 6 g pentane. Vacuum dry the solids for 45 mins. 2.56 g of sMAO-silica-4 is obtained.

[0272] e) sMAO of silica-5

[0273] In a glove box, 2.8 g of MAO toluene solution (Albermarle, 13.6 wt% Al) and 8.5 g of anhydrous toluene were mixed in 25 ml of Wheaton CELSTIR. TM Combine the ingredients. Set the stirring speed to 450 rpm. Slowly add 1.98 g of silica-5 to CELSTIR. TM Stir the slurry at room temperature for 5 minutes. Then CELSTIR TMPlace in a sand bath heated to 100°C. Heat the slurry at 100°C for another hour with a stirring rate of 285 rpm. Filter the final slurry through a 25 ml Optichem disposable polyethylene sieve. The solids collected in the sieve are first washed twice with 6 g toluene, then three times with 4.5 g pentane. Vacuum dry the solids for 2 hours. 2.80 g of sMAO-silica-5 is obtained.

[0274] f) Comparative Example 1: sMAO-D948-200 of D948 silica calcined at 200°C in 25 ml WheatonCELSTIR TM 1.01 g of D948 silica calcined at 200 °C was slurried in 6 g of toluene. CELSTIR was then used. TM The mixture was then heated to 100°C in a sand bath, and 3.0 g of MAO toluene solution (Albermarle, 13.6 wt% Al) was slowly added to the slurry. The slurry was stirred at 100°C for 1 hour. The slurry was filtered, washed three times with 6 g of toluene, and twice with 6 g of pentane. The solid was dried under vacuum for 45 minutes. 1.46 g of a free-flowing white solid, "sMAO-D948-200", was obtained.

[0275] g) Comparative Example 2: sMAO of D948 silica calcined at 600°C.

[0276] 40.7 g of calcined 948 silica was slurried in 200 ml of toluene. MAO (71.4 g in a 30 wt% toluene solution, 351.1 mmol of Al) was slowly added to the slurry. The slurry was then heated to 80 °C and stirred for 1 hour. The slurry was filtered, washed three times with 70 ml of toluene, and once with pentane. The solid was dried under vacuum overnight to give 60.7 g of a free-flowing white solid, "sMAO-D948-600".

[0277] Preparation of bridged monocyclopentadienyl titanium compounds under load .

[0278] Small-scale preparation of supported catalysts for high-yield experiments

[0279] Representative process: (Support: sMAO-silica-3; Catalyst A)

[0280] In a drying oven, combine 20 mg of catalyst A and 2.28 g of toluene in a 20 mL glass vial. Vortex the mixture for 10 minutes to produce a feed solution. In another 20 mL glass vial, weigh 0.492 g of sMAO-silica-3. Add 2.0 g of toluene to the vial, followed by 1.00 g of the catalyst A / toluene feed solution. Seal the vial with a Teflon-lined cap and vortex at room temperature for 90 minutes. Filter the slurry through a 25 mL Optichem disposable polyethylene sieve. Wash the collected solid three times with 3 g of toluene, then three times with 2 g of pentane, and then dry under vacuum. Obtain 0.466 g of catalyst A supported on sMAO-silica-3.

[0281] Preparation of supported catalysts on a 50-gram scale

[0282] Representative process: (Support: sMAO-silica-2; Catalyst A)

[0283] In a glove box, 44.6 g of MAO toluene solution (Albermarle, 13.6 wt% Al) and 140 g of anhydrous toluene were mixed in 250 ml of Wheaton CELSTIR solution. TM Combine the ingredients. Set the stirring speed to 500 rpm. Gradually and slowly add 34.66 g of sMAO-silica-2 in 5 g increments to CELSTIR. TM Stir the slurry at room temperature for 15 minutes. Then CELSTIR TM Place in a sand bath heated to 100°C. Heat the slurry at 100°C for an additional 3 hours with a stirring rate of 200 rpm. Filter the final slurry through a 250 ml Optichem disposable polyethylene sieve. Transfer the solids collected in the sieve back to a 250 ml Wheaton CELSTIR. TM It was then slurried in 130g of toluene. 0.767g of catalyst A (1.75mmol) was added to CELSTIR. TM The mixture was stirred at room temperature for 90 minutes. The slurry was then filtered and washed three times with 120 g of toluene and twice with 80 g of pentane. The solid was dried under vacuum for 16 hours to obtain 47.59 g of a light yellow free-flowing powder.

[0284] Example 1: Ethylene / 1-hexene copolymerization.

[0285] High-yield slurry-phase ethylene / hexene copolymerization experiment.

[0286] Preparation of catalyst slurry for high-yield operation: In a drying oven, weigh 45 mg of the loaded catalyst into a 20 ml glass vial. Add 15 ml of toluene to the vial to obtain a slurry containing 3 mg of loaded catalyst per ml of slurry. Vortex the mixture before injection.

[0287] Starting material preparation: Solvents, polymerization-grade toluene, and isohexane were supplied by ExxonMobil Chemical Company and thoroughly dried and degassed before use. Polymer-grade ethylene was used, and purification was performed in one step via a series of columns: 500cc Oxyclear cylinders from Labclear (Oakland, CA), followed by cylinders packed with dried solvent purchased from Aldrich Chemical Company. The molecular sieve column was 500cc and packed with a dryer purchased from Aldrich Chemical Company. A 500cc column of molecular sieve. TnOAl (tri-n-octylaluminum, pure) was used as a 2 mmol / L solution in toluene.

[0288] Reactor Instructions and Preparation: Polymerization was carried out in an inert atmosphere (N2) drying oven using an autoclave equipped with an external heater for temperature control, a glass insert (reactor internal volume = 22.5 mL), a baffle inlet, regulated nitrogen, ethylene, and hexene supplies, and a disposable PEEK mechanical stirrer (800 RPM). The autoclave was purged with dry nitrogen before use.

[0289] Ethylene / 1-hexene copolymerization:Prepare the reactor as described above, then purge with ethylene. Add isohexane, 1-hexene, and TnOAl via syringe at room temperature and atmospheric pressure. Then bring the reactor to the process temperature (85°C) and add ethylene to the process pressure (130 psig = 896 kPa) while stirring at 800 RPM. Add the transition metal compound (100 μL of a 3 mg / mL toluene slurry, unless otherwise specified) via syringe to the reactor under process conditions. TnOAl is used as 200 μL of a 20 mmol / L solution in isohexane. Amounts of reagents not specified above are given in Table 1. No other reagents are used. Introduce ethylene into the autoclave during polymerization (using a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+ / - 2 psig). Monitor the reactor temperature, typically maintained at + / - 1°C. Stop the polymerization by adding approximately 50 psi of O2 / Ar (5 mol% O2) gas mixture to the autoclave for approximately 30 seconds. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added or after a maximum polymerization time of 45 minutes, except for the quenching time for each run. The reactor is cooled and vented. The polymer is separated after the solvent is removed under vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as reaction time per kilogram of polymer per mmol of transition metal compound per hour (kg / mmol·hr). (Data are in Table 1).

[0290] Table 1: HTPT evaluation of catalyst AD supported in slurry ethylene / 1-hexene polymerization: activity, Mw, PDI and 1-hexene binding capacity. Operating conditions: isohexane as solvent, 85°C, 130 psi ethylene pressure, 30 μl (6 mol% in feed) 1-hexene, with added hydrogen.

[0291]

[0292] Table 1 shows that the bridged monocyclopentadienyl titanium compound AD supported on sMAO-silica-3 exhibits good to excellent activity. The resulting PE resin has ultra-high Mw, a slightly broadened Mw / Mn ratio, and high comonomer bonding.

[0293] Example 2: Gas-phase polymerization of a supported, bridged monocyclopentadienyl titanium compound AC.

[0294] Polymerization was carried out in a gas-phase fluidized bed reactor with a 6” body and a 10” extension section. Circulating and feed gases were fed into the reactor body through a porous distribution plate, and the reactor was controlled at 300 psi and 70 mol% ethylene. The reactor temperature was maintained by heating the circulating gas. The supported catalyst was located at the Sono reactor in Sonneborn (Parsippany, NJ). A 10 wt% slurry is supplied. The slurry is diluted and fed to the reactor via nitrogen and isopentane feed in the catalyst probe. Product is collected from the reactor as needed to maintain the required bed weight. Table 3 lists the average process conditions.

[0295] Table 3. Average process conditions for catalyst AC supported in gas-phase polymerization.

[0296] catalyst A B C carrier sMAO-silica-2 sMAO-silica-2 sMAO-silica-2 Temperature (°C) 85 85 85 Pressure (psi) 300 300 300 Ethylene (mol%) 70.0 70.0 70.0 Hydrogen (ppm) 1931 1200 1487 Hexene (mol%) Bed weight (g) 1424 1951 1373 Duration of stay (hr) 6.1 3.4 2.7 Circulating gas velocity (ft / s) 1.47 1.56 1.50 Production speed (g / hr) 233 572 516 <![CDATA[Activity (g 聚合物 / g 负载的催化剂 )]]> 777 2772 1568 Catalyst slurry feed (cc / hr) 3.4 2.3 3.7 MI I2.1 (g / 10min) 0.38 1.50 2.55 HLMI I21 (g / 10min) 12.66 39.73 64.87 MIR(I21 / I2.1) 33.40 26.48 25.44 <![CDATA[Density (g / cm 3 )]]> 0.9257 0.9242 0.9304 Bulk density (g / cc) 0.4260 0.4279 0.4433 Mw (g / mol) GPC of PE 145387 98711 85427 Mw / Mn 4.37 5.67 5.38 C6's Wt%(SCB)GPC 5.24 6.72 5.24 <![CDATA[g' vis (LCB)GPC]]> 0.942 0.963 0.942

[0297] Melt index (MI), recorded in g / 10min, is also known as I2 and is determined according to ASTM 1238 at 190°C and a 2.16 kg load.

[0298] The high-load melt index (HLMI), recorded in g / 10min, is also known as I21, and is determined according to ASTM 1238 at 190°C and a 21.6 kg load.

[0299] The melt index ratio (MIR) is the MI as determined by ASTM 1238 divided by the HLMI.

[0300] Density was determined according to ASTM D 1505.

[0301] Bulk density was measured according to ASTM D1895.

[0302] The MI, HLMI, MIR, and density data in the table are averages based on several measurements.

[0303] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures that do not conflict with this document. As will be apparent from the foregoing general description and specific embodiments, while the forms of the invention have been illustrated and described, various modifications may be made without departing from the spirit and scope of the invention. Therefore, this is not intended to limit the invention. Similarly, the term “comprising” is considered synonymous with the term “including.” Similarly, whenever a composition, an element, or a group of elements is preceded by the transitional phrase “comprising,” it should be understood and contemplated that the transitional phrase “consistently composed of,” “comprises of,” “selected from the group consisting of,” or “is” between the composition, one or more elements, and vice versa. Similarly, the terms “comprising,” “consistently composed of,” also include the product of combinations of elements listed after the term.

[0304] The present invention also relates to the following embodiments:

[0305] 1. A catalyst system comprising a fluorinated silica support, an alkylaluminoxane activator, and a reaction product of a bridged monocyclopentadienyl group 4 transition metal compound, wherein the fluorinated silica support is not calcined at 400°C or higher.

[0306] 2. The catalyst system described in Implementation Scheme 1, wherein the transition metal compound is represented by the following formula:

[0307] T y Cp m MG n X q

[0308] Each Cp independently represents a substituted or unsubstituted cyclopentadienyl group, M is a Group 4 transition metal, and G is a formula JR*. z The heteroatomic groups are represented, where J is N, P, O, or S, and R* is C1-C. 20 The hydrocarbon group, z is 1 or 2, T is the bridging group, y is 1, X is the leaving group, and m = 1, n = 1, 2 or 3, q ​​= 1, 2 or 3, and the sum of m + n + q equals the oxidation state of the transition metal.

[0309] 3. The catalyst system described in Implementation Scheme 2, wherein M is Ti.

[0310] 4. The catalyst system described in Embodiment 2 or Embodiment 3, wherein each Cp is a substituted or unsubstituted cyclopentadiene, indene or fluorene, M is titanium, and each X independently represents a halogen group, hydrogen group, alkyl group, alkenyl group or arylalkyl group.

[0311] 5. The catalyst system according to any one of the foregoing embodiments, wherein the activator further comprises a noncoordinate anionic activator.

[0312] 6. The catalyst system according to any one of the foregoing embodiments, wherein the activator comprises methylaluminoxane.

[0313] 7. The catalyst system according to any one of the foregoing embodiments, wherein G is a heteroatom group represented by formula NR*, and wherein R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

[0314] 8. The catalyst system of any one of the foregoing embodiments, wherein the bridged monocyclopentadienyl transition metal compound comprises one or more of the following:

[0315] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium,

[0316] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride

[0317] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0318] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride

[0319] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)M(R)2;

[0320] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0321] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0322] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0323] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0324] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2;

[0325] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2;

[0326] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0327] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0328] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2;

[0329] M is selected from Ti, Zr, and Hf, and R is selected from halogens or C1-C5 alkyl groups.

[0330] 9. The catalyst system according to any one of the foregoing embodiments, wherein the sum of m+n+q is equal to 2, 3 or 4.

[0331] 10. The catalyst system according to any one of the foregoing embodiments, wherein J is N or O, and R* is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof.

[0332] 11. The catalyst system of any one of the foregoing embodiments, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C.

[0333] 12. A method for producing ethylene polymers, comprising: i) reacting ethylene and optionally C3-C4 polymers in a gas phase or slurry phase. 20 The comonomer is contacted with a catalyst system comprising a fluorinated silica support, an alkylaluminoxane activator, and a bridged monocyclopentadienyl group 4 transition metal compound, wherein the fluorinated support is not calcined at 400°C or higher, and ii) an ethylene polymer comprising at least 50 mol% ethylene is obtained.

[0334] 13. The method of embodiment 12, wherein the ethylene polymer comprises ethylene and at least one C3-C 20 The copolymer monomers have a bimodal composition distribution.

[0335] 14. The method of embodiment 12 or embodiment 13, wherein the ethylene polymer has a multi-peak molecular weight distribution determined by gel permeation chromatography.

[0336] 15. The method of any one of embodiments 12-14, wherein the catalyst system is prepared by a method comprising: combining a fluorinated compound with a polar solvent, then combining it with a slurry of a nonpolar solvent and a silica support, removing the nonpolar solvent, and then combining the calcined support with a second solvent that may be the same as or different from the nonpolar solvent, a bridged monocyclopentadienyl group 4 transition metal compound, and an activator, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C before or after combining with the activator and / or catalyst compound.

[0337] 16. The method of embodiment 15, wherein the polar solvent is water, and the ratio of water to nonpolar solvent (by weight) is 1:10 to 1:1,000.

[0338] 17. The method of embodiment 15 or embodiment 16, wherein the nonpolar solvent is toluene, pentane, hexane, benzene or chloroform.

[0339] 18. The method of any one of embodiments 12-17, wherein the fluoride compound is one or more of the following: NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, and NH4HF2.

[0340] 19. The method of any one of embodiments 12-18, wherein the catalyst system comprises a catalyst compound.

[0341] 20. The method of any one of embodiments 12-19, wherein the activator comprises methylaluminoxane.

[0342] 21. The method of any one of embodiments 12-20, wherein the activator further comprises a noncoordinate anionic activator.

[0343] 22. The method of any one of embodiments 12-21, wherein the method is carried out at a temperature of about 0°C to about 300°C, at a pressure ranging from about 0.35 MPa to about 10 MPa, and for a time of up to 300 minutes.

[0344] 23. The method of any one of embodiments 12-22, wherein the comonomer is present and is selected from propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

[0345] 24. The method of any one of embodiments 12-23, wherein the fluorinated supported catalyst system is prepared by a method comprising: combining a fluorinated compound with water, then combining it with a slurry of a nonpolar solvent and a support, removing the nonpolar solvent, and then combining the calcined support with a second solvent that may be the same as or different from the nonpolar solvent, two catalyst compounds, and an activator, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C before or after combining with the activator and / or catalyst compounds.

[0346] 25. The method of embodiment 24, wherein the ratio of water to nonpolar solvent (by weight) is 1:10 to 1:1000; the nonpolar solvent is toluene, pentane, hexane, benzene or chloroform; and the fluoride compound is one or more of the following: NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2 and NH4HF2.

Claims

1. A catalyst system comprising a fluorinated silica support, an alkylaluminoxane activator, and a bridged monocyclopentadienyl Group 4 transition metal compound as reaction products, wherein the fluorinated silica support is not calcined at 400°C or higher, and wherein the fluorinated silica support is obtained by combining the silica support with a fluoride compound in a polar solvent; wherein the fluoride compound is one or more of the following: NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, and NH4HF2; wherein the fluorine mmol / g ratio of the fluorinated silica support is greater than 0.4 to less than or equal to 1.2, and the bridged monocyclopentadienyl transition metal compound comprises one or more of the following: Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium, Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium, Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2; µ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2; Where M is Ti, and R is Cl or methyl; The activator mentioned above comprises methylaluminoxane; The catalyst system is prepared by a method comprising: combining a fluoride compound with a polar solvent, then combining it with a slurry of a nonpolar solvent and a silica support, removing the nonpolar solvent, and then combining the calcined support with a second solvent, which may be the same as or different from the nonpolar solvent, a bridged monocyclopentadienyl group 4 transition metal compound, and an activator, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C before or after combining with the activator and / or catalyst compound; and The calcined support and activator are combined by the following method: the fluorinated support is slowly added in solid form to a solution of methylaluminoxane in a nonpolar solvent under vigorous stirring.

2. The catalyst system of claim 1, wherein the activator further comprises a noncoordinate anionic activator.

3. Methods for producing ethylene polymers, including: i) To introduce ethylene and optionally C3-C into the gas phase or slurry phase. 20 The comonomer is contacted with a catalyst system comprising a fluorinated silica support, an alkylaluminoxane activator, and a bridged monocyclopentadienyl Group 4 transition metal compound, wherein the fluorinated silica support is not calcined at 400°C or higher, and wherein the fluorinated silica support is obtained by combining the silica support with a fluoride compound in a polar solvent; and ii) an ethylene polymer comprising at least 50 mol% ethylene is obtained; The fluoride compound is one or more of the following: NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, and NH4HF2; wherein the fluorine mmol / g ratio in the fluorinated silica support is greater than 0.4 and less than or equal to 1.2, and the bridged monocyclopentadienyl transition metal compound comprises one or more of the following: Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium, Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium, Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2; µ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2; Where M is Ti, and R is Cl or methyl; The activator mentioned above comprises methylaluminoxane; The catalyst system is prepared by a method comprising: combining a fluoride compound with a polar solvent, then combining it with a slurry of a nonpolar solvent and a silica support, removing the nonpolar solvent, and then combining the calcined support with a second solvent, which may be the same as or different from the nonpolar solvent, a bridged monocyclopentadienyl group 4 transition metal compound, and an activator, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C before or after combining with the activator and / or catalyst compound; and The calcined support and activator are combined by the following method: the fluorinated support is slowly added in solid form to a solution of methylaluminoxane in a nonpolar solvent under vigorous stirring.

4. The method of claim 3, wherein the ethylene polymer comprises ethylene and at least one C3-C 20 The copolymer monomers have a bimodal composition distribution.

5. The method of claim 3 or claim 4, wherein the ethylene polymer has a multi-peak molecular weight distribution determined by gel permeation chromatography.

6. The method of claim 3, wherein the polar solvent is water, and the ratio of water to nonpolar solvent is 1:10 to 1:1,000 by weight.

7. The method of claim 3 or claim 6, wherein the nonpolar solvent is toluene, pentane, hexane, benzene or chloroform.

8. The method of claim 3, wherein the catalyst system comprises a catalyst compound.

9. The method of claim 3, wherein the activator further comprises a noncoordinate anionic activator.

10. The method of claim 3, wherein the method is carried out at a temperature of 0°C to 300°C, at a pressure ranging from 0.35 MPa to 10 MPa, and for a time of up to 300 minutes.

11. The method of claim 3, wherein the comonomer is present and is selected from propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

12. The method of claim 3, wherein the fluorinated supported catalyst system is prepared by a method comprising: combining a fluorinated compound with water, then combining it with a slurry of a nonpolar solvent and a support, removing the nonpolar solvent, and then combining the calcined support with a second solvent that may be the same as or different from the nonpolar solvent, two catalyst compounds, and an activator, wherein the fluorinated support is calcined at a temperature of 100 to below 400°C before or after combining with the activator and / or catalyst compounds.

13. The method of claim 12, wherein the ratio of water to nonpolar solvent is 1:10 to 1:1000 by weight; and the nonpolar solvent is toluene, pentane, hexane, benzene, or chloroform.

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