Abstract: Catalyst systems and methods for making and using the same. A method of methylating a catalyst composition while substantially normalizing the entiomeric distribution is provided. The method includes slurrying the organometallic compound in dimethoxyethane (DME), and adding a solution of RMgBr in DME, wherein R is a methyl group or a benzyl group, and wherein the RMgBr is greater than about 2.3 equivalents relative to the organometallic compound. After the addition of the RMgBr, the slurry is mixed for at least about four hours. An alkylated organometallic is isolated, wherein the methylated species has a meso/rac ratio that is between about 0.9 and about 1.2.
Type:
Grant
Filed:
August 15, 2019
Date of Patent:
October 12, 2021
Assignee:
Univation Technologies, LLC
Inventors:
Francis C. Rix, Alexander D. Todd, C. Jeff Harlan
Abstract: This invention relates to a polyethylene composition, and films therefrom, comprising at least 65 wt % ethylene derived units and from 0.1 to 35 wt % of C3-C12 olefin comonomer derived units, where the polyethylene composition has: a) an RCI,m of less than 85 kg/mol; b) a Tw1?Tw2 value of from ?15 to ?40° C.; and c) an Mw1/Mw2 value of less than 1.5 where the film has a) a heat seal initiation temperature of X ° C. or less at 5 N of force, where X=0.0015×Y(psi)+62.6 (where Y is the average 1% Secant modulus ((MD+TD)/2)) of the film; b) a dart drop impact of 300 g/mil or more; c) an MD Elmendorf tear of 230 g or more; and d) average 1% Secant modulus ((MD+TD)/2) of 20,000 psi or more.
Type:
Grant
Filed:
May 13, 2019
Date of Patent:
September 28, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Dongming Li, Jian Yang, Kevin A. Stevens, Yan Jiang, Gregory J. Smith-Karahalis
Abstract: A catalytic system based at least on a preformation monomer selected from the group consisting of 1,3-dienes, ethylene, ?-olefins and their mixtures, on a metallocene of formula {P(Cp)(Flu)LnG} and on an organometallic compound as cocatalyst is provided. In the formula, Ln denotes a metal atom which is a rare earth metal, G denotes a group comprising the borohydride BH4 unit or denotes a halogen atom X selected from the group consisting of chlorine, fluorine, bromine and iodine, Cp denotes a cyclopentadienyl group of formula C5H4, Flu denotes a fluorenyl group of formula C13H8, P being a group bridging the two Cp and Flu groups and comprising a silicon or carbon atom. Such a catalytic system exhibits an improved stability of the catalytic activity over time, in particular on storage.
Type:
Grant
Filed:
November 28, 2017
Date of Patent:
September 28, 2021
Assignee:
COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
Abstract: Methods for olefin polymerization are described. The methods include a) forming a first polyolefin under a first set of polymerization conditions in the presence of a first catalyst composition and a first concentration of at least a first continuity additive composition, the first polyolefin composition having a target density, ?1, and a target Flow Index, FI1; and b) forming a second polyolefin composition under a second set of polymerization conditions in the presence of a second catalyst composition and a second concentration of a second continuity additive composition, the second polyolefin composition having a target density, ?2, and a target Flow Index, FI2; wherein the process is essentially free of providing a polymerization neutralizing composition between steps a) and b).
Type:
Grant
Filed:
August 5, 2019
Date of Patent:
September 14, 2021
Assignee:
Univation Technologies, LLC
Inventors:
Bruce J. Savatsky, R. Eric Pequeno, Brandon C. Locklear
Abstract: A compound by the name 1,1,1-tris(di(3,5-dimethoxyphenyl)phosphino-methyl)ethane. The compound can be represented by the structure of formula (I): The compound is useful as a ligand for ruthenium to form an organometallic complex. The complex is an active catalyst for the hydrogenolysis of amides to form amines and optionally alcohols.
Type:
Grant
Filed:
May 10, 2019
Date of Patent:
September 7, 2021
Assignee:
Eastman Chemical Company
Inventors:
Jürgen Klankermayer, Stefan Westhues, Walter Leitner, Robert Thomas Hembre
Abstract: A copolymer of a 1,3-diene and of an olefin selected from the group consisting of ?-monoolefins, ethylene and mixtures thereof is provided. The copolymer bears, at one of its chain ends, an alkoxysilyl or silanol function, functional group F1, and the copolymer is different from a copolymer of a 1,3-diene and a vinylaromatic monomer.
Type:
Grant
Filed:
June 6, 2018
Date of Patent:
August 31, 2021
Assignee:
COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
Abstract: The present invention relates to a hybrid supported metallocene catalyst and a polyolefin preparation method using the same. Using the hybrid supported metallocene catalyst can not only significantly reduce the amount of wax produced when polymerizing olefin monomers, but can also enhance the stress cracking resistance of the polyolefin that is prepared.
Type:
Grant
Filed:
January 12, 2017
Date of Patent:
August 17, 2021
Assignee:
LG CHEM, LTD.
Inventors:
Eun Kyoung Song, Hyuck Ju Kwon, Yi Young Choi, Bog Ki Hong, Kyung Jin Cho, Joong Soo Kim, Sun Mi Kim
Abstract: A process for making a poly alpha-olefin (PAO) having a relatively high vinylidene content (or combined vinylidene and tri-substituted vinylene content) and a relatively low vinyl and/or di-substituted vinylene content, as well as a relatively low molecular weight. The process includes: contacting a feed containing a C2-C32 alpha-olefin with a catalyst system comprising activator and a bis-cyclopentadienyl metallocene compound, typically a cyclopentadienyl-benzindenyl group 4 transition metal compound.
Type:
Grant
Filed:
February 7, 2019
Date of Patent:
August 10, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Jian Yang, Jo Ann M. Canich, Hua Zhou, Jennifer L. Rapp
Abstract: Embodiments of the present disclosure directed towards bimodal polymerization catalysts. As an example, the present disclosure provides a bimodal polymerization catalyst system including a non-metallocene olefin polymerization catalyst and a zirconocene catalyst of Formula I: (Formula I) where each of R1, R2, and R4 are independently a C1 to C20 alkyl, aryl or aralkyl group or a hydrogen, where R3 is a C1 to C20 alkyl, aryl or aralkyl group, and where each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen.
Abstract: The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene. The method includes introducing the first reactor effluent, a second alpha-olefin and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer.
Type:
Grant
Filed:
August 9, 2019
Date of Patent:
August 3, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Patrick C. Chen, Mark H. Li, Jennifer L. Rapp, Monica D. Lotz, Babak LotfizadehDehkordi, Craig J. Emett, Najeeb M. Kuzhiyil, Jian Yang
Abstract: Disclosed is a method for polymerizing olefins comprising passing a heterogeneous single-site catalyst to a solution or slurry polymerization reactor in the absence of pre-polymerization, wherein the polymerization reactor operates at a temperature of at least 50° C. The heterogeneous single-site catalyst may be suspended and/or dissolved in a solvent selected from the group consisting of oils, aliphatic hydrocarbons and mixtures thereof. Also, the heterogeneous single-site catalyst may be passed to the polymerization reactor at a velocity of greater than 1 m/s or 3 m/s.
Abstract: Disclosed herein are ethylene-based polymers generally characterized by a Mw ranging from 70,000 to 200,000 g/mol, a ratio of Mz/Mw ranging from 1.8 to 20, an IB parameter ranging from 0.92 to 1.05, and an ATREF profile characterized by one large peak. These polymers have the dart impact, tear strength, and optical properties of a metallocene-catalyzed LLDPE, but with improved processability, melt strength, and bubble stability, and can be used in blown film and other end-use applications.
Type:
Grant
Filed:
August 20, 2019
Date of Patent:
July 13, 2021
Assignee:
Chevron Phillips Chemical Company LP
Inventors:
Mark L. Hlavinka, Chung Ching Tso, Yongwoo Inn, Deloris R. Gagan, Randy S. Muninger
Abstract: The present disclosure provides benzimidazolium borate activators comprising benzimidazolium cations having linear alkyl groups, catalyst systems comprising, and processes for polymerizing olefins using such activators. Specifically, the present disclosure provides polymerization activator compounds which may be prepared in, and which are soluble in aliphatic hydrocarbon and alicyclic hydrocarbon solvents.
Type:
Grant
Filed:
April 25, 2019
Date of Patent:
July 13, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Catherine A. Faler, Margaret T. Whalley, John R. Hagadorn
Abstract: This invention relates to production of propylene-predominant copolymers using a transition metal complex and at least two different non-coordinating anion activators. An olefinic feed comprising a C3-C40 alpha olefin, ethylene, and a diene monomer is contacted under polymerization reaction conditions with a catalyst system comprising a first non-coordinating anion activator, a second non-coordinating borate activator differing from the first non-coordinating anion activator, and a transition metal complex comprising a tetrahydro-s-indacenyl or tetrahydro-as-indacenyl group bound to a group 3-6 transition metal. A molar ratio of the first non-coordinating anion activator to the second non-coordinating anion activator is sufficient to produce a melt flow rate under the polymerization reaction conditions for the resulting copolymer of about 30 g/10 min or below as determined by ASTM D-1238 (230° C., 2.16 kg).
Type:
Grant
Filed:
March 18, 2019
Date of Patent:
July 6, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Rhutesh K. Shah, Jo Ann M. Canich, Edward J. Blok
Abstract: The present disclosure provides methods for producing an olefin polymer including: i) contacting alpha-olefin with a first catalyst system comprising a first non-metallocene catalyst, a first activator, and a reversible chain transfer agent to form a first polymer; ii) contacting the first polymer with a coupling agent in the presence of a catalyst, an activator; and iii) obtaining a second polymer. The present disclosure further provides polymers having a g?vis value from about 0.4 to about 0.8 and a vinyl unsaturation content of 0.8 or greater vinyls/1000 carbons, and preferably low gel content.
Type:
Grant
Filed:
March 1, 2019
Date of Patent:
June 22, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
John R. Hagadorn, Jo Ann M. Canich, Jingwen Zhang, Peijun Jiang, Britni J. Brobey
Abstract: The present disclosure provides borate or aluminate activators comprising cations having branched alkyl groups, catalyst systems comprising, and methods for polymerizing olefins using such activators.
Type:
Grant
Filed:
April 25, 2019
Date of Patent:
June 22, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Catherine A. Faler, Margaret T. Whalley, John R. Hagadorn
Abstract: A system and method of producing polyethylene, including: polymerizing ethylene in presence of a catalyst system in a reactor to form polyethylene, wherein the catalyst system includes a first catalyst and a second catalyst; and adjusting reactor conditions and an amount of the second catalyst fed to the reactor to control melt index (MI), density, and melt flow ratio (MFR) of the polyethylene.
Type:
Grant
Filed:
February 18, 2019
Date of Patent:
June 15, 2021
Assignee:
Univation Technologies, LLC
Inventors:
Timothy M. Boller, Ching-Tai Lue, Francis C. Rix, Daniel P. Zilker, Jr., C. Jeff Harlan, James M. Farley, Fathi David Hussein, Dongming Li, Steven A. Best
Abstract: In at least one embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin to a first catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The first alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes at least 60 wt % of PAO dimer and 40 wt % or less of higher oligomers, where the higher oligomers are oligomers that have a degree of polymerization of 3 or more. The process includes introducing the first reactor effluent and a second alpha-olefin to a second catalyst composition including an acid catalyst in a second reactor to form a second reactor effluent comprising PAO trimer.
Type:
Grant
Filed:
August 9, 2019
Date of Patent:
June 8, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Patrick C. Chen, Mark H. Li, Jennifer L. Rapp, Pramod J. Nandapurkar, Brian H. Wahn, Babak LotfizadehDehkordi, Craig J. Emett, Najeeb M. Kuzhiyil, Jian Yang
Abstract: The present disclosure provides methods for preparing a catalyst system comprising contacting in an aliphatic solvent at least one support material, at least one hydrocarbyl aluminum compound and at least one non-hydrolytic active oxygen-containing compound to form a supported alumoxane (catalyst system precursor) and contacting the supported alumoxane with at least one catalyst compound having a Group 3 through Group 12 metal atom or lanthanide metal atom. The supported alumoxane may be heated prior to contact with the catalyst compound.
Type:
Grant
Filed:
September 17, 2018
Date of Patent:
June 1, 2021
Assignee:
ExxonMobil Chemical Patents Inc.
Inventors:
Charles J. Harlan, Steven C. Haas, Lubin Luo, Francis C. Rix, Xuan Ye
Abstract: In one aspect, a chelating phosphine-phosphonic diamide (PPDA) ligand is described herein for constructing transition metal complexes operable for catalysis of olefin polymerization, including copolymerization of ethylene with polar monomer.