Silica supported polyolefin catalyst systems

Abstract

An olefin catalyst system is provided that includes a silica support. For example, in one embodiment, an olefin polymerization catalyst system includes a silica support, a catalyst precursor compound, and an activator. The silica support includes a plurality of silica gel particles. Each particle includes a rigid network of amorphous silica. The particles have an average aspect ratio of about 1.2 or less, an average pore volume of about 1.4 ml / g to about 3 ml / g, and an average pore size of about 200 m2 / g to about 950 m2. 2 The gel particles are spherical, single gel particles having an average surface area of ​​1 / g and a median particle size of about 4 μm to about 100 μm.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 320,579, filed March 16, 2022, which is hereby incorporated by reference in its entirety for all purposes. [Background technology]

[0002]

[0002] Polyolefins are generally prepared by reacting olefin monomers in the presence of a catalyst consisting of a support and catalytic components deposited within the pores and on the surface of the support. For example, typical polyolefin catalysts include Ziegler-Natta catalysts, metallocene catalysts, and chromium catalysts, all of which may contain support materials.

[0003]

[0003] The properties of the resulting polymer depend to a large extent on the catalyst, with variations in the catalyst properties resulting in variations in, for example, molecular weight, melt index, bulk density, particle shape, particle size, particle size distribution, and reaction temperature that can be used to carry out the polymerization. The properties of the catalyst and its performance also depend to a large extent on the properties of the material used to support the catalyst, which in turn depends on the method of its manufacture.

[0004]

[0004] Silica supports have been used primarily because they form highly active polymerization catalysts. One known method of forming silica support particles is to crush silica gel and spray dry the crushed particles. Certain properties of the silica particles, such as surface area, pore structure, and particle size, can be influenced by controlling the crushing and spray drying process. In this way, the properties of the silica support can be controlled to suit a variety of different catalyst components and desired polymer types. However, conventional spray-dried silica support particles also have drawbacks. For example, they tend not to be spherical, and particle agglomeration reduces catalyst performance. Thus, there is a need for spherical silica-supported polyolefin catalysts made from non-agglomerated support particles that have a surface area and pore structure suitable for use in polyolefin catalysts. Summary of the Invention [Means for solving the problem]

[0005]

[0005] The present disclosure relates generally to an olefin catalyst system comprising a silica support. For example, in one embodiment, an olefin polymerization catalyst system comprises a silica support, a catalyst precursor compound, and an activator. The silica support comprises a plurality of silica gel particles. Each particle comprises a rigid network of amorphous silica. The particles have an average aspect ratio of about 1.2 or less, an average pore volume of about 1.4 ml / g to about 3 ml / g, and an average pore size of about 200 m 2 / g ~ approx. 950m 2 The gel particles are spherical, single gel particles having an average surface area of ​​1 / g and a median particle size of about 4 μm to about 100 μm.

[0006] In another embodiment, an olefin polymerization catalyst system includes a silica support and a chromium compound. The silica support includes a plurality of silica gel particles. Each particle includes a rigid network of amorphous silica. The particles have an average aspect ratio of about 1.2 or less, an average pore volume of about 1.4 ml / g to about 3 ml / g, and an average pore size of about 200 m 2 / g ~ approx. 950m 2 The gel particles are spherical, single gel particles having an average surface area of ​​1 / g and a median particle size of about 4 μm to about 100 μm.

[0007] In another embodiment, an olefin polymerization catalyst system includes a silica support, a magnesium halide, a transition metal compound, an alkylaluminum cocatalyst, and an electron donor compound. The silica support includes a plurality of silica gel particles. Each particle includes a rigid network of amorphous silica. The particles have an average aspect ratio of about 1.2 or less, an average pore volume of about 1.4 ml / g to about 3 ml / g, and an average pore size of about 200 m. 2 / g ~ approx. 950m 2 The gel particles are spherical, single gel particles having an average surface area of ​​1 / g and a median particle size of about 4 μm to about 100 μm.

[0008] Also described is a method for polymerizing olefins. The method includes contacting an olefin monomer with a catalyst system including a silica support and a catalyst precursor compound to form polyolefin particles. The silica support includes a plurality of silica gel particles. Each particle includes a rigid network of amorphous silica. The particles have an average aspect ratio of about 1.2 or less, an average pore volume of about 1.4 ml / g to about 3 ml / g, and an average pore size of about 200 m. 2 / g ~ approx. 950m 2 The gel particles are spherical, single gel particles having an average surface area of ​​1 / g and a median particle size of about 4 μm to about 100 μm.

[0009]

[0009] Other features and aspects of the disclosure are discussed in further detail below. [Brief description of the drawings]

[0010] [Figure 1] 1 is a process flow diagram of a production method according to the present disclosure. [Diagram 2]

[0011] FIG. 2 shows an SEM image of silica particles produced in Example 1. [Diagram 3]

[0012] FIG. 2 shows an SEM image of silica particles produced in Example 2. [Figure 4]

[0013] FIG. 1 shows an SEM image of silica particles produced in Example 3. [Diagram 5]

[0014] FIG. 1 shows an SEM image of the polymer produced in Example 11. [Figure 6]

[0015] FIG. 1 shows an SEM image of the polymer produced with the catalyst of Example 14B. [Figure 7]

[0016] FIG. 1 shows an SEM image of the polymer produced with the catalyst of Example 15B. [Figure 8]

[0017] FIG. 1 shows an SEM image of the polymer produced with the catalyst of Example 16B. [Figure 9]

[0018] FIG. 16 shows an SEM image of the polymer produced with the catalyst of Example 16C. [Figure 10]

[0019] FIG. 1 shows an SEM image of the polymer produced in Example 24. [Figure 11]

[0020] FIG. 2 shows an SEM image of the polymer produced in Example 25. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011]

[0021] Various embodiments are described herein below. Please note that the specific embodiments are not intended as an exhaustive description or a limitation to the broader aspects discussed herein. An aspect described in connection with a particular embodiment is not necessarily limited to that embodiment and can be implemented together with any other embodiment.

[0012]

[0022] When used herein in relation to numerical ranges, the terms "approximately," "about," "substantially," and similar terms will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which they are used. If terms are used that are not clear to those of ordinary skill in the art given the context in which they are used, those terms will be plus or minus 10% of the disclosed value. When "approximately," "about," "substantially," and similar terms are used in relation to structural features (e.g., to describe their shape, size, orientation, direction, etc.), these terms are meant to cover minor structural variations that may result, for example, from the manufacturing or assembly process, and are intended to have a broad meaning consistent with commonly accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. Thus, these terms should be interpreted to indicate that minor or insignificant modifications or variations of the subject matter described and claimed are considered to be within the scope of the present disclosure as described in the appended claims.

[0013]

[0023] In describing elements (particularly in the context of the claims that follow), the use of the terms "a" and "an" and "the" and similar referents should be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context. Recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually set forth herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better illuminate the embodiments and does not impose limitations on the scope of the claims unless otherwise specified. No language in this specification should be construed as indicating any element not recited in the claims as essential.

[0014]

[0024] In general, the present disclosure relates to olefin catalyst systems containing silica supports formed from spherical, mono-gel silica particles having a combination of particle size, pore volume, and surface area that are particularly suitable for use as catalyst supports. The spherical, mono-gel nature of the particles offers various advantages over conventional silica supports, such as those formed by spray-drying agglomeration processes.

[0015]

[0025] For example, catalysts containing single gel support particles tend to perform better in olefin polymerization processes than catalysts containing agglomerated support particles. As used herein, single gel particles refer to particles that are not formed from an agglomerate of smaller particles. Agglomerates refer to products that combine particles held together by a variety of physical-chemical forces. More specifically, agglomerates consist of multiple continuous component primary particles that are joined and connected at contact points. In contrast to agglomerates, single gel particles cannot be separated into smaller particles without fracturing the particles.

[0016]

[0026] Furthermore, because the particles are highly spherical, when used in gas phase polymerization processes they tend to be less prone to static build-up compared to less spherical particles, and thus the use of the catalysts described herein in gas phase olefin polymerization processes can reduce or even eliminate the amount of antistatic agent required in the polymerization vessel.

[0017]

[0027] As previously mentioned, the particles also have a combination of pore volume, surface area, and particle size that is particularly suitable for loading the catalyst components and for use in olefin polymerization processes. For example, the particles have a relatively high surface area as determined by the BET method using nitrogen adsorption as described hereinafter. Generally, the average surface area of ​​the particles is about 200 m. 2 / g or more, in some embodiments, about 400 m 2 / g or more, in some embodiments, about 500m 2 / g or more, in some embodiments, about 600 m 2 / g or more, in some embodiments, about 700m2 / g or more. Typically, the average surface area of ​​the particles is about 950 m 2 / g or less, in some embodiments, about 800 m 2 / g or less, in some embodiments, about 700 m 2 / g or less, in some embodiments, about 600 m 2 / g or less, in some embodiments, about 500 m 2 / g or less.

[0018]

[0028] The particles also have a relatively high pore volume as measured by nitrogen pore volume as described herein below. For example, the average pore volume of the particles is generally about 1.4 cc / g or more, in some embodiments about 1.8 cc / g or more, in some embodiments about 2 cc / g or more, and in some embodiments about 2.25 cc / g or more. Typically, the pore volume is about 3 cc / g or less, in some embodiments about 2.6 cc / g or less, in some embodiments about 2.25 cc / g or less, and in some embodiments about 2 cc / g or less.

[0019]

[0029] The support particles can also have a pore size suitable for the particular catalytic component loaded thereon. For example, it may be desirable for some of the catalytic component or activator to penetrate into the pores of the support. In this regard, the average pore size of the pores of the support particles as measured by nitrogen porosimetry can be relatively large, for example, about 30 angstroms or more, in some embodiments about 50 angstroms or more, in some embodiments about 70 angstroms or more, in some embodiments about 100 angstroms or more, and in some embodiments about 150 angstroms or more. Typically, the average pore size is about 300 angstroms or less, in some embodiments about 250 angstroms or less, and in some embodiments about 200 angstroms or less.

[0020]

[0030] Surface areas are determined by BET nitrogen adsorption analysis after activation of the samples at 400 °C for 30 min in vacuum. Surface areas are calculated from multipoint values ​​of nitrogen volumetric uptake in the adsorption branch at low partial pressures [P / Po = ~0.05-0.15]. The adsorption branch of the isotherm is stopped at a partial pressure of P / Po = 0.995 and then the descending branch of the isotherm is measured. Nitrogen pore volume is calculated by applying Gurvich's law at P / Po = 0.995. Pore diameters are reported as calculated BJH desorption mean diameters.

[0021]

[0031] Traditionally, it has been difficult to produce spherical, single gel silica particles that have both high pore volume and high surface area. However, in some embodiments, the silica particles described herein have an average pore volume of about 2.3 cc / g or more and a surface area of ​​about 350 m 2 / g. Such a combination allows for high catalyst loading of the support and high catalyst activity during polymerization.

[0022]

[0032] The particle size that is desired to be imparted to the support particles depends on the type of polymerization reaction in which the final supported catalyst is used. Typically, the median particle size (D50) of the particles, as measured by the laser diffraction method described hereinbelow, is about 4 μm or more, in some embodiments about 10 μm or more, in some embodiments about 20 μm or more, in some embodiments about 30 μm or more, and in some embodiments about 50 μm or more. The median particle size is typically about 100 μm or less, in some embodiments about 75 μm or less, and in some embodiments about 50 μm or less.

[0023]

[0033] Regardless of their average size, the particles can have a relatively narrow particle size distribution. The width of the particle size distribution is given by:

[0024]

number

[0025] [In the formula, D 10 , D50 , and D. 90 represent the 10th, 50th, and 90th percentiles of the particle size (diameter) distribution, respectively, i.e., D of 100 microns 90 means that 90% by volume of the particles have a diameter less than or equal to 100 microns. In this regard, the distribution span of the particles may be about 1.5 or less, in some embodiments about 1.45 or less, in some embodiments about 1.4 or less, in some embodiments about 1.3 or less, and in some embodiments from about 0.9 to about 1.25. A narrow particle size distribution may also contribute to reducing static forces when used in gas phase polymerization processes.

[0026]

[0034] The silica particles of the present disclosure can be prepared by a water-in-oil emulsion process.The inventors have unexpectedly discovered that the emulsion process described herein can produce silica particles with the unique properties described above.In addition, they have found that the particle size, particle size distribution, pore size, pore volume, and surface area of ​​the particles can be controlled by manipulating certain aspects of the emulsion process.

[0027]

[0035] In the water-in-oil emulsification process, a silica sol is first prepared by mixing an alkali silicate with an acid. The sol is then mixed with oil and surfactants to produce an emulsion. In the emulsion formed during this process, the oil phase is continuous and the sol forms stable spherical droplets dispersed in the oil phase. The pH can then be adjusted by adding a basic compound to the emulsion, which can help control the gelation process and the final pore structure within the emulsion.

[0028]

[0036] This process is described in more detail with reference to FIG. 1. First, in step 101, a silica sol is formed by first combining a mineral acid and an alkali silicate. The alkali silicate can include sodium silicate, potassium silicate, lithium silicate, and the like. The alkali silicate typically contains about 5 wt.% to about 50 wt.% (SiO in the alkali silicate). 2 Based on the amount of the alkali silicate, the solution is provided as an aqueous solution having a concentration of, for example, about 10 wt.% to about 35 wt.%. The mineral acid can be sulfuric acid, hydrochloric acid, nitric acid, and the like. In some embodiments, the alkali silicate is sodium silicate and the mineral acid is sulfuric acid. In other embodiments, the alkali silicate is sodium silicate and the mineral acid is hydrochloric acid. To form a sol, the alkali silicate can be added to a vessel containing the mineral acid. The flow rate is adjusted to obtain a desired throughput at industrial scale. For example, at laboratory scale, the alkali silicate can be added to the mineral acid at a flow rate of about 1 ml / min to about 250 ml / min, for example, about 5 ml / min to about 200 ml / min, preferably about 50 ml / min to about 200 ml / min. Alternatively, the alkali silicate and the mineral acid can be combined at one time by pouring one into the other. The concentration of the mineral acid is typically about 10 wt.% to about 50 wt.%, in some embodiments about 15 wt.% to about 40 wt.%, and in some embodiments about 18 wt.% to about 35 wt.%. The weight ratio of the mineral acid to the alkaline silicate preferably results in a pH of less than 7. The weight ratio of the mineral acid to the alkaline silicate is typically about 1:10 to about 2:1, in some embodiments about 1:7 to about 1:1, and in some embodiments about 1:5 to about 1:2.

[0029]

[0037] In some embodiments, the concentration and amount of aqueous alkali silicate and mineral acid are selected to reach a specified pH value.For example, in some embodiments, the pH of the resulting mixture is controlled to remain below about 4, such as below about 3, such as below about 1.5. The pH of the resulting mixture is usually about 1 or more.

[0030]

[0038] During the sol formation process, the temperature should be controlled to a relatively low temperature, for example, in some embodiments, the temperature is controlled to about 40° C. or less, in some embodiments, about 30° C. or less, and in some embodiments, about 20° C. or less.

[0031]

[0039] To form the sol, the mineral acid and the alkali silicate can be continuously mixed in a container using a mixer, such as a static or in-line mixer. The mixer can be operated at any suitable speed for a period of time sufficient to form the sol. For example, in some embodiments, the mixture can be mixed for a period of time from about 2 minutes to about 1 hour, such as from about 5 minutes to about 45 minutes, such as from about 10 minutes to about 40 minutes.

[0032]

[0040] After the sol is formed, it is pumped or otherwise combined with the oil and surfactant to form a water-in-oil emulsion in step 102. The oil and surfactant can be combined to form a surfactant / oil mixture, and this mixture is added to the sol. The amount of surfactant can be controlled to form stable spherical silica sol droplets. In some embodiments, the surfactant is present in the mixture in an amount ranging from about 3 wt. percent to about 25 wt. percent of the total surfactant / oil mixture. Preferably, the surfactant is present in the mixture in an amount ranging from about 5 wt. percent to about 15 wt. percent. Alternatively, the oil and surfactant are added separately to the sol in amounts sufficient to provide a surfactant / oil mixture having the wt. percentages described above.

[0033]

[0041] The oil is not particularly limited except that it should be non-reactive and immiscible with the aqueous alkali silicate and mineral acid. Representative oils include n-octane, gasoline, kerosene, isoparaffinic hydrocarbon oils, etc., alicyclic hydrocarbons such as cyclononane, cyclodecane, etc., aromatic hydrocarbons such as toluene, xylene, ethylbenzene, tetralin, etc., and mixtures of alkanes, such as mineral oil.

[0034]

[0042] A wide range of surfactants, such as glycerol monocaprylate, glycerol monolaurate, glycerol mono / dicoccoate, glycerol dilaurate, glycerol monostearate, glycerol monostearate distillate, glycerol distearate, glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monoisostearate, glycerol monoricinoleate, glycerol monohydroxystearate, POE glycerol monostearate, acetylated glycerol monostearate glycerol phthalate, succinylated glycerol monostearate, diacetylated glycerol monostearate tartrate, modified glycerol phthalate resin, triglycerol monostearate, triglycerol monooleate, triglycerol monoisostearate, decaglycerol tetraoleate, decaglycerol deca stearate, pentaerythritol monolaurate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, pentaerythritol monooleate , pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol tetraricinoleate, sorbitan monolaurate, POE sorbitan monolaurate, sorbitan monopalmitate, POE sorbitan monopalmitate, sorbitan monostearate, POE sorbitan monostearate, sorbitan tristearate, POE sorbitan tristearate, sorbitan monooleate, POE sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, POE sorbitan trioleate Oleate, POE sorbitol hexaoleate, POE sorbitol oleate laurate, POE sorbitol polyoleate, POE sorbitol, beeswax esters, sucrose monolaurate, sucrose cocoate, sucrose monomyristate, sucrose monopalmitate, sucrose dipalmitate, sucrose monostearate, sucrose distearate, sucrose monooleate, sucrose dioleate, lauryl lactate, cetyl lactate, sodium lauryl lactate, sodium stearoyl lactate,Sodium isostearoyl-2-lactylate, sodium stearoyl-2-lactylate, calcium stearoyl-2-lactylate, sodium capryl lactate, lauryl alcohol, and cetyl alcohol can be used.

[0035]

[0043] In one embodiment, the surfactant comprises at least one sorbitan ester. The sorbitan esters include sorbitan fatty acid esters, where the fatty acid moiety of the ester comprises a carboxylic acid of from about 10 to about 100 carbon atoms, in one embodiment from about 12 to about 24 carbon atoms. The sorbitans are a mixture of anhydrosorbitols, primarily 1,4-sorbitan and isosorbide (Formulas I and II):

[0036] [ka]

[0037]

[0044] Sorbitan (also called monoanhydrosorbitol or sorbitol anhydride) is a general term for anhydrides that can be derived from sorbitol by removing one molecule of water. The sorbitan fatty acid esters of this invention are mixtures of partial esters of sorbitol and its anhydrides with fatty acids. These sorbitan esters can be represented by the following structure, which can be any one of monoesters, diesters, triesters, tetraesters, or mixtures thereof (Formula III):

[0038] [ka]

[0039]

[0045] In formula (III), each Z independently represents a hydrogen atom or C(O)R-, and each R independently represents a hydrocarbyl group of from about 9 to about 99 carbon atoms, more preferably from about 11 to about 23 carbon atoms. Examples of sorbitan esters include sorbitan stearate and sorbitan oleate, such as sorbitan stearate (i.e., monostearate), sorbitan distearate, sorbitan tristearate, sorbitan monooleate, and sorbitan sesquioleate. Sorbitan esters also include polyoxyalkylene sorbitan esters, in which the alkylene group has from about 2 to about 30 carbon atoms. These polyoxyalkylene sorbitan esters have formula IV:

[0040] [ka]

[0041] wherein each R is independently an alkylene group of from about 2 to about 30 carbon atoms; R' is a hydrocarbyl group of from about 9 to about 99 carbon atoms, more preferably from about 11 to about 23 carbon atoms; and w, x, y, and z represent the number of repeating oxyalkylene units. For example, ethoxylation of sorbitan fatty acid esters results in a series of more hydrophilic surfactants, which is the result of the hydroxy groups of sorbitan reacting with ethylene oxide. One major class of these ethoxylated sorbitan esters is one that contains from about 2 to about 80 ethylene oxide units, in one embodiment from about 2 to about 30 ethylene oxide units, in one embodiment about 4, in one embodiment about 5, and in one embodiment about 20 ethylene oxide units. Typical examples are polyoxyethylene (hereinafter "POE") (20) sorbitan tristearate, POE (4) sorbitan monostearate, POE (20) sorbitan trioleate, POE (5) sorbitan monooleate, and POE (80) sorbitan monooleate. As used herein, the number in parentheses refers to the number of ethylene oxide units present in the composition.

[0042]

[0046] Useful surfactants of the type listed in the table above can be generally represented by the following classes of chemical compounds, some of which are commercially available and suitable provided they are used in accordance with the teachings herein to produce stable emulsions: (a) Sorbitol esters of the general formula:

[0043] [ka]

[0044] [wherein the groups X are the same or different and each represents OH or R 1 COO - ;R 1 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 7 to 22 carbon atoms, optionally substituted by hydroxyl, provided that at least one of the radicals X is R 1 COO - is], (b) a fatty acid ester of the general formula:

[0045] [ka]

[0046] [In the formula, R 2 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon group having 7 to 22 carbon atoms, optionally substituted by a hydroxyl group; R 3 is linear or branched C 1 ~C 10 alkylene; n is an integer greater than or equal to 6; R 4 is H, linear or branched C 1 ~C 10 Alkyl or

[0047] [ka]

[0048] and R5 is R 2 as defined above for and (c) a polyalkoxylated alkylphenol of the general formula:

[0049] [ka]

[0050] [In the formula, R 6 is linear or branched C 1 ~C 20 alkyl; m is an integer greater than or equal to 8; R 7 and R 8 are R in formula (II), 3 and R 4 as defined above for

[0051] Typically, the weight ratio of the sol to the oil and surfactant mixture can be from about 1:5 to about 5:1, such as from about 1:4 to about 4:1, such as from about 1:3 to about 2:1, such as from about 1:2 to about 2:1. In some embodiments, the oil is a mineral oil and the surfactant is a sorbitan ester, such as sorbitan monooleate, and the weight ratio ranges from 1:2 to 2:1.

[0052]

[0048] The temperature can be controlled during the emulsion formation process to obtain the desired silica sol droplet size. For example, the temperature can be maintained at greater than about 30°C, such as from about 40°C to about 80°C, such as from about 50°C to about 65°C, while forming the emulsion.

[0053] The mixing speed should be high enough to form a stable emulsion, i.e., an emulsion that does not separate upon standing at room temperature for a desired period of time, and to obtain the desired silica sol droplet size. Such mixing speed can be achieved using an overhead type mixer, such as a Dispermat mixer, or an in-line type mixer, such as a Silverson mixer. After the sol is sufficiently pumped or otherwise thoroughly mixed into the reaction vessel, the emulsion can be continued to mix for a period of time sufficient to maintain a stable emulsion. For example, in some embodiments, mixing can be continued for a period of time from about 1 minute to about 1 hour.

[0054] After formation of the emulsion, the process proceeds to step 103, where the pH of the emulsion is optionally adjusted. The pH can be adjusted using a basic compound. For example, any base known or hereafter discovered can be used to adjust the pH in the various embodiments described herein. In various embodiments, the base is NaOH, aqueous ammonia, ammonium hydroxide (e.g., NH 4 OH), KOH, Na 2 CO 3 , TMAOH (tetramethylammonium hydroxide), NaAlO 2, and mixtures thereof. Additionally, the base used can be in the form of a solution having a concentration ranging from 0.2 to 50 percent. In various embodiments, the above-mentioned base can have a pH of at least 7, such as from about 8 to about 14, such as from about 9 to about 13. The amount of basic compound used is determined by the target pH to be reached. For example, in some embodiments, the basic compound is added until the pH reaches a value of about 3 or more, in some embodiments about 4 or more, in some embodiments about 5 or more, in some embodiments about 6 or more, in some embodiments about 7 or more, and in some embodiments about 8 or more. The pH typically reaches about 12 or less, in some embodiments about 11 or less, in some embodiments about 10 or less, and in some embodiments about 9 or less. For example, in some embodiments, ammonium hydroxide is added until the pH reaches about 3 to about 10, such as from about 5 to about 9. The emulsion can be mixed continuously when the basic compound is added and for a period of time thereafter to promote pH stabilization. Optionally, the mixing speed can be reduced at this stage. For example, in some embodiments, the mixing speed is reduced to about 10% to about 60% of the mixing speed used to form the emulsion.

[0055] It should be understood that the pH is not necessarily adjusted and that step 103 is optional. The pore characteristics of the resulting silica particles can be controlled by adjusting the pH of the emulsion during gelation. Thus, the pH should be adjusted to the level required to obtain the desired pore characteristics. Thus, in some cases, the pH does not need to be adjusted at all.

[0056] After the optional pH adjustment step, the process can proceed to step 104, where the silica is gelled. The gelling step can optionally include adding water to the emulsion and optionally continuously mixing while increasing the temperature. The volume of water added at this stage is not critical and can be from about 0.25 to about 10 times the volume of the mixture in the vessel. In other embodiments, no water is added.

[0057]

[0053] The gelation temperature can range from about 50°C to about 95°C, in some embodiments from about 75°C to about 85°C, for example, from about 75°C to about 85°C. The mixing speed can be maintained at a speed similar to that of step 103. This temperature and mixing speed can be maintained for a time sufficient to gel the silica. For example, in some embodiments, the gelation time can be from about 20 minutes to about 2 hours, for example, from about 30 minutes to about 90 minutes. In some embodiments, the resulting silica gel can be aged prior to separation, for example by Ostwald ripening, in which the resulting silica gel is maintained at a temperature of from about 50°C to about 95°C, in some embodiments from about 70°C to about 90°C, in some embodiments from about 75°C to about 85°C, for a period of from about 10 minutes to about 10 hours, in some embodiments from about 30 minutes to about 5 hours, in some embodiments from about 45 minutes to about 2 hours. The pH can optionally be adjusted during the aging step. In this manner, the surface area and pore size can be adjusted in situ and the gel network can be strengthened.

[0058] After the gelation step, the process can proceed to separation at step 105. Any suitable method can be used to separate the solid silica gel particles from the oil and water phases of the mixture. For example, in some embodiments, mixing is discontinued such that the oil and surfactant separate from the formed silica particles. In some embodiments, the solid particles can be filtered from the mixture.

[0059] The resulting silica particles can then be optionally washed in step 106, for example by stirring in acid, water, and / or alcohol. The particles can then be dried in step 107 using any suitable method. For example, in some embodiments, the particles can be dried at a temperature and for a time sufficient to remove a desired amount of moisture. In some embodiments, the particles can be dried in a vacuum oven at a temperature of about 40° C. to about 80° C. for about 30 minutes to about 24 hours. In some embodiments, the particles can be dried in a conventional oven at a temperature of about 90° C. to about 130° C. for about 30 minutes to about 24 hours. In some embodiments, the particles can be dried using a spray dryer. In other embodiments, the particles can be dried by flash drying or by co-evaporation with an organic solvent.

[0060]

[0056] In some embodiments, the emulsion is demulsified by adding a demulsifier to facilitate separation of the oil and surfactant from the emulsion. In some embodiments, the demulsifier is water or an acid, such as a mineral acid. For example, in some embodiments, deionized water or aqueous mineral acid is added to the emulsion as the demulsifier. For example, when an aqueous sulfuric acid composition is used as the demulsifier, the concentration of sulfuric acid can be about 1 wt.% to about 30 wt.%, and in some embodiments, about 5 wt.% to about 15 wt.%, of the total aqueous composition. The demulsifier can be added to the emulsion in a weight ratio of about 1:5 to about 5:1, and in some embodiments, about 1:2 to about 1:1, based on the weight of the emulsion.

[0061]

[0057] Demulsification can occur at elevated temperatures. For example, the temperature can be from about 50°C to about 95°C, in some embodiments from about 60°C to about 90°C, and in some embodiments from about 70°C to about 80°C. During demulsification, the mixture can optionally be agitated by any suitable means. For example, in some embodiments, after the demulsifier is added, the mixture is agitated at elevated temperature for about 30 minutes to about 5 hours, for example, from about 1 hour to about 3 hours. In other embodiments, the mixture is held at elevated temperature without agitation for about 30 minutes to about 5 hours, for example, from about 1 hour to about 3 hours.

[0062] After demulsification, the particles can be separated from the remaining mixture by any suitable means. For example, in some embodiments, the mixture can be transferred to a separatory funnel to separate the aqueous phase from the oil phase. The silica particles can then be separated from the remaining liquid. In some embodiments, for example, the particles can be repeatedly filtered and redispersed as necessary.

[0063] After separation, the particles can optionally be aged as shown in FIG. 1, step 106a. The particles can be aged at elevated temperature in an ammonia solution. In some embodiments, the particles are redispersed in an aqueous medium, heated, and combined with ammonium hydroxide for a suitable period of time. The pH of the particles redispersed in the aqueous medium can be about 1 to about 5, such as about 2 to about 4. The temperature of aging can be about 50° C. to about 95° C., in some embodiments about 70° C. to about 90° C., and in some embodiments about 75° C. to about 85° C. Ammonium hydroxide can be added until the pH of the solution reaches about 6 to about 9, such as about 7 to about 8. In some embodiments, the particles are aged for a period of about 10 minutes to about 10 hours, in some embodiments about 30 minutes to about 5 hours, and in some embodiments about 45 minutes to about 2 hours.

[0064]

[0060] When the particles are aged in such a solution, they can then be filtered and dried. For example, in some embodiments, the particles can be filtered from the ammonia solution, redispersed in water if necessary, and then filtered and dried to remove the water and any solvent to form a powder. In some embodiments, after filtering from the ammonia solution, the particles can be redispersed in deionized water and then dried at an elevated temperature for a suitable period of time. Any suitable temperature can be used to dry the particles. In some embodiments, for example, the particles are dried at a temperature of about 50°C to about 250°C, in some embodiments about 80°C to about 200°C, in some embodiments about 100°C to about 150°C, for a period of about 1 hour to about 48 hours, for example, about 5 hours to about 24 hours.

[0065]

[0061] The emulsification process used to form the silica particles can provide additional advantages over conventional silica carriers. For example, in conventional spray-dried silica carriers, the grinding step tends to produce extremely small silica particles, referred to as "fines." Even if the silica particles are highly classified to remove the fines, it is difficult to prevent some of the fines from remaining attached to the carrier particles and entering the polymerization reactor, causing static electricity and clogging, especially in gas-phase reactors. Advantageously, however, the silica carrier of the present disclosure can have a very low content of fines, since no grinding step is required when using the described emulsification process. For example, in some embodiments, the number percentage of silica particles having a particle size of 1 μm or less is about 7% or less, in some embodiments about 4% or less, and in some embodiments less than about 2% to 1%.

[0066] During the above process, silica gel particles are formed within the emulsion droplets to provide porous, spherical silica particles. Each particle contains a rigid network of amorphous silica. Thus, the particles tend to be highly spherical. One way to measure the sphericity of the particles is to take images of many particles and calculate the aspect ratio of each particle using the largest and smallest diameters of each particle that can be determined from the images. The average aspect ratio of the particles can then be calculated using the aspect ratios of the individual particles. Thus, particles with low aspect ratios are more spherical than particles with higher aspect ratios. In this regard, the particles formed by any of the above processes can be highly spherical and have a low average aspect ratio, for example, about 1.2 or less, in some embodiments about 1.17 or less, in some embodiments about 1.15 or less, in some embodiments about 1.12 or less, and in some embodiments about 1.1 or less. For example, in some embodiments, at least 75% of the particles have an aspect ratio of about 1.2 or less, for example about 1.1 or less. In some embodiments, at least 50% of the particles have an aspect ratio of about 1.1 or less. Typically, the aspect ratio is 1.0 or more.

[0067]

[0063] Such highly spherical carrier particles can help produce polymer particles with good morphology and high bulk density. For example, the polyolefin particles produced as described herein can have a settled bulk density of less than 0.4 g / cc. Furthermore, the average aspect ratio of the polyolefin particles produced can be less than about 1.2.

[0068]

[0064] As explained above, the silica support can be used in a variety of different catalytic forms. Ziegler-Natta, metallocene, and chromium catalysts, cocatalysts, and activator components can be impregnated in and on the supports described herein. For example, the catalyst components that are desired to be impregnated in the support can be dissolved or suspended in an organic solvent, to which the support is added and slurried. The solvent can then be evaporated. The evaporation can occur in a cone dryer, which avoids placing high stress on the core material. As is well known in the art, many variations on this topic are possible, and the particular impregnation technique will depend on the particular catalyst system used.

[0069] "Ziegler-Natta" catalysts are conventionally understood to include transition metal (IIIB to VIIIB) halides, alkyl, aryl, or alkoxy compounds in combination with elements from Groups I to III of the Periodic Table, and mixtures thereof. A typical example is TiCl 4 and AlEt 3 Preferred Ziegler-Natta systems are those that use magnesium chloride / titanium halide complexes or alkoxy compounds and aluminum alkyls deposited on a silica support. Methods for producing catalysts are known in the art. Electron donors may also be used in the Ziegler-Natta catalyst systems of the present invention and include esters, ethers, amines, silanes and alcohols, and mixtures thereof.

[0070] One suitable method for providing a silica supported Ziegler-Natta type catalyst is described in US Pat. No. 5,633,419, which is incorporated herein by reference. For example, the Ziegler-Natta catalyst composition can include a magnesium halide, a transition metal compound, an alkylaluminum cocatalyst, and an electron donor compound. These components can be incorporated into or supported on a silica support. For example, the catalyst components can be formed by impregnating a silica support with a solution of magnesium halide or a magnesium-containing precursor that can be converted to magnesium halide upon halogenation.

[0071]

[0068] The silica support can be impregnated by immersing the support particles in a magnesium halide solution, such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride dissolved in a polar solvent, agitating the solution for a sufficient period of time, and then removing the solvent.

[0072] Alternatively, the support may be a compound of formula R 2-n MgX n .xMR' y where each R is independently a hydrocarbyl group having 1 to 20 carbon atoms, each X is independently halo or hydrocarbyloxy having 1 to 20 carbon atoms in the hydrocarbyl moiety, n is 0 to 2 except that if X is halo, then n is up to 1, M is aluminum, zinc or boron, each R' is independently hydrogen, hydrocarbyl or hydrocarbyloxy having 1 to 20 carbon atoms in the hydrocarbyl moiety, y has a value equal to the valence of M and x has a value from 0 to 10. After impregnation of the silica support with the hydrocarbon soluble magnesium compound, a magnesium halide can be formed by halogenation.

[0073] In some embodiments, the halogenating agent is selected from the group consisting of alkylaluminum halides, advantageously alkylaluminum sesqui- or dihalides, hydrogen halides, silicon halides, and boron halides.

[0074] The transition metal compound can then be added to the supported magnesium halide component in any manner known in the art. The transition metal compound can be a Group 4 or Group 5 transition metal compound, such as a halide, hydrocarbyl oxide or mixed halide / hydrocarbyl oxide of titanium, zirconium, hafnium, or vanadium. For example, suitable Group 4 transition metal compounds have the formula MX 4-a (OR) a where M is titanium, zirconium or hafnium, each R is independently an alkyl group having from 1 to about 20, preferably from about 1 to about 10, more preferably from 2 to about 8 carbon atoms; X is a halogen atom, preferably chlorine; and a has a value of 0 to 4. Suitable Group 5 transition metal compounds are preferably vanadium compounds, such as those of the formula VX 4 and V(O)X 3 where each X is independently OR or a halide atom, preferably chloride, and each R is independently an alkyl group having 1 to about 20, preferably about 2 to about 8, and more preferably about 2 to about 4 carbon atoms.

[0075]

[0072] A variety of different types of internal electron donors can also be incorporated into the catalyst component in any suitable manner. In one embodiment, the internal electron donor is an aryl diester, such as a phenylene substituted diester. In one embodiment, the internal electron donor has the following chemical structure:

[0076] [ka]

[0077] [In the formula, R 1 , R 2、 R 3 and R 4 are each a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl group having a branched or linear structure or a cycloalkyl group having 7 to 15 carbon atoms; E 1 and E2 are the same or different and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, substituted alkyl having 1 to 20 carbon atoms, aryl having 1 to 20 carbon atoms, substituted aryl having 1 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms and optionally containing a heteroatom; X 1 and X 2 are each O, S, an alkyl group, or NR 5 and R 5 is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen. may have:

[0078] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl, alkylaryl, and alkynyl- groups.

[0079]

[0074] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. As used herein, "heteroatom" refers to an atom other than carbon or hydrogen. A heteroatom can be a non-carbon atom of Groups IV, V, VI, and VII of the Periodic Table. Non-limiting examples of heteroatoms include: halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted hydrocarbyl groups also include halohydrocarbyl groups and silicon-containing hydrocarbyl groups. As used herein, the term "halohydrocarbyl" group refers to a hydrocarbyl group substituted with one or more halogen atoms. As used herein, the term "silicon-containing hydrocarbyl group" refers to a hydrocarbyl group substituted with one or more silicon atoms. The silicon atom may or may not be within a carbon chain.

[0080] In one embodiment, the substituted phenylenediester has the following structure (I):

[0081] [ka]

[0082] In some embodiments, structure (I) is an isopropyl group, R 1 and R 3 Includes: R 2 , R 4 and R 5 ~R 14 are each hydrogen. In some embodiments, structure (I) is R 1 , R 5 , and R 10 as a methyl group, R 3 is a t-butyl group. 2 , R 4 , R 6 ~R 9 and R 11 ~R14 are each hydrogen.

[0083] In some embodiments, structure (I) is R 1 , R 7 , and R 12 as a methyl group, R 3 is a t-butyl group. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0084] In some embodiments, structure (I) is R 1 as a methyl group, R 3 is a t-butyl group. 7 and R 12 are each ethyl groups. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0085] In some embodiments, structure (I) is R 1 , R 5 , R 7 , R 9 , R 10 , R 12 , and R 14 as a methyl group, R 3 is a t-butyl group. 2 , R 4 , R 6 , R 8 , R 11 , and R 13 are each hydrogen.

[0086] In some embodiments, structure (I) is R 1 as a methyl group, R 3 is a t-butyl group. 5 , R 7 , R 9 , R 10 , R 12 , and R 14 Each of R is an i-propyl group. 2 , R 4 , R 6 , R 8 , R 11 , and R 13 are each hydrogen.

[0087] In some embodiments, the substituted phenylene aromatic diester is R 1 ~R 14 Each of the options above includes a structure selected from the group consisting of structures (II)-(V), which are described in detail in U.S. Pat. No. 8,536,372, which is incorporated herein by reference.

[0088] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each of R is an ethoxy group. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0089] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each R is a fluorine atom. 2 , R 4 , R 5 , R 6 , R8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0090] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each R is a chlorine atom. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0091] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each is a bromine atom. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0092] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each is an iodine atom. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11, R 13 , and R 14 are each hydrogen.

[0093] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 6 , R 7 , R 11 , and R 12 Each R is a chlorine atom. 2 , R 4 , R 5 , R 8 , R 9 , R 10 , R 13 , and R 14 are each hydrogen.

[0094] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 6 , R 8 , R 11 , and R 13 Each R is a chlorine atom. 2 , R 4 , R 5 , R 7 , R 9 , R 10 , R 12 , and R 14 are each hydrogen.

[0095] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 2 , R 4 , and R 5 ~R 14 are each a fluorine atom. In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each of R is a trifluoromethyl group.2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0096] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each of R is an ethoxycarbonyl group. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0097] In one embodiment, R 1 is a methyl group, and R 3 is a t-butyl group. 7 and R 12 Each of R is an ethoxy group. 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0098] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 is a t-butyl group. 7 and R 12 Each of R is a diethylamino group. 2 , R 4 , R 5 , R6 , R 8 , R 9 , R 10 , R 11 , R 13 , and R 14 are each hydrogen.

[0099] In some embodiments, structure (I) is a methyl group, R 1 Including R 3 R is the 2,4,4-trimethylpentan-2-yl group. 2 , R 4 , and R 5 -R 14 are each hydrogen.

[0100] In some embodiments, structure (I) has R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , 1 and R 3 Includes: R 2 , R 4 , and R 5 -R 14 are each hydrogen. In some embodiments, structure (I) has R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 1 and R 4 Includes: R 2 , R 3 , R 5 ~R 9 , and R 10 ~R 14 are each hydrogen.

[0101] In some embodiments, structure (I) is a methyl group, R 1 Includes: R 4 is an i-propyl group. 2 , R 3 , R 5 ~R 9 , and R 10 ~R 14 are each hydrogen. In some embodiments, structure (I) has R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , 1 , R 3 , and R 4 Includes: R 2, R 5 ~R 9 , and R 10 ~R 14 are each hydrogen.

[0102] In another embodiment, the internal electron donor can be a phthalate compound. For example, the phthalate compound can be dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl butyl phthalate, ethyl butyl phthalate, or ethyl propyl phthalate.

[0103] In addition to the catalyst components described above, the Ziegler-Natta catalyst system of the present disclosure can also include a cocatalyst. The cocatalyst can include hydrides of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium, alkyl, or aryl, and combinations thereof. In some embodiments, the cocatalyst is represented by the formula R 3 Al, where each R is an alkyl, cycloalkyl, aryl, or hydride group; at least one R is a hydrocarbyl group; two or three R groups can be joined together in a cyclic group to form a heterocyclic structure; each R can be the same or different; and each R, which is a hydrocarbyl group, has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms. In further embodiments, each alkyl group can be straight or branched chain, and such hydrocarbyl groups can be mixed groups, i.e., the group can contain alkyl, aryl, and / or cycloalkyl groups. Non-limiting examples of suitable groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl.

[0104]

[0102] Non-limiting examples of suitable hydrocarbyl aluminum compounds are as follows: triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum. In some embodiments, the cocatalyst is selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

[0105] Alternatively, the olefin polymerization catalyst system may comprise a catalyst precursor compound, such as a metallocene component, and an activator, loaded onto a silica support. Metallocene catalysts may comprise "half sandwich" and "full sandwich" compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bonded to at least one Group 3 to Group 12 metal atom, and one or more leaving groups bonded to at least one metal atom.

[0106]

[0104] The Cp ligands are one or more rings or ring systems, at least a portion of which include π-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogs. The rings or ring systems typically include atoms selected from Groups 13-16, and in some embodiments, the atoms that make up the Cp ligands are selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, where carbon makes up at least 50% of the ring members. For example, the Cp ligands can be selected from substituted and unsubstituted cyclopentadienyl ligands and ligands that are isotropic to cyclopentadienyl. Non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, and hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "H"). 4 Ind), their substituted variants (discussed and described in more detail below), and their heterocyclic variants.

[0107]

[0105] The metal atom "M" of the metallocene compound can be selected from group 3 to 12 and lanthanide group atoms; or can be selected from group 3 to 10 atoms; or can be selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni; or can be selected from group 4, 5, and 6 atoms; or can be Ti, Zr, or Hf atoms; or can be Hf; or can be Zr. The oxidation state of the metal atom "M" can range from 0 to +7; or can be +1, +2, +3, +4, or +5; or can be +2, +3, or +4. The groups bonded to the metal atom "M" are such that the compounds described below in the structures and structures are electrically neutral unless otherwise indicated. The Cp ligand forms at least one chemical bond with the metal atom M to form the "metallocene catalyst component". The Cp ligands are distinct from the leaving groups attached to the metal atom M, which are not highly susceptible to substitution / abstraction reactions.

[0108] In one embodiment, the metallocene catalyst may be represented by the formula:

[0109] [ka]

[0110] In the above formula, M is a metal of Group IIIB to Group VIII of the Periodic Table of the Elements; 5 R x ) and (C 5 R m are the same or different cyclopentadienyl or substituted cyclopentadienyl groups bonded to M; R are the same or different and are hydrogen or a hydrocarbyl group containing 1 to 20 carbon atoms, such as an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group, or two carbon atoms bonded together to form C 4 ~C 6 forms a ring; R' is two (C 5 R x ) and (C 5 Rm ) C bridging the ring 1 ~C 4 is a substituted or unsubstituted alkylene group, a dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or amine group; Q is a hydrocarbyl group having 1 to 20 carbon atoms, such as an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl group, a hydrocarboxy group having 1 to 20 carbon atoms, or a halogen, which may be the same or different from each other; z is 0 or 1; y is 0, 1, or 2; z is 0 when y is 0; n is 0, 1, 2, 3, or 4 depending on the valence state of M; and ny is 1 or greater.

[0111] Illustrative, but non-limiting, examples of metallocenes represented by the formula above include dialkyl metallocenes, such as bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafnium dimethyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl, bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium dimethyl; monoalkyl metallocenes, such as bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)hafnium dimethyl and diphenyl; cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconium phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide; trialkyl metallocenes such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium trineopentyl, and cyclopentadienyl hafnium trimethyl; monocyclopentadienyl titanocenes such as pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride; bis(pentamethylcyclopentadienyl)titanium diphenyl, of the formula bis(cyclopentadienyl)titanium=CH 2and derivatives of this reagent; substituted bis(cyclopentadienyl)titanium(IV) compounds such as bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl or dihalides; dialkyl, trialkyl, tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds such as bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes such as dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylphosphinedicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclo pentadienyltitanium diphenyl or dichloride and other dihalide complexes, etc.; as well as bridged metallocene compounds such as isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisopropylmethylene(2,5-Dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride ethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)hafnium dichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, ditert-butylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienylfluorenyl)titanium dichloride, racemic ethylenebis(1-indenyl)zirconium(IV) dichloride, racemic ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic dimethylsilylbis(1-indenyl)zirconium(IV) dichloride, racemic dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenebis(1-indenyl)zirconium(IV) dichloride, racemic 1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride, ethylidene(1-indenyltetramethylcyclopentadienyl)zirconium(IV) dichloride, racemic-dimethylsilylbis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV) dichloride, racemic-ethylenebis(1-indenyl)hafnium(IV) dichloride, racemic-ethylenebis(4,5,6,7-tetrahydro-1-indenyl ) hafnium(IV) dichloride, racemic-dimethylsilylbis(1-indenyl)hafnium(IV) dichloride, racemic-dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)hafnium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl ) hafnium(IV) dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) hafnium(IV) dichloride, racemic-ethylenebis(1-indenyl)titanium(IV) dichloride, racemic-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, racemic-dimethylsilylbis(1-indenyl)titanium(IV) dichloride, racemic-dimethylsilylbis(4 ,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)titanium(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, and ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV) dichloride.

[0112] Activators may also be used with the metallocene catalyst. For example, the activator may be an aluminoxane, a borane, or a borate compound. Activators that may be used have the following general formula: M 3 M 4 vX 2 c R 3 b-c [In the formula, M 3 are metals of groups IA, IIA and IIIA of the periodic table; M 4 is a metal in Group IA of the periodic table; v is a number from 0 to 1; each X 2 is any halogen; c is a number from 0 to 3; each R 3 is a monovalent hydrocarbon group or hydrogen; b is a number from 1 to 4; and bc is at least 1. Includes those having the following.

[0113] Compounds having only one Group IA, IIA or IIIA metal suitable for the practice of the present invention have the formula: M 3 R 3 k [In the formula, M 3 is a Group IA, IIA or IIIA metal, e.g., lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k is M 3 is equal to 1, 2 or 3 depending on the valence of the atom, which itself is usually M 3 depends on the particular group (i.e., Group IA, Group IIA, or Group IIIA) to which each R 3 can be any monovalent hydrocarbon radical. The compounds having the appropriate R 3 Examples of groups are those described above in relation to formula (V). 3 In some embodiments, the activator is selected from methylaluminoxane, tris-perfluorophenylborate, and trityl tetra-perfluorophenylborate.

[0114]

[0110] Advantageously, the silica supports described herein can accommodate relatively high activator loadings. For example, in some embodiments, the organoaluminum compound is loaded onto the support such that the catalyst system contains about 10 wt.% Al or more. Typically, the Al loading is about 25 wt.% or less.

[0115]

[0111] The olefin polymerization catalyst system may further include a chromium compound supported by or incorporated into a silica support. More specifically, the chromium catalyst may be prepared by contacting a silica support with a chromium compound, such as a salt that is at least partially soluble in water or an organic liquid medium. In some embodiments, an aqueous solution or suspension of a chromium salt may be contacted with an aqueous slurry of support particles.

[0116]

[0112] Chromium compounds suitable for use in forming the subject catalyst compositions can be selected from any chromium salt of an inorganic or organic acid that has some degree of solubility in the medium used to mix the appropriate salt with the silica. A preferred medium is water. For example, suitable inorganic salts include chromium halides such as chromium dichloride, chromium chloride hexahydrate, chromium dibromide, chromium bromide hexahydrate, chromium tribromide, chromium difluoride; as well as chromium nitrate; chromic anhydride, chromium phosphate; chromium sulfate. (II) chromium sulfate pentahydrate and octahydrate; chromium orthophosphate; and mixtures thereof.

[0117]

[0113] Organochromium compounds suitable as a source of chromium atoms for forming the present catalyst include salts of organic acids, such as chromium acetate, chromium acetate hydrate, chromium acetylacetonate, chromium propionate, chromium oxalate hydrate, chromium oxalate hexahydrate; amine complexes, such as hexamine chromium III chloride; chloropentamine chromium chloride; hexaurea chromium III fluorosilicate; chromocene, and the like, and mixtures thereof.

[0118] Certain chromium compounds found to be useful in the present invention have greater solubility in organic solvents. These compounds include, for example, chromocene, bis-(triphenylsilyl)chromate, and the like. In such cases, the salt may be contacted with the support using an organic liquid solution, followed by vacuum evaporation of the organic solvent at temperatures from ambient to about 40°C.

[0119]

[0115] In some embodiments, the chromium precursors include chromium sulfate, chromium nitrate, chromium acetate, and chromium acetylacetonate.

[0116] The chromium precursor may be immobilized on the support by contacting the support with a solution of the chromium precursor salt.

[0120] In each case, the chromium precursor is introduced as an aqueous or organic solution, or slurry. The materials may be contacted for a period of time from about 15 to about 150 minutes, with about 15 to 100 minutes being preferred. In one particular case, the materials are mixed for 15 to 60 minutes and then allowed to remain in the mixer without agitation for a period of up to about 180 minutes. The materials are usually mixed at a temperature of ambient to about 40°C.

[0121] The resulting supported chromium catalyst is then dried. The chromium precursor treated support product is subjected to oxidation to oxidize the chromium atoms to chromium (VI) oxide. The oxidation is typically carried out at a temperature and for a time sufficient to reduce the total volatiles to about 0.1-8 wt.%, where the total volatiles are determined by measuring the weight loss upon destructive calcination of a sample at 1000°C. However, the oxidation is typically carried out by heating the chromium precursor treated support to a temperature typically between about 157 and 815°C (about 600 and about 1800°F), preferably between about 427 and about 871°C (about 800 and about 1600°F), and most preferably between about 427 and about 704°C (about 800 and about 1300°F), typically for a period of about 1 minute to about 600 minutes (e.g., 50 to 600 minutes), preferably about 50 to about 300 minutes. The oxidizing atmosphere should be dry air or other oxygen-containing gas. The oxidation should be carried out in a manner that avoids sintering.

[0122] The catalyst system can be used to produce a variety of polyolefins by contacting an olefin monomer with a catalyst system comprising a silica support and any of the catalyst precursor compounds described above. The polymerization process can be a bulk polymerization process, a solution phase process, a slurry phase process, or a gas phase process.

[0123]

[0120] In a slurry olefin polymerization process, the silica support generally has a median particle diameter of from about 5 μm to about 100 μm, for example, from about 20 μm to about 80 μm.

[0121] In gas phase olefin polymerization processes, the silica support preferably has a median particle diameter of about 20 μm or more, such as about 30 μm or more, for example from about 50 μm to about 100 μm.

[0124]

[0122] In solution and high pressure olefin polymerization processes, the silica support preferably has a median particle diameter of from about 4 μm to about 40 μm, such as from about 5 μm to about 30 μm, for example, from about 6 μm to about 20 μm.

[0125]

[0123] Suitable olefins that can be polymerized in contact with the catalyst composition include, for example, alpha-olefins having from 2 to about 20, preferably from about 2 to about 12, more preferably from about 2 to about 8 carbon atoms, and combinations of two or more of such alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methylpentene-1, 1-hexene, 1-octene, and combinations of ethylene and / or propene with one or more of such other alpha-olefins.

[0126]

[0124] Slurry processes typically use inert hydrocarbon diluents and temperatures from about 0°C to just before the temperature at which the resulting polymer is substantially soluble in the inert polymerization medium. The preferred temperatures are from about 60°C to about 105°C. Pressures generally range from 1 to 100 bar. Solution processes are carried out at temperatures from the temperature at which the resulting polymer is soluble in the inert solvent or the particular monomer to about 275°C, preferably from about 130°C to about 260°C, more preferably from about 150°C to about 240°C. As the inert solvent, typically hydrocarbons, preferably aliphatic hydrocarbons, are used. In solution processes, pressures typically range from 1 to 100 bar. Typical operating conditions for gas phase polymerization are 20°C to 100°C, more preferably from 40°C to 80°C. In gas phase processes, pressures typically range from subatmospheric to 100 bar. High pressure processes are carried out at temperatures from about 100°C to about 400°C and pressures ranging from 500 to 3000 bar.

[0127] The invention having been generally described above will be more readily understood by reference to the following examples which are provided by way of illustration and are not intended to be limiting of the invention. EXAMPLES

[0128] Test Method:

[0127] Surface area, pore volume, and average pore diameter were measured by nitrogen adsorption. The instrument used for the analysis was an autosorb iQ2 TPX from Quantachrome Instrument. The nitrogen adsorption method is known as BET and is described in S. Brunauer, PH Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309.

[0129]

[0128] Prior to analysis, the samples were activated in vacuum at a temperature of 400 °C for 30 min. Surface areas were calculated from multipoint values ​​of nitrogen volumetric uptake in the adsorption branch at low partial pressures [P / Po = 0.05-0.15]. The adsorption branch of the isotherm was stopped at a partial pressure of P / Po = 0.995, and then the descending branch of the isotherm was measured. Pore volumes were calculated by applying the Gurvich law at P / Po = 0.995. Pore diameters are reported as calculated BJH desorption mean diameters.

[0130]

[0129] The silica gels of this invention are typical mesoporous materials (pore size 2-50 nm, IUPAC definition) and usually show type IV isotherms (IUPAC classification). Therefore, nitrogen porosimetry is a suitable method for characterization, and the determination of surface area using the BET method and pore volume from nitrogen adsorption and desorption isotherms using the BJH method are well-established and suitable methods used in this invention.

[0131]

[0130] Median particle size (D50) and particle size distribution were measured after 2 minutes of sonication using a Malvern MS3000 particle size analyzer from Brightwell Technologies Inc. Measurements were performed using a refractive index of 1.49.

[0132] Aspect ratios were determined from SEM micrographs using Image-Pro Premier software. For each particle in the sample image, the aspect ratio was calculated by dividing the longest diameter by the shortest diameter. The aspect ratios of the individual particles in each sample were then averaged to determine the average aspect ratio of the particles within the sample. For each sample for which an aspect ratio is provided, approximately 150 particles were used in the calculation.

[0133]

[0132] Melt flow rate was determined according to ISO 1133-1:2011 (technically equivalent to ASTM D1238-13) at a load of 2.16 kg and a temperature of 190°C.

[0134] Example 1

[0133] Porous spherical silica material was obtained using an emulsification process. First, a sol was prepared by reacting sodium silicate with mineral acid. The sol was prepared at a temperature of 15°C and pH 1.5 by adding 200g sodium silicate (14wt.%) to 53g acid (18.5% HCl) at a flow rate of 10ml / min and mixing with an overhead mixer at 960 rpm for 20 minutes. The sol was then pumped into a mixture of mineral oil (300g) and surfactant (sorbitan monooleate, 15g). An emulsion was prepared by continuously mixing the mixture at a speed of 960 rpm and temperature (60°C) for 10 minutes with an overhead mixer. The gelation process was controlled by adjusting the pH by adding 2.9g ammonium hydroxide to the emulsion. The emulsion was then mixed at 250 rpm for 5 minutes. 400ml water was added to the emulsion. The temperature was then increased to 80°C. The emulsion was mixed at 250 rpm for 1 hour for gelation. After gelation, the mixture was cooled for 30 minutes to allow the oil phase to separate from the water phase. The water phase containing the silica particles was collected and the silica particles were filtered from the water phase. The silica particles were washed with 200 ml water at pH 4, 60°C while mixing at 250 rpm for 40 minutes and then filtered. The washing process was repeated two more times. The particles were then washed with isopropanol and then dried in a vacuum oven at 60°C for 1 hour. The resulting particles were spherical porous silica with a D50 particle size of 14 μm and a span of 1.5. The BET surface area of ​​the resulting particles was 456 m 2 The particle size was 1.5 ml / g, the pore volume was 1.5 ml / g, and the average pore diameter was about 101 Å. An image of the particle is shown in Figure 4. An image of the particle is shown in Figure 2.

[0135] Example 2

[0134] Porous spherical silica material was obtained using an emulsification process. First, a sol was prepared by reacting sodium silicate with mineral acid. The sol was prepared by adding 253 g of sodium silicate (14 wt.%) to 50.5 g of acid (18.5% HCl) at a flow rate of 10 ml / min at a temperature of 15°C and pH 1.5, and mixing with an overhead mixer at 960 rpm for 20 minutes. The sol was then pumped into a mixture of oil (150 g) and surfactant (sorbitan monooleate, 10 g). An emulsion was prepared by continuously mixing the mixture at a speed of 960 rpm and a stable temperature (60°C) for 10 minutes using an overhead mixer. The gelation process was controlled by adjusting the pH by adding 2.4 g of ammonium hydroxide to the emulsion. The emulsion was then mixed at 250 rpm for 5 minutes. 400 ml of water was added to the emulsion. The temperature was then increased to 80°C. The emulsion was mixed at 250 rpm for 1 hour for gelation. After gelation, the mixture was cooled for 30 minutes to allow the oil phase to separate from the water phase. The water phase containing the silica particles was collected and the silica particles were filtered from the water phase. The silica particles were washed with 200 ml of water at pH 4, 60°C while mixing at 250 rpm for 40 minutes and then filtered. The washing process was repeated two more times. The particles were then washed with isopropanol and then dried in a vacuum oven at 60°C for 1 hour. The resulting particles were spherical porous silica with a D50 particle size of 17 μm and a span of 1.3. The BET surface area of ​​the resulting particles was 917 m 2 / g, pore volume was 1.9 ml / g, and average pore diameter was about 101 Å. An image of the particles is shown in Figure 3.

[0136] Example 3

[0135] Porous spherical silica material was obtained using an emulsification process. First, a sol was prepared by reacting sodium silicate with mineral acid. The sol was prepared by adding 201 g of sodium silicate (14 wt.%) to 53.5 g of acid (18.5% HCl) at a flow rate of 10 ml / min at a temperature of 15°C and pH 1.5, and mixing with an overhead mixer at 960 rpm for 20 minutes. The sol was then pumped into a mixture of oil (91 g) and surfactant (sorbitan monooleate, 7.7 g). An emulsion was prepared by continuously mixing the mixture with an overhead mixer at a speed of 960 rpm and a stable temperature (60°C) for 10 minutes. The gelation process was controlled by adjusting the pH by adding 1.0 g of ammonium hydroxide to the emulsion. The emulsion was mixed at 250 rpm for another 5 minutes. 400 ml of water was added to the emulsion. The temperature was then increased to 80°C. The emulsion was mixed at 250 rpm for 1 hour for gelation. After gelation, the mixture was cooled for 30 minutes to allow the oil phase to separate from the water phase. The water phase containing the silica particles was collected and the silica particles were filtered from the water phase. The silica particles were washed with 200 ml of water at pH 4, 60°C while mixing at 250 rpm for 40 minutes and then filtered. The washing process was repeated two more times. The particles were then washed with isopropanol and dried in a vacuum oven at 60°C for 1 hour. The resulting particles were spherical porous silica with a D50 particle size of 9 μm and a span of 1.1. The BET surface area of ​​the resulting particles was 505 m 2 / g, pore volume was 2.5 ml / g, and average pore diameter was about 189 Å. An image of the particles is shown in Figure 4.

[0137]

[0136] Table 1 summarizes the properties of the silica particles produced in Examples 1-3.

[0138] [Table 1]

[0139] Example 4

[0137] An emulsification process was used to obtain mesoporous silica materials. First, sodium silicate was reacted with an acid to create a sol, which was then added to oil and a surfactant to generate an emulsion. The sol was prepared by mixing sodium silicate (18%) with an acid (50.0 g, 42% H) at controlled temperature (≤25°C) and pH (≤1.5). 2 SO 4 The sol was then pumped into the mixed mineral oil (CX) and surfactant (sorbitan monooleate) at a flow rate of 10 ml / min. After the sol was completely pumped, an emulsion was made by continuous mixing (using a Rushton impeller) at a speed of 400 rpm and ambient temperature for 25 minutes. The pH was adjusted to control the gelation process of the sol by adding 6.0 g of ammonium hydroxide to the emulsion over a period of 2 minutes. Mixing was continued for another 5 minutes at a reduced speed of 250 rpm. The temperature was increased to 80°C without stirring and the emulsion was left for 1 hour. After 1 hour of reaction, 400 ml of 10% sulfuric acid was added over a period of 1 hour at a speed of 250 rpm, maintaining the temperature at 80°C. The mixture was then allowed to cool for 30 minutes to allow the oil and surfactant to separate from the resulting silica particles. The mixture was then filtered to separate the oil and surfactant from the silica particles. The silica particles were then washed with 250 ml of water at 80° C. with mixing at 250 rpm for 30 minutes, followed by filtration. The washing process was repeated two more times. The particles were then washed once with isopropanol, after which the sample was dried in a vacuum oven at 60° C. for 2 hours. The resulting particles had a D50 particle size of 25 μm and a span of 1.71. The average BET surface area of ​​the resulting particles was 741 m. 2 / g, the average pore volume was 2.55 ml / g, and the average pore diameter was approximately 132 Å.

[0140] Example 5

[0138] An emulsification process was used to obtain mesoporous silica materials. First, sodium silicate was reacted with an acid to create a sol, and then oil and surfactants were added to the sol to generate an emulsion. The sol was prepared by mixing sodium silicate (18 wt.%) with an acid (136.3 g, 15.4 wt.% H2O) at controlled temperature (up to 25°C) and pH (approximately 1.5). 2 SO 4 ) and mixed at 500 rpm for 30 minutes. A mixture of CX mineral oil (153.7 g) and surfactant (sorbitan monooleate, 8.4 g) was added to the sol. An emulsion was made by continuous mixing at a speed of 400 rpm and ambient temperature for 25 minutes. The pH was adjusted by adding 6 g of ammonium hydroxide to the emulsion to control the gelation process of the sol. The emulsion was mixed at 250 rpm for another 5 minutes. The temperature was then increased to 80°C without mixing and left at 80°C for 1 hour. 400 mL of water was then added and the mixture was mixed at 250 rpm and 80°C for 1 hour. After the reaction, the mixture was allowed to cool and the oil phase was separated from the water phase. The oil phase was separated and the particles were filtered from the water phase. The silica particles were then washed with 250 ml of water at 80°C while mixing at 250 rpm for 30 minutes. The washing process was repeated two more times. The particles were then washed with isopropanol, after which the sample was dried in a vacuum oven at 60° C. for 2 hours. The resulting particles had a D50 particle size of 26 μm and a span of 1.63. The average BET surface area of ​​the resulting particles was 506 m. 2 / g, the average pore volume was 1.91 ml / g, and the average pore diameter was approximately 155 Å.

[0141] Example 6

[0139] An emulsification process was used to obtain mesoporous silica materials. First, sodium silicate was reacted with acid to create a sol, which was then mixed with a surfactant and pumped into oil to generate an emulsion. The sol was prepared by mixing 275.68 g of sodium silicate (14 wt.%) with acid (50.14 g, 42 wt.% H) at controlled temperature (up to 25°C) and pH (1.81). 2 SO 4) at a flow rate of 10 ml / min and mixed at 960 rpm for 20 minutes. A surfactant (sorbitan monooleate, 9.91 g) was added to the sol and mixed at 960 rpm for 5 minutes. The sol was then pumped into mineral oil (117.5 g) and mixed continuously at a speed of 960 rpm and a stable temperature (60°C) for 10 minutes after the sol was completely pumped to form an emulsion. 300 mL of DI water was added to the emulsion. The pH was adjusted by adding 1.54 g of 20% ammonia hydroxide with 200 mL of water to the emulsion. The pH reached 2.5. Then 1.06 g of 20% ammonia hydroxide and 10 mL of water were added and the pH reached 4.2. The temperature was increased to 80°C. The emulsion was then mixed at 250 rpm for 1 hour. After reaction, the mixture was left overnight to separate. The mixture was then filtered to separate the oil and surfactant from the silica particles. The silica particles were then washed with acidified water (pH 4) at 80°C while mixing at 250 rpm for 90 minutes. The washing step was repeated two more times. The particles were then washed once with isopropanol, after which the sample was dried in a vacuum oven at 60°C for 1 hour. The resulting particles had a diameter of 526.2 mm. 2 / g BET surface area, average pore volume was 1.634 ml / g, and average pore diameter was 153.5 Å.

[0142] Example 7

[0140] An emulsification process was used to obtain mesoporous silica materials. First, sodium silicate and acid were reacted to form a sol, and then the sol was pumped into a surfactant and oil mixture to generate an emulsion. The sol was prepared by adding 201.35 g of sodium silicate (14 wt.%) to acid (53.35 g HCl (1:1)) at a flow rate of 10 ml / min and mixing at 960 rpm for 20 minutes. Surfactant (sorbitan monooleate, 7.61 g) and 90.80 g of mineral oil were combined and mixed at 960 rpm and 60°C. The sol was then pumped into the mineral oil / surfactant mixture at a flow rate of 10 ml / min and continuously mixed at a speed of 960 rpm and a stable temperature (60°C) for 10 minutes after the sol was completely pumped to form an emulsion. 400 ml of DI water was added to the emulsion. The pH was adjusted by adding 1.01 g of 20% ammonia hydroxide to the emulsion. The temperature was raised to 80°C. The emulsion was then mixed at 250 rpm for 1 hour. After reaction, the mixture was left overnight to separate. The mixture was then filtered to separate the oil and surfactant from the silica particles. The silica particles were then washed with acidified water (pH~4) at 80°C while mixing at 250 rpm for 90 minutes. The washing process was repeated two more times. The particles were then washed once with isopropanol before the sample was dried in a vacuum oven at 60°C for 1 hour. The resulting particles had a mass of 480.04 m. 2 / g BET surface area, average pore volume was 2.149 ml / g, and average pore diameter was 189.8 Å.

[0143] Example 8

[0141] Under an argon atmosphere, 3.52 g of silica particles produced in Example 3 (SA of 505 cm2 / g, PV of 2.53 cc / g, PD of 188 Å) and 6.48 g of dry toluene were mixed using a magnetic stir bar. MAO (30 wt% in toluene, 4.36 g) was diluted with 7 g of toluene and slowly added to the silica support. The resulting mixture was stirred for 4 hours, then filtered and washed with 10 mL of toluene. After adding 10 mL of fresh toluene, 0.384 g of a solution prepared from 0.771 g of di(1-butyl-3-methylcyclopentadienyl)zirconium dichloride in 2.303 g of toluene was added to the stirred slurry of alkylated silica. The mixture was stirred for 4 hours, filtered, and washed with 15 ml of toluene followed by two washes with 15 ml of heptane. The solid catalyst was dried under high vacuum for approximately 16 hours. ICP analysis of catalyst: Al, 11.6 wt%, Zr, 0.42 wt%.

[0144] Example 9

[0142] Under an argon atmosphere, 3.54 g of silica produced in Example 7 and 6.50 g of dry toluene were mixed using a magnetic stir bar. MAO (30 wt% in toluene, 4.36 g) was diluted with 4 g of toluene and slowly added to the silica support. The resulting mixture was stirred for 4 hours, then filtered and washed with 10 mL of toluene. After adding 10 mL of fresh toluene, 0.386 g of a solution prepared from 0.771 g of di(1-butyl-3-methylcyclopentadienyl)zirconium dichloride in 2.303 g of toluene was added to the stirred slurry of alkylated silica. The mixture was stirred for 4 hours, filtered and washed twice with 15 ml of toluene followed by 15 ml of heptane. The solid catalyst was dried under high vacuum for approximately 16 hours. ICP analysis of the catalyst material: Al, 10.8 wt%, Zr, 0.34 wt%.

[0145] Example 10 (Comparative)

[0143] 3.45 g of Grace silica XPO-2538 (SA of 522 cm2 / g, PV of 1.86 cc / g, PD of 152 Å) and 6.48 g of dry toluene were mixed under an argon atmosphere using a magnetic stir bar. MAO (30 wt% in toluene, 4.42 g) was diluted with 5 g of toluene and slowly added to the silica support. The resulting mixture was stirred for 4 hours, then filtered and washed with 10 mL of toluene. After adding 10 mL of fresh toluene, 0.382 g of a solution prepared from 0.771 g of di(1-butyl-3-methylcyclopentadienyl)zirconium dichloride in 2.303 g of toluene was added to the stirred slurry of alkylated silica. The mixture was stirred for 4 hours, filtered and washed with 15 ml of toluene followed by two washes with 15 ml of heptane. The solid catalyst was dried under high vacuum for approximately 16 hours. ICP analysis of catalyst material: Al, 11.7 wt%; Zr, 0.40 wt%.

[0146] Example 11 Dry sodium chloride (400 g) was charged to a nitrogen inerted reactor and treated with 8 g of silica containing 10 wt% solid MAO as a scavenger. After heating the reactor to 50° C. with stirring, 60 mg of the catalyst produced in Example 4 was added along with 2 mg of silica-MAO scavenger. The mixing speed was then increased. A mixture of ethylene, hydrogen and 1-hexene was added to obtain a total pressure of 225 psi. The temperature was increased to 85° C. and polymerization was carried out for 1 hour. The H2 / ethylene molar ratio was maintained at 0.0005 and the 1-hexane / ethylene molar ratio was maintained at 0.028. The reactor was then depressurized and cooled to ambient temperature after which the polymer was collected, washed with water to remove sodium chloride and silica, and dried under vacuum. SEM imaging showed mostly spherical resin particles. The particles are shown in FIG. 8. Activity, 900gPE / gCat; SBD, 0.45g / cc; MI(2.16kg), 0.36g / 10 min; Density, 0.928g / cc.

[0147] Example 12 The same procedure was used as in Example 8, but with the silica produced in Example 5. SEM imaging showed mostly spherical resin particles. Activity, 1100 g PE / g Cat; SBD, 0.43 g / cc; MI (2.16 kg), 0.86 g / 10 min; Density, 0.931 g / cc.

[0148] Example 13 The same procedure was used as in Example 8, but with the silica formed in Example 6. SEM imaging showed a granular morphology reflecting the shape of the silica support, and very little attrition during catalyst preparation and polymerization. Activity, 900 g PE / g Cat; SBD, 0.40 g / cc; MI (2.16 kg), 0.69 g / 10 min, density, 0.929 g / cc.

[0149] Example 14A A portion of Example 4 was dried at 200° C. for 4 hours (761 M 2 10 grams was then weighed into a 4 ounce plastic container, followed by the addition of 0.68 grams of chromium(III) acetylacetonate 97% (CrAcAc) to create a 1% Cr catalyst sample. The container was shaken for approximately 5 minutes to disperse the CrAcAc throughout the silica.

[0150] Example 14B Activation of Cr Catalyst: Five grams of Example 14A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 843°C (1550°F) with a ramp rate of 6.7°C. Once at temperature, it was held for 6 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask which was then placed in a desiccator. The catalyst was analyzed by ICP to have a Cr content of 1.05%.

[0151] Example 14C Activation of Cr Catalyst: Five grams of Example 14A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 1300°F (704.4°C) at a ramp rate of 6.7°C. Once at temperature, it was held for 5 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask which was then placed in a desiccator. The catalyst was analyzed by ICP to have a Cr content of 1.01%.

[0152] Example 15A A portion of Example 5 was dried at 200° C. for 4 hours (566M 2 10 grams was then weighed into a 4 oz. plastic container, followed by the addition of 0.68 grams of chromium(III) acetylacetonate 97% (CrAcAc) to create a 1% Cr catalyst sample. The container was shaken for approximately 5 minutes to distribute the CrAcAc throughout the silica.

[0153] Example 15B Activation of Cr Catalyst: Five grams of Example 15A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 843°C (1550°F) with a ramp rate of 6.7°C. Once at temperature, it was held for 6 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask which was then placed in a desiccator. The catalyst was analyzed by ICP to have a Cr content of 0.98%.

[0154] Example 15C Activation of Cr Catalyst: Five grams of Example 15A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 1300°F (704.4°C) at a ramp rate of 6.7°C. Once at temperature, it was held for 5 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask which was then placed in a desiccator. The catalyst was analyzed by ICP to have a Cr content of 0.98%.

[0155] Example 16A

[0153] 10 g of silica particles produced in Example 6 were calcined at 150°C for 4 hours. 26.6 g of heptane was added to the calcined silica and mixed to form a slurry at ambient temperature. 1.14 g of TiPT (tetraisopropyl titanate) was then added to the slurry and mixed at room temperature for 30 minutes. The temperature was then increased to 40°C for 3 hours and the solvent was removed under vacuum to form 2 wt.% Ti silica. 10 grams of the 2 wt.% Ti silica was weighed into a 4 oz plastic container and then 0.68 grams of chromium (III) acetylacetonate 97% (CrAcAc) was added to make the 1% Cr catalyst sample. The container was shaken for approximately 5 minutes to disperse the CrAcAc throughout the silica.

[0156] Example 16B Activation of Cr Catalyst: Five grams of Example 16A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 843°C (1550°F) with a ramp rate of 6.7°C. Once at temperature, it was held for 6 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask, which was then placed in a desiccator. Analysis of the catalyst by ICP showed a Cr content of 1.10% and a Ti content of 2.15%.

[0157] Example 16C Activation of Cr catalyst: Five grams of Example 16A was placed in a quartz glass flask supported in a furnace. The flask was connected to a cylinder of Ultra Zero grade air with a flow of 52 l / hr for fluidization. The furnace was programmed to reach a temperature of 1300°F (704.4°C) with a ramp rate of 6.7°C. Once at temperature, it was held for 5 hours. Upon completion, the flask was immediately removed from the furnace and allowed to cool to ambient temperature. The activated catalyst was transferred to another flask, which was then placed in a desiccator. Analysis of the catalyst by ICP showed a Cr content of 1.14% and a Ti content of 2.16%.

[0158] Example 17

[0156] 842.49℃(1550 o For polymerization testing of Cr catalysts activated with 1,2-dimethylformamide (F), 40 mg to 60 mg samples of Cr catalyst were charged to a nitrogen inerted 103°C reactor. 1.25 lbs of isobutane was added to the reactor to replace the nitrogen. The agitator was started and ethylene was added to obtain a total pressure of 550 psi. After 5 minutes, 4.5 ml of 1-hexene was added to the reactor. Polymerization was carried out to obtain productivity of PE3600 to 4400 g / g catalyst. The reactor was then depressurized and cooled to ambient temperature, after which the polymer was collected and dried in vacuum for 7 minutes. Results for Examples 14A, 15A, and 16A were compared using a Grace commercial reference HA30 (nominal 400 ml) 2 / g surface area and 1.4cc / g pore volume) and HA30W (nominal 500m 2 The results are summarized in Table 2 along with the surface area (1.5cc / g surface area and 1.5cc / g pore volume). SEM images of the polymer fluff are shown in Figures 5-8.

[0159]

[0157]

[0160] [Table 2]

[0161] Example 18 Catalyst samples activated at 1300°F were polymerized at target temperatures and hexene amounts to produce resins with densities of 0.9518-0.9530 and melt indexes of 0.27-0.40. For these polymerizations, 40-60 mg samples were charged to a nitrogen inerted reactor at 102-105°C. 1.25 lbs of isobutane was added to the reactor to replace the nitrogen. The agitator was started and ethylene was added to obtain a total pressure of 550 psi. After 5 minutes, 3.0-6.0 ml of 1-hexene was added to the reactor. Polymerizations were carried out to yield productivity of 3600-4400 g.PE / g.catalyst. The reactor was then depressurized and the polymer was collected after cooling to ambient temperature and dried in vacuum for 7 minutes. The Environmental Stress Cracking Resistance (ESCR) of these resins was tested according to ASTM procedure #D1693-07a. The polymerization results are shown in Table 3.

[0162]

[0159]

[0163] [Table 3]

[0164] Example 19

[0160] 13 grams of spherical silica support (431 ml) prepared according to the method described in Example 3 2100 g of silica (surface area of ​​1.0 cc / g, pore volume of 2.19 cc / g, pore diameter of 190 Angstroms, and span of 1.15) was calcined at 500° C. for 4 hours to produce a material with less than 1% total volatiles. This material was transferred to a glove box and 10 grams was charged to a 500 mL Schlenk flask and slurried in 110 mL of heptane. 13.3 grams of 20 wt % butylethylmagnesium in hexane was added dropwise to the silica slurry. The reaction mixture was transferred to a 1 L autoclave reactor and stirred at 25° C. for 1 hour. Anhydrous hydrogen chloride was bubbled through the reaction mixture for approximately 2 minutes until titration with 0.04% bromothymol blue indicated complete conversion. 0.99 g of TiCl4 was added to the reactor and the reaction mixture was stirred at 25° C. for 1 hour, after which 36 mL of 1.0 M diethylaluminum chloride in hexane was slowly transferred to the precatalyst to produce a deep maroon color. The reaction mixture was stirred at 25° C. for an additional 2 hours, then transferred to a Schlenk flask and dried under high vacuum at room temperature for 2 hours to give 15 grams of catalyst.

[0165] Ethylene at 150 PSI was charged to a deactivated 2-L autoclave reactor at 50° C. 0.8 mL of 20% TEAL in heptane combined with 40 mL of 1-hexene was charged to the reactor under ethylene pressure with 500 mL of isobutane, followed by 5 mg of the catalyst in isohexane. After 215 PSI was dosed from the 500 mL vessel, the reactor was stirred at 500 rpm and held at 50° C. for 5 minutes. The reactor was heated to 85° C. and an active ethylene stream was introduced to maintain a total pressure of 370 PSI. After polymerization was carried out for 1 hour, the reactor was depressurized and the resin was collected for analysis. SEM imaging showed a mixture of agglomerates and spherical resin particles. Activity, 6102gPE / gCat;SBD, 0.25g / cc;MI(2.16kg) 1.23g / 10min.

[0166] Example 20 (Comparative) 50 grams of granular silica support (XPO-2538) was calcined at 600° C. for 4 hours to produce a material with less than 1% total volatiles. This material was transferred to a glove box and 15 grams was charged to a 500 mL Schlenk flask and slurried in 90 mL of heptane. 20.7 grams of 20 wt % butylethylmagnesium in hexane was added dropwise to the silica slurry. The reaction mixture was transferred to a 1 L autoclave reactor and stirred at 25° C. for 1 hour. Anhydrous hydrogen chloride was bubbled through the reaction mixture for approximately 2 minutes until titration with 0.04% bromothymol blue indicated complete conversion. 1.5 g of TiCl4 was added to the reactor and the reaction mixture was stirred at 25° C. for 1 hour before 55 ml of 1.0 M diethylaluminum chloride in hexane was slowly transferred to the precatalyst to produce a deep maroon color. The reaction mixture was stirred at 25° C. for an additional 2 hours, then transferred to a Schlenk flask and dried under high vacuum at room temperature for 2 hours to give 22 grams of catalyst.

[0167] The same polymerization procedure as in Example 19 was used and SEM shows the typical aggregated morphology. Activity, 6217 g PE / g Cat; SBD, 0.28 g / cc; MI (2.16 kg), 1.21 g / 10 min.

[0168] Example 21

[0164] An emulsification process was used to obtain mesoporous silica materials. First, sodium silicate was reacted with an acid to form a sol, and then oil and surfactants were added to the sol to produce an emulsion. Sodium silicate (18 wt.%) was mixed with acid (136.3 g, 15.4 wt.% H) at controlled temperature (up to 25°C) and pH (approximately 1.5). 2 SO 4) and mixed at 500 rpm for 30 minutes to prepare a sol. A mixture of CX mineral oil (153.7 g) and surfactant (sorbitan monooleate, 8.4 g) was added to the sol. An emulsion was prepared by continuous mixing at a speed of 400 rpm at ambient temperature for 25 minutes. The pH was adjusted by adding 6 g of ammonium hydroxide to the emulsion to control the gelation process of the sol. The emulsion was mixed at 250 rpm for another 5 minutes. The temperature was then increased to 80° C. without mixing and left at 80° C. for 1 hour. 400 mL of 10 wt.% sulfuric acid was then added and the mixture was mixed at 250 rpm and 80° C. for 1 hour. After the reaction, the mixture was allowed to cool and the oil phase was separated from the aqueous phase. The oil phase was separated and the particles were filtered from the aqueous phase. The silica particles were then washed at 80° C. with 250 ml of water while mixing at 250 rpm for 30 minutes. The washing process was repeated two more times. The particles were then washed with isopropanol and the sample was dried in a vacuum oven at 60° C. for 2 hours. The resulting particles had a D50 particle size of 32 μm. The average BET surface area of ​​the resulting particles was 670 m. 2 / g, and the average pore volume was 2.75 ml / g.

[0169] Example 22 Under argon atmosphere, 1.91 g of spherical silica prepared according to Example 21 and calcined at 600° C. was added to a 20 mL vial with a small stir bar and dispersed in 5 mL of toluene. MAO (4.4 g of a 30% solution in toluene) was added dropwise while gently stirring the silica slurry. The mixture was stirred for 2 hours and then allowed to settle. The supernatant was decanted, 5 mL of toluene was added, and the washing procedure was repeated. Rac-dimethylsilylenebis(2-methylindenyl)zirconium dichloride (0.031 g) was dissolved in 1 mL of toluene and added dropwise to the silica suspension with gentle stirring and stirred for 1 hour. The catalyst was isolated by filtration, washed with toluene, and then dried under high vacuum. ICP analysis of the catalyst: Al, 16.5 wt %, Zr, 0.17 wt %.

[0170] Example 23 (Comparative)

[0166] d50 of 27 μm, 300 m 2 The catalyst was prepared in the same manner as in Example 22, except that a spray-dried spheroidal silica support was used having an SA of 1.0 cc / g and a PV of 1.6 cc / g.

[0171] Example 24 A 2L autoclave reactor was purged with argon above 100°C and then flushed with liquid propylene. Under argon atmosphere, 0.5 ml of 25% triethylaluminum in heptane and 3 ml of additional heptane were added to the charge vessel, and the mixture was flushed with 600 mL of propylene into the prepared autoclave. The temperature was raised to 70°C and stirring was started. Approximately 100 mg of catalyst prepared according to Example 22 was weighed into a separate charge vessel under argon atmosphere and dispersed in 5 ml of heptane. The catalyst was flushed into the autoclave reactor with 450 mL of propylene, and the reaction was allowed to proceed for 1 hour after reaching 70°C. The autoclave was then cooled to below 25°C and vented to collect the polymer, which was dried in a stream of air. Activity, 3500 gPP / gCat; SBD, 0.42 g / cc. The polypropylene resin had a spheroidal morphology as shown in Figure 9.

[0172] Example 25 (Comparative) The catalyst prepared according to Example 25 was used to follow the same propylene polymerization procedure outlined in Example 24. Activity, 2300 g PP / g Cat; SBD, 0.43 g / cc. The polypropylene resin had a mixture of spheroidal and irregular morphology as shown in FIG. 10.

[0173]

[0169] Item 1. An olefin polymerization catalyst system comprising a silica support, a catalyst precursor compound, and an activator, wherein the silica support comprises a plurality of silica gel particles, each particle comprising a rigid network of amorphous silica; the particles are spherical, single gel particles; the particles have an average aspect ratio of about 1.2 or less; the particles have an average pore volume of about 1.4 ml / g to about 3 ml / g; and the particles have an average pore volume of about 200 m. 2 / g ~ approx. 950m 2 / g; and the particles have a median particle size of about 4 μm to about 100 μm.

[0174]

[0170] Item 2. The olefin polymerization catalyst system of item 1, wherein at least 75% of the particles have an aspect ratio of about 1.2 or less.

[0171] Item 3. The olefin polymerization catalyst system of items 1 or 2, wherein at least 50% of the particles have an aspect ratio of about 1.1 or less.

[0175]

[0172] Item 4. The olefin polymerization catalyst system of any one of Items 1 to 3, wherein the catalyst precursor compound comprises a metallocene component.

[0173] Item 5. The olefin polymerization catalyst system of any one of Items 1 to 4, wherein the activator comprises an organoaluminum compound.

[0176]

[0174] Item 6. The olefin polymerization catalyst system of any one of items 1 to 5, wherein the activator comprises an aluminoxane.

[0175] Item 7. The olefin polymerization catalyst system of any one of items 1 to 6, wherein the activator comprises a borane or a borate.

[0177]

[0176] Item 8. An olefin polymerization catalyst system according to any one of Items 1 to 7, wherein the percentage of silica particles having a particle size of 1 μm or less is about 1% or less.

[0177] Item 9. The olefin polymerization catalyst system of any one of items 1 to 8, wherein the silica particles have not been subjected to spray drying agglomeration.

[0178]

[0178] Item 10. The olefin polymerization catalyst system of any one of items 1 to 9, wherein the silica particles have an average pore size of about 30 angstroms to about 300 angstroms.

[0179] Item 11. The olefin polymerization catalyst system of any one of items 1 to 10, wherein the silica particles have an average pore size of about 100 to about 240 angstroms.

[0179]

[0180] Item 12. The olefin polymerization catalyst system of any one of items 1 to 11, wherein the silica particles have a span of about 1.5 or less.

[0181] Item 13. The olefin polymerization catalyst system of any one of items 1 to 12, wherein the silica particles have a span of 0.9 or more.

[0180]

[0182] Item 14. The olefin polymerization catalyst system of any one of items 1 to 13, wherein the activator comprises an organoaluminum compound and is loaded onto the support such that the catalyst system contains about 10 wt.% Al or more.

[0181]

[0183] Item 15. Particles having an average pore volume greater than 2.3 ml / g and 350 m 2 5. The olefin polymerization catalyst system of any one of items 1 to 4, having an average pore diameter greater than 1 / g.

[0184] Item 16. The olefin polymerization catalyst system of any one of items 1 to 15, wherein the silica particles have a median particle size of about 5 μm to about 60 μm.

[0182]

[0185] Item 17. An olefin polymerization catalyst system comprising a silica support and a chromium compound, wherein the silica support comprises a plurality of silica gel particles, each particle comprising a rigid network of amorphous silica; the particles are spherical, single gel particles; the particles have an average aspect ratio of about 1.2 or less; the particles have an average pore volume of about 1.4 ml / g to about 3 ml / g; and the particles have an average pore volume of about 200 m 2 / g ~ approx. 950m 2 / g; and the particles have a median particle size of from about 4 μm to about 100 μm.

[0183]

[0186] Item 18. The olefin polymerization catalyst system of item 17, wherein at least 75% of the particles have an aspect ratio of about 1.2 or less.

[0187] Item 19. The olefin polymerization catalyst system of item 17 or 18, wherein at least 50% of the particles have an aspect ratio of about 1.1 or less.

[0184]

[0188] Item 20. The olefin polymerization catalyst system of any one of items 17 to 19, wherein the chromium compound is chromium oxide.

[0189] Item 21. The olefin polymerization catalyst system of any one of Items 17 to 20, wherein the chromium compound is a chromium salt.

[0185]

[0190] Item 22. The olefin polymerization catalyst system according to any one of items 17 to 21, further comprising a titanium compound, an aluminum compound, or a fluorine compound impregnated in a silica support.

[0191] Item 23. The olefin polymerization catalyst system according to any one of Items 17 to 22, wherein the percentage of silica particles having a particle size of 1 μm or less is about 1% or less.

[0186]

[0192] Item 24. The olefin polymerization catalyst system of any one of items 17 to 23, wherein the silica particles have not been subjected to spray drying agglomeration.

[0193] Item 25. The olefin polymerization catalyst system of any one of items 17 to 24, wherein the silica particles have an average pore size of about 30 angstroms to about 300 angstroms.

[0187]

[0194] Item 26. The olefin polymerization catalyst system of any one of items 17 to 25, wherein the silica particles have an average pore size of about 100 to about 240 angstroms.

[0195] Item 27. The olefin polymerization catalyst system of any one of items 17 to 26, wherein the silica particles have a span of about 1.5 or less.

[0188]

[0196] Item 28. The olefin polymerization catalyst system of any one of items 17 to 27, wherein the silica particles have a span of 0.9 or more.

[0197] Item 29. Particles having an average pore volume greater than 2.3 ml / g and 350 m 2 29. The olefin polymerization catalyst system of any one of items 17 to 28, having an average pore diameter greater than 1 / g.

[0189]

[0198] Item 30. The olefin polymerization catalyst system of any one of items 17 to 29, wherein the silica particles have a median particle size of about 5 μm to about 60 μm.

[0199] Item 31. An olefin polymerization catalyst system comprising a silica support, a magnesium halide, a transition metal compound, a cocatalyst, and an electron donor compound, wherein the silica support comprises a plurality of silica gel particles, each particle comprising a rigid network of amorphous silica; the particles are spherical, single gel particles; the particles have an average aspect ratio of about 1.2 or less; the particles have an average pore volume of about 1.4 ml / g to about 3 ml / g; and the particles have an average pore volume of about 200 m 2 / g ~ approx. 950m 2 / g; and the particles have a median particle size of from about 4 μm to about 100 μm.

[0190]

[0200] Item 32. The olefin polymerization catalyst system of item 31, wherein at least 75% of the particles have an aspect ratio of about 1.2 or less.

[0201] Item 33. The olefin polymerization catalyst system of item 31 or 32, wherein at least 50% of the particles have an aspect ratio of about 1.1 or less.

[0191]

[0202] Item 34. The olefin polymerization catalyst system of any one of items 31 to 33, wherein the transition metal compound is a compound of a Group 4 metal.

[0203] Item 35. The olefin polymerization catalyst system of any one of items 31 to 34, wherein the electron donor compound is an internal electron donor compound.

[0192]

[0204] Item 36. The olefin polymerization catalyst system of any one of items 31 to 35, wherein the electron donor compound is an external electron donor compound.

[0205] Item 37. The olefin polymerization catalyst system according to any one of Items 31 to 36, wherein the percentage of silica particles having a particle size of 1 μm or less is about 1% or less.

[0193]

[0206] Item 38. The olefin polymerization catalyst system of any one of items 31 to 37, wherein the silica particles have not been subjected to spray drying agglomeration.

[0207] Item 39. The olefin polymerization catalyst system of any one of items 31 to 38, wherein the silica particles have an average pore size of about 30 angstroms to about 300 angstroms.

[0194]

[0208] Item 40. The olefin polymerization catalyst system of any one of items 31 to 39, wherein the silica particles have an average pore size of about 100 to about 240 angstroms.

[0209] Item 41. The olefin polymerization catalyst system of any one of items 31 to 40, wherein the silica particles have a span of about 1.5 or less.

[0195]

[0210] Item 42. The olefin polymerization catalyst system of any one of items 31 to 41, wherein the silica particles have a span of 0.9 or more.

[0211] Item 43. Particles having an average pore volume greater than 2.3 ml / g and 350 m 2 43. The olefin polymerization catalyst system of any one of items 31 to 42, having an average pore diameter greater than 1 / g.

[0196]

[0212] Item 44. The olefin polymerization catalyst system of any one of items 31 to 43, wherein the silica particles have a median particle size of about 5 μm to about 60 μm.

[0213] Item 45. A method for polymerizing olefins, comprising contacting an olefin monomer with a catalyst system comprising a silica support and a catalyst precursor compound to form polyolefin particles, wherein the silica support comprises a plurality of silica gel particles, each particle comprising a rigid network of amorphous silica; the particles are spherical, single gel particles; the particles have an average aspect ratio of about 1.2 or less; the particles have an average pore volume of about 1.4 ml / g to about 3 ml / g; and the particles have an average pore volume of about 200 m. 2 / g ~ approx. 950m 2 / g; and the particles have a median particle size of from about 4 μm to about 100 μm.

[0197]

[0214] Item 46. The method of item 45, wherein the resulting polyolefin particles have a particle size distribution such that the number percentage of particles having a particle size of 1 μm or less is about 1% or less.

[0215] Item 47. The process of items 45 or 46, wherein the olefin is polymerized in a gas phase reactor.

[0198]

[0216] Item 48. The method of any one of items 45 to 47, wherein the polyolefin particles have a settled bulk density of greater than 0.4 g / cc.

[0217] Item 49. The method of any one of items 45 to 48, wherein the polyolefin particles have an aspect ratio of about 1.2 or less.

[0199]

[0218] Item 50. The method of any one of items 45 to 49, wherein at least 75% of the particles have an aspect ratio of about 1.2 or less.

[0219] Item 51. The method of any one of items 45 to 50, wherein at least 50% of the particles have an aspect ratio of about 1.1 or less.

[0200]

[0220] Item 52. The method of any one of items 45 to 51, wherein the polyolefin comprises polyethylene.

[0221] Item 53. The method of any one of items 45 to 52, wherein the polyolefin comprises polypropylene.

[0201]

[0222] Item 54. The method of any one of items 45 to 53, wherein the polyolefin comprises a polyα-olefin.

[0223] These and other modifications and variations of the present invention may be implemented by those skilled in the art without departing from the spirit and scope of the present invention as specifically described by the appended claims. It should further be understood that aspects of the various embodiments may be interchanged in whole or in part. It should also be appreciated by those skilled in the art that the above description is merely illustrative and is not intended to limit the present invention as further described in such appended claims.

[0202]

[0224] While certain particular embodiments have been illustrated and described, it is to be understood that changes and modifications can be made in accordance with ordinary skill in the art without departing from the science and technology in its broader aspects as defined in the following claims.

[0203]

[0225] The embodiments described herein by way of example may suitably be practiced in the absence of any element or elements, limitations not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc., should be read expansively and without limitation. Furthermore, the terms and expressions used herein are used as terms of description without limitation, and in using such terms and expressions, there is no intention to exclude any equivalents of the features shown and described or any portion thereof, but it is recognized that various modifications are possible within the scope of the technology described in the claims. In addition, the phrase "consisting essentially of" is understood to include the elements specifically described and additional elements that do not materially affect the basic and novel characteristics of the technology described in the claims. The phrase "consisting of" excludes any elements not specified.

[0204]

[0226] The present disclosure is not limited with respect to the specific embodiments described in this application. Many modifications and variations can be made without departing from the spirit and scope thereof, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the present disclosure, in addition to those recited herein, will be apparent to those skilled in the art from the above description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which may of course vary. It is also to be understood that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to be limiting.

[0205]

[0227] Furthermore, when features or aspects of the disclosure are described in terms of a Markush group, one of skill in the art will recognize that the disclosure also is described in terms of every individual member of that Markush group or any subgroup thereof.

[0206]

[0228] As will be understood by those of skill in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein include any and all possible subranges and combinations of subranges. Any recited range can be readily recognized as being fully described, with that same range being at least equally divisible into halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily subdivided into a lower third, a middle third, and an upper third, etc. As will also be understood by those of skill in the art, all terms such as "less than," "at least," "greater than," "less than," etc., refer to ranges that are inclusive of the recited numbers and can then be subdivided into subranges as discussed above. Finally, as will be understood by those of skill in the art, a range includes each individual member.

[0207]

[0229] All publications, patent applications, issued patents, and other documents mentioned in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the text incorporated by reference are excluded to the extent that they conflict with definitions in this disclosure.

[0208]

[0230] Other embodiments are set forth in the following claims.

Claims

1. An olefin polymerization catalyst system comprising a silica support, a catalyst precursor compound, and an activator, wherein the silica support comprises a plurality of silica gel particles, Each particle contains a rigid reticular structure of amorphous silica; The particles are spherical single gel particles; The particles have an average aspect ratio of approximately 1.2 or less; The particles have an average pore volume of approximately 1.4 ml / g to approximately 3 ml / g; The particles are approximately 200m ２ / g ~ approx. 950m ２ It has an average surface area of ​​ / g; The particles have a median particle size of approximately 4 μm to approximately 100 μm. Olefin polymerization catalyst system.

2. The olefin polymerization catalyst system according to claim 1, wherein the catalyst precursor compound contains a metallocene component.

3. The olefin polymerization catalyst system according to claim 1, wherein the activator contains an organoaluminum compound.

4. The olefin polymerization catalyst system according to claim 1, wherein the activator contains an aluminoxane.

5. The olefin polymerization catalyst system according to claim 1, wherein the activator comprises borane or borate.

6. The olefin polymerization catalyst system according to claim 1, wherein the activator contains an organoaluminum compound, and the catalyst system is loaded onto a carrier such that it contains about 10 wt.% or more of Al.

7. An olefin polymerization catalyst system comprising a silica support and a chromium compound, wherein the silica support comprises a plurality of silica gel particles, Each particle contains a rigid reticular structure of amorphous silica; The particles are spherical single gel particles; The particles have an average aspect ratio of approximately 1.2 or less; The particles have an average pore volume of approximately 1.4 ml / g to approximately 3 ml / g; The particles are approximately 200m ２ / g ~ approx. 950m ２ It has an average surface area of ​​ / g; The particles have a median particle size of approximately 4 μm to approximately 100 μm. Olefin polymerization catalyst system.

8. The olefin polymerization catalyst system according to claim 7, wherein the chromium compound is chromium oxide or a chromium salt.

9. The olefin polymerization catalyst system according to claim 7, further comprising a titanium compound, an aluminum compound, or a fluorine compound impregnated into a silica support.

10. An olefin polymerization catalyst system comprising a silica support, magnesium halide, a transition metal compound, a cocatalyst, and an electron donor compound, wherein the silica support comprises a plurality of silica gel particles. Each particle contains a rigid reticular structure of amorphous silica; The particles are spherical single gel particles; The particles have an average aspect ratio of approximately 1.2 or less; The particles have an average pore volume of approximately 1.4 ml / g to approximately 3 ml / g; The particles are approximately 200m ２ / g ~ approx. 950m ２ It has an average surface area of ​​ / g; The particles have a median particle size of approximately 4 μm to approximately 100 μm. Olefin polymerization catalyst system.

11. The olefin polymerization catalyst system according to claim 10, wherein the transition metal compound is a group 4 metal compound.

12. The olefin polymerization catalyst system according to claim 1, 7, or 10, wherein at least 75% of the particles have an aspect ratio of about 1.2 or less, and / or at least 50% of the particles have an aspect ratio of about 1.1 or less.

13. Silica particles have an average pore size of approximately 30 angstroms to approximately 300 angstroms, and / or particles have an average pore volume greater than 2.3 ml / g and 350 m ２ An olefin polymerization catalyst system according to claim 1, 7, or 10, having an average pore diameter greater than / g.

14. The olefin polymerization catalyst system according to claim 1, 7, or 10, wherein the silica particles have a span of about 1.5 or less and / or 0.9 or more, and / or the fraction of hundreds of silica particles having a particle size of 1 μm or less is about 1% or less, and / or the silica particles have a median particle size of about 5 μm to about 60 μm.

15. A method for polymerizing an olefin, comprising the step of contacting an olefin polymerization catalyst system according to claim 1 with an olefin monomer.

16. The method according to claim 15, wherein the obtained polyolefin particles have a particle size distribution such that the fraction of a hundred particles having a particle size of 1 μm or less is about 1% or less, and / or the polyolefin particles have a settling bulk density greater than 0.4 g / cc.

17. The method according to claim 15, wherein the polyolefin particles have an aspect ratio of about 1.2 or less, and / or at least 75% of the particles have an aspect ratio of about 1.2 or less, and / or at least 50% of the particles have an aspect ratio of about 1.1 or less.

18. The method according to claim 15, wherein the polyolefin contains polyethylene.

19. The method according to claim 15, wherein the polyolefin comprises polypropylene.

20. The method according to claim 15, wherein the polyolefin comprises a poly-α-olefin.

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