WO2015073610A1 - Complexes de métaux de transition pyridyldiamido, production et utilisation associees - Google Patents

Complexes de métaux de transition pyridyldiamido, production et utilisation associees Download PDF

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Publication number
WO2015073610A1
WO2015073610A1 PCT/US2014/065352 US2014065352W WO2015073610A1 WO 2015073610 A1 WO2015073610 A1 WO 2015073610A1 US 2014065352 W US2014065352 W US 2014065352W WO 2015073610 A1 WO2015073610 A1 WO 2015073610A1
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WIPO (PCT)
Prior art keywords
group
borate
complex
tetrakis
substituted
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PCT/US2014/065352
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English (en)
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WO2015073610A9 (fr
Inventor
John R. Hagadorn
Ilya S. BORISOV
Arkady K. GOLENISHCHEV
Georgy P. GORYUNOV
Dmitry V. Uborsky
Alexander Z. Voskoboynikov
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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.)
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Publication date
Priority claimed from US14/511,752 external-priority patent/US9290519B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to CN201480061598.3A priority Critical patent/CN105722842A/zh
Priority to CN202010731985.0A priority patent/CN111875630B/zh
Priority to EP14861664.2A priority patent/EP3068810B1/fr
Publication of WO2015073610A1 publication Critical patent/WO2015073610A1/fr
Publication of WO2015073610A9 publication Critical patent/WO2015073610A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B

Definitions

  • WO 2005/095469 shows catalyst compounds that use tridentate ligands through two nitrogen atoms (one amido and one pyridyl) and one oxygen atom.
  • US 2004/0220050A1 and WO 2007/067965 disclose complexes in which the ligand is coordinated in a tridentate fashion through two nitrogen (one amido and one pyridyl) and one carbon (aryl anion) donors.
  • a key step in the activation of these complexes is the insertion of an alkene into the metal-aryl bond of the catalyst precursor (Froese, R. D. J. et al, J. Am. Chem. Soc. 2007, 129, pp. 7831-7840) to form an active catalyst that has both five-membered and a seven- membered chelate rings.
  • US 2010/0227990 Al discloses ligands that bind to the metal center with a NNC donor set instead of an NNN or P donor set.
  • WO/0238628 A2 discloses ligands that bind to the metal center with a C donor set instead of an NNN or NNP donor set.
  • Guerin, F.; McConville, D. FL; Vittal, J. J. Organometallics 1996, 15, p. 5586 discloses a ligand family and group 4 complexes that use a NNN-donor set, but do not feature 7-membered chelate ring or either of dihydroindenyl- and tetrahydronaphthalenyl- groups.
  • references of interest also include: 1) Vaughan, A; Davis, D. S.; Hagadorn, J. R. in Comprehensive Polymer Science, Vol. 3, Chapter 20, "Industrial catalysts for alkene polymerization”; 2) Gibson, V. C; Spitzmesser, S. K. Chem. Rev. 2003, 103, 283; and 3) Britovsek, G. J. P.; Gibson, V. C; Wass, D. F. Angew. Chem. Int. Ed. 1999, 38, 428.
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 metal
  • R 2 is -E(R12)(R13)_ w j m g being carbon, silicon, or germanium;
  • R 10 & R 1 1 and/or R 12 & R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
  • L is an anionic leaving group, where the L groups may be the same or different and any two
  • n 0, 1, 2, 3, or 4;
  • This invention further relates to a process to make the above complex, a process to make intermediates for the above complex and methods to polymerize olefins using the above complex.
  • neutral stoichiometric activator and Lewis acid activator can be used interchangeably.
  • non-coordinating anion includes neutral stoichiometric activators, ionic stoichiometric activators, ionic activators, and Lewis acid activators.
  • aryl or "aryl group” means a six carbon aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4- bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or thee ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S.
  • R1 is selected from the group consisting of hydrocarbyls, and substituted hydrocarbyls, or silyl groups;
  • Gl is carbon, nitrogen, oxygen, silicon, or sulfur, preferably carbon.
  • G2 is nitrogen, phosphorous, oxygen, sulfur, or selenium, preferably nitrogen, oxygen, or sulfur.
  • R17 is selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, silyl, and germyl groups (preferably alkyl, aryl, heteroaryl, and silyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cycloalkyl, cyclooctyl, cyclododecyl, phenyl, substituted phenyl, 2-substituted phenyl, ortho-tolyl, 2,6- disubstitutedphenyl, and isomers thereof, including cyclohexyl).
  • germyl groups preferably alkyl, aryl, heteroaryl, and silyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hex
  • each R12, R13, R6 and R7 is independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino (preferably hydrogen, alkyl, aryl, alkoxy, silyl, amino, aryloxy, heteroaryl, halogen, and phosphino), R12 and R13 and/or R6 and R7 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R12 and R13 and/or R6 and R7 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.
  • At least one of R12 and R13 is a CI to CI 00 (preferably C6 to C40, preferably C7 to C30, preferably C8 to C20) substituted or unsubstituted hydrocarbyl group (preferably aryl, phenyl, substituted phenyl, alkyl or aryl substituted phenyl, C2 to C30 alkyl or aryl substituted phenyl, 2-substituted phenyl, 2- isopropylphenyl, 2,4,6-trimethylphenyl, and the like).
  • CI to CI 00 preferably C6 to C40, preferably C7 to C30, preferably C8 to C20
  • substituted or unsubstituted hydrocarbyl group preferably aryl, phenyl, substituted phenyl, alkyl or aryl substituted phenyl, C2 to C30 alkyl or aryl substituted phenyl, 2-substituted phenyl, 2-
  • R3, R4, and R5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, (preferably hydrogen, alkyl, alkoxy, aryloxy, halogen, amino, silyl, and aryl), and wherein adjacent R groups (R3 & R4 and/or R4 & R5) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings, preferably R3, R4, and R5 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecy
  • R8, R9, R10, and Rl l are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R8 & R9, and/or R9 & R10, and/or R10 & Rl 1) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings, preferably R8, R9, RIO, and Rl 1 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pheny
  • the R groups above and other R groups mentioned hereafter contain up to 30 carbon atoms, preferably no more than 30 carbon atoms, especially from 2 to 20 carbon atoms.
  • Rl and R17 may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF3, N02, alkoxy, dialkylamino, aryl, and alkyl groups with between one to ten carbons.
  • each L may be independently selected from halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl.
  • the selection of the leaving groups depends on the synthesis route adopted for arriving at the complex and may be changed by additional reactions to suit the later activation method in polymerization.
  • alkyl is preferred when using non-coordinating anions such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate or tris(pentafluorophenyl)borane.
  • two L groups may be linked to form a dianionic leaving group, for example, oxalate.
  • M is preferably a Group 4 metal, preferably Zr or Hf.
  • Rl, R3, R4, R5, and R17 may each contain no more than 30 carbon atoms.
  • E is carbon and Rl and R17 are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, CI, Br, I, CF3, N02, alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyls groups with from one to ten carbons.
  • the pyridyldiamido transition metal complex is represented by the Formula (A) above, and M is a Group 4 metal preferably Zr or Hf, preferably Hf.
  • the pyridyldiamido transition metal complex is represented by the Formula (C) above, and Q3 is C(H)C(H)C(H), Rl is 2,6- diisopropylphenyl, and R17 is phenyl.
  • Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen and
  • the Mw/Mn, i.e., the molecular weight distribution ("MWD"), of the polymer produced when using CTA in batch polymerization process is lower than the MWD relative to the polymer produced under the same conditions when chain transfer agent is not present, preferably the MWD is at least 30% less, preferably at least 50% less, preferably at least 100% less.
  • MWD molecular weight distribution
  • the catalyst support materials select to include silica, alumina, silica-alumina, and their mixtures.
  • Other inorganic oxides may serve either alone or in combination with the silica, alumina, or silica- alumina. These are magnesia, titania, zirconia, and the like.
  • Lewis acidic materials such as montmorillonite and similar clays may also serve as a support. In this case, the support can optionally double as the activator component; however, an additional activator may also be used.
  • Useful supports typically have a surface area of from 10-700 m2/g, a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 ⁇ . Some embodiments select a surface area of 50-500 m2/g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 20- 200 ⁇ . Other embodiments select a surface area of 100-400 m2/g, a pore volume of 0.8-3.0 cc/g, and an average particle size of 30-100 ⁇ . Useful supports typically have a pore size of 10-1000 Angstroms, alternatively 50-500 Angstroms, or 75-350 Angstroms.
  • Non-limiting examples of useful dienes include, cyclopentadiene, norbornadiene, dicyclopentadiene, 5- ethylidene-2-norbornene, 5-vinyl-2-norbornene, 1 ,4-hexadiene, 1,5-hexadiene, 1,5- heptadiene, 1,6-heptadiene, 6-methyl-l,6-heptadiene, 1,7-octadiene, 7-methyl-l,7-octadiene, 1,9-decadiene, and 9-methyl-l,9-decadiene.
  • alkyl is an alkyl group.
  • the system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165°C. 1,2,4-trichlorobenzene was used as the eluent.
  • the polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1 to 0.9 mg/mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an infrared absorption detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.
  • DSC Differential Scanning Calorimetry

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des complexes de métaux de transition pyridyldiamido destinés à la polymérisation d'alcène, éventuellement avec un agent de transfert de chaîne.
PCT/US2014/065352 2013-11-15 2014-11-13 Complexes de métaux de transition pyridyldiamido, production et utilisation associees WO2015073610A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480061598.3A CN105722842A (zh) 2013-11-15 2014-11-13 吡啶基二氨基过渡金属络合物，其的生产和用途
CN202010731985.0A CN111875630B (zh) 2013-11-15 2014-11-13 吡啶基二氨基过渡金属络合物，其的生产和用途
EP14861664.2A EP3068810B1 (fr) 2013-11-15 2014-11-13 Complexes de métaux de transition pyridyldiamido, production et utilisation associees

Applications Claiming Priority (6)

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US201361904551P 2013-11-15 2013-11-15
US61/904,551 2013-11-15
EP14153044 2014-01-29
EP14153044.4 2014-01-29
US14/511,752 2014-10-10
US14/511,752 US9290519B2 (en) 2013-11-15 2014-10-10 Pyridyldiamido transition metal complexes, production and use thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018022249A1 (fr) * 2016-07-29 2018-02-01 Exxonmobil Chemical Patents Inc. Complexes hétérocycliques amido de métaux de transition, leur production et leur utilisation
US10150821B2 (en) 2016-07-29 2018-12-11 Exxonmobil Chemical Patents Inc. Heterocyclic amido transition metal complexes, production and use thereof
CN109563109A (zh) * 2016-07-29 2019-04-02 埃克森美孚化学专利公司 杂环氨基过渡金属配合物、其制备和用途

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WO2002038628A2 (fr) 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
US20040220050A1 (en) * 2003-05-02 2004-11-04 Frazier Kevin A. High activity olefin polymerization catalyst and process
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WO2007130306A2 (fr) 2006-05-05 2007-11-15 Dow Global Technologies Inc. Complexes d'hafnium orthométallés de ligands imidazoles
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US20110224391A1 (en) 2008-07-25 2011-09-15 Hagadorn John R Pyridyldiamido Transition Metal Complexes, Production and Use Thereof
US20110301310A1 (en) 2008-07-25 2011-12-08 Hagadorn John R Pyridyldiamido Transition Metal Complexes, Production And Use Thereof
US8394902B2 (en) 2008-07-25 2013-03-12 Exxonmobil Chemical Patents Inc. Pyridyldiamido transition metal complexes, production and use thereof
US20140087987A1 (en) 2012-09-24 2014-03-27 Exxonmobil Chemical Patents Inc. Production of Vinyl Terminated Polyethylene

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US20140087987A1 (en) 2012-09-24 2014-03-27 Exxonmobil Chemical Patents Inc. Production of Vinyl Terminated Polyethylene

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VAUGHAN, ADAVIS, D. S.HAGADORN, J. R.: "Comprehensive Polymer Science", vol. 3, article "Industrial catalysts for alkene polymerization"

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018022249A1 (fr) * 2016-07-29 2018-02-01 Exxonmobil Chemical Patents Inc. Complexes hétérocycliques amido de métaux de transition, leur production et leur utilisation
US10150821B2 (en) 2016-07-29 2018-12-11 Exxonmobil Chemical Patents Inc. Heterocyclic amido transition metal complexes, production and use thereof
CN109563109A (zh) * 2016-07-29 2019-04-02 埃克森美孚化学专利公司 杂环氨基过渡金属配合物、其制备和用途

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