WO2020018254A1 - Catalyseurs pour la polymérisation d'oléfines - Google Patents

Catalyseurs pour la polymérisation d'oléfines Download PDF

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Publication number
WO2020018254A1
WO2020018254A1 PCT/US2019/039798 US2019039798W WO2020018254A1 WO 2020018254 A1 WO2020018254 A1 WO 2020018254A1 US 2019039798 W US2019039798 W US 2019039798W WO 2020018254 A1 WO2020018254 A1 WO 2020018254A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
catalyst compound
hydrocarbyl
ethylene
hydrogen
Prior art date
Application number
PCT/US2019/039798
Other languages
English (en)
Inventor
Catherine A. Faler
Margaret T. WHALLEY
Crisita Carmen H. ATIENZA
David A. Cano
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2020018254A1 publication Critical patent/WO2020018254A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • References of interest include: Domow, A., Petsch, G., Archiv der Pharmazie und Berichte der Deutschen Pharmazeuticiantechnik (1951), 284, 153; Arndts, D., Loesel, W., Roos, O., Ger. Offen. (1993), DE 4220353 Al 19931223; and Majima, K., Tosaki, S.,
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst including W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gP/gcat/hr. Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used per hour (gP/molcat/hr).
  • mole percentages when using the two pre-catalysts, where both are activated with the same activator, can be from 10% to 99.9% A to 0.1% to 90% B, alternatively 25% to 99% A to 0.5% to 75% B, alternatively 50% to 99% A to 1% to 50% B, and alternatively 75% to 99% A to 1% to 10% B.
  • cocatalyst and“activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • + may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, such as carboniums and ferroceniums.
  • Z d + can be triphenyl carbonium.
  • Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Non-polar solvents can be alkanes, such as isopentane, hexane, n- heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.
  • the activator-support can be, or can include, fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof.
  • Flow rate in the apparatus is then increased to 1.0 mL/minute, and the DRI is allowed to stabilize for 2 hours before injecting the first sample.
  • the molecular weight is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards.
  • PS monodispersed polystyrene
  • DSC Differential Scanning Calorimetry
  • melting Temperature Tm
  • DSCQ200 differential scanning calorimetry
  • the sample is first equilibrated at 25°C and subsequently heated to 220°C using a heating rate of l0°C/min (first heat).
  • the sample is held at 220°C for 3 min.
  • the sample is subsequently cooled down to -l00°C with a constant cooling rate of l0°C/min (first cool).
  • the sample is equilibrated at -l00°C before being heated to 220°C at a constant heating rate of l0°C/min (second heat).
  • Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents.
  • the uniaxial orientation can be accomplished using cold drawing or hot drawing methods.
  • Biaxial orientation can be accomplished using tenter frame equipment or a double bubble process and may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • Potassium cyclopentadienide (KCp) was prepared according to the procedure described in J. Organomet. Chem. 1975, Y.84, C1-C4. MAO was obtained as a 30 wt% MAO in toluene solution from Albemarle (e.g., 13.6 wt% Al or 5.04 mmol/g).
  • Catalyst 1 was found to be an active catalyst for olefin polymerization upon activation with MAO.
  • High molecular weight polymers formed at 80°C and under 95 psig in the presence of MAO and l-octene were obtained in good yield with an Mw value of 350 Kg/mol or greater, an Mn value of 190 Kg/mol or greater, and an Mw/Mn of about 2.
  • Catalyst 1 demonstrated a high l-octene incorporation with comonomer content of at least 8.5 wt% or greater.

Abstract

La présente invention concerne des composés catalytiques ayant un ligand tridenté d'amine bis(phénolate) à liaison éthylène. Les catalyseurs de la présente invention fournissent de préférence des valeurs d'activité catalytique de 250gP/mmolCat/h ou plus et des polyoléfines, telles que des copolymères de polyéthylène, ayant une teneur en comonomère de 8,5 % en poids ou plus, un Mn de 190 000 g/mol ou plus, un Mw de 350 000 g/mol ou plus, et un Mw/Mn étroit (par exemple environ 2). Les catalyseurs, les systèmes catalytiques et les procédés de la présente invention peuvent fournir des polymères ayant une teneur élevée en comonomère (par exemple, 8,5 % en poids ou plus).
PCT/US2019/039798 2018-07-16 2019-06-28 Catalyseurs pour la polymérisation d'oléfines WO2020018254A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201862698470P 2018-07-16 2018-07-16
US62/698,470 2018-07-16
EP18190754.4 2018-08-24
EP18190754 2018-08-24

Publications (1)

Publication Number Publication Date
WO2020018254A1 true WO2020018254A1 (fr) 2020-01-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/039798 WO2020018254A1 (fr) 2018-07-16 2019-06-28 Catalyseurs pour la polymérisation d'oléfines

Country Status (1)

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WO (1) WO2020018254A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022035585A1 (fr) * 2020-08-13 2022-02-17 Exxonmobil Chemical Patents Inc. Compositions polymères contenant un cycle obtenues à l'aide de complexes de catalyseur de bis(phénolate) de métal de transition et procédé de production associé

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090412A2 (fr) * 2006-02-08 2007-08-16 Saudi Basic Industries Corporation Composition de catalyseur et procede d'oligomerisation de l'ethylene
WO2013101478A1 (fr) * 2011-12-28 2013-07-04 Chevron Phillips Chemical Company Lp Systèmes de catalyseurs pour la fabrication d'oligomères et de polymères d'alpha-oléfine
CN105418672A (zh) * 2015-11-16 2016-03-23 吉林大学 一种含双芳氧基大空阻[o,n,o]三齿配体钛、锆的配合物及其用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090412A2 (fr) * 2006-02-08 2007-08-16 Saudi Basic Industries Corporation Composition de catalyseur et procede d'oligomerisation de l'ethylene
WO2013101478A1 (fr) * 2011-12-28 2013-07-04 Chevron Phillips Chemical Company Lp Systèmes de catalyseurs pour la fabrication d'oligomères et de polymères d'alpha-oléfine
CN105418672A (zh) * 2015-11-16 2016-03-23 吉林大学 一种含双芳氧基大空阻[o,n,o]三齿配体钛、锆的配合物及其用途

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MAJIMA, K. ET AL.: "Enantio- and diastereoselective construction of vicinal quaternary and tertiary carbon centers by catalytic Michael reaction of a-substituted b-keto esters to cyclic enones", TETRAHEDRON LETTERS, vol. 46, 2005, pages 5377 - 5381, XP025384812, DOI: 10.1016/j.tetlet.2005.05.139 *
SUN, Q. ET AL.: "Regioselective addition of C(sp3)-H bonds of alkyl pyridines to olefins catalysed by cationic zirconium complexes", CHEM. COMMUN., vol. 53, 2017, pages 7401 - 7404, XP055676188 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022035585A1 (fr) * 2020-08-13 2022-02-17 Exxonmobil Chemical Patents Inc. Compositions polymères contenant un cycle obtenues à l'aide de complexes de catalyseur de bis(phénolate) de métal de transition et procédé de production associé

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