Abstract: Disclosed are novel bridged bi-aromatic phenol ligands and transition metal compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds.
Abstract: Methods for producing polyolefin polymers may use a predictive melt index regression to estimate the melt index of the polyolefin during production based on the composition of the gas phase and, optionally, the concentration of catalyst in the reactor or reactor operating conditions. Such predictive melt index regression may include multiple terms to account for concentration of ICA in the reactor, optionally concentration of hydrogen in the reactor, optionally concentration of comonomer in the reactor, optionally the catalyst composition, and optionally reactor operating conditions. One or more terms may independently be represented by a smoothing function that incorporates a time constant.
Type:
Application
Filed:
November 24, 2015
Publication date:
March 28, 2019
Applicant:
Univation Technologies, LLC
Inventors:
Bruce J. Savatsky, Daniel N. Thomas, JR., Timothy R. Lynn
Abstract: New methods of preparing bridged bi-aromatic ligands are disclosed. The methods employ direct di-ortho-lithiation of aromatic rings of bridged protected bi-aromatic diphenols. The ligands may be used to prepare transition metal compounds useful as catalysts in olefin polymerization.
Type:
Grant
Filed:
April 19, 2016
Date of Patent:
March 26, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Catherine Anne Faler, C. Jeff Harlan, Kevin P. Ramirez
Abstract: Catalyst systems and methods for making and using the same are described. A method includes selecting a catalyst blend using a blend polydispersity index (bPDI) map. The polydispersity map is generated by generating a number of polymers for at least two catalysts. Each polymer is generated at a different hydrogen to ethylene ratio. At least one catalyst generates a higher molecular weight polymer and another catalyst generates a lower molecular weight polymer. A molecular weight for each polymer is measured. The relationship between the molecular weight of the polymers generated by each of the catalysts and the ratio of hydrogen to ethylene is determined. A family of bPDI curves for polymers that would be made using a number of ratios of a blend of the at least two catalysts for each of a number of ratios of hydrogen to ethylene.
Type:
Grant
Filed:
December 6, 2017
Date of Patent:
March 26, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Francis C. Rix, Ching-Tai Lue, Timothy M. Boller, Garth R. Giesbrecht, C. Jeff Harlan
Abstract: Catalyst systems and methods for making and using the same. A method for making a catalyst support includes forming a mixture of a support material and a fluoride donor. The mixture is added to a fluidized bed reactor. The mixture is fluidized to form a fluidized bed while maintaining a flow rate of a fluidizing gas of about 0.1 ft./sec at less than about 370° C. and greater than about 0.35 ft./sec at temperatures greater than about 370° C. The mixture is calcined to decompose the fluoride donor, forming a fluorinated support.
Type:
Grant
Filed:
August 19, 2014
Date of Patent:
March 19, 2019
Assignee:
Univation Technologies, LLC
Inventors:
John H. Moorhouse, Kevin J. Cann, Phuong A. Cao, Mark G. Goode, C. Jeff Harlan, Wesley R. Mariott
Abstract: Disclosed herein are methods of controlling polymer properties in polymerization processes that use a chromium-based catalyst. An embodiment discloses a method of producing a polyolefin comprising: contacting a reaction mixture and a reduced chromium oxide catalyst in a gas-phase reactor to produce the polyolefin, wherein the reaction mixture comprises a monomer and a co-monomer; and changing a reaction temperature in the gas-phase reactor by about 1° C. or more whereby a gas molar ratio of the co-monomer to the monomer is changed by about 2% or more and a co-monomer content of the polyolefin at substantially constant density is changed by about 2% or more. Additional methods and compositions are also provided.
Type:
Grant
Filed:
September 25, 2014
Date of Patent:
March 12, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Mark G. Goode, Francois Alexandre, Kevin J. Cann, Barbara J. Kopp, William A. Matthews, John H. Moorehouse, Cliff R. Mure
Abstract: A method for transitioning a gas phase polymerization reactor between metallocene catalysts is provided. The method comprises first reducing the superficial gas velocity and increasing the height of the fluidized bed within the reactor prior to stopping a feed comprising a first metallocene catalyst. The method further comprises introducing a first polymerization neutralizer to the reactor, wherein the first polymerization reactor does not comprise water, and then introducing a second polymerization neutralizer to the reactor, wherein the second polymerization neutralizer is different from the first polymerization neutralizer. After this, the method comprises purging the reactor with an inert gas and then introducing a feed comprising a second metallocene catalyst to the reactor.
Type:
Grant
Filed:
April 6, 2016
Date of Patent:
March 5, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Brandon C. Locklear, R. Eric Pequeno, Richard B. Pannell, Fathi David Hussein, Rich John Stolz, William A. Matthews
Abstract: A catalyst system for polymerizing olefin-based polymers and interpolymers is disclosed. The catalyst system may include a supported chromium catalyst and a Ziegler-Natta catalyst comprising a bulking agent, Mg, and Ti. The Ziegler-Natta catalysts in catalyst systems disclosed herein run exceptionally well without addition of excessive amounts of co-catalyst, thus allowing for use of chromium based supported catalysts that would otherwise be overwhelmed by aluminum alkyl. Further, embodiments disclosed herein may be run without an internal electron donor, and the lack of an internal electron donor in the system also prevents poisoning of the chromium catalysts by the internal electron donor. By including or co-feeding a chromium based catalyst with these Ziegler-Natta catalysts, it has been found that the molecular architecture of the resulting polyolefins, such as polyethylenes, may provide for resins with excellent processing properties.
Type:
Grant
Filed:
November 1, 2013
Date of Patent:
March 5, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Kevin J. Cann, Robert J. Jorgensen, Wesley R. Mariott, Mark G. Goode, John H. Moorhouse
Abstract: A system and method for feeding a chromium-based catalyst to a polymerization reactor; adding a reducing agent to the chromium-based catalyst, and polymerizing an olefin into a polyolefin in the polymerization reactor in the presence of the chromium-based catalyst.
Type:
Application
Filed:
August 31, 2018
Publication date:
February 28, 2019
Applicant:
Univation Technologies, LLC
Inventors:
Kevin R. Gross, Kevin J. Cann, Mark G. Goode, John H. Moorhouse
Abstract: Catalyst systems and methods for making and using the same. A method for making a catalyst support includes forming a mixture of a support material and a fluoride donor. The mixture is added to a fluidized bed reactor. The mixture is fluidized to form a fluidized bed while maintaining a ratio of a pressure drop across a distributor plate to a pressure drop across the fluidized bed of greater than about 7%. The mixture is calcined to decompose the fluoride donor, forming a fluorinated support.
Type:
Grant
Filed:
August 19, 2014
Date of Patent:
February 19, 2019
Assignee:
Univation Technologies, LLC
Inventors:
John H. Moorhouse, Kevin J. Cann, Phuong A. Cao, Mark G. Goode, C. Jeff Harlan, Wesley R. Mariott
Abstract: Systems and methods for monitoring a particle/fluid mixture are provided. The method can include flowing a mixture comprising charged particles and a fluid past a particle accumulation probe. The method can also include measuring electrical signals detected by the probe as some charged particles pass the probe without contacting the probe while other charged particles contact the probe. The measured electrical signals can be manipulated to provide an output. The method can also include determining from the output if the charged particles contacting the probe have, on average, a different charge than the charged particles that pass the probe without contacting the probe.
Abstract: Disclosed are novel bridged bi-aromatic phenol ligands and transition metal catalyst compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds, and polymerization processes utilizing the transition metal compounds for the production of olefin polymers.
Abstract: A system and method for feeding a chromium-based catalyst to a polymerization reactor; adding a reducing agent to the chromium-based catalyst, and polymerizing an olefin into a polyolefin in the polymerization reactor in the presence of the chromium-based catalyst.
Type:
Grant
Filed:
September 1, 2015
Date of Patent:
February 5, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Kevin R. Gross, Kevin J. Cann, Mark G. Goode, John H. Moorhouse
Abstract: A film formed from a polyethylene copolymer using a reduced chromium oxide catalyst, ethylene monomers and a co-monomer selected from butene monomers or 1-hexene, where the polyethylene copolymer has a density in the range of from about 0.935 to about 0.950 g/cm3 and an I21/I5 in a range of about 18.0 to about 30.0. The film formed from the polyethylene copolymer has a dart drop impact (g/im) that significantly greater as compared to a film of the polyethylene copolymer formed using a silyl chromate catalyst in place of the reduced chromium oxide catalyst. A method of making such films is also provided.
Type:
Application
Filed:
January 23, 2017
Publication date:
January 31, 2019
Applicant:
Univation Technologies, LLC
Inventors:
Cliff R. Mure, Dongming Li, Barbara J. Kopp, Mark G. Goode
Abstract: Catalyst systems and methods for making and using the same. A method for making a catalyst support includes forming a mixture of a support material and a fluoride donor. The mixture is added to a fluidized bed reactor. The mixture is fluidized to form a fluidized bed with a height to diameter ratio of at least about 2.3. The mixture is calcined to decompose the fluoride donor, forming a fluorinated support.
Type:
Grant
Filed:
August 19, 2014
Date of Patent:
January 29, 2019
Assignee:
Univation Technologies, LLC
Inventors:
John H. Moorhouse, Kevin J. Cann, Phuong A. Cao, Mark G. Goode, C. Jeff Harlan, Wesley R. Mariott
Abstract: Catalyst systems and methods for making and using the same. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, includes contacting ethylene and a comonomer with a catalyst system. The catalyst system includes a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system. The first catalyst compound includes a compound with the general formula (C5HaR1b)(C5HcR2d)HfX2. The second catalyst compound includes at least one of the following general formulas: In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.
Type:
Grant
Filed:
November 7, 2017
Date of Patent:
January 29, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Ching-Tai Lue, Francis C. Rix, C. Jeff Harlan, Laughlin G. McCullough
Abstract: Polymerization process control methods for making polyethylene are provided. The process control methods include performing a polymerization reaction in a polymerization reactor to produce the polyethylene, where ethylene, and optionally one or more comonomers, in the polymerization reaction is catalyzed by an electron donor-free Ziegler-Natta catalyst and an alkyl aluminum co-catalyst. A melt flow ratio (I21/I2) of the polyethylene removed from the polymerization reactor is measured and an amount of long chain branching (LCB) of the polyethylene from the polymerization reactor is controlled by adjusting a weight concentration of the alkyl aluminum co-catalyst present in the polymerization reactor.
Type:
Application
Filed:
September 19, 2018
Publication date:
January 17, 2019
Applicant:
Univation Technologies, LLC
Inventors:
Wesley R. Mariott, Kevin J. Cann, John H. Moorhouse, Mark G. Goode, Thomas Oswald
Abstract: Polyolefin polymerization performed by contacting in a reactor an olefin monomer and optionally a comonomer with a catalyst system in the presence of induced condensing agents (ICA) and optionally hydrogen. The ICA may include two or more ICA components where the composition of the ICA (i.e., the concentration of each ICA component) may affect the polyolefin production rate. Changes to the relative concentration of the two or more ICA components may be according to ICA equivalency factors that allow for increasing the polyolefin production rate while maintain a sticking temperature, increasing polyolefin production rate while increasing the dew point approach temperature of the ICA, or a combination thereof.
Type:
Grant
Filed:
November 24, 2015
Date of Patent:
January 8, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Bruce J. Savatsky, Brandon C. Locklear, R. Eric Pequeno, Abarajith S. Hari, David M. Glowczwski
Abstract: Catalyst systems and methods for making and using the same are described herein. A catalyst system can include at least three catalysts. The three catalysts include a metallocene catalyst, a first non-metallocene including a ligand complexed to a metal through two or more nitrogen atoms, and a second non-metallocene including a ligand complexed to a metal through one or more nitrogen atoms and an oxygen atom.
Type:
Grant
Filed:
April 5, 2017
Date of Patent:
January 8, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Juliet Bauer Wagner, Garth R. Giesbrecht, Sun-Chueh Kao, Stephen P. Jaker
Abstract: The catalyst productivity of a polyolefin catalyst in the methods disclosed herein may be increased by increasing the concentration of an induced condensing agent (ICA) in the reactor system. The effect the increased ICA concentration may have on a melt index may be counteracted, if necessary, in various ways.
Type:
Grant
Filed:
November 24, 2015
Date of Patent:
January 1, 2019
Assignee:
Univation Technologies, LLC
Inventors:
Bruce J. Savatsky, Natarajan Muruganandam, Timothy R. Lynn, James M. Farley, Daniel P. Zilker, Jr., Fathi David Hussein