RU2775371C1 - Methods for determining concentrations of transition metal compounds in multicomponent liquid systems - Google Patents

Abstract

FIELD: polymerization reactor system.

SUBSTANCE: invention relates to a polymerization reactor system and its operation. The polymerization reactor system comprises a reactor for contacting the catalyst system with an olefin monomer and optionally an olefin comonomer under polymerization reaction conditions to form an olefin polymer; a catalyst preparation vessel for bringing into contact a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst to form a catalyst system; and an analytical system for determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound present in the polymerization reactor system.

EFFECT: improvement of methods for obtaining a multicomponent catalytic system.

45 cl, 15 dwg, 1 tbl

Description

LINK TO RELATED APPLICATIONS

This application was filed July 10, 2018 as a PCT International Patent Application and claims priority from U.S. Patent Application No. 16/006,976 filed June 13, 2018 and U.S. Patent Application No. 15/655,929 filed July 21, 2017, the description of which is incorporated herein by reference in its entirety.

FIELD OF TECHNOLOGY

The present invention relates to methods for determining the concentration of transition metal compounds in solutions containing more than one transition metal compound, and in particular relates to the use of UV-visible spectroscopy (ultraviolet visible) to determine the concentration of individual transition metal compounds.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer and linear low density polyethylene (LLDPE) copolymer are produced by various combinations of catalyst systems and polymerization processes. Many olefin polymerization processes use a catalyst system containing more than one transition metal compound. Accurate determination of the relative and absolute concentrations of each transition metal compound allows better control of the polymerization processes and the resulting polymer products. It would be useful if real-time monitoring or measurement of the appropriate amount of each transition metal compound present in the catalyst feed streams, catalyst systems, and polymerization reactor systems could be performed to improve the control of the polymerization process. In addition, it would be useful to determine the concentration of the first transition metal compound in solutions where the UV-visible spectrum overlaps with that of the second transition metal compound and/or where the second transition metal compound is in large excess relative to the first transition metal compound. Accordingly, it is primarily to this end that the present invention is directed.

SUMMARY OF THE INVENTION

This summary of the invention is presented to select in a simplified form concepts that are further described below in the detailed description. This summary is not intended to define the required or essential features of the claimed subject matter. Also, this summary is not intended to limit the scope of the claimed subject matter.

Methods for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound are described herein. In accordance with an aspect of the present invention, one such method may include (i) introducing a sample solution into a sample chamber, (ii) irradiating the sample in the chamber with a long wavelength light beam in the visible ultraviolet spectrum, and (iii) generating an absorption profile of the sample by subtracting the reference an absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain an absorption profile of the first transition metal compound; and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in the solution.

In another aspect, a method of operating a polymerization reactor system is described, and in this aspect, the method may include (i) contacting a catalyst system containing a first transition metal compound, a second transition metal compound, an activator, and optionally a cocatalyst with an olefin monomer, and optionally olefin comonomer in a reactor in a polymerization reactor system under polymerization reaction conditions to produce an olefin polymer, (ii) determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound, and (iii) adjusting the flow rate of the first transition metal compound into the reactor when the concentration of the first transition metal compound in the solution reaches a predetermined level. In yet another aspect, a method for preparing a catalyst composition is described, and in this aspect, the method may include (i) contacting a first transition metal compound, a second transition metal compound, a solid activator, and optionally a cocatalyst a (e.g., in a container for catalyst composition) to form a catalyst composition, (II) determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, separating the solution from (or obtained from) the catalyst composition, and (III) adjusting the relative amount, at least one component of the catalyst composition based on the concentration of the first transition metal compound in solution (or based on a certain concentration). In these and other aspects, the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound can be determined by a method comprising the steps of: (i) feeding a sample of the solution into a sample chamber, (ii) irradiating the sample in the chamber with a long wavelength UV-visible light beam, and (iii) generating an absorption profile of the sample, subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound, and correlating the profile absorbing the first transition metal compound with a standard to determine the concentration of the first transition metal compound in solution.

In addition, various polymerization reactor systems are described herein. One such polymerization reactor system may include (A) a reactor for contacting the catalyst system with an olefin monomer and optionally an olefin comonomer under polymerization reaction conditions to form an olefin polymer, (B) a catalyst production vessel for contacting a compound of the first a transition metal compound, a second transition metal compound, an activator, and optionally a cocatalyst to form a catalyst system; and (C) an analytical system capable of determining the concentration of the first transition metal compound in a solution containing the first transition metal compound and the second transition metal compound present in the polymerization reactor system. In accordance with specific aspects of the present invention, the analytical system may include an ultraviolet visible spectrometer.

Catalyst production systems are also described in this document. One such catalyst production system may include (a) a catalyst production vessel for contacting a first transition metal compound, a second transition metal compound, and a solid activator (and co-catalyst, if used) to form a catalyst composition, (b) an activator feed stream, (c) a feed stream of a first transition metal compound to introduce a first transition metal compound into a catalyst production vessel, (d) a feed stream of a second transition metal compound to introduce a second transition metal compound into a catalyst preparation vessel, (e) a catalyst system feed stream capable of withdrawing the catalyst composition from the catalyst preparation vessel (e.g., and introducing the catalyst composition into the reactor), and (f) an analytical system capable of determining c compounds of the first transition metal in a solution containing a compound of the first transition metal and a second transition metal compound, the solution is separated from (or obtained from) the catalyst composition. If the cocatalyst is a component of the catalyst composition, the catalyst production system may further include a cocatalyst feed stream for introducing the cocatalyst into the catalyst production vessel. In addition, the catalyst production system may further include (g) a controller that is configured to control an activator feed flow rate, a cocatalyst additive flow rate, a first transition metal compound feed flow rate, and/or a second transition metal compound feed flow rate into the catalyst production vessel. based on or in accordance with the concentration determined by the analytical system.

Both the above brief description and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be construed as limiting. In addition, additional features and variants may be proposed in addition to the features and variants set forth herein. For example, specific aspects may be directed to various combinations and subcombinations of the features described in the Detailed Description.

BRIEF DESCRIPTION OF GRAPHICS

The following figures form part of this specification and are included to further demonstrate certain aspects of the present invention. The present invention may be better understood with reference to one or more of these figures in combination with the detailed description of the specific embodiments of the invention presented herein.

Fig. 1 illustrates a schematic block diagram of a polymerization reactor system consistent with aspects of the present invention.

On FIG. 2 is a graph of UV-visible absorption profiles versus wavelength for various concentrations of the transition metal compound MET-2 in toluene.

On FIG. 3 shows linear calibration curves correlating absorbance with the concentration of the transition metal compound MET-2 in toluene at various wavelengths.

On FIG. 4 shows plots of UV-visible absorption profiles versus wavelength for various concentrations of the transition metal compound MET-2 in 1-hexene.

On FIG. 5 shows linear calibration curves correlating absorbance with the concentration of the transition metal compound MET-2 in 1-hexene at various wavelengths.

On FIG. 6 is a plot of UV-visible absorption profiles versus wavelength for various concentrations of the transition metal compound MET-1 in toluene.

On FIG. 7 shows linear calibration curves correlating absorbance with the concentration of the transition metal compound MET-1 in toluene at various wavelengths.

On FIG. 8 is a plot of UV-visible absorption profiles versus wavelength for various concentrations of the transition metal compound MET-1 in 1-hexene.

On FIG. 9 shows linear calibration curves correlating absorbance with the concentration of the transition metal compound MET-1 in 1-hexene at various wavelengths.

On FIG. 10 shows plots of UV-visible absorption profiles versus wavelength for samples 1-5 with a solvent reference.

On FIG. 11 shows plots of UV-visible absorption profiles versus wavelength for samples 1-5, sample 5 being the reference absorption profile.

On FIG. 12 is a linear calibration curve correlating absorbance at 380 nm with the concentration of the transition metal compound MET-1 using the data collected in FIG. eleven.

On FIG. 13 is a plot of MET-1 and MET-3 solution concentrations and total metallocene absorbed versus the amount of carrier activator.

On FIG. 14 is a plot of the amount of MET-1 and MET-3 absorbed versus total MET-1 and total MET-3 for different amounts of carrier activator.

Fig. 15 illustrates a schematic block diagram of a catalyst production system in accordance with aspects of this invention.

DEFINITIONS

To better define the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present description. If a term is used in this specification that is not specifically defined in this specification, the definition from the IUPAC Compendium of Chemical Terminology, 2nd ^Ed (1997) may be used, provided that such definition does not conflict with any other description or definition used herein. , or does not render undefined or invalid any claim in which such definition is used. To the extent that any definition or use given in any document incorporated herein by reference conflicts with the definition or use given herein, the definition or use given herein shall take precedence.

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

Unless expressly stated otherwise in certain circumstances, all percentages, parts, ratios and similar amounts used herein are by weight.

As used herein, while systems, processes, and methods, often described in terms of "comprising" various components, devices, or steps, systems, processes, and methods may also "consist essentially of" or "consist of" various components, devices, or steps. , unless otherwise specified.

Singular terms are intended to include plural alternatives, such as at least one. For example, the description of "polymerization reactor", "transition metal compound", or "wavelength" is intended to include one or mixtures or combinations of more than one, polymerization reactor, transition metal compound, or wavelength, unless otherwise indicated.

For any particular compound or group described herein, any given name or structure (general or specific) is intended to include all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents, unless otherwise noted. . Such name or structure (general or specific) also includes all enantiomers, diastereomers and other optical isomers (if any), whether in enantiomeric or racemic form, as well as mixtures of stereoisomers. which will be recognized by a person skilled in the art, unless otherwise indicated. For example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a t-butyl group.

The term "about" means that quantities, sizes, compositions, parameters and other quantities and characteristics are not and should not be exact, but may be approximate and/or more or less, as desired, taking into account tolerances, conversion factors, rounding, measurement errors and the like, and other factors known to those skilled in the art. In general, an amount, size, composition, parameter, or other quantity or characteristic is "exemplary" or "approximate", whether explicitly stated as such or not. The term "about" also includes amounts that differ due to different equilibrium conditions for the composition obtained from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalent values. The term "about" may mean a value within 10% of the specified numerical value, preferably within 5% of the specified numerical value.

This document describes various ranges of numerical values. When describing or claiming herein a range of any type, the intent is to describe or claim individually every possible number such range can reasonably contain, including the endpoints of the range, as well as any subranges and combinations of subranges contained therein, if not otherwise specified. As a representative example, the present description indicates that the conditions of the polymerization reaction may include a temperature of the polymerization reaction in the range from about 60°C to about 115°C in certain aspects. With the description that the temperature may be in the range of about 60°C to about 115°C, the intent is to indicate that the temperature may be any temperature within the range and, for example, may be about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 10°C or about 115°C. In addition, the temperature may be in any range from about 60°C to about 115°C (for example, the temperature may be in the range from about 70°C to about 110°C), and this also includes any combination of ranges from about 60°C. C to about 115°C. Likewise, all other ranges described herein should be interpreted in the same way as this example.

The term "polymer" in this document is used, as a rule, to include homopolymers, copolymers, olefin terpolymers, and so on, as well as their alloys and mixtures. The term "polymer" also encompasses impact, block, graft, random and alternating copolymers. The copolymer is made from an olefin monomer and one olefin comonomer, and the terpolymer is made from an olefin monomer and two olefin comonomers. Accordingly, "polymer" encompasses copolymers and terpolymers. Similarly, the term "polymerization" encompasses homopolymerization, copolymerization, terpolymerization. Therefore, the term ethylene polymer will encompass ethylene homopolymers, ethylene copolymers (eg, ethylene/α-olefin copolymers), ethylene terpolymers, and the like, as well as combinations or mixtures thereof. Thus, the term ethylene polymer encompasses polymers often referred to in the art as LLDPE (Linear Low Density Polyethylene) and HDPE (High Density Polyethylene). As an example, an ethylene copolymer can be made from ethylene and a comonomer such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, then the resulting polymer can be characterized as an ethylene/1-hexene copolymer. The term "polymer" also covers all possible geometric configurations, unless otherwise indicated, and such configurations may include isotactic, syndiotactic and statistical symmetry. The term "polymer" is also intended to include all high molecular weight polymers and includes lower molecular weight polymers or oligomers. The term "polymer" is intended to encompass oligomers (including dimers and trimers) derived from any olefin monomer described herein (as well as an olefin monomer and one olefin comonomer, an olefin monomer and two olefin comonomers, etc.).

As used herein, the term "contacting" is used to describe systems, compositions, processes, and methods in which components are brought into contact or combined with each other in any order, in any manner, and over any period of time, unless otherwise indicated. For example, the components may be combined by milling or mixing using any suitable technique.

The term "spectrometer" is used herein generically to include devices that may be referred to in the art as a spectrometer or spectrophotometer, and the like.

As used herein, the term "near real time" refers to the delay that is introduced by automatic data processing between the occurrence of an event and the use of the processed data. For example, classifying an event as a near-real-time event refers to the occurrence of the event in real time, minus the processing time, as near the time of the real event. That is, the time interval between receiving data for analysis and executing it and displaying (for example, on a computer screen or alternative device) or performing an operation (for example, adjusting the flow rate of the first and/or second transition metal compound), which is from 1 minute to 10 minutes, for example, a time interval from 3 seconds to 3 minutes.

As used herein, the term "real-time" or "virtually real-time" may refer to the moment the item being measured is captured at the moment the capture occurs, such as instantaneous or near-instantaneous streaming or transmission of data or information. The real-time data may be UV-visible spectrum analysis data or sensor readout data, which can be provided instantaneously, for example, within 2 seconds, to a computer system, to a computer-readable medium or to a controller, etc., as soon as UV-visible spectral analysis readings obtained.

Although any methods, devices and materials similar or equivalent to those described herein are used in the practice or testing of the invention, exemplary methods, devices and materials are described in this document.

All publications and patents referenced herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the concepts and techniques described in the publications that may be used in connection with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are methods for determining the concentration of a first transition metal compound in solutions containing a first transition metal compound and a second transition metal compound, and associated processes for operating polymerization reactor systems. Also described herein are polymerization reactor systems comprising analytical systems for determining the concentration of a first transition metal compound in solutions containing a first transition metal compound and a second transition metal compound, and processes for operating such reactor systems. Without wishing to be bound by any theory, it is believed that such reactor systems (and associated processes) may offer improved control and/or real-time monitoring or measurement of the amount of transition metal compounds present in catalyst component feed streams, catalyst systems, and polymerization reactor systems, which ultimately leads to improved quality control and polymerization process consistency. Advantageously, the reactor systems (and associated methods) described herein allow concentrations of a first transition metal compound to be determined with exceptional accuracy even when the absorption profiles of the first transition metal compound and the second transition metal compound overlap significantly, and/or where one of compounds of the first and second transition metals is in great excess relative to the other. Advantageously, the reactor systems (and associated methods) described herein can be used in circumstances where the respective uptake profiles of transition metal compounds cannot be deconvoluted or determined independently. Accordingly, since accurate information about the concentration of the first transition metal compound can be determined, the polymerization reactor systems (and associated methods) described herein can monitor, control, adjust, and/or fine-tune the concentration of the first transition metal in real time. time in the production cycle of a particular grade of polymer resin.

METHODS FOR DETERMINING CONCENTRATIONS OF TRANSITION METAL COMPOUNDS

Aspects of the present invention are directed to methods for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound. Such methods may include (or consist essentially of, or consist of) (i) introducing a sample of the solution into the sample chamber, (ii) irradiating the sample in the chamber with a light beam with a long wavelength (one or more) in the UV-visible spectrum, and (iii) generating (e.g., collecting or deriving) an absorption profile of the sample, subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound, and correlating the absorption profile of the first transition metal compound with the determination standard concentration of the first transition metal compound in solution. In general, features of the methods described herein (e.g., transition metal compounds, solution, light wavelength, absorption profiles, and standard, among others) are described independently herein, and these features can be combined in any combination for further descriptions of the methods described. In addition, other process steps may be performed before, during and/or after any of the steps listed in the described methods, unless otherwise indicated.

In step (i), a sample solution containing first and second transition metal compounds (at least two transition metal compounds) is fed into the sample chamber. The sample chamber may be a flow cell, although any suitable design and configuration of the sample chamber may be used. The second transition metal compound may contain one second transition metal compound, two different second transition metal compounds, and so on. Accordingly, a solution containing transition metal compounds may contain two different transition metal compounds or more than two different transition metal compounds. As a non-limiting example, the solution may contain two metallocene compounds: one bridged metallocene compound and one unbridged metallocene compound, two different bridged metallocene compounds, or two different unbridged metallocene compounds.

Typically, the solution includes a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent, although the methods described herein may be used for other types of solvents such as chlorinated hydrocarbons, ethers, alcohols, and so on. Typical hydrocarbon solvents may include, but are not limited to, propane, cyclohexane, cyclohexene, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, 1-hexene, toluene, and the like, as well as combinations thereof. Other suitable hydrocarbon solvents may include the ISOPAR® family of mixed aliphatic hydrocarbon solvents such as, for example, ISOPAR® C, ISOPAR® E, ISOPAR® G, ISOPAR® H, ISOPAR® L, ISOPAR® M and the like, as well as mixtures thereof. . Without wishing to be bound by any theory, it is believed that the type of transition metal compounds and the type of solvent present in solution may affect the wavelength or wavelengths to be used in the systems and methods/processes described herein. In particular aspects of this invention, the systems and methods/processes described herein are well suited for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent. The hydrocarbon solvent may include, for example, 1-hexene, isobutane, toluene or cyclohexene and the like, as well as mixtures or combinations thereof.

The choice of solvent can affect the absorption profiles of certain transition metal compounds. Accordingly, aspects of the present invention may use a reference solution containing a second transition metal compound and a hydrocarbon solvent, where the hydrocarbon solvent is identical to the hydrocarbon solvent present in the sample solution containing the first transition metal compound and the second transition metal compound. In such aspects, any solvent influences can be minimized, resulting in improved accuracy in determining the concentration of the first transition metal compound.

The sample in the sample chamber may be irradiated with a long wavelength light beam in the UV-visible spectrum in step (ii). This can be done, for example, with a UV-visible spectrometer, discussed below. The wavelength of the light beam may be one wavelength or more than one wavelength, such as a range of wavelengths. In one aspect, the wavelength of the light beam may comprise wavelengths in the visible spectrum (380 nm to 780 nm). In another aspect, the wavelength of the light beam may comprise wavelengths in the range of 200 nm to 750 nm. However, in another aspect, the wavelength of the light beam may comprise wavelengths in the range of 300 nm to 600 nm. Thus, any suitable wavelength range may be used depending on, for example, the particular transition metal compounds or the particular hydrocarbon solvent. Often step (ii) can be performed in the wavelength range of 300-600 nm. In addition, if desired, ultraviolet radiation/radiation can be filtered in some aspects of the present invention.

In step (iii), an absorption profile of the sample is generated which contains a solution of first and second transition metal compounds. Optionally, a reference absorption profile of a reference solution may be generated, which may contain a reference solution of the second transition metal compound. The reference absorption profile, generated before or simultaneously with the absorption profile of the sample, can be subtracted from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound. Typically, the reference absorbance profile is not generated at the same time as the absorbance profile of the sample; in these circumstances, the standard is usually analyzed before testing the sample. However, if the UV instrument is equipped with both a sample chamber and a reference chamber, the absorbance profiles of the sample and reference can be generated at the same time.

In some cases, actual absorption profiles can be generated and collected or output, for example, as an absorption versus wavelength plot that can be viewed on a monitor or computer screen or printed out. In other cases, absorption profiles are generated but not collected or displayed in visible form. For example, data from the absorbance profile of a sample (for example, absorbance as a function of wavelength) can be directly converted to data on the concentration of the first transition metal compound by subtracting the reference absorbance profile from the absorbance profile of the sample and then correlating the absorbance profile of the first transition metal compound with the standard to determine concentration.

Any of the absorption profiles described herein (eg, sample, reference, first transition metal compound) may contain an absorption peak at a single wavelength in some aspects of this invention. For example, the absorption profile of the first transition metal compound may contain an absorption peak at maximum absorption. Thus, absorption peak data for a first transition metal compound in solution at one wavelength can be used to determine the concentration of the first transition metal compound in solution. Alternatively, any absorption profiles described herein may include an absorption curve (peaks and/or areas under the curves versus wavelength) over a wavelength range, such as 200 nm to 750 nm or 300 nm to 600 nm, and etc. Thus, data from the wavelength absorption curve can be used to determine the concentration of the first transition metal compound in solution. In another aspect, any absorption profiles described herein may include an absorption curve (peaks and/or areas under the curves versus wavelength) over a subset of wavelengths spanning less than 200 nm, less than 150 nm, less than 100 nm, or less than 50 nm. Thus, data from the absorption curve over a specific subset of wavelengths can be used to determine the concentration of the first transition metal compound in solution. Other suitable absorption profile options are readily apparent from this description.

Generally, the respective concentrations of the first and second transition metal compounds in the sample are not limited to any particular range. However, in some aspects, the concentration of the first transition metal compound in the sample may be such that the absorption peak at one wavelength in the absorption profile of the first transition metal compound (e.g., absorption peak at 380 nm) is less than 2, less than 1, or less than 0.5. In particular aspects, the concentration of the first transition metal compound in the sample may be such that the absorption peak at one wavelength in the absorption profile of the first transition metal compound is in the range of from about 0.1 to about 2, from about 0.1 to about 1, from about 0.3 to about 1, or about 0.5 to about 1.

Likewise, the respective concentrations of the first and second transition metal compounds in solution are not limited to any particular range. For example, the concentration of the first transition metal compound in solution and the concentration of the second transition metal compound in solution can independently be less than about 5 wt. %, less than about 2 wt. %, less than about 1 wt. %, less than about 0.8 wt. %, less than about 0.5 wt. %, less than about 0.2 wt. %, less than about 0.1 wt. %, less than about 0.05 wt. % or less than about 0.01 wt. %.

Illustrative and non-limiting ranges for the concentration of the first transition metal compound in solution and the concentration of the second transition metal compound in solution, independently, may include from about 0.01 wt. % to about 5 wt. %, from about 0.01 wt. % to about 1 wt. %, from about 0.01 wt. % to about 0.5 wt. %, from about 0.05 wt. % to about 0.2 wt. %, from about 0.01 wt. % to about 0.1 wt. % or from about 0.1 wt. % to about 0.3 wt. %.

As an alternative or in addition to determining the absolute concentration of the first transition metal compound, the methods described herein can be used to determine the relative concentrations (or relative amounts) of the first and second transition metal compounds. In certain aspects, the weight ratio of the first transition metal compound to the second transition metal compound (first:second) in solution may be less than about 1:1, less than about 1:4, less than about 1:10, or less than about 1: twenty. In other aspects, the weight ratio of the first transition metal compound to the second transition metal compound in solution may range from about 50:1 to about 1:50, from about 10:1 to about 1:10, from about 2:1 to about 1 :2, about 1:20 to about 1:1, about 1:100 to about 1:2, about 1:50 to about 1:5, about 1:50 to about 1:10, or from about 1 :20 to about 1:10.

The absorption profile of a first transition metal compound, whether from a single wavelength, a narrow subset of wavelengths (e.g. spanning less than 50 nm or 100 nm), or from a broad spectrum of wavelengths (e.g. 300 nm to 600 nm) can be correlated with standard for determining the concentration of the first transition metal compound in solution. For example, data from an absorption profile of a first transition metal compound may be correlated with a standard, and the standard may include a calibration curve. The correlation step may be performed manually or may be performed automatically. If calibration curves are used, these calibration curves can be generated by any procedure known to those skilled in the art. Thus, the step of correlating the absorption profile of the first transition metal compound with the standard may include any suitable method that converts the absorption profile (or peak) of the first transition metal compound into the concentration of the first transition metal compound in solution. As an example, absorbance data can be generated for a sample having a known concentration of first transition metal compound (wt %) in a reference solution (eg, with a specific hydrocarbon solvent) at a single wavelength or over a wide range of wavelengths. This can then be repeated by maintaining a constant concentration of the second transition metal compound to cover the range of concentrations of the first transition metal compound.

Typically, the correlation step may include any suitable method or technique that converts the absorption profile of the first transition metal compound—whether from a single wavelength, a narrow subset of wavelengths, or a broad spectrum of wavelengths—to a concentration of the first transition metal compound in solution. . The correlation step may be performed manually or may be configured to automatically convert data from the absorption profile of the first transition metal compound to the concentration of the first transition metal compound in solution.

Without being limited to this, in some aspects of this invention, the generation and subtraction operations in step (iii) can be performed over a wide range of wavelengths, such as in the range of 300-600 nm, while the correlation operation can often be performed at a single wavelength. In addition, the path lengths used in sample absorption profile generation and in the reference absorption profile can often be the same, although this is not a requirement. In addition, step (iii) may be performed sequentially or simultaneously and may be performed manually or may be computerized (eg, to automatically determine the concentration of the first transition metal compound in solution).

The methods described herein are applicable to a wide range of circumstances in which the concentrations of transition metal compounds in a solution (or mixture from which a solution can be obtained) may be of interest. In one aspect, the solution containing the first and second transition metal compounds may be a feed stream to a catalyst production vessel. A catalyst production vessel can be any vessel or device that is capable of bringing into contact (eg, mixing or grinding) two or more components of a catalyst system to form a catalyst system. Any two or more components may be pre-contacted for a suitable period of time prior to contact with the remaining components to form the finished catalyst system, which may then be transferred from the catalyst preparation vessel to the reactor as needed. Often, transition metal compounds (two or more) and activator (one or more), or alternatively transition metal compounds (two or more), activator (one or more) and co-catalyst, are often contacted in a catalyst preparation vessel to form a catalyst system.

In another aspect, the solution containing the first and second transition metal compounds may be a liquid (or homogeneous) catalyst system containing transition metal compounds. The catalyst system may contain, in addition to transition metal compounds, components including a liquid activator (or liquid activator solution), such as MAO, as well as a liquid co-catalyst (or solution of co-catalyst), if desired, in the catalyst system.

In yet another aspect, the solution containing the first and second transition metal compounds may be a solution from a polymerization reactor (e.g., a solution reactor or a slurry reactor) in which solids or particles from the sample stream (reactor mixture) have been removed, for example, by sieving, filtering, centrifuging, and the like, including combinations or two or more of these techniques, as well as any other suitable technique for removing solids or particulates from a mixture to form a solution.

In yet another aspect, the solution containing the first and second transition metal compounds may be a solution from a stream of a heterogeneous or supported catalyst system in which solid particles or particles from the sample stream (mixture of the catalyst system) have been removed by any suitable technique or by any technique. described in this document.

REACTOR POLYMERIZATION SYSTEMS

Various polymerization reactor systems and processes for operating or managing such systems are disclosed and described herein. For example, in one aspect, a method of operating a polymerization reactor system may include (i) contacting a catalyst system containing a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst with an olefin monomer and an optional olefin comonomer in a reactor in polymerization reactor system under polymerization reaction conditions to produce an olefin polymer, (ii) determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, the concentration is determined by the above method, and (iii) adjusting the flow rate of the first transition metal compound metal into the reactor when the concentration of the first transition metal compound in the solution has reached a predetermined level. Therefore, the flow rate (or feed rate) of the first transition metal compound can be controlled manually and/or automatically based on a certain concentration. Generally, the process features for operating the reactor polymerization systems described herein (e.g., transition metal compounds, catalyst system, olefin monomer, olefin comonomer, reactor, method for determining the concentration of a first transition metal compound, and controlling the flow rate of a first transition metal compound, among others) are independently described herein and may be combined in any combination to further describe the methods described. Additionally, unless otherwise indicated, the other steps of the method are performed before, during and/or after any of the steps listed in the described methods.

Step (II) is directed to determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound. Step (II) may include the steps of (i) introducing a sample solution into the sample chamber, (ii) irradiating the sample in the chamber with a long wavelength light beam in the UV-visible spectrum, and (iii) generating an absorption profile of the sample by subtracting the reference absorption profile of the compound of the second of the transition metal in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound; and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in the solution. Accordingly, the specific features relating to step (II) may be the same as those disclosed and described herein, as long as they relate to methods for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound. transition metal.

The methods described herein are applicable to a wide range of circumstances in which the concentration of a transition metal compound in a solution (or mixture from which a solution can be obtained) may be of interest. In one aspect, the solution containing the first transition metal compound and the second transition metal compound may be a feed stream to a catalyst production vessel. In this aspect, the flow rate of the first transition metal compound into the reactor can be controlled by adjusting the flow rate of the feed to the catalyst production vessel, and/or by adjusting the relative flow rate (the ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) to a catalyst production vessel and/or by controlling the flow rate of the catalyst system exiting the catalyst production vessel and entering the reactor.

As an example, if the concentration of the first transition metal compound is below the target concentration, the flow rate of the first transition metal compound into the reactor can be increased by increasing the relative flow rate (ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) into the vessel to get a catalyst. This can be achieved, for example, by increasing the feed rate of the first transition metal compound to the catalyst production vessel while maintaining a constant feed rate of the second transition metal compound to the catalyst production vessel.

As another example, if the concentration of the first transition metal compound is below the target concentration, the flow rate of the first transition metal compound to the reactor can be increased by increasing the relative flow rate (ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) in reactor. This can be achieved, for example, by increasing the feed rate of the first transition metal compound into the reactor while maintaining a constant feed rate of the second transition metal compound into the reactor.

In another aspect, the catalyst system may be a liquid (or homogeneous) catalyst system, and the solution containing the first transition metal compound and the second transition metal compound may be a sample of the liquid catalyst system. In this aspect, the flow rate of the first transition metal compound into the reactor can be controlled by adjusting the relative flow rate (the ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) into the reactor and/or by adjusting the flow rate of the liquid catalyst system entering the reactor.

In yet another aspect, the polymerization reactor system includes a polymerization reactor (e.g., a solution polymerization reactor or a slurry polymerization reactor), and the solution containing the first transition metal compound and the second transition metal compound may be a solution obtained from a mixture sample from the reactor polymerization. In this aspect, the flow rate of the first transition metal compound into the polymerization reactor can be controlled by adjusting the relative flow rate (the ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) into the reactor and/or by adjusting the flow rate of the catalyst system entering the polymerization reactor . Solid particles or particles from the mixture sample from the polymerization reactor can be removed by any suitable method. Optionally, cooling the sample mixture may be beneficial. This process can be useful for determining the amount of the first transition metal compound that is not impregnated into, on, or associated with any solid catalyst components and/or polymer particles, for example, to determine the amount of the first transition metal compound (or the percentage of the first transition metal compound). transition metal) that is present in solution.

In yet another aspect, the catalyst system may be a heterogeneous or supported catalyst system, and the solution containing the first transition metal compound and the second transition metal compound may be a solution obtained from a sample stream of the heterogeneous catalyst system or supported catalyst system. In this aspect, the flow rate of the first transition metal compound to the polymerization reactor can be controlled by adjusting the relative flow rate (the ratio of the flow rate of the first transition metal compound to the flow rate of the second transition metal compound) into the reactor and/or by adjusting the flow rate of the catalyst system entering the polymerization reactor. . As noted above, this process can be useful in determining the amount of first transition metal compound not impregnated in, on, or bound to the solid catalyst components of the catalyst system, for example, to determine the amount of first transition metal compound (or percentage of first transition metal compound) that is present in solution.

In accordance with the aspects described herein, in step (III), when the concentration of the first transition metal compound in the solution reaches a predetermined level, the flow rate of the first transition metal compound into the reactor can be controlled. The target level can be easily set by one of skill in the art depending on, for example, historical and prevailing conditions in the polymerization reactor system. As non-limiting examples, the target level may be a decrease in a certain percentage of the concentration of the first transition metal compound (for example, in excess of what is considered acceptable during normal primary production), or an increase in a certain percentage of the concentration of the first transition metal compound in solution (for example, in excess of which is considered acceptable during normal primary production). For example, the target concentration of the first transition metal compound in solution may be 0.1 wt. % and specified lower and upper control limits may be 0.09 wt. % and 0.11 wt. %, respectively, for normal primary production. If the measured concentration of the first transition metal compound in solution was 0.08 wt. %, then the feed rate of the first transition metal compound to the catalyst production vessel (and, in turn, to the polymerization reactor) can be increased to bring the concentration of the first transition metal compound to an acceptable level within the specified range of 0.09-0.11 wt . %. Conversely, if the concentration of the first transition metal in solution was too high (eg, 0.12+ wt %), then the feed rate of the first transition metal compound may be reduced to bring the concentration to an acceptable level within the specified limits.

In another aspect of the present invention, a polymerization reactor system is provided, and in this aspect, the polymerization reactor system may include (A) a reactor for contacting the catalyst system with an olefin monomer and additional olefin comonomer under polymerization reaction conditions to produce an olefin polymer, (B) a catalyst preparation vessel for bringing into contact a first transition metal compound, a second transition metal compound, an activator and an optional co-catalyst to form a catalyst system, and (C) an analytical system for determining the concentration of the first transition metal compound in a solution containing the first transition metal compound, and a second transition metal compound present in the polymerization reactor system. Typically, features of any of the polymerization reactor systems described herein (e.g., polymerization reactor, catalyst system, olefin monomer (and olefin comonomer, if used), polymerization conditions, olefin polymer, catalyst production vessel, analytical system, among others) ) are described independently herein, and these features may be combined in any combination to further describe the described polymerization reactor systems. In addition, other reactor system devices or components other than the reactor, catalyst production vessel, and analytical system may be present in the described polymerization reactor systems, unless otherwise noted. In addition, the catalyst system may be contacted with an olefin monomer and an olefin comonomer (eg contacted with ethylene and an α-olefin comonomer such as 1-hexene) in a polymerization reactor in certain aspects discussed herein.

The analytical system may include any analytical system or instrument that is capable of determining the concentration of a first transition metal compound in a solution that contains a first transition metal compound and a second transition metal compound. For example, the analytical system may include a spectrometer (UV-visible) in the visible ultraviolet region (eg, alone or in combination with other analytical instruments/methods, such as a fluorescence spectroscopy method; a UV-visible-IR system, and so on). In one aspect of this invention, the analytical system may include a visible ultraviolet spectrometer with an integrated computer system such that the spectrometer and the integrated computer system are capable of measuring (or configured to measure) the absorption profile of a sample of the first transition metal compound in solution, capable of subtracting ( or configure to subtract) the reference absorption profile of the second transition metal compound from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and are able to correlate (or configure to correlate) the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution . In this aspect, the UV-visible spectrometer has a "built-in" computer system that performs absorption profile measurements and converts the absorption profile data into a first transition metal compound concentration. In other aspects, the UV-visible spectrometer can simultaneously or sequentially measure the reference absorption profile of a reference solution (comprising a second transition metal compound and a hydrocarbon solvent).

In another aspect of this invention, the analytical system may include a visible ultraviolet spectrometer and an external computer system such that the visible ultraviolet spectrometer is capable of measuring (or configured to measure) an absorption profile of a sample of a first transition metal compound in solution, and an external computer system is capable of subtracting (or configuring to subtract) the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound, and is capable of correlating (or configuring to correlate) the absorption profile of the first transition metal compound with the standard for determining the concentration of the first transition metal compound in solution. In this aspect, the UV-visible spectrometer can perform an absorbance measurement and generate data and an absorbance profile, but an external computer system can receive output from the UV-visible spectrometer and determine the concentration of the first transition metal compound.

Optionally, the analytical system may further comprise a filter assembly for filtering a sample solution containing the first and second transition metal compounds prior to analysis by the UV-visible spectrometer.

As described herein, absorption profiles (eg, sample absorption profile, reference absorption profile, and absorption profile of the first transition metal compound) may independently include an absorption peak at one wavelength in some aspects of this invention. Thus, the absorption peak data for the first transition metal compound in the sample solution at one wavelength can be used to determine the concentration of the first transition metal compound in the sample solution. Additionally or alternatively, absorption profiles can independently include an absorption curve (peaks and/or areas under the curves versus wavelength) over a wavelength range, such as 200 nm to 750 nm or 300 nm to 600 nm, and so on. . Thus, wavelength absorption curve data can be used to determine the concentration of the first transition metal compound in the sample solution. In another aspect, the absorption profiles may independently include an absorption curve (peaks and/or areas under the curves versus wavelength) for a subset of wavelengths spanning less than 200 nm, less than 150 nm, less than 100 nm, or less than 50 nm. Thus, data from absorption curves over a specific subset of wavelengths can be used to determine the concentration of the first transition metal compound in solution. Other suitable variations and combinations of absorption profile will be apparent from this description.

Each absorption profile may be generated independently and, as such, may independently include an absorption peak or absorption curve in any of the wavelength ranges described herein. Accordingly, in some aspects, the sample absorption profile and the reference absorption profile independently may include an absorption curve, while the absorption profile of the first transition metal compound may include an absorption peak. Similarly, the sample absorption profile may include an absorption curve in a different wavelength range than the reference absorption profile. Thus, after subtracting the reference absorption profile from the absorption profile of the sample, the resulting absorption profile of the first transition metal compound may include an absorption curve at the same or different wavelengths, or at the same wavelength.

In addition, converting the absorption profile of the first transition metal compound to the concentration of the first transition metal may include correlating the absorption in one peak of the absorption profile of the first transition metal compound with the standard. If the calibration curves are used as a standard, these calibration curves can be obtained using any procedure known to a person skilled in the art. As an example, absorbance data can be obtained from a sample having a known concentration of a first transition metal compound and a second transition metal compound (wt %) in a reference solution (e.g. with a specific hydrocarbon solvent) at one wavelength or over a wide range of wavelengths. . Absorption data can then be obtained for a range of concentrations of the first transition metal compound while the concentration of the second transition metal compound remains constant. Alternatively, the correlation step may include any suitable technique for converting the absorption profile (or peak) of the first transition metal compound into the concentration of the first transition metal compound in solution.

The catalyst production vessel may include any vessel or device that is capable of bringing into contact (eg, mixing or grinding) two or more components of the catalyst system to form the catalyst system. The catalyst preparation vessel may be a mixing vessel or other suitable agitated vessel or vessel. If necessary, the catalyst system can be delivered from the catalyst production vessel to the reactor. Often, transition metal compounds (two or more) and activator (one or more), or alternatively transition metal compounds (two or more), activator (one or more) and co-catalyst, are often contacted in a catalyst preparation vessel to form a catalyst system. Capacities and methods for obtaining multi-component catalysts are described, for example, in US patent No. 7,615,596 (for example, pre-contactor), which is fully incorporated into the present description by reference.

Optionally, the polymerization reactor system may further comprise a controller that is capable of controlling the flow rate of the first transition metal compound into the reactor system based on or in accordance with the concentration determined by the analytical system. Thus, a polymerization reactor system may include a reactor, a catalyst production vessel, an analytical system, and a controller. The controller, which may include any suitable processing unit or computer system, may be used to analyze data regarding the concentration of the first transition metal compound in solution and adjust the flow rate of the first transition metal compound into the reactor system based on the determined concentration. In another aspect, the controller may be programmed with an algorithm to control the flow rate of the first transition metal compound into the reactor system based on the concentration determined by the analytical system. For example, if the concentration detected by the analytical system is too low, the flow rate can be increased by the controller. In yet another aspect, a controller for controlling the flow rate of the first transition metal compound may comprise a controller operable to receive information about the concentration of the first transition metal compound in order to identify a new target concentration of the first transition metal compound (e.g., increase or decrease the flow rate to achieve desired effect on the concentration of the first transition metal compound) and provide a control signal to appropriately adjust the flow rate of the first transition metal compound into the reactor system.

The controller can operate as needed, at predetermined intervals, or continuously, depending on the requirements of the reactor system. Thus, it is contemplated that the concentration of the first transition metal compound can be monitored and/or adjusted and/or controlled continuously. Accordingly, in particular aspects of this invention, the polymerization reactor system and controller can operate in real time or near real time, so that the concentration of the first transition metal compound can be determined and that determined concentration is used instantaneously or almost instantaneously by adjusting the flow rate or feed rate. compounds of the first transition metal.

The controller or computing device may be implemented using a personal computer, network computer, server, mainframe, or other similar microcomputer-based workstation. The controller or computing device may include any computer operating environment such as handheld devices, multiprocessor systems, sender microprocessor or programmable electronic devices, minicomputers, mainframe computers, and the like. The controller or computing device may also be used in distributed computing environments where tasks are performed by remote processing devices. In addition, the controller or computing device may include a mobile terminal such as a smartphone, a cellular phone, a wireless application protocol (WAP) cellular phone, a personal digital assistant (PDA), an intelligent pager, a laptop computer, a PDA, a conventional telephone, a point of sale wireless access (Wi-Fi) or fax machine. The above systems and devices are examples, and the controller or computing device may include other systems or devices. The controller or computing device may also be implemented via a system on a chip (SOC) where each and/or many of the components shown above may be integrated into a single integrated circuit. Such a SOC device may include one or more processing units, graphics units, communication units, system virtualization units, and various application functionality that may be integrated (or "burnt") on a chip substrate as a single integrated circuit. Other methodologies and controller arrangements will be apparent to those skilled in the art given this description.

The controllers of the systems described herein can control the flow rate of the first transition metal compound into or within the polymerization reactor system in any manner that provides accurate and nearly instantaneous control of the concentration of the first transition metal compound.

The systems described herein are applicable to a wide range of circumstances where the concentration of a first transition metal compound in a solution (or mixture from which a solution can be obtained) that contains a first transition metal compound and a second transition metal compound may be of interest. In one aspect, the solution containing the first transition metal compound and the second transition metal compound may be a feed stream to a catalyst production vessel. In this aspect, the controller may control the flow rate of the first transition metal compound into the reactor by adjusting the flow rate of the feed to the catalyst production vessel and/or by adjusting the relative flow rate of the first and second transition metal compound into the catalyst production vessel and/or by adjusting the rate the stream of the catalytic system leaving the container for obtaining a catalyst and entering the reactor.

In another aspect, the catalyst system may be a liquid (or homogeneous) catalyst system, and the solution containing the first and second transition metal compounds may be a sample of the liquid catalyst system. In this aspect, the controller may control the flow rate of the first transition metal compound into the reactor by adjusting the relative flow rate of the first and second transition metal compounds into the reactor and/or by adjusting the flow rate of the liquid catalyst system entering the reactor.

In yet another aspect, the polymerization reactor system may include a polymerization reactor (e.g., a solution reactor or a slurry reactor) containing the reaction mixture, and the solution containing the first and second transition metal compounds may be a solution obtained from or separated from the sample stream from polymerization reactor. In this aspect, the controller controls the flow rate of the first transition metal compound into the reactor by adjusting the relative flow rate of the first and second transition metal compounds into the reactor and/or by controlling the flow rate of the catalyst system entering the reactor. As described herein, solid particles or particles from the sample stream (reaction mixture) can be removed by any suitable method. Optionally, cooling the sample stream may be helpful. This process can be useful in determining the amount of a first transition metal compound that is not impregnated into, onto, or associated with solid catalyst components and/or polymer particles, for example, to determine the amount of a first transition metal compound (or fraction thereof) that is present in solution.

In yet another aspect, the solution containing the first and second transition metal compounds may be a solution obtained from or separated from a sample feed stream of a supported heterogeneous or catalyst system. In this aspect, the flow rate of the first transition metal compound into the reactor can be controlled by adjusting the relative flow rate in the reactor and/or by adjusting the flow rate of the catalyst system entering the reactor. As stated above, this process can be useful for determining the amount of the first transition metal compound that is not impregnated into, on or associated with the solid catalyst components of the catalyst system, for example, to determine the amount of the first transition metal compound (or fraction thereof) that is present. in solution.

An exemplary polymerization reactor system 100 in accordance with aspects of this invention is shown in FIG. 1. Polymerization reactor system 100 includes a catalyst preparation vessel 110, a reactor 120, an analytical system 140, and a controller 150. Analytical system 140 may include a UV-visible spectrometer as described herein. Polymerization reactor system 100 in FIG. 1 includes a first transition metal compound solution feed stream 102 and a second transition metal compound solution feed stream 104. which form a combined transition metal compound solution feed stream 105 to the catalyst production vessel (separate feed streams to the catalyst production vessel for the other catalyst components are not shown). ). In other aspects not shown in FIG. 1, feed streams 102 and 104 can be independently fed directly to catalyst preparation vessel 110 and/or reactor 120. As shown in FIG. 1, the sample stream 132 from the combined feed stream 105 may be fed to the analytical system 140 to determine the concentration of the first transition metal compound in the combined feed stream 105 prior to its introduction into the catalyst preparation vessel 110.

Polymerization reactor system 100 includes a catalyst system feed stream 115 from catalyst production vessel 110 to reactor 120. Catalyst system feed stream 115 may be a liquid (or homogeneous) or supported (or heterogeneous) catalyst system containing a first transition metal compound. Sample stream 134 from catalyst system feed stream 115 may be fed to analytical system 140 to determine the concentration of the first transition metal compound in a solution portion of the feed stream (e.g., solids or particles in catalyst system 115 feed stream may be removed prior to analysis).

Polymerization reactor system 100 includes sample stream 136 from reactor 120. Sample stream 136 from reactor 120 may be fed to analytical system 140 to determine the concentration of the first transition metal compound in a portion of the reactor contents solution (e.g., solids or particles in reactor 136 sample stream may be removed prior to analysis).

First transition metal compound concentration information or data 145 from analytical system 140 may be provided to controller 150, which may then monitor or adjust 155 the rate of combined feed stream 105 and/or the feed rate of catalyst system 115. Alternatively or additionally, controller 150 may independently control or adjust 155 the feed rate of the first transition metal compound solution 102 and/or the feed rate of the second transition metal compound solution 104 to control or adjust 155 the relative feed flow rate of the feedstock 102 and 104. Thus, the controller 150 controls or adjusts 155 the rate flow of the first transition metal compound to the reactor 120 based on or in accordance with the concentration determined by the analytical system 140. For example, if the concentration determined by the analytical system 140 is too low, the flow rate of one or multiple feed streams can be increased by the controller 150.

The described polymerization reactor systems and methods of operating them are intended to cover any olefin polymerization process using any/all types of polymerization reactors and polymerization reaction conditions. As used herein, the term "polymerization reactor" includes any polymerization reactor suitable for the polymerization (including oligomerization) of olefin monomers and comonomers (one or more comonomers, if used) to produce homopolymers, copolymers, terpolymers, and the like. Various types of polymerization reactors include reactors that refer to slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, and the like, or combinations thereof. The polymerization conditions for various types of reactors are well known to those skilled in the art. Gas phase reactors may include fluidized bed reactors or multi-stage horizontal reactors. Slurry reactors may include vertical or horizontal loops. High pressure reactors may include autoclaves or tubular reactors. These types of reactors can usually be operated continuously. Continuous process reactors may use batch or continuous release products. Reactor polymerization systems and processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer and/or diluent.

The polymerization reactor systems described herein may include one type of polymerization reactor or multiple reactors of the same or different type. The polymerization reactor system may include a solution reactor, a gas phase reactor, a slurry reactor, or a combination thereof. Polymer production in multiple reactors may include multiple steps in at least two separate polymerization reactors connected to each other by a transfer device that allows the polymers produced in the first polymerization reactor to be transferred to the second reactor. The desired polymerization conditions in one of the reactors may differ from those of the other reactor(s). Alternatively, multi-reactor polymerization may involve manual transfer of polymer from one reactor to subsequent reactors to continue the polymerization. Multiple reactor systems can include any combination, including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with loop reactors and/or gas phase reactors. Several reactors can operate in series, in parallel, or simultaneously.

In accordance with one aspect of the invention, the polymerization reactor system includes at least one loop slurry reactor, for example, containing vertical or horizontal loops. Monomer, diluent, catalyst, and optionally comonomer may be continuously fed into the loop reactor where polymerization takes place. In general, continuous processes may include the continuous supply of monomer/comonomer, catalyst and diluent to the polymerization reactor and the continuous removal from this reactor of a suspension containing polymer particles and diluent. The reactor effluent may be evaporated to remove solid polymer from liquids that contain diluent, monomer and/or comonomer. Various technologies can be used for this separation step, including, but not limited to, evaporation, which includes any combination of heat and pressure reduction, cyclone or hydrocyclone separation, or centrifugation separation.

A typical slurry polymerization process (also known as a particle formation process) is described, for example, in US Pat.

Suitable diluents for use in slurry polymerization include, but are not limited to, the monomer to be polymerized and hydrocarbons that are liquids under the polymerization conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some polymerization reactions proceed in bulk when no diluent is used, such as in the bulk polymerization of propylene to form polypropylene homopolymers.

In accordance with another aspect of this invention, the polymerization reactor system may contain at least one gas phase reactor (for example, a fluidized bed reactor). Such reactor systems may use a continuous recycle stream containing one or more monomers circulating continuously through a fluidized bed in the presence of a catalyst under polymerization conditions. The recycle stream can be withdrawn from the fluidized bed and returned back to the reactor. Simultaneously, polymeric product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors may include a multi-stage gas phase olefin polymerization process in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while a catalyst containing the polymer formed in the first polymerization zone is fed to the second polymerization zone. One type of gas phase reactor is described in US Pat. Nos. 5,352,749; 4,588,790; 5,436,304;

In accordance with another aspect of the invention, the polymerization reactor system may include a pressure reactor, for example, may include a tubular reactor or an autoclave. Tubular reactors have several zones into which fresh monomer, initiators or catalysts are fed. The monomer may be introduced into the inert gas stream and fed into one zone of the reactor. Initiators, catalysts and/or catalyst components may be introduced into the gas stream and fed into another zone of the reactor. For polymerization, the gas streams can be mixed. To create optimal polymerization reaction conditions, heat and pressure can be applied, as appropriate.

According to yet another aspect of the invention, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer/comonomer is brought into contact with the catalyst composition by suitable agitation or other means. You can use the media, including an inert organic diluent or excess monomer. If desired, the monomer/comonomer can be brought into contact with the product of the catalytic reaction in the vapor phase, in the presence or absence of liquid material. The polymerization zone can maintain temperatures (eg up to 150-180° C.) and pressure levels that result in the formation of a polymer solution in the reaction medium. Agitation can be used to provide better temperature control and maintain uniformity of polymerization mixtures throughout the polymerization zone. Appropriate means are used to dissipate the exothermic heat of polymerization.

In some aspects, the polymerization reactor system may include any combination of a feedstock supply system, a catalyst supply system, and/or catalyst components, and/or a polymer recovery system, including continuous systems. In other aspects, suitable reactor systems may include feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, discharge, laboratory analysis, and process control.

Polymerization conditions that can be monitored, adjusted and/or controlled for efficiency and to provide desired polymer properties may include, but are not limited to, reactor temperature, reactor pressure, reactor catalyst system flow rate, monomer (and comonomer, if used) in the reactor, monomer concentration in the reactor, olefin polymer yield rate, recycle rate, hydrogen flow rate (if used), reactor cooling state, and the like. The polymerization temperature can affect catalyst performance, polymer molecular weight and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature, in accordance with the Gibbs free energy equation. Typically, this includes from about 60°C to about 280°C, for example, from about 60°C to about 185°C, from about 60°C to about 115°C, or from about 130°C to about 180 °C, depending on the type of polymerization reactor, polymer brand, and so on. In some reactor systems, the polymerization temperature, in General, may be in the range from about 70°C to about 110°C or from about 125°C to about 175°C.

Suitable pressure also varies depending on the type of polymerization reactor. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psi (6.9 MPa). The pressure for gas phase polymerization can typically be in the range of 200 psi to 500 psi (1.4 MPa to 3.4 MPa). High pressure polymerization in tubular or autoclave reactors is typically carried out at pressures of about 20,000 to 75,000 psi (138 to 517 MPa). Polymerization reactors can also operate at supercritical conditions, which typically occur at higher temperatures and pressures (eg, above 92° C. and 700 psi (4.83 MPa)). Operating at the supercritical point on the pressure/temperature diagram (supercritical zone) provides benefits to the polymerization reaction process.

The concentration of reactants entering the polymerization reactor system can be controlled to obtain resins with certain physical and mechanical properties. The proposed end product that will be formed from the polymer resin, and the method of molding this product, ultimately determine the desired properties and characteristics of the polymer. Mechanical properties include tensile, bending, impact, creep, stress relaxation and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting point, glass transition temperature, crystallization temperature, stereoregularity, cracking, long chain branching, and rheological measurements.

The aspects discussed herein are also directed to and encompass polymers (or oligomers) produced by any of the polymerization reactor systems and methods described herein. Articles may be formed from and/or may contain polymers (or oligomers) obtained in accordance with the systems and methods described herein.

CATALYST SYSTEMS

The methods, processes, and reactor systems described herein are applicable to, but are not limited to, any catalyst system suitable for the polymerization of an olefin monomer. In this document, "catalyst system" may also be referred to as "catalyst composition" or "catalyst mixture". Compounds of the first and second transition metals may independently include, for example, a transition metal (one or more than one) from Group 3-12 of the Periodic Table of the Elements (Chemical and Engineering News, 63(5). 27, 1985). In one aspect, the first and/or second transition metal compound may comprise a Group 3, 4, 5 or 6 transition metal or a combination of two or more transition metals. The first and/or second transition metal compound(s) may independently include chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof, in some aspects, or may contain chromium, titanium, zirconium, hafnium, or a combination thereof, in other aspects. Accordingly, the first and/or second transition metal compound(s) may independently contain chromium or titanium or zirconium or hafnium alone or in combination. In addition, catalyst systems containing more than two transition metal compounds are contemplated herein, and these additional transition metal compounds (e.g., a third transition metal compound) may independently include any suitable transition metal such as chromium, titanium, zirconium, hafnium, vanadium. , or a combination of them.

In some aspects of the present invention, the compound(s) of the first and/or second transition metal, independently of each other, may contain any suitable non-metallocene compound. In general, the methods, processes, and reactor systems described herein are most applicable to transition metal compounds, such as non-metallocene compounds, where the absorption characteristics of the first transition metal compound and the second transition metal compound overlap and cannot be deconvoluted.

Illustrative and non-limiting examples of suitable transition metal compounds encompassed herein may include the following compounds (R and R'=halide or C ₁ -C ₁₈ hydrocarbyl group, n=an integer from 0 to 4, Ph=phenyl, tBu=tert -butyl, py=pyridine):

Alternatively or additionally, in certain aspects, the first and/or second transition metal compound(s) may independently comprise a metallocene compound, and the metallocene compound may comprise an unbridged metallocene compound. In one aspect, the metallocene compound may comprise an unbridged zirconium or hafnium metallocene compound and/or an unbridged binuclear zirconium and/or hafnium metallocene compound. In another aspect, the metallocene compound may comprise an unbridged zirconium or hafnium metallocene compound containing two indenyl groups, or a cyclopentadienyl and an indenyl group. In yet another aspect, the metallocene compound may include an unbridged zirconium or hafnium metallocene compound containing two indenyl groups. In yet another aspect, the metallocene compound may comprise an unbridged zirconium or hafnium metallocene compound containing cyclopentadienyl and indenyl groups.

In one aspect, the metallocene compound may comprise an unbridged zirconium-based metallocene compound containing two indenyl groups, or a cyclopentadienyl and an indenyl group, while in another aspect the metallocene compound may comprise a dinuclear unbridged alkenyl-linked metallocene compound.

Illustrative and non-limiting examples of unbridged metallocene compounds that are suitable for use as the transition metal compounds described herein may include the following compounds (Ph=phenyl, stereochemistry not shown):

and the like, as well as combinations thereof.

The first and/or second transition metal compound(s) are not limited solely to the unbridged metallocene compounds such as described above, or to the suitable unbridged metallocene compounds described in US Pat. by reference in their entirety. For example, the first and/or second transition metal compound(s) may comprise an unbridged binuclear metallocene compound such as those described in US Pat. Illustrative and non-limiting examples of binuclear metallocene compounds suitable for use in the present invention may include the following compounds (stereochemistry not shown):

and the like, as well as combinations thereof.

Alternatively, the first and/or second transition metal compound(s) may independently contain a bridged metallocene compound. In one aspect, the bridged metallocene compound may comprise a bridged metallocene compound based on zirconium or hafnium. In another aspect, the bridged metallocene compound may comprise a bridged metallocene compound based on zirconium or hafnium with an alkenyl substituent. In another aspect, the bridged metallocene compound may comprise a bridged metallocene compound based on zirconium or hafnium with an alkenyl substituent and a fluorenyl group. In yet another aspect, the bridged metallocene compound may comprise a bridged metallocene compound based on zirconium or hafnium with a cyclopentadienyl group and a fluorenyl group and with an alkenyl substituent in the bridge group and/or in the cyclopentadienyl group.

In one aspect, the bridged metallocene compound may comprise a monoatomic bridged metallocene compound with a fluorenyl group. In another aspect, the bridged metallocene compound may comprise a monoatomic bridged metallocene compound with a fluorenyl group and either a cyclopentadienyl group or an indenyl group. In yet another aspect, the bridged metallocene compound may comprise a monoatomic bridged metallocene compound with a fluorenyl group and a cyclopentadienyl group. In yet another aspect, the bridged metallocene compound may comprise a monoatomic bridged metallocene compound with a fluorenyl group and an indenyl group.

In these and other aspects, the bridged metallocene compound may contain an aryl substituent (eg, a phenyl group) on the bridge atom. Additionally or alternatively, the bridged metallocene compound may contain an alkenyl substituent, for example on the bridge atom and/or on the fluorenyl group and/or on the cyclopentadienyl or indenyl group.

Illustrative and non-limiting examples of suitable bridged metallocene compounds encompassed herein may include the following compounds (Me=methyl, Ph=phenyl, t-Bu=t-butyl, stereochemistry not shown):

and the like, as well as combinations thereof.

Additional examples of bridged metallocene compounds that are suitable for use as described herein may include, but are not limited to, the following compounds (stereochemistry not shown):

and the like, as well as combinations thereof.

The first and/or second transition metal compound(s) is not limited solely to bridged metallocene compounds such as those described above. Other suitable bridged metallocene compounds are described in US Pat.

The catalyst system, in addition to the first transition metal compound and the second transition metal compound, may include an activator (one or more) and optionally a co-catalyst. Exemplary activators may include, but are not limited to, aluminoxane compounds, organoboron or organoboron compounds, ionizing ionic compounds, activator carriers (eg, a solid oxide treated with an electron withdrawing anion), and the like, or combinations thereof. Commonly used polymerization cocatalysts may include, but are not limited to, alkyl metal cocatalysts or organometallic cocatalysts, where the metal includes boron, aluminum, and the like. For example, alkylboron and/or organoaluminum (eg, alkylaluminum) compounds can often be used as cocatalysts in such catalyst systems. Representative compounds may include, but are not limited to, tri-n-butylborane, tripropylborane, triethylborane, trimethylaluminum, triethylaluminum. tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, including combinations thereof.

The cocatalysts that are used in the catalyst systems of this invention are not limited to the cocatalysts described above. Другие подходящие сокатализаторы хорошо известны специалистам в данной области техники, включая, например, описанные в патентах США №3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599 7,601,665, 7,884,163, 8,114,946 и 8,309,485, которые полностью включены в данный документ посредством ссылки.

SOLID OXIDES

In some aspects, the catalyst system may contain a solid oxide. Typically, the solid oxide may contain oxygen and one or more elements selected from group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table or contain oxygen and one or more elements selected from the lanthanide or actinide elements (see Hawley's Condensed Chemical Dictionary, 11th ^Ed ., John Wiley & Sons, 1995; Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-hiterscience, 1999). For example, the inorganic oxide may contain oxygen and an element or elements selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.

Suitable examples of solid oxide materials or compounds that can be used as catalyst system components include, but are not limited to, Al ₂ O ₃ , B ₂ O ₃ , BeO, Bi ₂ O ₃ , CdO, CO ₃ O ₄ , Cr ₂ O ₃ , CuO, Fe ₂ O ₃ , Ga ₂ O ₃ , La ₂ O ₃ , Mn ₂ O ₃ , MoO ₃ , NiO, P ₂ O ₅ , Sb ₂ O ₅ , SiO ₂ , SnO ₂ , SrO, ThO ₂ , TiO ₂ , V ₂ O ₅ , WO ₃ , Y ₂ O ₃ , ZnO, ZrO ₂ and the like, including their mixed oxides and combinations thereof.

The solid oxide may include oxide materials such as alumina, their "mixed oxide" compounds such as silica-alumina, and combinations or mixtures of more than one solid oxide material. Mixed oxides such as silica-alumina may be one or more chemical phases with more than one metal in combination with oxygen to form a solid oxide. Examples of mixed oxides that can be used herein include, but are not limited to, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-titania, oxide alumina-zirconia, alumina-zinc oxide, alumina-boron oxide, silica-boron oxide, aluminum phosphate, aluminophosphate, aluminophosphate-silica, titanium dioxide-zirconia, and the like, or combinations thereof. Silica-coated aluminas are included in this document; such oxide materials are described, for example, in US Pat. No. 7,884,163, the disclosure of which is incorporated herein by reference in its entirety.

The percentage of each oxide in the mixed oxide may vary depending on the respective oxide materials. As an example, silica-alumina typically has an alumina content of 5 to 95 wt. %. According to one aspect, the content of alumina in silica-alumina can be from 5 to 50 wt. % alumina or from 8 to 30 wt. % aluminum oxide. In another aspect, high alumina silica-alumina compounds can be used, in which the alumina content of these materials is typically between 60 and 90 wt. % alumina or from 65 to 80 wt. % aluminum oxide.

In one aspect, the solid oxide may include silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc aluminate, alumina- boron oxide, silica-boron oxide, aluminum phosphate, aluminophosphate-aluminophosphate-silicon dioxide, titanium dioxide-zirconium dioxide, or a combination thereof; alternatively, silica-alumina; alternatively silica-coated alumina; alternatively, silica-titanium dioxide; alternatively, silica-zirconium dioxide; alternatively, alumina-titanium dioxide; alternatively, alumina-zirconium dioxide; alternatively zinc aluminate; alternatively, alumina-boron oxide; alternatively silica-boron oxide; alternatively, aluminum phosphate; alternatively, aluminophosphate; alternatively, aluminophosphate-silica; or, alternatively, titanium dioxide-zirconium dioxide.

In another aspect, the solid oxide comprises silica, alumina, titanium dioxide, zirconia, magnesium oxide, boron oxide, zinc oxide, any mixed oxide thereof, or any combination thereof. For example, the solid oxide may contain silicon dioxide, alumina, titanium dioxide, or a combination thereof; alternatively, silicon dioxide; alternatively, alumina; alternatively, titanium dioxide; alternatively, zirconia; alternatively, magnesium oxide; alternatively, boron oxide; or alternatively, zinc oxide.

In some aspects, the solid oxide may have a pore volume greater than 0.1 ^cc /g, or alternatively greater than 0.5 ^cc /g. Often, the solid oxide may have a pore volume in excess of 1.0 ^cc /g. Additionally or alternatively, the solid oxide may have a surface area greater than 100 m ² /g; alternatively, more than 250 m ² /g; or alternatively more than 350 m ² /g. For example, the solid oxide may have a surface area of 100 to 1000 m ² /g, 200 to 800 m ² /g, or 250 to 600 m ² /g.

ACTIVATORS-CARRIERS

The present invention encompasses various catalyst systems that may contain an activator carrier. In one aspect, the carrier activator comprises a solid oxide treated with an electron withdrawing anion. Alternatively, in another aspect, the carrier activator comprises a solid oxide treated with an electron withdrawing anion, wherein the solid oxide contains a metal ion that is a Lewis acid. Non-limiting examples of suitable carrier activators are described, for example, in US Pat.

Solid oxide encompasses oxide materials such as alumina and its "mixed oxides" such as silica-alumina, coatings of one oxide on another, and combinations and mixtures thereof. Mixed oxides such as silica-alumina are one or more chemical phases with more than one metal combined with oxygen to form a solid oxide. Examples of mixed oxides that are used to form the activator-carrier, alone or in combination, include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina zirconium dioxide, zinc aluminate, alumina-boron oxide, silica-boron oxide, aluminophosphate-silicon dioxide, titanium dioxide-zirconia and the like. As used herein, solid oxide also encompasses oxide materials such as silica-coated alumina as described in US Pat. No. 7,884,163.

Accordingly, in one aspect, the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconia, magnesium oxide, boron oxide, zinc oxide, any of them. mixed oxide or any combination thereof. In another aspect, the solid oxide comprises alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconia, magnesium oxide, boron oxide, or zinc oxide, and any mixed oxide thereof. or any mixture of them. In another aspect, the solid oxide comprises silica, alumina, titanium dioxide, zirconia, magnesium oxide, boron oxide, zinc oxide, any mixed oxide thereof, or any combination thereof. In yet another aspect, the solid oxide comprises silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boron oxide, or any combination thereof. In yet another aspect, the solid oxide comprises alumina, silica-alumina, silica-coated alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or, alternatively, silica-coated alumina.

Used solid oxides based on silica-alumina or silica-coated alumina have a silica content of from about 5 to about 95 wt. %. In one aspect, the content of silicon dioxide in these solid oxides is from about 10 to about 80 wt. % or from about 20 to about 70 wt. % silicon dioxide. In another aspect, such materials have a silica content in the range of about 15 to about 60 wt. %, or from about 25 to about 50 wt. % silicon dioxide. The solid oxides contemplated herein have any suitable specific surface area, pore volume, and particle size as understood by those skilled in the art.

An electron-withdrawing component used to treat a solid oxide is any component that, when processed, increases the Lewis or Bronsted acidity of the solid oxide (compared to a solid oxide that has not been treated with at least one electron-withdrawing anion). In one aspect, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, acid, or other compound, such as a volatile organic compound, that serves as a source or parent compound for that anion. Examples of electron withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, and the like, including mixtures thereof. and combinations. Additionally, other ionic or nonionic compounds are also used which serve as sources of these electron withdrawing anions. In some aspects provided herein, the electron-withdrawing anion is or contains fluoride, chloride, bromide, phosphate, triflate, bisulfate or sulfate, and the like, or any combination thereof. In other aspects, the electron withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and the like, or combinations thereof. At the same time, in other aspects, the electron withdrawing anion contains fluoride and/or sulfate.

The activator carrier can typically contain from about 1 wt. % to about 25 wt. % electron-withdrawing anion based on the mass of the activator-carrier. In specific aspects, proposed in this document, the activator-carrier may contain from about 1 to about 20 wt. %, from about 2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 to about 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12 wt. %, or from about 4 to about 10 wt. % electron-withdrawing anion based on the total weight of the activator-carrier.

In one aspect, the carrier activator comprises fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina , fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated silica-coated alumina, fluorinated-chlorinated alumina, silica-coated, sulphated silica-coated alumina, phosphated silica-coated alumina, and the like, as well as any mixture or combination thereof. In another aspect, the carrier activator used in the catalyst systems described herein is or contains a fluorinated solid oxide and/or a sulfated solid oxide, non-limiting examples of which include fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica-coated alumina, sulfated silica-coated alumina, and the like, as well as combinations thereof. In yet another aspect, the carrier activator comprises fluorinated alumina; alternatively, chlorinated alumina; alternatively, sulfated alumina; alternatively, fluorinated silica-alumina; alternative, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia; alternatively, sulfated alumina coated with silica; alternatively, fluorinated-chlorinated alumina coated with silicon dioxide; or, alternatively, silica-coated fluorinated alumina. In some aspects, the carrier activator may comprise a fluorinated solid oxide, while in other aspects, the carrier activator may comprise a sulfated solid oxide.

Various methods are used to obtain the carrier activators used in this invention. Methods for contacting a solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and amounts to be introduced, impregnation with metals or metal ions (for example, zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, или их комбинацией), и различные методики и условия прокаливания описаны, например, в патентах США №6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894 . Other suitable methods and procedures for the preparation of carrier activators (eg, fluorinated solid oxides, sulfated solid oxides, etc.) are well known to those skilled in the art.

OLEFIN MONOMERS AND OLEFIN POLYMERS

As used herein, olefin monomers generally include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. Included are homopolymerization processes using a single olefin, such as ethylene, propylene, butene, hexene, octene, and the like, as well as copolymerization, homopolymerization, terpolymerization, and similar polymerization reactions using an olefin monomer with at least one different olefin compound. As previously described, polymerization processes are intended to encompass oligomerization processes as well.

For example, the resulting ethylene copolymers, ethylene terpolymers, typically contain a large amount of ethylene (>50 mole percent) and a small amount of comonomer (<50 mole percent). The comonomers that can be copolymerized with ethylene can often have from 3 to 20 carbon atoms in their molecular chain.

The present invention uses acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized and unfunctionalized olefins. For example, typical unsaturated compounds that can be polymerized to form olefin polymer compositions include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2- pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four normal octenes (eg 1-octene), four normal nonenes, five normal decenes, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins may also be polymerized, including but not limited to cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, as described herein. Styrene can also be used as a monomer or as a comonomer. In one aspect, the olefin monomer may contain a C ₂ -C ₂₄ olefin; alternatively, C ₂ -C ₁₂ olefin; alternatively, C ₆ -C ₂₄ olefin; alternatively, C ₂ -C ₁₀ α-olefin; alternatively, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, or styrene; alternatively, ethylene, propylene, 1-butene, 1-hexene or 1-octene; alternatively, ethylene or propylene; alternatively, ethylene; or alternatively propylene.

When a copolymer (or alternatively a terpolymer) is desired, the olefin monomer may include, for example, ethylene or propylene that is copolymerized with at least one comonomer. According to one aspect of the present invention, the olefin monomer during polymerization may contain ethylene. In this aspect, examples of suitable olefin comonomers include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, or their combinations. In another aspect, the olefin monomer may contain ethylene and the olefin comonomer may contain an α-olefin, while in yet another aspect, the comonomer may include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene or any combination thereof; or alternatively, the olefin comonomer may contain 1-butene, 1-hexene, 1-octene, or a combination thereof.

Typically, the amount of comonomer introduced into the polymerization reactor to obtain a copolymer may be from about 0.01 wt. % (wt. %) up to about 50 wt. % comonomer based on the total weight of monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the polymerization reactor system is from about 0.01 wt. % to about 40 wt. % comonomer based on the total weight of monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the polymerization reactor system is from about 0.1 wt. % to about 35 wt. % comonomer based on the total weight of monomer and comonomer. In yet another aspect, the amount of comonomer introduced into the polymerization reactor system is from about 0.5 wt. % to about 20 wt. % comonomer based on the total weight of monomer and comonomer.

According to one aspect of this invention, at least one monomer/reagent is ethylene, so the polymerization reaction is a homopolymerization involving only ethylene, or a copolymerization with another acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefin. In addition, the methods described herein are intended to ensure that the olefin also includes diolefin compounds, which include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, etc. similar.

Olefin polymers covered herein include any polymer (or oligomer) derived from any of the olefin monomer (and optionally comonomer(s)) described herein. For example, the olefin polymer comprises ethylene homopolymer, propylene homopolymer, ethylene copolymer (eg, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene), random propylene copolymer, propylene block copolymer, and the like, including combinations thereof. In addition, the olefin polymer (or oligomer) may include, in certain aspects, an olefin dimer, an olefin trimer, or an olefin tetramer, and include mixtures or combinations thereof. Thus, the olefin polymer includes the products of oligomerization of C ₆ -C ₂₄ olefins (or C ₆ -C ₂₄ α-olefins, or 1-hexene, or 1-octene, or 1-decene, or 1-dodecene, or 1-tetradecene, or 1-hexadecene).

OBTAINING THE CATALYST

The described methods for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound can also be used in the process of preparing a catalyst composition. One such method for preparing a catalyst composition may include (i) contacting a first transition metal compound, a second transition metal compound, a solid activator, and an optional cocatalyst (e.g., in a catalyst preparation vessel) to form the catalyst composition, (ii) determining the concentration of the first transition metal compound, transition metal in a solution containing a first transition metal compound and a second transition metal compound, a solution separated from (or derived from) the catalyst composition, and (III) adjusting the relative amount of at least one component of the catalyst composition depending on the concentration of the first transition metal in solution (or depending on a certain concentration). Therefore, the amount of at least one component of the catalyst composition added (eg, flow rate or feed rate to the catalyst production vessel) can be manually and/or automatically adjusted depending on the determined concentration. Generally, the features of the methods for preparing the catalyst composition described herein (e.g., transition metal compounds, solid activator, cocatalyst (if present), method for determining the concentration of the first transition metal compound, and adjusting the relative amount of at least one component, among others) ) are independently described herein and may be combined in any combination to further describe the described processes. Additionally, unless otherwise indicated, the other steps of the method are performed before, during and/or after any of the steps listed in the described methods.

Referring first to step (I), in which a first transition metal compound, a second transition metal compound, a solid activator, and optionally a co-catalyst may be contacted to form a catalyst composition. Thus, in one aspect, step (I) may include contacting a first transition metal compound, a second transition metal compound, and a solid activator, while in another aspect, step (I) may include contacting a first transition metal compound with a second transition metal compound. metal, solid activator and co-catalyst. The respective catalyst components may be contacted in any order or sequence. For example, the solid activator and cocatalyst may be first contacted (precontacted) prior to contact with the transition metal compounds. Similarly, a mixture of first and second transition metal compounds (eg, in a solvent) may be contacted with the solid activator and co-catalyst, or the transition metal compounds may be contacted sequentially. The solid activator may be present as a suspension of the activator in a suitable diluent and the co-catalyst may be in solution in a suitable solvent. Solvents or diluents for the transition metal compounds, solid activator, and cocatalyst can be any of the hydrocarbon solvents described herein, either alone or in any combination. Thus, a solution containing transition metal compounds may contain any of the aforementioned hydrocarbon solvents.

Let us now turn to Fig. 1, a first transition metal compound solution feed stream 102 and a second transition metal compound solution feed stream 104 may form a combined transition metal compound solution feed stream 105 in a catalyst production vessel 110. Alternatively, feed streams 102 and 104 may be independently fed directly into a catalyst production vessel. catalyst production 110. Separate feed streams for activator and co-catalyst to the catalyst production vessel are not shown.

Typically, the amounts of each component (and hence the relative amounts) used to form the catalyst composition are known. However, when a combined transition metal compound solution feed stream 105 is used, the relative amounts of the respective transition metal compounds may not be known or known with reasonable accuracy. Under such circumstances, as shown in FIG. 1, sample stream 132 from combined feed stream 105 may be fed to an analytical system 140 to determine the concentration of a first transition metal compound in combined feed stream 105 prior to its entry into catalyst preparation vessel 110.

As described herein, the first transition metal compound and the second transition metal compound, independently, may contain any suitable transition metal compound or any transition metal compound, be it a non-metalocene compound, a bridged metallocene compound, an unbridged metallocene compound, and so on. Likewise, the cocatalyst (when present) may contain any suitable cocatalyst or any cocatalyst described herein. In specific aspects of the present invention, the cocatalyst may contain an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and the like.

In the aspects of the present invention described herein above relating to the method of operation of the polymerization reactor system, the catalyst composition may be a liquid (or homogeneous) catalyst system. With regard to the process for obtaining a catalyst composition, these processes are most applicable to heterogeneous or supported catalyst systems. Therefore, the activator can be any suitable solid activator or any solid activator described herein. In one aspect, the solid activator may comprise a solid alumoxane, while in another aspect, the solid activator may comprise an activator supported on any suitable carrier such as a solid oxide (e.g., supported MAO), and in yet another aspect, the solid activator may comprise a carrier activator (eg, a solid oxide treated with an electron-withdrawing anion). If desired, combinations of more than one solid activator can be used.

Step (II) is directed to determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound. A solution containing a first transition metal compound and a second transition metal compound may be separated from (or obtained from) the catalyst composition. Step (II) may include the steps of (i) introducing a sample solution into the sample chamber, (ii) irradiating the sample in the chamber with a long wavelength light beam in the UV-visible spectrum, and (iii) generating a sample absorption profile for the sample by subtracting the reference an absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain an absorption profile of the first transition metal compound; and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in the solution. Accordingly, the specific features relating to step (II) may be the same as those disclosed and described herein as long as they relate to methods for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound. transition metal.

In step (II), the solution containing the first transition metal compound and the second transition metal compound may be separated from the catalyst composition using any suitable method for separating liquids from solids. In one aspect, for example, the catalyst composition may be screened, filtered and/or centrifuged to separate the solution (or liquid portion) containing the first transition metal compound and the second transition metal compound from the solid portion of the catalyst composition. In another aspect, a settling tube such as that described in US Pat. No. 9,708,426 (incorporated herein by reference in its entirety) can be used to separate the liquid and solid fractions of the catalyst composition. In yet another aspect, a modified flow cell may be used. For a modified flow cell, a standard flow cell used for UV-visible analysis may be provided with an extended bottom portion, which may be the same or a different diameter and may be made from the same or a different material as the standard flow cell. The expanded bottom can be configured to act as a settling tube so that higher density solids settle to the bottom of the modified flow cell and liquid (i.e., a solution containing transition metal compounds) occupies the top of the modified flow cell. A portion of the liquid (solution) in the modified flow cell can then be irradiated (in step (ii)) with a light beam at wavelengths in the UV-visible spectrum.

Referring now to step (III), the relative amount of at least one component of the catalyst composition can be adjusted based on the concentration of the first transition metal compound in solution (or based on a certain concentration). Thus, the amount of added at least one component of the catalyst composition - the first transition metal compound, the second transition metal compound, solid activator and/or co-catalyst, if present - can be adjusted based on a certain concentration. Accordingly, based on the concentration of the first transition metal compound in the solution, the amount of the first transition metal compound in the catalyst composition can be increased or decreased (for example, the addition amount or feed rate to the catalyst production vessel can be increased or decreased). Additionally or alternatively, the amount of the second transition metal compound in the catalyst composition may be increased or decreased (eg, the amount added or the feed rate to the catalyst production vessel may be increased or decreased). Additionally or alternatively, the amount of solid activator in the catalyst composition may be increased or decreased (eg, the amount added or the feed rate to the catalyst production vessel may be increased or decreased). Additionally or alternatively, the amount of co-catalyst in the catalyst composition may be increased or decreased (eg, the amount added or the feed rate to the catalyst production vessel may be increased or decreased).

In accordance with the aspects described herein, in step (III), the relative amount of at least one component of the catalyst composition can be adjusted based on the concentration of the first transition metal compound in solution. Controlling the relative amount of a particular catalyst component can be readily determined by one of ordinary skill in the art depending on, for example, historical and prevailing conditions in the catalyst production vessel and on the overall composition (eg, desired composition) of the catalyst composition. An illustrative methodology is presented in the following Examples.

In another aspect of the present invention, a catalyst production system is provided, and in this aspect, the catalyst production system may include (a) a catalyst production vessel for bringing into contact a first transition metal compound, a second transition metal compound, and a solid activator (and co-catalyst, if used) to form a catalyst composition, (b) an activator feed stream for introducing a solid activator into the catalyst production vessel, (c) a first transition metal compound feed stream for introducing a first transition metal compound into the catalyst production vessel, (d) a second transition metal compound feed stream for introducing a second transition metal compound into the catalyst production vessel, (e) a catalyst system feed stream for withdrawing the catalyst composition from the catalyst production vessel (e.g., and introducing the catalyst co (f) an analytical system capable of determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, the solution is separated from (or obtained from) the catalyst composition (e.g., catalyst system feed stream) .

Typically, features of any of the catalyst production systems described herein (e.g., catalyst production vessel, activator feed stream, first transition metal compound feed stream, second transition metal compound feed stream, catalyst system feed stream, analytical system, among others) ) are described herein independently, and these features can be combined in any combination to further describe the described catalyst production systems. In addition, other devices or components of the catalyst production system may be present in the described catalyst production systems, unless otherwise indicated. For example, the catalyst production system may further include a cocatalyst feed stream for introducing the cocatalyst into the catalyst production vessel.

The analytical system may include any analytical system or device that is capable of determining the concentration of a first transition metal compound in a solution that contains a first transition metal compound and a second transition metal compound. For example, the analytical system may include an ultraviolet-visible (UV-visible) spectrometer (eg, alone or in combination with another analytical device/method, such as a fluorescence spectroscopy method; a UV-visible-IR system; and so on).

In one aspect of this invention, the analytical system may include a visible ultraviolet spectrometer with an integrated computer system, as described herein; The UV Visible Spectrometer has a "built-in" computer system. In another aspect of this invention, the analytical system may include an ultraviolet-visible spectrometer and an external computer system, as described herein; The UV-visible spectrometer can perform an absorbance measurement and generate data and an absorbance profile, but an external computer system can receive output from the UV-visible spectrometer and determine the concentration of the first transition metal compound.

Typically, the analytical system may further comprise a liquid/solid separation device configured to separate the solution (containing the first transition metal compound and the second transition metal compound) from the solid portion of the catalyst composition or catalyst system feed stream prior to analysis with an analytical instrument such as UV Visible Spectrometer. While not limited to, a liquid-solid separation device may include a screening device (e.g., a strainer), a filter assembly, a centrifuge device, a settling tube, and the like, or a combination thereof, to separate or separate a solution (or liquid portion) containing a first transition metal compound and a second transition metal compound from the solid portion of the catalyst composition. Additionally or alternatively, the liquid/solid separation device may comprise a modified flow cell as described herein; a standard flow cell used for UV-visible analysis can be provided with an extended bottom designed to act as a settling tube so that higher density solids settle to the bottom of the modified flow cell and liquid (i.e. a solution containing transition metal compounds) occupies the top of the modified flow cell.

For a catalyst production system, any of the features or capabilities of the catalyst production capacity, absorption profile (e.g., sample absorption profile, reference absorption profile, and first transition metal compound absorption profile), and correlation techniques (e.g., calibration curves) may be the same. , as described herein for the polymerization reactor system or for the operating processes of the polymerization reactor system.

In one aspect of the catalyst production system, a first transition metal compound feed stream and a second transition metal compound feed stream may be fed directly into a catalyst production vessel, while in another aspect, a first transition metal compound and a second transition metal compound may be combined together and fed into a vessel. to get a catalyst. Optionally, the activator and co-catalyst feed streams may be combined together (pre-contacted) and the pre-contacted mixture may then be fed into a catalyst preparation vessel.

The catalyst production system may further comprise (g) a controller that is configured to control an activator feed flow rate, a first transition metal compound feed flow rate, and/or a second transition metal compound feed flow rate into the catalyst production vessel based on or according to concentration, certain analytical system. If the cocatalyst is fed into the catalyst production vessel, the controller can be further configured to control the cocatalyst feed flow rate.

For a catalyst production system, any of the features or options for the controller may be the same as those described herein for the polymerization reactor system or for the operating processes of the polymerization reactor system. For example, if it is determined that "free" transition metal compounds are in the solution being analyzed by the analytical system, the flow rate of the activator feed into the catalyst preparation vessel can be increased such that after increasing the rate of addition of the solid activator, all of the transition metal compounds can be absorbed. or impregnated with a solid activator.

In the described catalyst production systems, the controller may adjust the relative amount of at least one component of the catalyst composition based on the concentration of the first transition metal compound in solution (or based on a certain concentration). Accordingly, based on the concentration of the first transition metal compound in solution, the flow rate of the activator feedstock into the catalyst production vessel can be increased or decreased; additionally or alternatively, the feed flow rate of the first transition metal compound compound may be increased or decreased; additionally or alternatively, the feed flow rate of the second transition metal compound can be increased or decreased; and additionally or alternatively, the cocatalyst feed flow rate may be increased or decreased.

An exemplary catalyst production system 200 in accordance with aspects of this invention is shown in FIG. 15. Catalyst production system 200 includes catalyst production vessel 210, analytical system 240, and controller 250. Reactor 220 is also shown in FIG. 15. Catalyst production system 200 includes a first transition metal compound solution feed stream 202 and a first transition metal compound solution feed stream 204 (which form a combined transition metal compound solution feed stream 205 in a catalyst production vessel 210), and an activator feed stream 206, and cocatalyst feed stream 208 to catalyst production vessel 210. Although not shown, feed streams 202 and 204 may independently be fed directly to catalyst production vessel 210. As shown in FIG. 15, the sample stream 232 from the combined feed stream 205 may be fed to an analytical system 240 and a UV-visible spectrometer 260 to determine the concentration of the first transition metal compound in the combined feed stream 205 prior to its introduction into the catalyst preparation vessel 210.

Catalyst system feed stream 215 may flow through valve 292 from catalyst preparation vessel 210 and enter reactor 220. Catalyst system feed stream 215 may be a supported (or heterogeneous) catalyst system containing a first transition metal compound and a second transition metal compound. Sample stream 234 from catalyst system feed stream 215 may flow through valve 294 and enter analytical system 240 to determine the concentration of the first transition metal compound in the solution portion of stream 234. Sample stream may enter flow cell 270 with settling tube 280 (tube shown with a smaller diameter than the flow cell, but its diameter may be the same or greater than the diameter of the flow cell). The flow cell 270 and settling tube 280 (e.g., a modified flow cell) can be configured to separate or separate the solid components of the catalyst system sample stream 234 from the liquid components so that the UV-visible spectrometer 260 can analyze the liquid portion in the flow cell 270. After analysis, the catalyst sample stream 285 may flow through valve 296 and be recycled with the catalyst system feed stream 215.

Information or data 245 on the concentration of the first transition metal compound from the analytical system 240 can be provided to the controller 250, which can then monitor or adjust 255 the rate of the activator feed stream 206, and/or the rate of the cocatalyst feed stream 208, and/or the rate of the combined feed stream 205 to the catalyst preparation vessel 210. Additionally or alternatively, the feed rate of the first transition metal compound 202 and/or the feed stream of the second transition metal compound 204 may be controlled or controlled 255. Thus, the controller 250 controls or controls 255 the feed rate of the activator feed. 206, the feed rate of the cocatalyst 208, the feed rate of the first transition metal compound 202, and/or the feed rate of the second transition metal compound 204 into the catalyst production vessel 210 based on or according to the concentration, o defined analytical system 240.

The following is an illustrative and non-limiting example of the operation of the catalyst production system of FIG. 15. The first metallocene compound, the second metallocene compound, the carrier activator and the organoaluminum co-catalyst may be continuously fed into the catalyst preparation vessel. The first and second metallocene compound feed streams are combined prior to entering the catalyst preparation vessel, and the respective concentrations of the first and second metallocene may be known or measured continuously or as needed using an analytical system containing a UV-visible spectrometer using the techniques described in this document.

The active catalyst composition formed in the catalyst preparation vessel may be continuously fed into the polymerization reactor. The path that the catalyst composition takes from the catalyst production vessel to the reactor can be switched between two possible paths. In Path 1, the catalyst composition flows through valve 292 directly into the reactor, without interruption or metering, and follows this path most of the time. However, when it is desired to analyze the catalyst composition, Path 2 is chosen: the catalyst composition enters the analytical system before eventually entering the reactor.

For Path 2, valve 292 is closed and both valve 294 and valve 296 are open for a desired period of time, which can be as little as 1-5 seconds or 1-5 minutes, although this is not limited. This causes the catalyst composition to follow the sample flow 234 and allows the flow cell 270 and settling tube 280 to be purged with fresh sample of the catalyst composition from the catalyst preparation vessel 210. After the desired period of time has elapsed, valve 294 and valve 296 close, valve 292 opens, and the catalyst composition again flows through valve 292 into the reactor.

Although valve 294 and valve 296 are closed, the catalyst composition slurry present between the two valves may settle and the supernatant solution containing "free" first metallocene and second metallocene compounds can be analyzed with a UV-visible spectrometer 260 through flow cell 270. By measuring the respective amounts of "free" metallocenes, the amount of the respective metallocene compounds adsorbed/impregnated onto the activator support can be determined (by comparison with the combined feed streams of the first and second metallocene compounds entering the catalyst preparation vessel).

It is also advantageous that these measurements can be performed in real time, with minimal intervention and minimal waste. The controller 250 can be further configured to control the valve open/close functions and their frequency and duration. In addition, the catalyst production system may include more than one analytical device; for example, one UV-visible instrument may be used to measure the concentrations of transition metal inputs to the catalyst preparation vessel, and a second UV-visible instrument may be used to measure "free" transition metal concentrations in a portion of the supported catalyst composition solution.

FLOW CELL DEVICE AND RELATED METHODS

While this may refer to methods for determining the appropriate concentrations of transition metal compounds in a solution separated (or obtained) from a sample mixture from a reactor or from a supported heterogeneous or catalyst system, a method is described for measuring the properties of a liquid in a vessel containing a liquid-solid mixture. A method for measuring the properties (eg, transition metal concentration) of a liquid (solution) in a vessel (eg, reactor or catalyst preparation vessel) containing a liquid-solid mixture may include (i) sampling the liquid-solid mixture from the vessel, ( ii) passing a sample of the liquid-solid mixture through the flow cell, (iii) intermittently stopping the flow of the sample of the liquid-solid mixture in the flow cell for a period of time sufficient for the solid to settle in the lower part (first part) of the flow cell device and to so that the liquid occupies the top (second part) of the flow cell device, (iv) irradiating the liquid at the top of the flow cell with a beam of long wavelength light in the UV-visible spectrum to measure the properties of the liquid, and (v) restoring flow through the flow cell. Optionally, the sample may be returned to the vessel. Thus, during the preparation of the catalyst composition, the solution can be separated from the catalyst composition, and the corresponding concentrations can be determined using a method comprising the following steps: feeding the flow of the catalyst composition into the sample chamber containing the flow cell, periodically stopping the flow of the catalyst composition in the flow cell cell for a period of time sufficient for sedimentation of the solid fraction in the lower part (first part) of the flow cell and for the sample solution (liquid) to occupy the upper part (second part) of the flow cell and irradiate the sample in the upper part of the flow cell with a light beam with a long waves in the UV-visible spectrum. Subsequently, the stream may be recovered through the flow cell, and optionally, the catalyst composition stream may be returned to the catalyst production vessel or introduced into the reactor.

Turning now to liquid-solid mixtures, a flow cell consistent with aspects of this invention can be configured to compartment solids at the bottom of the flow cell and for liquid to occupy the top of the flow cell and the top of the flow cell can be configured to irradiate the liquid with a long wavelength light beam in the UV-visible spectrum (for example, the top of the flow cell can be configured to analyze the liquid using a UV-visible spectrometer). Thus, in a catalyst production system, the analytical system may contain a flow cell that separates (or separates) the solid fraction of the catalyst composition from the bottom of the flow cell and to place the solution (liquid fraction) in the upper part of the flow cell and the top of the flow cell can be configured to irradiate the solution with a light beam with a long wavelength in the UV-visible spectrum (for example, the top of the flow cell can be configured to analyze the solution using a UV-visible spectrometer). Aspects of liquid-solid deposition that can be applied to the methods and systems presented herein are described in US Pat. No. 9,708,426, which is incorporated herein by reference in its entirety.

EXAMPLES

The invention is further illustrated by the following examples, which should in no way be construed as limiting the scope of the present invention. Various other aspects, modifications and their equivalents, which upon reading the description in this document will become apparent to a person skilled in the art, do not depart from the essence of this invention or the scope of the appended claims.

The chemical structures for the first, second, and third transition metal compounds used in the examples are shown below as MET-1, MET-2, and MET-3, respectively.

SOLUTIONS CONTAINING A SINGLE TRANSITION METAL COMPOUND

Separate stock solutions of MET-1 and MET-2 were prepared and used to further prepare solutions of transition metal compounds at various concentrations used in the examples. To prepare stock solutions, the corresponding transition metal compound was weighed into a metal balance pan using an analytical balance contained in the glove box. The glove box atmosphere was maintained at less than 0.1 ppm oxygen and less than 0.1 ppm water. The solvent (1-hexene or toluene), previously dried over molecular sieves, was measured to a known volume using a volumetric flask. All of the measured solvent was used to quantitatively rinse the corresponding transition metal compound from the metal weighing dish into a glass vial (approximately 20-30 ml by volume). A small stirrer was added to the vial and the vial was closed with a septum and a metal closure. The contents of the vial were stirred with a magnetic stirrer in a glove box at about 1000 rpm and monitored for dissolution. The dissolution was complete in about 30 minutes, depending on the transition metal compound, solvent and concentration. Thus, four stock solutions were obtained (MET-1 in 1-hexene, MET-1 in toluene, MET-2 in 1-hexene, and MET-2 in toluene). The concentration of the transition metal compound in each initial solution was 0.1 wt. %.

Then, for each stock solution, an aliquot of the stock solution was taken with a syringe and added to a separate vial. An equal volume of the same solvent was added to the aliquot, and the vial was loaded with a stirrer and closed as before for the stock solution. The mixture was allowed to mix, resulting in a solution having half the original concentration of the original solution. This procedure was repeated successively to obtain a series of solutions with the transition metal concentration halved with each repetition.

The homogeneity of each sample was checked by visual inspection in the glove box. Quartz cuvettes, previously dried in an oven at 110° C. for several hours, were loaded with appropriate lids into a glove box. One cuvette was loaded with approximately 3-3.5 ml of pure solvent (either 1-hexene or toluene, and the same solvent used in the respective stock solutions and dilutions) and limited as a reference cell. The remaining cuvettes were loaded with approximately 3-3.5 ml of metallocene solution and securely capped to prevent accidental exposure to the atmosphere. The cuvettes were removed from the glove box and analyzed using a Shimadzu UV-2550 UV-visible spectrometer. Samples were typically analyzed in the 300-800 nm wavelength range in 0.5 nm steps.

The raw data for each assay consisted of a file containing wavelength (nm) and absorbance profile (A.U.) columnar data. The data from all analyzed samples were copied from the raw data files into a single spreadsheet. Absorption profiles versus wavelength for each combination of (1) transition metal compound and (2) solvent were plotted on a single plot. Typical plots are shown in Fig. 2 (MET-2 in toluene), FIG. 4 (MET-2 in 1-hexene), FIG. 6 (MET-1 in toluene) and FIG. 8 (MET-1 in 1-hexene). Each transition metal compound in each solvent had a characteristic peak whose absorption maximum varied with concentration. Representative wavelengths were chosen within this absorption peak (eg, one at the maximum and two additional, one on each side of the maximum). For each representative wavelength, the dependence of absorption on transition metal concentration was shown. Least squares regression on the absorbance and concentration data resulted in a calibration curve for this combination of transition metal compound and solvent at this typical wavelength. Illustrative calibration curves are shown in FIG. 3 (MET-2 in toluene), FIG. 5 (MET-2 in 1-hexene), FIG. 7 (MET-1 in toluene) and FIG. 9 (MET-1 in 1-hexene).

As seen from FIG. 2-9, each UV-visible absorption profile depends on the transition metal compound, the solvent, and the concentration of the transition metal compound in the solvent. In addition, the linear calibration curves were extremely accurate in correlating the measured absorption profile with the concentration of the corresponding transition metal compound in the solvent at the selected wavelengths: R2 statistical values were greater than 0.99 in all cases.

SOLUTIONS CONTAINING TWO TRANSITION METAL COMPOUNDS

In a subsequent series of experiments, stock solutions of MET-1 in toluene and MET-2 in toluene were prepared and then combined to obtain solutions containing two transition metal compounds: MET-1 and MET-2. The respective compositions of samples 1-5 are shown in Table I.

Absorption spectra (1 mm path) for each of samples 1-5 were obtained in a manner similar to that described above using only the solvent in the reference cell. The resulting spectra were collected into a single plot shown in FIG. 10. As seen in FIG. 10, the characteristic peak of MET-1 at 380 nm is difficult to distinguish due to the overlapping absorbance from MET-2 in this range.

Indeed, where the concentration of MET-1 was much less than the concentration of MET-2 (samples 3-4, the weight ratio of MET-1 : MET-2 ranged from ~1:3 to 1:12). the absorption profiles obtained showed very little difference with a solution containing only MET-2 (sample 5). In fact, even when MET-1 and MET-2 concentrations were more similar (e.g. samples 1-2, MET-1 : MET-2 weight ratio was ~1:1 to 1:1.4), MET-2 uptake near 380 nm overlaps the characteristic peak of the absorption profile of MET-1/toluene (see Fig. 6). Thus, FIG. 10 alone cannot provide sufficient data to determine the concentration of MET-1 in a solution containing both MET-1 and MET-2.

Surprisingly, however, when the "reference" absorbance profile of sample 5 (0.2 wt% MET-2 in toluene) was subtracted from the absorbance profiles in FIG. 10, the result is FIG. 11. Sample 5 is now the baseline and the characteristic MET-1 peak at 380 nm and its dependence on MET-1 concentration can be easily recognized and quantified for samples 1-4. Fig. 12 is a linear calibration curve correlating absorbance at 380 nm with MET-1 transition metal compound concentration using the data from FIG. 11. The statistical value of R2 was greater than 0.99. Thus, the concentration of a first transition metal compound (MET-1) can be accurately determined in a solution containing a first transition metal compound (MET-1) and a second transition metal compound (MET-2), even in samples containing a large excess of a second transition metal compound. metal (MET-2) and/or where the second transition metal compound (MET-2) has an overlapping absorption band.

The methods, processes, and reactor systems described herein can also be applied to a solution containing three or more transition metal compounds. For example, in a solution containing transition metal compounds MET-A, MET-B, and MET-C, the concentration of transition metal compound MET-A can be determined using similar procedures in which the reference absorption profile of compounds MET-B and MET -C together (in hydrocarbon solvent) are subtracted from the sample uptake profile, resulting in a MET-A uptake profile, which can then be correlated to a standard to determine the concentration of MET-A in solution.

PREPARATION OF A CATALYST WITH TWO TRANSITION METAL COMPOUNDS

Stock solutions of MET-1 in toluene and MET-3 in toluene were prepared and then stirred for 1 hour at room temperature with various amounts of a sulfated alumina (AS) support activator to give a supported catalyst system containing about 0.22 wt. . % MET-1 and 0.37 wt. % MET 3. No co-catalyst was added so that interactions between transition metal compounds and carrier activator could be investigated. Fig. 13 shows the corresponding concentrations of transition metal compounds that are present without the presence of a carrier activator (zero mg). As increasing amounts of carrier activator were added (from 50 to 500 mg), the respective amounts of "free" MET-1 and MET-3 present in solution (eg, not impregnated into, onto, or not bound to the carrier activator) decreased. Appropriate MET-1 and MET-3 concentrations can be determined by separating the solution (and "free" MET-1 and MET-3) from the solid catalyst components via filtration and then the solution concentrations can be determined as described herein and shown in Fig. 10-12.

As shown in FIG. 13, when 300 mg (or more) of carrier activator (AN) was present, there was no "free" MET-1 and MET-3 in solution—all MET-1 and MET-3 were absorbed or impregnated onto the solid carrier activator. Also of considerable interest is Fig. 13 showing that MET-1 is more rapidly absorbed by the carrier activator (preferably absorbed). There was virtually no "free" MET-1 in solution at activator-carrier levels of 150 mg or more.

Fig. 14 illustrates the data of FIG. 13 is different. The dotted line (100% uptake) starting at the origin reflects the conditions under which the amount of activator carrier (AH) present is such that all MET-1 and MET-3 present is absorbed or impregnated on the activator carrier - there is no "free" MET-1 and MET-3. This occurs at activator-carrier loadings in the range of 300-500 mg. The faster relative uptake of MET-1 (compared to MET-3) is shown by the MET-1 line (as a function of carrier activator) approaching the dotted line at significantly lower carrier activator loadings. For example, when 100 mg of carrier activator was present, the MET-1 line is very close to the dashed line (~0.12 MET-1 was absorbed from the added ~0.13 MET-1), while the MET-3 line is not close to the dashed line. lines. At 100 mg of carrier activator, only ~0.035 MET-3 was absorbed out of ~0.12 MET-3 added. Thus, in order to obtain a catalyst composition with equal amounts of MET-1 and MET-3 uptake at a fixed amount of 100 mg of carrier activator, the amount of MET-1 added may be reduced, the amount of MET-3 added may be increased, or both.

The amount of "free" transition metal compounds in solution compared to the amount taken up or impregnated by the solid activator is extremely important for catalyst preparation. From the data in Fig. 13-14, for example, about 300 mg of solid activator was enough to remove any "free" transition metal compound - everything was absorbed or impregnated. Thus, if the typical loading of solid activator was 500 mg or 600 mg or more during the catalyst preparation step, these data demonstrate that the amount of solid activator can be significantly reduced, resulting in reduced waste and increased cost and efficiency.

As another example, if a MET-1 and MET-3 catalyst system was used to produce a polymer that required property improvement that was positively affected by the addition of more MET-1, the data in FIG. 13-14 demonstrate that this can be easily achieved without adding more catalyst composition. Rather, given the rapid and preferential uptake of MET-1, the amount of MET-1 fed into the catalyst preparation vessel can be increased, resulting in an increase in relative amount compared to the amount of MET-3 present in the overall catalyst composition.

As one of ordinary skill in the art can readily appreciate, numerous other possibilities for altering and optimizing the catalyst system can be ascertained from UV-visible spectroscopy data similar to those shown in FIG. 13-14 and adjusting the relative amount of at least one catalyst composition component based on the concentration of the first transition metal compound (and/or second transition metal compound) in solution as determined by UV-visible spectroscopy techniques are described herein. Thus, depending on the determined concentration(s), the amount of the first transition metal compound in the catalyst composition can be increased or decreased and/or the amount of the second transition metal compound in the catalyst composition can be increased or decreased, and/or the amount of solid activator in the catalyst composition may be increased or decreased and/or the amount of cocatalyst in the catalyst composition may be increased or decreased to optimize the catalyst composition with more certainty and predictability of the result.

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

Aspect 1. A method for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound, the method comprising:

(i) feeding a sample of the solution into the sample chamber;

(ii) irradiating the sample in the chamber with a light beam with a long wavelength in the UV-visible region of the spectrum; and

(iii) generating an absorption profile of the sample by subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution.

Aspect 2 The method as defined in aspect 1 wherein the solution containing the first transition metal compound and the second transition metal compound is a feed stream to a catalyst preparation vessel.

Aspect 3 The method defined in Aspect 1 wherein the solution containing the first transition metal compound and the second transition metal compound is a liquid (or homogeneous) catalyst system containing the first transition metal compound, the second transition metal compound and other catalyst components.

Aspect 4 The method defined in Aspect 1, wherein the solution containing the first transition metal compound and the second transition metal compound is a solution of a heterogeneous catalyst system (for example, a solution obtained from a mixture of samples of a catalyst system, such as a catalyst production vessel) or a solution from a polymerization reactor (for example, a solution obtained from a mixture of samples from a polymerization reactor).

Aspect 5. The process for obtaining a catalyst composition, including:

(I) contacting a first transition metal compound, a second transition metal compound, a solid activator, and an additional co-catalyst (eg, in a catalyst preparation vessel) to form a catalyst composition;

(II) determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, where the solution is separated from (or derived from) the catalyst composition and the concentration is determined through the steps:

(i) feeding a sample of the solution into the sample chamber;

(ii) irradiating the sample in the chamber with a long wavelength light beam in the UV-visible region of the spectrum; and

(iii) generating an absorption profile of the sample by subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution; and

(III) adjusting the relative amount of at least one component of the catalyst composition based on the concentration of the first transition metal compound in solution (or based on a certain concentration).

Aspect 6 The process as defined in aspect 5 wherein a first transition metal compound, a second transition metal compound, a solid activator and a co-catalyst are brought into contact in step (I).

Aspect 7 The process as defined in aspect 6 wherein a solution containing both a first and a second transition metal compound is contacted with a co-catalyst and a solid activator slurry in step (I).

Aspect 8. The process of any one of aspects 5-7, wherein the solution is separated from (or obtained from) the catalyst composition using any suitable technique or any technique described herein, e.g., screening (e.g., straining), filtration, centrifugation , settling, etc., or any combination thereof.

Aspect 9. The process as defined in any of aspects 5-8 wherein the relative amount of a first transition metal compound, a second transition metal compound, a solid activator, a co-catalyst (if used), or any combination thereof, is controlled in step (III).

Aspect 10. The process of operating a polymerization reactor system, including:

(I) contacting a catalyst system comprising a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst with an olefin monomer and optionally an olefin comonomer in a reactor in a polymerization reactor system under polymerization reaction conditions to form an olefin polymer;

(II) determining the concentration of the first transition metal compound in a solution containing the first transition metal compound and the second transition metal compound, the concentration being determined through the following steps:

(i) feeding a sample of the solution into the sample chamber;

(ii) irradiating the sample in the chamber with a long wavelength light beam in the UV-visible region of the spectrum; and

(iii) generating an absorption profile of the sample, subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound, and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution; and

(III) adjusting the flow rate of the first transition metal compound in the reactor when the concentration of the first transition metal compound in the solution reaches a predetermined level (or adjusting the flow rate of the first transition metal compound based on the determined concentration).

Aspect 11 The process defined in aspect 10 wherein the solution containing a first transition metal compound and a second transition metal compound is a feed stream to a catalyst preparation vessel and the flow rate of the first transition metal compound to the reactor is controlled by controlling the feed flow rate into the catalyst production vessel, and/or by controlling the relative flow rate (ratio of first:second transition metal compound) into the catalyst production vessel, and/or by controlling the flow rate of the catalyst system leaving the catalyst production vessel and entering the reactor.

Aspect 12. The process defined in aspect 10, wherein the catalyst system is a liquid (or homogeneous) catalyst system and the solution containing the first transition metal compound and the second transition metal compound is a sample of the liquid catalyst system, and in which the flow rate of the compound of the first transition metal into the reactor is controlled by adjusting the relative flow rate (ratio of first:second transition metal compound) into the reactor and/or by adjusting the flow rate of the liquid catalyst system entering the reactor.

Aspect 13 The process as defined in aspect 10 wherein the polymerization reactor system comprises a polymerization reactor containing a mixture and a solution containing a first transition metal compound and a second transition metal compound is a solution obtained from a mixture sample from the polymerization reactor (e.g., solution polymerization reactor, slurry polymerization reactor), and wherein the flow rate of the first transition metal compound into the polymerization reactor is controlled by controlling the relative flow rate (ratio of first:second transition metal compound) into the reactor, and/or by controlling the flow rate of the catalyst system entering the polymerization reactor.

Aspect 14 The method or process as defined in any of the previous aspects, wherein the sample chamber comprises a flow cell.

Aspect 15. The method or process defined in any of aspects 1-14, wherein the wavelength is one wavelength.

Aspect 16. The method or process defined in any of aspects 1-14, wherein the wavelength is a range of wavelengths.

Aspect 17. The method or process defined in any one of aspects 1-14, wherein the wavelength comprises wavelengths in the visible spectrum (380 nm to 780 nm).

Aspect 18. The method or process defined in any of aspects 1-14, wherein the wavelength includes wavelengths in the range of 200 nm to 750 nm.

Aspect 19. The method or process as defined in any of aspects 1-14, wherein the wavelength includes wavelengths in the range of 300 nm to 600 nm.

Aspect 20. The method or process as defined in any of aspects 1-19, wherein the absorption profile of the sample (either reference or first transition metal compound) contains an absorption peak at a single wavelength.

Aspect 21. The method or process as defined in any of aspects 1-19, wherein the absorption profile of the sample (or reference or first transition metal compound) comprises an absorption curve (e.g., peaks and/or areas under the curves) over a wavelength range from 200 nm to 750 nm or 300 nm to 600 nm.

Aspect 22. The method or process as defined in any of aspects 1-19, wherein the absorption profile of the sample (or reference compound or first transition metal compound) comprises an absorption curve over a subset of wavelengths spanning less than 200 nm, less than 150 nm, less than than 100 nm or less than 50 nm.

Aspect 23 The method or process as defined in any of the preceding aspects, wherein the correlation step is performed at one wavelength, and wherein the absorption peak at one wavelength (in the absorption profile of the first transition metal compound) is less than 2, or less than 1.

Aspect 24 The method or process as defined in any of the previous aspects, wherein the reference solution comprises a second transition metal compound and a hydrocarbon solvent.

Aspect 25: The method or process defined in any of the previous aspects, wherein the standard comprises a calibration curve.

Aspect 26 The method or process as defined in any of the preceding aspects, wherein the step of correlation comprises any suitable method that converts an absorption profile (or peak) of the first transition metal compound into a concentration of the first transition metal compound in solution.

Aspect 27. A catalyst production system comprising:

(a) a catalyst preparation container for bringing into contact a first transition metal compound, a second transition metal compound, and a solid activator and optionally a co-catalyst to form a catalyst composition;

(b) an activator feed stream for introducing the solid activator into the catalyst preparation vessel;

(c) a feed stream of the first transition metal compound for introducing the first transition metal compound into the catalyst preparation vessel;

(d) a feed stream of the second transition metal compound for introducing the second transition metal compound into the catalyst preparation vessel;

(e) a catalyst system feed stream for withdrawing the catalyst composition from the catalyst production vessel (eg, and introducing the catalyst composition into the reactor, if necessary); and

(e) an analytical system for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound, in which the solution is separated from (or obtained from) the catalyst composition (for example, from the feed stream of the catalyst system).

Aspect 28 The system as defined in aspect 27 wherein the catalyst production system further comprises a co-catalyst feed stream for introducing the co-catalyst into the catalyst production vessel.

Aspect 29. The system as defined in aspect 27 or 28, wherein the catalyst production system further comprises (g) a controller for controlling an activator feed flow rate, a first transition metal compound feed flow rate, and/or a second transition metal compound feed flow rate (and /or cocatalyst flow rate, if used) into the catalyst preparation vessel based on or in accordance with the concentration determined by the analytical system.

Aspect 30 The system as defined in any one of aspects 27-29 wherein a first transition metal compound feed stream and a second transition metal compound feed stream are fed directly to a catalyst preparation vessel.

Aspect 31 The system as defined in any one of aspects 27-29 wherein a first transition metal compound feed stream and a second transition metal compound feed stream are combined prior to a catalyst production vessel.

Aspect 32. The system as defined in any of aspects 27-31, wherein the assay system further comprises a liquid/solid separator configured to separate a solution (containing a first transition metal compound and a second transition metal compound) from the catalyst composition (e.g., from the feed stream of the catalytic system).

Aspect 33: A polymerization reactor system comprising:

(A) a reactor for contacting the catalyst system with an olefin monomer and an optional olefin comonomer under polymerization reaction conditions to form an olefin polymer;

(B) a catalyst preparation vessel for contacting a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst to form a catalyst system; and

(C) an analytical system capable of determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound present in the polymerization reactor system.

Aspect 34. The system as defined in any one of aspects 27-33, wherein the analytical system comprises a visible ultraviolet spectrometer with an integrated computer system for measuring an absorption profile of a sample in solution, for subtracting a reference absorption profile of a second transition metal compound in a reference solution from the profile absorbing the sample to obtain an absorption profile of the first transition metal compound; and correlating the absorption profile of the first transition metal compound with a standard to determine the concentration of the first transition metal compound in solution.

Aspect 35. The system as defined in any one of aspects 27-33, wherein the analytical system comprises a visible ultraviolet spectrometer and an external computer system, a visible ultraviolet spectrometer capable of measuring the absorption profile of a sample in solution, and an external computer system configured to subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound; and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution.

Aspect 36 The system as defined in any one of aspects 34-35, wherein the assay system further comprises a filter assembly for filtering a sample solution prior to analysis with a visible-ultraviolet spectrometer.

Aspect 37. The system as defined in any of aspects 34-36, wherein the absorption profile of the sample (either reference or first transition metal compound) contains an absorption peak at a single wavelength.

Aspect 38. The system as defined in any of aspects 34-36, wherein the absorption profile of the sample (or reference or first transition metal compound) contains an absorption curve (e.g., peaks and/or areas under the curves) in the wavelength range from 200 nm up to 750 nm or from 300 to 600 nm.

Aspect 39. The system as defined in any of aspects 34-25, wherein the absorption profile of the sample (or reference compound or first transition metal compound) comprises an absorption curve over a subset of wavelengths spanning less than 200 nm, less than 150 nm, less than 100 nm or less than 50 nm.

Aspect 40. The system as defined in any of aspects 34-39, wherein the reference solution contains a second transition metal compound and a hydrocarbon solvent.

Aspect 41. The system as defined in any of aspects 34-40, wherein the standard contains a calibration curve.

Aspect 42. The system as defined in any of aspects 34-41, wherein the correlation step comprises any suitable technique for converting an absorption profile (or peak) of the first transition metal compound into a concentration of the first transition metal compound in solution.

Aspect 43. The system as defined in any of aspects 33-42, wherein the reactor system further comprises (D) a controller for controlling the flow rate of the first transition metal compound into the reactor based on (or in accordance with) a concentration determined by the analytical system.

Aspect 44. The system defined in aspect 43, wherein the controller comprises a processing unit.

Aspect 45. The system as defined in any one of aspects 43-44 wherein the solution containing a first transition metal compound and a second transition metal compound is a feed stream to a catalyst preparation vessel and the controller controls the flow rate of the first transition metal compound to the reactor by controlling the flow rate of feedstock into the catalyst production vessel, and/or by controlling the relative flow rate (ratio of first:second transition metal compound) into the catalyst production vessel, and/or by controlling the flow rate of the catalyst system exiting the catalyst production vessel and entering the reactor.

Aspect 46. The system as defined in any of aspects 43-44, wherein the catalyst system is a liquid (or homogeneous) catalyst system and the solution containing the first transition metal compound and the second transition metal compound is an example of the liquid catalyst system, and in wherein the controller controls the flow rate of the first transition metal compound into the reactor by controlling the relative flow rate (the ratio of the first:second transition metal compound) into the reactor and/or by controlling the flow rate of the liquid catalyst system entering the reactor.

Aspect 47 The system as defined in any one of aspects 43-44, wherein the polymerization reactor system comprises a polymerization reactor containing a mixture, and a solution containing a first transition metal compound and a second transition metal compound is a solution obtained from a mixture sample from the reactor polymerization reactor (for example, a solution polymerization reactor, a slurry polymerization reactor), and in which the controller controls the flow rate of the first transition metal compound in the polymerization reactor, by controlling the relative flow rate (ratio of the first:second transition metal compound) into the reactor and/or by controlling the rate flow of the catalytic system entering the polymerization reactor.

Aspect 48. The process or system as defined in any of aspects 10-26 or 33-47, wherein the reactor system comprises a single reactor.

Aspect 49. The process or system as defined in any of aspects 10-26 or 33-47, wherein the reactor system comprises two or more reactors.

Aspect 50. The process or system as defined in any of aspects 10-26 or 33-49, wherein the reactor system comprises a solution reactor, a gas phase reactor, a slurry reactor, or a combination thereof.

Aspect 51. The process or system as defined in any of aspects 10-26 or 33-50, wherein the reactor system comprises a slurry loop reactor.

Aspect 52. The process or system as defined in any of aspects 10-26 or 33-51, wherein the polymerization reaction conditions comprise a polymerization reaction temperature in the range of about 60°C to about 185°C, about 60°C to about 115 °C, or from about 130°C to about 180°C, and any suitable reaction pressure, for example, from about 200 to about 1000 psi. inch.

Aspect 53 The process or system as defined in any of Aspects 5-52, wherein the catalyst system (or catalyst composition) contains a solid oxide.

Aspect 54 The process or system as defined in any of Aspects 5-53, wherein the activator comprises a carrier activator (eg, fluorinated silica coated alumina or sulfated alumina).

Aspect 55 The process or system as defined in any of Aspects 5-53 wherein the activator comprises an alumoxane.

Aspect 56. The process or system as defined in any of Aspects 5-55, wherein the catalyst system includes a co-catalyst.

Aspect 57 The particular process or system as defined in any of Aspects 5-55, wherein the catalyst system includes an organoaluminum cocatalyst.

Aspect 58 The process or system as defined in any of aspects 10-26 or 33-57 wherein the olefin monomer comprises a C ₂ -C ₂₄ olefin.

Aspect 59 The process or system as defined in any of aspects 10-26 or 33-57, wherein the olefin monomer comprises propylene.

Aspect 60 The process or system as defined in any of aspects 10-26 or 33-57, wherein the olefin monomer comprises ethylene.

Aspect 61 The process or system as defined in any of aspects 10-26 or 33-57 wherein the catalyst system is contacted with ethylene and an olefin comonomer containing 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 62 The process or system as defined in any of aspects 10-26 or 33-57, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, or a propylene-based copolymer.

Aspect 63 The process or system as defined in any of aspects 10-26 or 33-57, wherein the olefin polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

Aspect 64 The method, process, or system as defined in any of Aspects 1-63, wherein the first transition metal compound and the second transition metal compound independently comprise any suitable non-metallocene compound.

Aspect 65 The method, process, or system as defined in any of Aspects 1-63, wherein the first transition metal compound and the second transition metal compound independently comprise any suitable metallocene compound.

Aspect 66 The method, process, or system as defined in any of Aspects 1-63, wherein the first transition metal compound and the second transition metal compound independently comprise chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof.

Aspect 67 The method, process, or system as defined in any of Aspects 1-63, wherein at least one of the first transition metal compound and the second transition metal compound is a bridged metallocene compound.

Aspect 68 The method, process, or system as defined in any of Aspects 1-63, wherein at least one of the first transition metal compound and the second transition metal compound is a non-bridging metallocene compound.

Aspect 69 The method, process, or system as defined in any of Aspects 1-68, wherein the solution comprises a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent.

Aspect 70. The method, process, or system as defined in any of aspects 1-68, wherein the solution comprises a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent containing 1-hexene, isobutane, toluene, or cyclohexene, as well as mixtures thereof or combinations.

Aspect 71. The method, process, or system as defined in any of aspects 1-70, wherein the weight ratio of the first transition metal compound to the second transition metal compound in solution is in the range of from about 50:1 to about 1:50, from about 10 :1 to about 1:10, about 2:1 to about 1:2, about 1:20 to about 1:1, etc.

Aspect 72 The method, process, or system as defined in any of Aspects 1-71, wherein the second transition metal compound comprises one second transition metal compound, two different second transition metal compounds, or three or more different second transition metal compounds.

Aspect 73. A method for measuring a property of a liquid in a container containing a liquid-solid mixture, comprising:

(i) taking a sample of the liquid-solid mixture from the container;

(ii) flowing a sample of the liquid-solid mixture through the flow cell;

(iii) intermittently stopping the flow of the sample liquid-solid mixture in the flow cell for a period of time sufficient for the solid to settle at the bottom of the flow cell and for the liquid to occupy the top of the flow cell;

(iv) irradiating the liquid at the top of the flow cell with a long wavelength light beam in the UV-visible spectrum to measure a property of the liquid; and

(v) restoration of flow through the flow cell.

Aspect 74: A liquid-solid flow cell wherein:

the flow cell is configured to separate the solid from the bottom of the flow cell and have the liquid occupy the top of the flow cell; and the top of the flow cell is configured to irradiate the liquid with a long wavelength light beam in the UV-visible spectrum.

Aspect 75. Analytical system for measuring the properties of a liquid in a mixture of liquid and solid, the system contains: a certain flow cell - aspect 74; and a UV-visible spectrometer providing exposure of the liquid at the top of the flow cell to measure the properties of the liquid.

Claims (112)

1. The operation process of the polymerization reactor system, where the specified process includes: (I) contacting a catalyst system including a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system reactor under polymerization reaction conditions to produce an olefin polymer ; (II) determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, wherein the concentration is determined by the following steps: (i) feeding a sample of the solution into the sample chamber; (ii) irradiating the sample in the chamber with a light beam with a long wavelength in the UV-visible region of the spectrum; and (iii) generating an absorption profile of the sample by subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution; and (III) controlling the flow rate of the first transition metal compound into the reactor when the concentration of the first transition metal compound in the solution reaches a predetermined level. 2. Process according to claim 1, wherein the solution containing the first transition metal compound and the second transition metal compound is: a feed feed stream to a catalyst production vessel; liquid or homogeneous catalyst system; a solution derived from a heterogeneous catalyst system or a supported catalyst system; or solution obtained from a mixture of samples from the reactor. 3. Process according to claim 1 or 2, characterized in that the wavelength in step (ii) includes wavelengths in the range from 300 nm to 600 nm; the absorption profile of the sample in step (iii) contains an absorption curve over a range of wavelengths; and the correlation step is performed at one wavelength. 4. The process according to any one of paragraphs. 1-3, characterized in that the first transition metal compound and the second transition metal compound independently include chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof; the olefin monomer includes a C ₂ -C ₂₄ olefin; and the polymerization reactor system includes a solution reactor, a gas phase reactor, a slurry reactor, or a combination thereof. 5. The process according to any one of paragraphs. 1-4, characterized in that the first transition metal compound is a non-bridging metallocene compound; and the second transition metal compound is a bridged metallocene compound. 6. The process according to any one of paragraphs. 1-4, characterized in that the second transition metal compound contains two or more different second transition metal compounds. 7. The process according to any one of paragraphs. 1-6, characterized in that the catalytic system contains a first metallocene compound, a second metallocene compound, an activator and a cocatalyst; and the catalyst system is brought into contact with ethylene and an olefin comonomer containing 1-butene, 1-hexene, 1-octene, or a mixture thereof. 8. The process according to any one of paragraphs. 1-7, characterized in that the reference solution contains a second transition metal compound and a hydrocarbon solvent. 9. Process according to claim 8, characterized in that the hydrocarbon solvent includes 1-hexene, isobutane, toluene, cyclohexene, or any combination thereof; and the weight ratio of the first transition metal compound to the second transition metal compound in solution ranges from about 1:50 to about 1:5. 10. The process according to any one of paragraphs. 1-9, characterized in that the sample absorption profile, the reference absorption profile, and the absorption profile of the first transition metal compound independently include an absorption curve over a wavelength range; and the standard includes a calibration curve. 11. The process according to any one of paragraphs. 1-10, characterized in that the solution containing the compound of the first transition metal and the compound of the second transition metal is a feedstock flow into a container for obtaining a catalyst, and the flow rate of the first transition metal compound into the reactor is controlled by adjusting the ratio of the flow rates of the first : second compound transition metal into a container for obtaining a catalyst. 12. Reactor polymerization system, containing: (A) a reactor for contacting the catalyst system with an olefin monomer and optionally an olefin comonomer under polymerization reaction conditions to form an olefin polymer; (B) a catalyst preparation vessel for contacting a first transition metal compound, a second transition metal compound, an activator, and optionally a co-catalyst to form a catalyst system; and (C) an analytical system capable of determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound present in the polymerization reactor system. 13. Reactor system according to claim 12, characterized in that the analytical system contains a spectrometer for the ultraviolet and visible regions. 14. Reactor system according to claim 13, characterized in that the analytical system further comprises a filter assembly for filtering a sample solution containing a first transition metal compound and a second transition metal compound, before analysis with a spectrometer for ultraviolet and visible regions. 15. Reactor system according to any one of paragraphs. 12-14, characterized in that the reactor system further comprises (D) a controller for controlling the flow rate of the first transition metal compound into the reactor based on the concentration determined by the analytical system. 16. Reactor system according to any one of paragraphs. 12-15, characterized in that the reactor system includes a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof; and the analytical system comprises an ultraviolet-visible spectrometer with an integrated computer system for measuring the absorption profile of a sample of the first transition metal compound in solution, for subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound, and for correlating the absorption profile of the first transition metal compound with a standard for determining the concentration of the first transition metal compound in solution. 17. Reactor system according to claim 15 or 16, characterized in that the solution contains a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent; and the solution is the feed stream entering the catalyst production vessel, and the controller controls the flow rate of the first transition metal compound into the reactor by adjusting the flow rate ratio of the first:second transition metal compound into the catalyst production vessel. 18. Reactor system according to any one of paragraphs. 15-17, characterized in that the controller controls the flow rate of the first transition metal compound into the reactor based on the concentrations determined by the analytical system in real time. 19. Reactor system according to any one of paragraphs. 12-18, characterized in that the reactor system comprises two or more reactors, at least one of which is a loop slurry reactor; polymerization reaction conditions include a reaction temperature in the range of about 60° C. to about 185° C., and a reaction pressure of less than about 1000 psi. inch; the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer; and the first transition metal compound and the second transition metal compound independently comprise a bridged or non-bridged metallocene compound. 20. A method for determining the concentration of a first transition metal compound in a solution containing a first transition metal compound and a second transition metal compound, wherein the method includes: (i) feeding a sample of the solution into the sample chamber; (ii) irradiating the sample in the chamber with a light beam with a long wavelength in the UV-visible region of the spectrum; and (iii) generating an absorption profile of the sample by subtracting the reference profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution . 21. The method according to p. 20, characterized in that the sample chamber in step (i) comprises a flow cell; the wavelength in step (ii) includes wavelengths in the range from 300 nm to 600 nm; the correlation step is performed at one wavelength; and the weight ratio of the first transition metal compound to the second transition metal compound in solution ranges from about 1:10 to about 10:1. 22. The process of obtaining a catalytic composition, including: (I) contacting a first transition metal compound, a second transition metal compound, a solid activator, and optionally a co-catalyst to form a catalyst composition; (II) determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, in which the solution is separated from the catalyst composition, and the concentration is determined through the steps: (i) supplying a sample of the solution to the sample chamber; (ii) irradiating the sample in the chamber with a light beam with a long wavelength in the UV-visible region of the spectrum; and (iii) generating an absorption profile of the sample by subtracting the reference profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain the absorption profile of the first transition metal compound and correlating the absorption profile of the first transition metal compound with the standard to determine the concentration of the first transition metal compound in solution ; and (III) adjusting the relative amount of at least one component of the catalyst composition based on the concentration of the first transition metal compound in solution. 23. The process of claim 22, wherein the solution feed stream containing both the first transition metal compound and the second transition metal compound is contacted with the solid activator slurry in step (I). 24. Process according to claim 22 or 23, characterized in that the first transition metal compound, the second transition metal compound, the solid activator and the co-catalyst are brought into contact in step (I). 25. The process according to any one of paragraphs. 22-24, characterized in that the solution is separated from the catalyst composition by sieving, filtering, centrifuging, settling, or any combination thereof. 26. The process according to any one of paragraphs. 22-25, characterized in that the relative amount of the first transition metal compound, the second transition metal compound, or both is controlled in step (III). 27. The process according to any one of paragraphs. 22-26, characterized in that the relative amount of the solid activator is regulated in step (III). 28. The method according to any one of paragraphs. 22-27, characterized in that the wavelength in step (ii) includes wavelengths in the range from 300 nm to 600 nm; the absorption profile of the sample in step (iii) contains an absorption curve over a range of wavelengths; and the correlation step is performed at one wavelength. 29. The process according to any one of paragraphs. 22-28, characterized in that the first transition metal compound and the second transition metal compound independently contain chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof. 30. The process according to any one of paragraphs. 22-29, characterized in that the first transition metal compound is a non-bridging metallocene compound; and the second transition metal compound is a bridged metallocene compound. 31. The process according to any one of paragraphs. 22-29, characterized in that the second transition metal compound contains two or more different second transition metal compounds. 32. The process according to any one of paragraphs. 22-31, characterized in that the reference solution contains a second transition metal compound and a hydrocarbon solvent. 33. Process according to claim 32, characterized in that the hydrocarbon solvent includes 1-hexene, isobutane, toluene, cyclohexene, or any combination thereof; and the weight ratio of the first transition metal compound to the second transition metal compound in solution ranges from about 1:50 to about 1:5. 34. The process according to any one of paragraphs. 22-33, characterized in that the sample absorption profile, the reference absorption profile, and the absorption profile of the first transition metal compound independently include an absorption curve over a wavelength range; and the standard includes a calibration curve. 35. A catalyst production system, comprising: (a) a container for obtaining a catalyst, ensuring that the first transition metal compound, the second transition metal compound and the solid activator are brought into contact to form a catalyst composition; (b) an activator feed stream for introducing the solid activator into the catalyst preparation vessel; (c) a first transition metal compound feed stream for introducing the first transition metal compound into the catalyst preparation vessel; (d) a second transition metal compound feed stream for introducing the second transition metal compound into the catalyst preparation vessel; (e) a catalyst system feed stream for withdrawing the catalyst composition from the catalyst production vessel; and (f) an analytical system for determining the concentration of the first transition metal compound in the solution containing the first transition metal compound and the second transition metal compound, in which the solution is separated from the catalyst composition. 36. The catalyst production system of claim. 35, characterized in that the catalyst production system further comprises (g) a controller that controls the feed flow rate of the activator, the flow rate of the first transition metal compound, and/or the flow rate of the second transition metal compound to the vessel to produce a catalyst based on the concentration determined by the analytical system. 37. The catalyst production system according to claim 35 or 36, characterized in that the analytical system contains a spectrometer for the ultraviolet and visible regions. 38. System for obtaining a catalyst according to any one of paragraphs. 35-37, characterized in that the catalyst preparation vessel further provides for bringing into contact the first transition metal compound, the second transition metal compound, the solid activator, and the co-catalyst to form a catalyst composition; and the catalyst production system further comprises a co-catalyst feed stream for introducing the co-catalyst into the catalyst production vessel. 39. System for obtaining a catalyst according to any one of paragraphs. 35-38, characterized in that the analytical system further comprises a liquid-solid separation device that separates the solution from the catalytic composition. 40. The catalyst production system according to claim 39, characterized in that the solution is separated from the feed stream of the catalyst system. 41. The system for obtaining a catalyst according to any one of paragraphs. 35-40, characterized in that the feed stream of the first transition metal compound and the feed stream of the second transition metal compound are introduced directly into the catalyst production vessel. 42. The system for obtaining a catalyst according to any one of paragraphs. 35-40, characterized in that the feed stream of the first transition metal compound and the feed stream of the second transition metal compound are combined before being introduced into the container to obtain a catalyst 43. The system for obtaining a catalyst according to any one of paragraphs. 35-42, characterized in that the analytical system contains a spectrometer for the ultraviolet and visible regions with an integrated computer system for measuring the absorption profile of the sample of the first transition metal compound in solution, subtracting the reference absorption profile of the second transition metal compound in the reference solution from the absorption profile of the sample to obtain an absorption profile of the first transition metal compound; and correlation of the absorption profile of the first transition metal compound with a standard for determining the concentration of the first transition metal compound in solution. 44. The system for obtaining a catalyst according to any one of paragraphs. 35-43, characterized in that the solution contains a first transition metal compound, a second transition metal compound, and a hydrocarbon solvent; and the activator feed stream contains a solid activator slurry. 45. System for obtaining a catalyst according to any one of paragraphs. 35-44, characterized in that the first transition metal compound and the second transition metal compound independently contain a bridged or non-bridged metallocene compound.

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