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WO2008112133A2 - Précurseurs de catalyseurs à base de pyridylamidohafnium, espèces actives de ces précurseurs et leurs utilisations pour polymériser des alcènes - Google Patents

Précurseurs de catalyseurs à base de pyridylamidohafnium, espèces actives de ces précurseurs et leurs utilisations pour polymériser des alcènes Download PDF

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Publication number
WO2008112133A2
WO2008112133A2 PCT/US2008/003010 US2008003010W WO2008112133A2 WO 2008112133 A2 WO2008112133 A2 WO 2008112133A2 US 2008003010 W US2008003010 W US 2008003010W WO 2008112133 A2 WO2008112133 A2 WO 2008112133A2
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methyl
copolymer
active species
pentene
propylene
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Ceased
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WO2008112133A3 (fr
Inventor
Geoffrey W. Coates
Gregory J. Domski
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Cornell University
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Cornell University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/7042—Compounds having saccharide radicals and heterocyclic rings
    • A61K31/7052—Compounds having saccharide radicals and heterocyclic rings having nitrogen as a ring hetero atom, e.g. nucleosides, nucleotides
    • A61K31/706—Compounds having saccharide radicals and heterocyclic rings having nitrogen as a ring hetero atom, e.g. nucleosides, nucleotides containing six-membered rings with nitrogen as a ring hetero atom
    • A61K31/7064—Compounds having saccharide radicals and heterocyclic rings having nitrogen as a ring hetero atom, e.g. nucleosides, nucleotides containing six-membered rings with nitrogen as a ring hetero atom containing condensed or non-condensed pyrimidines
    • A61K31/7068—Compounds having saccharide radicals and heterocyclic rings having nitrogen as a ring hetero atom, e.g. nucleosides, nucleotides containing six-membered rings with nitrogen as a ring hetero atom containing condensed or non-condensed pyrimidines having oxo groups directly attached to the pyrimidine ring, e.g. cytidine, cytidylic acid
    • A61K31/7072—Compounds having saccharide radicals and heterocyclic rings having nitrogen as a ring hetero atom, e.g. nucleosides, nucleotides containing six-membered rings with nitrogen as a ring hetero atom containing condensed or non-condensed pyrimidines having oxo groups directly attached to the pyrimidine ring, e.g. cytidine, cytidylic acid having two oxo groups directly attached to the pyrimidine ring, e.g. uridine, uridylic acid, thymidine, zidovudine

Definitions

  • Ci-symmetric dialkyl pyridylamidohafnium compounds which are used for the high temperature isoselective polymerization of propylene and for polymerization of various vinyl monomers.
  • the active species have limited usefulness for living polymerization of alkenes.
  • the inventors here have found that the Ci- symmetric catalysts give broad molecular weight distribution (PDI > 1.5 for polymers of propylene and 1-hexene).
  • One embodiment of the invention herein, denoted the first embodiment, is directed at pyridylamidohafnium catalyst precursors having the structure
  • R 1 and R 2 are both hydrogen, or selected from the group consisting of Ci-C 5 alkyl, silyl, and combinations thereof, and optionally, R 1 and R 2 may be joined together in a ring structure narrowed to avoid prior art, where each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 is independently selected from the group consisting of hydrogen, Cj-C 5 alkyl, silyl, and combinations thereof, and optionally, any combination of R 3 , R 4 , R 5 , R 6 , or R 7 , any combination of R 8 , R 9 , or R 10 , and any combination of R 11 , R 12 , R 13 , or R 14 may be joined together in a ring structure, where each of R 15 and R 16 is independently selected from the group consisting of halide, C]-C 5 linear or branched alkyl or benzyl, Ci-C
  • Another embodiment herein, denoted the second embodiment, is directed to active species generated from reaction of the compound of formula (I) and an activator.
  • Still another embodiment herein denoted the third embodiment is directed at diblock copolymer, triblock, or multiblock copolymer prepared using the active species of the second embodiment comprising in polymerized form propylene and one or more copolymerizable comonomers other than propylene, said copolymer containing therein two or more segments or blocks differing in comonomer content, crystallinity density, melting point or glass transition temperature.
  • Yet another embodiment herein denoted the fourth embodiment is directed to a method of living polymerization of a C 2 -C 2O alkene in a non-polar non-protic solvent carried out in the presence of the active species of the second embodiment, thereby providing a polydispersity index of no more than 1.30, e.g. less than 1.25, e.g. less than 1.20, e.g. less than 1.10.
  • Yet another embodiment herein denoted the fifth embodiment is directed at a diblock copolymer, triblock copolymer, or multiblock copolymer prepared using the active species of the second embodiment comprising in polymerized form 4-methyl-l- pentene and one or more copolymerizable comonomers other than 4-methyl-l- pentene, said copolymer containing therein two or more segments or blocks differing in comonomer content, crystallinity, density, melting point or glass transition temperature.
  • living polymerization means addition polymerization where the ability of a growing polymer chain to terminate has been removed and a polydispersity index of 1.30 or less is obtained.
  • M n and M w are determined using gel permeation chromatography in 1,2,4-C 6 H 3 Cl 3 at 140°C vs polystyrene or polyethylene standards.
  • the pyridylamidohafnium precursor of structure (I) preferably has Cs symmetry or pseudo-Cs symmetry (very close to Cs symmetry).
  • Cs and pseudo-Cs symmetry mean that the entire compound is symmetric with respect to a bisecting mirror plane passing through bridging group and the atoms bonded to the bridging group, i.e. the substituents on each coordinating group of a bridged ligand, which are reflectively coupled, are identical or similar.
  • Cs or pseudo-Cs symmetry also means that the coordinating groups are bilaterally or pseudobilaterally symmetric.
  • the pyridylamidohamium catalyst precursors as described above have an angle ⁇ CNC depicted below in structure (I) larger than 114 degrees
  • the angle CNC changes based on the steric demands of R 1 and R 2 . As this angle increases the stereoselectivity of the activated catalyst precursor increases.
  • the angle is determined by X-ray crystallography or is determined based on optimized structure by a Density Functional Theory (DFT) calculation using Gaussian 03 (latest in the Gaussian Series of electronic programs used by chemists) and Becke 3-Parameter (Exchange), Lee, Yang and Parr (correlation, density functional theory) (B3LYP) where Los Alamos National Laboratory 2-double-z (density functional theory) (LANL2DZ) is used as a basis set for Hf and 3-2 IG for H, C and N.
  • DFT Density Functional Theory
  • R 17 and R 21 are selected from H and methyl
  • R 18 and R 22 are selected from isopropyl and tert-butyl
  • R 19 and R 23 are selected from H, isopropyl and tert-butyl
  • R 20 and R 24 are selected from C 1 -C 4 linear or branched alkyl and benzyl.
  • Species having the structure (II) include those where:
  • R 17 is H
  • R 18 and R 19 are tert-butyl and R 20 is methyl (denoted precursor (3) hereinafter), and
  • R 17 is methyl
  • R 18 is isopropyl
  • R 19 is H
  • R 20 is methyl
  • Species having the structure (III) include those where:
  • R 21 is H
  • R 22 is isopropyl
  • R 23 is H
  • R 24 is methyl
  • R 21 is methyl
  • R 22 is isopropyl
  • R 23 is H
  • R 24 is methyl
  • the precursors can be made as follows: Pyridylimine ligand precursors of the catalyst precursors are prepared via a Schiff Base condensation between 6-phenyl-2- pyridine carboxaldehyde (for II) or 6-naphthyl-2-pyridinecarboxaldehyde (for III) and the appropriate aniline, e.g. 2,6-diisopropylaniline, 2,4,6-tri-tert-butylaniline, etc.
  • the imines are then reduced with either LiAlH 4 or more preferably with NaBH 3 CN with catalytic formic acid to give the corresponding pyridylamine ligand.
  • the resulting amines can be reacted with BuLi to obtain pyridylamido lithium salt which is reacted with HfCl 4 to form trichloropyridylamidohafhium intermediate which is reacted with MeMgBr to provide catalyst precursor.
  • 6-bromo-2-pyridine carboxaldehyde (Aldrich) can be reacted with Pd(PPh 3 ) 4 and phenylboronic acid with the addition OfNa 2 CO 3 by refluxing, e.g. for two hours.
  • 6-bromo-2-pyridine carboxaldehyde is reacted with 1 -naphthalene boronic acid, Pd(PPh 3 ) 4 and Na 2 CO 3 .
  • reaction is carried out the same as for precursor imine corresponding to catalyst precursor (1) but 6-naphthyl-2- pyridine carboxaldehyde is used instead of 6-phenyl-2-pyridine carboxaldehyde.
  • the imine precursors were converted to catalyst precursors as shown in working examples.
  • activator for the active species is B(C 6 Fs) 3 .
  • Methylaluminoxane as activator at low loadings also gives polypropylene with narrow polydispersity indices.
  • the two can be brought together in the presence of alkene to be polymerized.
  • the [HfJ: [B] mole ratio ranges for example from 0.5:1 to 1.5:1 and is preferably 1 :1.
  • the copolymerizable monomers other than propylene are C 2 -C 20 alkenes different from propylene, e.g. ethylene.
  • One case of the third embodiment is a triblock copolymer where end blocks are isotactic polypropylene ([m 4 ]>50%) having M w /M n of 1.30 or less, e.g. less than 1.25, e.g. less than 1.20, e.g.
  • the triblock copolymer is prepared by method comprising the steps of in a reactor initiating propylene polymerization at a temperature ranging from e.g. from 0 to 50°C, e.g. from 0 to 20°C, e.g.
  • the non-polar, non-protic solvent can be, for example, toluene, benzene, xylene, hexane, heptane or methylene chloride.
  • the propylene pressure in the reactor ranges, for example, from 5 psig to 50 psig.
  • the third embodiment is directed to a multiblock copolymer where the number of segments is not less than three and the end blocks are isotactic polypropylene and the end blocks are obtained by polymerizing propylene as in the paragraph directly above, and the segments between are obtained by introducing overpressure of monomer for a segment between and cycling between that monomer and other monomer or propylene with venting between segments and introducing propylene for the end block.
  • the M n for the multiblock copolymer ranges from 100 to 1,000 kg/mol determined via GPC in 1,2,4-C 6 H 3 Cl 3 at 140°C vs PE standards and the end blocks are isotactic polypropylene with polydispersity index of 1.30 or less, e.g. less than 1.25, e.g. less than 1.20, e.g. less than 1.10, with block lengths ranging from 20 to 200 kg/mol.
  • the alkene can be for example a C 3 -C 20 ⁇ -olefin, e.g. propylene or 1-hexene.
  • the temperature of reaction ranges from 0 to 50 0 C, e.g. 15 to 40°C, e.g. 20 to 30 0 C.
  • 1-hexene the mole ratio of 1-hexene to Hf is greater than 1,000 and the temperature of reaction is preferably 20 to 30 0 C.
  • propylene the mole ratio of propylene to Hf is considered to be greater than 1,000 and the temperature of reaction is preferably 10 to 35°C, e.g. 10 to 20 0 C or 25 to 35°C.
  • the pressure in the reactor ranges from 5 psig to liquid propylene.
  • the reaction solvent is a non-polar, non-protic solvent e.g. toluene, benzene, xylene, hexane, heptane or methylene chloride or the monomer itself can be said solvent, e.g. in propylene bulk polymerization.
  • the polymerization is preferably carried out using active species where the catalyst precursor is selected to obtain an isotacticity, [m 4 ] of at least 50%, e.g. more than 90%.
  • the copolymerizable monomers other than 4-methyl-l-pentene are C 2 -C 20 alkenes, e.g. ethylene or propylene.
  • One case of the fifth embodiment is a triblock or multiblock copolymer where the end blocks are isotactic poly(4-methyl-l-pentene) and poly(ethylene-co-4- methyll-pentene) is included as a midblock and the block lengths for the end blocks range from 20 to 300 kg/mol and the block lengths for midblocks range from 100 to 500 kg/mol and the M n for triblock copolymer ranges from 5,000 g/mol to 500,000 g/mol as determined via GPC in 1, 2, 4-C 6 H 3 Cl 3 at 140°C vs. PS standards and M w /M n for the triblock is 1.30 or less, e.g. 1.15 or less and the T m for the triblock exceeds, for example, 190°C.
  • Another case of the invention herein is directed to a method of preparing isotactic poly(4-methyl-l-pentene) comprising polymerizing 4-methyl-l-pentene at a temperature ranging from 0 to 50°C in a non-polar non-protic solvent in the presence of the active species of the second embodiment where the [Hf]: [B] mole ratio in the active species ranges from 0.5:1 to 1:5 where the mole ratio of 4-methyl-l-pentene to Hf is greater than 1 ,000 and of preparing a block copolymer with isotactic poly(4- methyl-1-pentene) end blocks and a poly(ethylene-co-4-methyl-l-pentene) midblock comprising in a reactor initiating polymerization of 4-methyl-l-pentene according to the aforedescribed method to provide a first isotactic poly(4-methyl-l-pentene) block, introducing and establishing an ethylene overpressure of 5-50 psig
  • M n for isotactic poly(4-methyl-l-pentene) can range, for example, from 5,000 g/mol to 500,000 g/mol as determined via GPC in 1,2,4-C 6 H 3 Cl 3 at 14O 0 C vs PS Standards.
  • the compound (1) was prepared following the general procedure described by Coalter, J.N., EI, et al. WO 2003/040195A1.
  • First 2,6-diisopropyl-N-((6- phenylpyridine-2-yl)methyl)aniline intermediate was prepared as detailed in Supporting Information for Domski, GJ., et al., Macromolecules 40(a), 3510 - 3513 (2007).
  • This intermediate (0.629g, 1.83 mmol) was dissolved in the minimum amount of dry toluene and cooled to 0°C. BuLi (1.20 mL of a 1.6 M solution in hexanes) was added to the ligand solution under N 2 .
  • This compound was prepared the same as catalyst precursor (1) except that an equimolar amount of 6-naphthyl-2-pyridine carboxaldehyde was substituted for the 6- phenyl-2-pyridine carboxaldehyde (made according to the procedure set forth in the Supporting Information described above).
  • catalyst precursor (3) was carried out the same as for catalyst precursor (1) except that an equimolar amount of 2,4,6-tri-tert-butylaniline was substituted for the diisopropylaniline (see reaction of 6-phenyl-2-pyridine carboxaldehyde and diisopropylaniline described in the Supporting Information above).
  • 6-acetyl-2-bromopyridine, Pd(OAc) 2 , PPh 3 , K 2 CO 3 and either phenyl boronic acid or 1 -naphthalene boronic acid were allowed to react in refluxing dimethoxyethane (DME) to furnish after work up and purification 6-acetyl- 2-phenylpyridine or 6-acetyl-2-(l-naphthyl)pyridine.
  • DME dimethoxyethane
  • the compound rac-2 has formula (II) where one R 17 is H and the other is Ph, R 18 is isopropyl, R 19 is H and R 20 is methyl.
  • the compound rac-3 has the formula (II) where R 17 is H, R 18 is 1-(4- 1 Bu- C 6 H 4 )Et, R 19 is methyl and R 20 is methyl.
  • Compound (1) has Cs symmetry.
  • Compounds rac-2 and rac-3 have Ci symmetry.
  • Compound (1) is the precursor catalyst (1) of Working Example I.
  • Compound (2) is the precursor (2) of Working Example III.
  • the compound rac-4 is the same as the compound rac-2 of Working Example V.
  • the compounds (5) and (6) are the same as precursor catalysts (5) and (6) of Working Example IV.
  • Compound 7 was made by a method analogous to that used to prepare (5) and (6) using AlEt 3 instead of AlMe 3 .
  • the compounds 1, 2, 3, 5, 6, 7 have Cs symmetry.
  • Catalyst was injected with 5 mL of toluene into a 10 mL toluene solution of activator (1 equiv.) with constant 30 psig propylene feed at 20 °C.
  • ⁇ Catalyst and activator (1 equiv.) were combined in 10 mL of toluene and injected into 20 mL toluene with constant 30 psig propylene feed at 20 °C.
  • c Catalyst was injected with 5 mL of toluene into a 25 mL toluene solution of activator (1 equiv.) with constant 30 psig propylene feed at 20 °C.
  • ⁇ Determined via GPC in 1,2,4-C 6 H 3 Cl 3 at 140 °C vs PE standards determined via integration of the methyl region of the 13 C NMR spectrum, determined via DSC (second heating).
  • the melting points of entries 1 and 2 in Table 5B indicate modest levels of isotacticity and the melting points for entries 3 and 4 in Table 5B indicate high levels of isotacticity.
  • Triblock Copolymer with Iso tactic Poly(4-Methyl-1-Pentene) End Blocks and a Polv(Ethylene-co-4-Methyl-l-Pentene Mid-Block Using 2/B(CJOi Catalyst

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Abstract

L'invention concerne des précurseurs de catalyseurs à base de pyridylamidohafnium Cs-symétriques et des espèces actives à base de ces précurseurs. Les espèces actives sont utiles pour la polymérisation vivante d'alcènes en C<SUB>2</SUB> à C<SUB>20</SUB> et permettent d'obtenir du polypropylène hautement isotactique. Elles sont également utiles pour obtenir un copolymère à séquences multiples avec des séquences terminales de polypropylène isotactique ou de poly(4-méthyl-1-pentène) isotactique.
PCT/US2008/003010 2007-03-13 2008-03-07 Précurseurs de catalyseurs à base de pyridylamidohafnium, espèces actives de ces précurseurs et leurs utilisations pour polymériser des alcènes Ceased WO2008112133A2 (fr)

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WO2010091047A1 (fr) 2009-02-06 2010-08-12 Dow Global Technologies Inc. Procédé de fabrication d'alkyl-aluminium
WO2013061974A1 (fr) 2011-10-24 2013-05-02 三菱化学株式会社 Composition élastomère thermoplastique et son procédé de production
US9321858B2 (en) 2013-04-23 2016-04-26 Exxonmobil Chemical Patents Inc. Pyridyldiamide metal catalysts and processes to produce polyolefins
US20190300631A1 (en) * 2016-05-27 2019-10-03 Cornell University Polyethylene and polypropylene block copolymers
WO2021210953A1 (fr) * 2020-04-16 2021-10-21 주식회사 엘지화학 Copolymère multibloc à base de polyoléfine-polystyrène et son procédé de préparation
WO2021210948A1 (fr) * 2020-04-16 2021-10-21 주식회사 엘지화학 Composé de ligand, composé de métal de transition et composition de catalyseur les comprenant
CN113527352A (zh) * 2020-04-17 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法与应用
CN113527351A (zh) * 2020-04-16 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法和应用
WO2023055205A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지화학 Copolymère multibloc et son procédé de préparation
WO2023055208A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지화학 Copolymère à blocs multiples, composition de résine et son procédé de fabrication
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WO2024051442A1 (fr) * 2022-09-08 2024-03-14 中国石油天然气股份有限公司 Catalyseur principal pour la préparation de poly(4-méthyl-1-pentène) et utilisation du catalyseur principal
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GB2629722A (en) * 2022-08-22 2024-11-06 Petrochina Co Ltd Main catalyst for preparing poly(4-methyl-1-pentene) and use of main catalyst
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US6750345B2 (en) * 2000-11-07 2004-06-15 Symyx Technologies, Inc. Substituted pyridyl amine catalysts, complexes and compositions
US6953764B2 (en) * 2003-05-02 2005-10-11 Dow Global Technologies Inc. High activity olefin polymerization catalyst and process
US20050261434A1 (en) * 2004-05-24 2005-11-24 Piraye Yaras Thermoplastic elastomeric blends having enhanced surface appearance

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US8247553B2 (en) 2009-02-06 2012-08-21 Dow Global Technologies Llc Process of making aluminum alkyls
WO2010091047A1 (fr) 2009-02-06 2010-08-12 Dow Global Technologies Inc. Procédé de fabrication d'alkyl-aluminium
WO2013061974A1 (fr) 2011-10-24 2013-05-02 三菱化学株式会社 Composition élastomère thermoplastique et son procédé de production
US9321858B2 (en) 2013-04-23 2016-04-26 Exxonmobil Chemical Patents Inc. Pyridyldiamide metal catalysts and processes to produce polyolefins
US11279780B2 (en) 2016-05-27 2022-03-22 Cornell University Polyethylene and polypropylene block copolymers
US20190300631A1 (en) * 2016-05-27 2019-10-03 Cornell University Polyethylene and polypropylene block copolymers
US12247092B2 (en) 2016-05-27 2025-03-11 Cornell University Polyethylene and polypropylene block copolymers
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WO2021210953A1 (fr) * 2020-04-16 2021-10-21 주식회사 엘지화학 Copolymère multibloc à base de polyoléfine-polystyrène et son procédé de préparation
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WO2021210948A1 (fr) * 2020-04-16 2021-10-21 주식회사 엘지화학 Composé de ligand, composé de métal de transition et composition de catalyseur les comprenant
CN114728991A (zh) * 2020-04-16 2022-07-08 株式会社Lg化学 配体化合物、过渡金属化合物和包含其的催化剂组合物
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JP2023511913A (ja) * 2020-04-16 2023-03-23 エルジー・ケム・リミテッド ポリオレフィン－ポリスチレン系多重ブロック共重合体及びこの製造方法
US20230093294A1 (en) * 2020-04-16 2023-03-23 Lg Chem, Ltd. Ligand Compound, Transition Metal Compound, and Catalyst Composition Including the Same
JP2023513454A (ja) * 2020-04-16 2023-03-31 エルジー・ケム・リミテッド リガンド化合物、遷移金属化合物およびこれを含む触媒組成物
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CN113527351A (zh) * 2020-04-16 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法和应用
CN114728991B (zh) * 2020-04-16 2024-12-20 株式会社Lg化学 配体化合物、过渡金属化合物和包含其的催化剂组合物
KR102731571B1 (ko) 2020-04-16 2024-11-21 주식회사 엘지화학 폴리올레핀-폴리스티렌계 다중블록 공중합체 및 이의 제조방법
CN113527352A (zh) * 2020-04-17 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法与应用
WO2023055208A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지화학 Copolymère à blocs multiples, composition de résine et son procédé de fabrication
WO2023055204A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지화학 Copolymère à blocs multiples et son procédé de préparation
WO2023055205A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지화학 Copolymère multibloc et son procédé de préparation
KR102887608B1 (ko) * 2021-10-01 2025-11-19 주식회사 엘지화학 열가소성 수지조성물
CN116655676A (zh) * 2022-02-18 2023-08-29 中国石油天然气股份有限公司 一种非茂金属催化剂、聚丁烯-1弹性体及其制备方法
GB2629722A (en) * 2022-08-22 2024-11-06 Petrochina Co Ltd Main catalyst for preparing poly(4-methyl-1-pentene) and use of main catalyst
WO2024051442A1 (fr) * 2022-09-08 2024-03-14 中国石油天然气股份有限公司 Catalyseur principal pour la préparation de poly(4-méthyl-1-pentène) et utilisation du catalyseur principal
CN118184915A (zh) * 2024-04-17 2024-06-14 天津大学 一种丙烯与α-烯烃多嵌段共聚物弹性体材料及其制备方法和应用

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