WO2014139861A1 - Complexes pour l'oligomérisation catalytique d'oléfines - Google Patents

Complexes pour l'oligomérisation catalytique d'oléfines Download PDF

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WO2014139861A1
WO2014139861A1 PCT/EP2014/054373 EP2014054373W WO2014139861A1 WO 2014139861 A1 WO2014139861 A1 WO 2014139861A1 EP 2014054373 W EP2014054373 W EP 2014054373W WO 2014139861 A1 WO2014139861 A1 WO 2014139861A1
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alkyl
optionally substituted
aryl
group
alone
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PCT/EP2014/054373
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Isabelle HAAS
Winfried Kretschmer
Rhett Kempe
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Universität Bayreuth
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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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table

Definitions

  • the invention relates to the oiigomerization of olefins, in particular the oiigomerization of ethylene, and to metal complexes which are able to provide catalyst compositions which efficiently and selectively catalyse the oiigomerization.
  • LAO ' s linear a-olefins
  • olefins having 4 to 10 carbon atoms C 4 -C 10 range
  • linear a-olefins are found as endproducts in various applications.
  • the light fractions 1 -butene, 1 -hexene and 1 -octene are used as comonomers in the rapidly growing polymer market, in particular for the production of LLDPE (Linear Low Density Polyethylene).
  • LLDPE Linear Low Density Polyethylene
  • the middle fractions, such as 1 -decene. 1 -dodecene and 1 -tetradecene are raw materials for synthetic oils, detergents and shampoos.
  • Heavy fractions can be used as additives for lubricating oils, tensides, oil field chemicals, and as waxes.
  • A!pha-olefins can be prepared via Fischer-Tropsch-Synthesis.
  • either the Coal-to-Liquid- process (CtL-process) or the Gas-to-Liquid-process (GtL-process) can be used.
  • CtL-process the Coal-to-Liquid- process
  • GtL-process Gas-to-Liquid-process
  • the coal is first reacted at very high temperatures (above 1000°C) with water vapour and air or oxygen to form synthesis gas which, subsequent to the separation of nitrogen oxides and sulphur dioxide, is reacted via heterogeneous catalysis to form hydrocarbons including ⁇ -o!efins and water.
  • GtL-process the GtL-process.
  • EP 1 362 837 A1 Further approaches for complex catalyzed oligomerization reactions to form a-olefins are disclosed in EP 1 362 837 A1 .
  • EP 2 070 593 A1 US 2010/0286349 A1 or WO 2012/080588 A1 .
  • the present invention provides complexes of the following formula (I), as well as catalyst systems using these complexes:
  • M is a metal selected from Zr and Hi;
  • X 1 and X 2 are independently selected from CI, Br, I, F, H, alkyl, -alkyl-O-alkyl, -aikyl-Q- aryl, alkoxy. aryloxy, aralkyl, -alkyl-SiR 3 R b R c and R 1 R 2 , wherein any alkyl group is optionally substituted by one or more substituents selected from OH, F, CI, Br.
  • any aryl group is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, OH, F, CI, Br, NH 2 , NH(C1 -8 alkyl) and N(C1 -8 alkyl) 2 ;
  • L is selected from CZ 3 , N, and PR 3 R 4 ;
  • Z 1 and Z 2 are independently selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, aryl, heteroaryl, aralkyl, -alkyl-O-alkyl, -alkyl-O-aryl, wherein any alkyl group, alone or as part of another group, and any alkenyl group is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and any aryl group, alone or as part of another group, and any heteroaryl group is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl. C1-8 alkoxy, F, CI, Br. and N(C1 -8 alkyl) 2 ;
  • Z 3 is selected from H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkoxy, aryl, aryloxy, heteroaryl. aralkyl, -alkyl-O-alkyl, -alkyl-O-aryl, F, CI. Br, NR R 2 , and PR 3 R 4 , wherein any alkyl group, alone or as part of another group, and any alkenyl group is optionally substituted by one or more substituents selected from F, CI.
  • Z 1 and Z 3 or Z 2 and Z 3 as defined above may be linked to form an optionally substituted five- to seven-membered heterocyclic ring incorporating the nitrogen atom to which Z 1 is attached or the nitrogen atom to which Z 2 is attached;
  • J is selected from a ligand of the formula (II) or (III):
  • Q 1 to 0° are independently selected from alkyl, cycloalkyl. heterocycloalkyl, alkenyl, alkoxy, aryl, aryloxy, heteroaryl, aralkyl, -alkyl-O-alkyl. -alkyl-O-aryt and NR D R 6 , wherein any alkyl group, alone or as part of another group, and any alkenyl group is optionally substituted by one or more substituents selected from F.
  • any aryl group alone or as part of another group, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 a!kyl) 2 ;
  • any suitable groups Q 1 and Q 2 as defined above may be linked to form a five- to seven-membered, carbocyclic or heterocyclic, saturated or unsaturated ring together with the carbon atom to which they are attached, or any suitable groups Q 5 and Q 4 as defined above or Q 4 and Q 5 as defined above may be linked to form a five- to seven-membered, heterocyclic, saturated or unsaturated ring together with the P-atom to which they are attached; R a , R° and R c are independently selected from alkyl and aryl; and
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, alkyl, cycloalkyl, alkenyl, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 ;
  • R 1 and R 2 as defined above, R 3 and R 4 as defined above or R 5 and R 6 as defined above may be linked to form an optionally substituted five- or six- membered heterocyclic ring including the N or P atom to which they are attached; or, where Q * and Q 2 .
  • Q 3 and Q 4 or Q 4 and Q 5 are NR 5 R 6
  • two groups R 5 or two groups R 6 as defined above may be linked to form an optionally substituted saturated or unsaturated heterocycle including the two N atoms of the groups NR 5 R 6 ;
  • one of Q 1 to Q 5 as defined above may be linked with one of Z 1 or Z 2 as defined above to form a metallacycle including .
  • the invention relates to processes for the oiigomerization of olefins, in particular of ethylene, which are catalyzed by the complexes or catalyst systems in accordance with the invention.
  • the complexes in accordance with the invention are able to provide highly active catalyst systems for the selective synthesis of a-olefins, in particular short chain ⁇ -o!efins in the C 4 -C 10 range.
  • the complexes can be conveniently prepared form starting compounds described in the literature, and they catalyze the oiigomerization of olefins under conditions which are significantly milder in terms of their high selectivity at lower temperatures and at a lower pressure compared to known industrial processes.
  • the amounts of catalysts which are required in order to achieve a satisfactory yield are very low, such that large amounts of products can be prepared using small amounts of catalysts.
  • the catalyst system in accordance with the invention has the additional advantage that a narrow product distribution of the a- olefins results.
  • a "catalyst composition” as referred to herein refers to a composition comprising the complex of the invention (i.e. the complex of formula (I) or any preferred embodiment thereof) as such or in an activated form obtainable by reacting the complex with an activator, which system can be contacted with the reactants to be subjected to the catalyzed reaction.
  • an activator which system can be contacted with the reactants to be subjected to the catalyzed reaction.
  • Typical examples are a solution or a dispersion of the complex or the activated complex, or a carrier on which the complex or the activated complex is immobilized, e.g. via adsorption.
  • the complex of the invention i.e. the complex of formula (I) or any preferred embodiment thereof
  • precatalyst refers to a complex in a form which is converted into the catalytically active species, e.g. via abstraction of a ligand, during the course of the catalyzed reaction.
  • the activation can be assisted by an activator or a co-catalyst.
  • Oligomerization in accordance with the understanding in polymer chemistry, relates to a process wherein monomers are covIERiy linked to each other to form a product (oligomer) containing a limited number of subunits derived from these monomers. Generally, the total number of subunits in an oligomer does not exceed 100.
  • a number of monomer subunits of 2 to 20 is preferred, a number of 2 to 15 is more preferred, and a number of 2 to 12 is further preferred and a number of 2 to 10 is particularly preferred.
  • oligomer mixtures obtained in an oligomerization reaction as carried out in the context of the invention show a distribution with respect to their chain lengths.
  • the peak (or peaks) of such a product distribution indicating the relative weight ratio of oligomers in the mixture versus the number of subunits contained in the oligomer lies in the range of 2 to 5, in particular 2 to 3.
  • alkyi represents a straight or branched chain saturated hydrocarbon residue which does not comprise any carbon-to-carbon double bonds or carbon-to-carbon triple bonds. Unless otherwise defined in a specific context, alkyi groups with 1 to 8 carbon atoms are generally preferred in the context of the invention. As exemplary groups, methyl, ethyl, propyl and butyl are mentioned.
  • alkenyl represents a straight or branched chain unsaturated hydrocarbon residue comprising one or more than one (such as two or three) carbon-to-carbon double bond(s) which does not comprise any carbon-to-carbon triple bonds. Unless otherwise defined in a specific context, alkenyl groups with 1 to 8 carbon atoms and one or two double bonds are generally preferred in the context of the invention.
  • aryl represents an aromatic hydrocarbon ring, in particular a 6 to 10 membered ring (unless a different number of ring members is indicated in a specific context), including bridged ring or fused ring systems containing at least one aromatic ring.
  • Aryl may, for example, refer to phenyl or naphthyl. Preferred as aryl groups are monocyclic groups with 6 or fused bicyclic groups with 9 or 10 ring members. Thus, generally preferred embodiments of "aryl” are phenyl or naphthyl, and particularly preferred is phenyl.
  • aralkyl represents an alkyl group as defined above, wherein one or more, preferably one hydrogen atom is replaced by an aryl group, preferably a phenyl group.
  • a particularly preferred aralkyl group is benzyl.
  • alkyl-O-alkyi refers to an alkyl group as defined above, wherein one hydrogen atom is replaced by an alkoxy group.
  • -alkyl-O-ary refers to an alkyl group as defined above, wherein one hydrogen atom is replaced by an aryloxy group.
  • a “heterocycie” is a ring comprising one or more (such as, e.g., one, two. or three) ring heteroatoms which may be selected from O, S, and N, including bridged ring or fused ring systems.
  • a heterocycie may be saturated or unsaturated, such that the term encompasses heteroalkyl rings as well as heteroraryl rings.
  • Preferred are 5 - 14 membered rings, and particular preference is given to monocyclic groups with 5 or 6 members and fused bicyclic groups with 8 to 10 ring members.
  • heteroaryl represents an aromatic ring, preferably a 5-14 membered ring (unless a different number of ring members is indicated in a specific context), including bridged ring or fused ring systems containing at least one aromatic ring, comprising one or more (such as, e.g. , one, two, or three) ring heteroatoms independently selected from O, S, and N. Particularly preferred as heteroaryl groups are monocyclic groups with 5 or 6 members and fused bicyclic groups with 8 to 10 ring members.
  • Heteroaryl may. for example, refer to thienyl (thiophenyl), benzo[b]thienyl.
  • pyrrolyl including, without limitation, 2H-pyrrolyl
  • imidazo!yl pyrazolyl
  • pyridyl pyridinyl; including, without limitation, 2-pyridyl, 3- pyridyl, and 4-pyridyl
  • cycloalkyl represents a saturated hydrocarbon ring, preferably a 3-1 1 membered ring (unless a different number of ring members is indicated in a specific context), including bridged ring, spiro ring or fused ring systems.
  • Cycloalkyl may, for example, refer to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl.
  • Preferred as cycloalkyl groups are monocyclic groups with 5 or 6 ring members or fused bicyclic groups with 9 or 10 ring members.
  • heterocycloalkyi represents a saturated ring, preferably a 3-1 1 membered ring (unless a different number of ring members is indicated in a specific context), including bridged ring, spiro ring or fused ring systems, containing one or more (such as, e.g.. one, two, or three) ring heteroatoms independently selected from O, S, and N.
  • Particularly preferred as heterocycloalkyi groups are monocyclic groups with 5 or 6 members and fused bicyclic groups with 8 to 10 ring members.
  • Heterocycloalkyi may, for example, refer to oxetanyl, tetrahydrofuranyl, piperidinyl, piperazinyl, aziridiny!, azetidinyl, pyrrolidinyl, imidazolidinyl, morpholinyl, pyrazo!idinyl, tetrahydrothienyl, octahydroquinolinyl, octahydroisoquinolinyl.
  • oxazolidinyi isoxazolidinyl, azepanyl, diazepanyl. oxazepanyl or 2-oxa-5-aza- bicycio[2.2.1 ]hept-5-yl.
  • two suitable groups can be linked to form a ring
  • the concerned groups should, in combination, be sufficiently long such that the resulting ring system can be stable.
  • two groups can be linked if they contain atoms between which a bond (including single or double bonds) can be formed.
  • a link can be formed between two carbon atoms in different groups via replacement of one or two hydrogen atom in each of the groups by a bond or a double bond between the groups.
  • M is a metai selected from Zr and Hf;
  • X 1 and X 2 are independently selected from CI, Br, I, F, H, alkyl, -alkyl-O-alkyi, -alkyl-O- aryl, alkoxy, aryioxy. aralkyi, -alkyl-SiR a R b R c , and NR 1 R 2 , wherein any alkyl group, alone or as part of another group such as -alkyl-O-alkyl, alkoxy or aralkyi, is optionally substituted by one or more substituents selected from OH.
  • any aryi group, aione or as part of another group such as -alkyl-O-aryl, aralkyi or aryioxy, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, OH, F, CI. Br. NH 2 , NH(C1 -8 alkyl) and N(C1 -8 alkyl) 2 ;
  • L is selected from CZ 3 , N, and PR 3 R 4 ;
  • Z 1 and Z 2 are independently selected from alkyl, cycloalkyl, heterocycloalkyi, alkenyl, aryi, heteroaryl, aralkyi, -alkyl-O-alkyl, -alkyl-O-aryl, wherein any alkyl group, alone or as part of another group such as -alkyl-O-alkyl or aralkyi.
  • any alkenyl group is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and any aryi group, alone or as part of another group, such as -alkyl-O-aryl or aralkyi, and any heteroaryi group, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F. CI, Br and N(C1 -8 alkyl) 2 ;
  • Z 3 is selected from alkyl, cycloalkyl, heterocycloalkyi, alkenyl, alkoxy, aryi, aryioxy, heteroaryi, aralkyi, -alkyl-O-alkyl, -alkyl-O-aryl, F, CI, Br, NR 1 R 2 , and PR 3 R 4 , wherein any alkyl group, alone or as pari of another group such as -alkyl-O-alkyl, alkoxy or aralkyi, and any alkenyl group, is optionally substituted by one or more substituents selected from OH, F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryi group, alone or as part of another group such as - alkyl-O-aryl, aralkyi or aryioxy, and any heteroaryl group, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1
  • J is selected from a ligand of the formula (II) or (III)
  • Q 1 to Q 5 are independently selected from alkyl, cycloalkyl, heterocycloalkyl. alkenyl, alkoxy, aryl, aryloxy, heteroaryl, aralkyl. -alkyl-O-alkyl, -alkyl-O-aryl and NR 5 R 6 , wherein any alkyl group, alone or as part of another group, and any alkenyl group is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group , alone or as part of another group, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 ;
  • any suitable groups Q 1 and Q 2 as defined above may be linked to form a five- to seven-membered, carbocyclic or heterocyclic, saturated or unsaturated ring together with the carbon atom to which they are attached, or any suitable groups Q 3 and Q 4 as defined above or Q 4 and Q 5 as defined above may be linked to form a five- to seven-membered, heterocyclic, saturated or unsaturated ring together with the P-atom to which they are attached;
  • R a , R u and R° are independently selected from alkyl and aryl;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, alkyl, cycloalkyl, alkenyl, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F.
  • R 3 and R 4 as defined above or R 5 and R 6 as defined above may be linked to form an optionally substituted five- or six- membered heterocyclic ring including the N or P atom to which they are attached; or, where Q 1 and Q 2 , Q 3 and Q 4 or Q 4 and Q 5 are NR 5 R 6 , two groups R 5 or two groups R 6 as defined above may be linked to form an optionally substituted, saturated or unsaturated heterocycle including the two N atoms of the groups NR 5 R 6 ; or one of Q 1 to Q 5 as defined above may be linked with one of Z or Z 2 as defined above to form a metallacycle including M.
  • the electron structure of the nitrogen metal bonds will be ultimately determined by the nature of associated groups Z ⁇ L, and Z 2 , and the actual structure will frequently be an intermediate between the idealized resonance structures (I) and ( ⁇ ) or (I").
  • the indication of a resonance structure such as (I), ([') or ( ⁇ ) for any complexes described herein is not to be seen as limiting the concerned compounds to the illustrated equivalent or non-equivalent types of nitrogen-metal bonds in accordance with the common practice in the art.
  • L is preferably CZ 3 .
  • Z 1 and Z 2 are preferably selected from alkyl, cycloalkyl, heterocycloalkyl, aryl. heteroaryl, aralkyi, -alkyl-O-alkyl, and -alkyl-O-aryl, wherein any alkyl group, alone or as part of another group such as aralkyi, -alkyl-O-alkyl, and -alkyl-O-aryl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and any aryl group, alone or as part of another group, such as aralkyi and -alkyl-O-aryl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • Z 1 and Z 2 are selected from alkyl, cycloalkyl, aryl, and aralkyi, wherein any alkyl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and any aryl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy. F, CI. Br and N(C1 -8 alkyl) 2 .
  • the alkyl group is not substituted and the aryl group is not substituted or substituted by one or more CI -8 alkyl groups.
  • Z 3 is preferably selected from H, alkyl, cycloalkyl, aryl, aralkyi. and NR 'R 2 , wherein any alkyl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy. F. CI, Br and N(C1 -8 alkyl) 2 .
  • the alkyl and the aryl group is not substituted
  • Z 1 and Z 3 or Z 2 and Z 3 are taken together to form a pyridine ring including the nitrogen atom to which Z 1 or Z 2 , respectively, is attached, which pyridine ring is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 . Preferably, it is unsubstituted.
  • the group Z or Z 2 which is not involved in the formation of the pyridine ring is defined in accordance with the preferred options listed above.
  • R 1 and R 2 are preferably independently selected from H, alkyl. cycloalkyl, aryl.
  • R 1 and R 2 as defined above may be linked to form an optionally substituted five or six-membered heterocyclic ring including the N atom to which they are attached. More preferably R 1 and R 2 are independently selected from H, alkyl, aryl, and aralkyi. and are in particular independently selected from H and C1 -8 alkyl.
  • the ligand containing Z , L and Z 2 is selected from one of the following formulae (IVa) to (IVc):
  • R 7 , R 8 , and R 9 are independently selected from alkyl, cycloalkyl, aryl, and aralkyi, wherein any aryl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from CI -8 alkyl, phenyl, C1 -8 alkoxy. F. CI, Br and N(C -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more CI -8 alkyl groups.
  • R ' . R 8 , and R 8 are independently selected from aryl and aralkyi, wherein any aryl group, alone or as part of aralkyi, is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups. It is particularly preferred that R 7 , R s , and R 9 are independently phenyl, optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups.
  • R 10 is selected from H, alkyl. cycloalkyl, aryl, and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy F, CI, Br and N(C1 -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 10 is selected from aryl and aralkyl, wherein any aryi group, alone or as part of aralkyl. is optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups. It is particularly preferred that R 10 is phenyl, optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups.
  • R 11 and R 2 are independently selected from H, alkyl, cycloalkyl, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, C!, Br and N(C1-8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl.
  • R 11 and R 12 may be linked to form an optionally substituted five or six-membered heterocyclic ring including the N atom to which they are attached.
  • R 11 and R 12 are independently selected from H, alkyl, aryl, and aralkyl, and are in particular independently selected from H and C1 -8 alkyl.
  • the compound of formula (I) has the following structure (la)
  • Q 1 and Q 2 are preferably independently selected from alkyl, aryl. aralkyl, and NR 5 R 6 , wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of another group such as -alkyl-O-aryl, aralkyl or aryloxy, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl. C1 -8 alkoxy. F, CI, Br and N(C -8 alkyl) 2 .
  • R 5 and R 6 are preferably independently selected from alky!, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1-8 alky!) 2 and wherein any aryl group, aione or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • Q 1 and Q 2 are both NR 5 R 6a , wherein the groups R 5 are independently selected from the preferred options listed above, and the two groups R 6a are taken together to form a 5- or 6- membered, preferably 5 membered, saturated or unsaturated heterocycle containing the two N atoms of the NR 5 R 6a groups as heteroatoms.
  • the heterocycle may carry one or more further substituents selected from C1-8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 a!kyl) 2 . Preferably, these further substituents are absent.
  • the ligand of formula (II) is selected from one of the following formulae (lla) to (lie):
  • R 13 and R 14 are independently selected from H, alkyl, cycloalkyl, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents seiected from C1 -8 alkyl, phenyl, C1 -8 alkoxy. F, CI, Br and N(C1 -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 13 and R 14 are independently selected from aryl and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups. It is particularly preferred that R 13 and R are independently phenyl, optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups.
  • R 15 and R 16 are independently selected from alkyl, cycloalkyl, aryl, and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy. F, CI, Br and N(C1 -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 15 and R 6 are independently selected from aryl and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups. It is particularly preferred that R 5 and R 16 are independently phenyl, optionally substituted in the ortho- and/or
  • R 17 , R 1 B , R 19 and R 20 are independently selected from H, alkyl, cycloalkyl, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl.
  • R 17 and R 18 or R 19 and R 20 as defined above may be linked to form an optionally substituted five or six-membered heterocyclic ring including the N atom to which they are attached.
  • R 7 , R 18 , R 19 and R 20 are independently selected from H, alkyl, aryl, and aralkyl, and are in particular independently selected from H and C1 -8 alkyl.
  • Q 3 to Q 5 are preferably independently selected from alkyl, aryl, aralkyl, and NR 5 R 6 , wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br and N(C1-8 alkyl) 2 and wherein any aryl group, alone or as part of another group such as -alkyl-O-aryl, aralkyl or aryloxy, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • R 5 and R s are preferably independently selected from alkyl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl. is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • one of Q 3 and Q 5 is defined in accordance with the above preferred embodiments of Q 3 to Q 5 , and the other two. i.e. Q 3 and Q 4 or Q 4 and Q 5 , are both NR R 6a , wherein the groups R 5 are independently selected from the preferred options listed above, and the two groups R 6a are taken together to form a 5- or 6- membered, preferably 5 membered, saturated or unsaturated heterocycle containing the two N atoms of the NR 5 R 6a groups as heteroatoms.
  • the heterocycle may carry one or more further substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • these further substituents are absent.
  • the ligand of formula (III) is selected from one of the following formulae (Ilia) to (Illd):
  • R to R are independently selected from H, alkyl, cycloalky!, aryl, and aralkyl, wherein any alkyl group, alone or as part of aralkyl. is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl. is optionally substituted by one or more substituents selected from C1-8 alkyl, phenyl. C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 2" ' to R 24 are independently selected from alkyl. aryl and aralkyl. wherein any aryl group, alone or as part of aralkyl. is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups. It is particularly preferred that R 13 and R 14 are independently phenyl, optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups.
  • R 21 to R 24 are independently selected from alkyl, cycloalkyl, aryl, and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 21 to R 24 are independently selected from alkyl, aryl and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups. It is particularly preferred that R 21 to R 24 are independently t-butyl or phenyl.
  • R 25 and R 26 are independently selected from H, alkyl, cycloalkyl. aryl. and aralkyl, wherein any alkyl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from F , CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyl, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1-8 alkyl) 2 .
  • the aryl group is not substituted or substituted by one or more C1 -8 alkyl groups.
  • R 25 and R 26 are independently selected from alkyl, aryl and aralkyl, wherein any aryl group, alone or as part of aralkyl, is optionally substituted in the ortho- and/or para- position by one or more C1 -8 alkyl groups, it is particularly preferred that R 25 and R 26 are independently phenyl, optionally substituted in the ortho- and/or para-position by one or more C1 -8 alkyl groups.
  • R 27 to R 32 are independently selected from H, alkyl, cycloalkyl, aryi, and aralkyi, wherein any alkyl group, alone or as part of aralkyi. is optionally substituted by one or more substituents selected from F, CI, Br and N(C1 -8 alkyl) 2 and wherein any aryl group, alone or as part of aralkyi, is optionally substituted by one or more substituents selected from C1 -8 alkyl, phenyl, C1 -8 alkoxy, F, CI, Br and N(C1 -8 alkyl) 2 .
  • R 27 to R 32 are independently selected from H, alkyl, aryl, and aralkyi, and are in particular independently selected from H and C1 -8 alkyl.
  • these ligands are independently selected from CI. Br, alkyl, -alkyl-SiR a R b R°, alkoxy, aryloxy. and aralkyi, wherein any alkyl group, alone or as part of alkoxy or aralky!.
  • X 1 and X 2 are independently selected from CI, Br, alkyl, aralkyi, and - aikyi-SiR a R b R c .
  • alkyl methyl is preferred.
  • aralkyi benzyl is preferred.
  • -alkyl- SiR a R R c it is preferred that -alkyl- is ⁇ CH 2 -, and that R a to R c are independently selected from methyl and phenyl, and it is particularly preferred that -alkyl- is -CH 2 -, and that R a to R c are all methyl (Me), or that two of them are methyl and one of them is phenyl (Ph).
  • X and X 2 are independently selected from methyl, benzyl. -CH 2 -SiMe 3 and -CH 2 -SiMe 2 Ph, Most preferred is benzyl.
  • the variables M, X 1 , X 2 , R 7 , R 8 , R 13 and R 14 have the meanings defined above, including preferred definitions thereof.
  • the complex in accordance with the invention has the formula (If) or (Ig) below.
  • X 1 and X 2 are independently selected from CI, Br, alkyi, alkoxy, aryloxy, aralkyl, and -CH 2 - SiR a R a R " , wherein R a to R c are independently selected from methyl and phenyl, and preferably from alkyl, especially methyl, and aralkyl, especially benzyl, and are most preferably benzyl,
  • R d to R° are independently selected from H and C1 -8 alkyl, and preferably R d , R f , R 9 , R .
  • R j , R 1 , R m and R° are independently selected from C1 -8 alkyl and R e , R h , R k and R" are selected from H and C1 -8 alkyl.
  • the invention provides a method for the oligomerization o an olefin, especially ethylene, which method comprises the step of contacting the complex of formula (I), including its preferred embodiments, with an olefin.
  • the complex of formula (I) is contacted with the olefin in the presence of an activator.
  • the complex in accordance with the invention is used in the form of a catalyst composition.
  • a complex in accordance with the invention (or a mixture of two or more complexes of the invention) can be dissolved or dispersed in a solvent.
  • suitable solvents include aromatic solvents, such as toluene, benzene and xylene, alkanes, such as the commercially available products Isopar® (Exxon) and Parafol ⁇ (SASOL), and cycloalkanes such as cyclohexane.
  • the complex can be supported on a carrier.
  • This carrier can be, for example, a metal halide or a metal oxide.
  • the metal oxide can be selected from alumina, borla, magnesia, thoria, zirconia, silica, or mixtures thereof.
  • polymeric materials may be used.
  • the olefin to be oligomerized and the activator can be first charged into the reactor wherein the oligomerization reaction is carried out before the complex or the catalyst composition containing the complex in accordance with the invention is added to the reactor.
  • the components can also be contacted in a different order or can be premixed before injection into the reactor.
  • an activator or an activator and a co-activator can be incorporated together with the complex of formula (I) into the catalyst composition in accordance with the invention, e.g. by combining the complex or complexes and the activator or activators in the solvent contained in the catalyst composition.
  • the activator can be reacted with the complex in accordance with the invention in order to transform the complex into a catalytically active cationic species which offers a coordination site for the olefin to be oligomerized.
  • the transformation proceeds via removal of one of the ligands X and X 2 as an anion from the complex of formula (I).
  • an alumoxane can be used as an activator in accordance with the invention.
  • An alumoxane component useful as an activator typically is a cyclic or linear oligomeric aluminum compound represented by the general formula -(AI(R')-0) n - (cyclic) or R'-(AI(R')-0)n-AIR' 2 (linear), wherein R' is independently a C1 -C20 alky! radical, for exampie, methyl, ethyl, propyl, butyl, or pentyl, and "n" is an integer from 3-50. Most preferably, R' is methyl and "n" is at least 4.
  • alumoxanes are methyl alumoxane (MAO), modified methyl alumoxane (MMAO), ethyl alumoxane. iso-butyl or dry-alumoxane from which all volatiles are removed.
  • the amount of the alumoxane to be reacted with the complex in accordance with the invention generally ranges from 20 mol aluminoxane/mol complex to 10000 mol aluminoxane/mol complex, and preferably from 100 mol aluminoxane/mol complex to 500 mol aluminoxane/mol complex.
  • ionic activators can be used such as those which contain an anion selected from tetrakis-perfluorophenylborate, tetrakis-perfluoronaphthylborate, tetrakis-perfluorophenyl- aluminate or tetrakis-perfluor-m-xyleneborate.
  • the ionic activators combine the above anion with a non-coordinating cation.
  • Suitable ionic activators are dialkyl ammonium salts of the above anions, such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakls(pentafluorophenyl) borate; tri-substituted phosphonium salts of the above anions, such as: triphenyiphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafiuorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis- (pentafluorophenyl) borate; di-substituted oxonium salts of the above anions, such as: diphenyloxonium tetrakis(pentafluorophenyl)
  • a further class of activators that can be used are Lewis acid activators, such as triphenyl boron, tris-perfluorophenyl boron, tris-perfluoronaphthylboron, tris-perfluor-m-xyleneboron or tris-perfluorophenyl aluminum.
  • the amount of the ionic activator or the Lewis acid activator to be reacted with the complex in accordance with the invention generally ranges from 1 mol activator/mol complex to 2 mol activator/mol complex, and preferably from 1 mol activator/mol complex to 1 , 1 mol activator/mol complex.
  • a compound can be used which is capable of alkylating the transition metal complex, such that when used in combination with an activator such as a Lewis acid activator or an ionic activator, an active catalyst is formed.
  • Co-activators include alumoxanes, such as methyl alumoxane, modified alumoxanes such as modified methyl alumoxane, aluminum alkyls such trimethyl aluminum, tri-isobutyl aluminum, triethyl aluminum, and tri-isopropyl aluminum and aluminium alkyl halides.
  • the amount of the co-activator is generally in the range of 1 mole to 1000 moles per mole of the complex in accordance with the invention, preferably in the range of 5 mole to 50 moles per mole of the complex in accordance with the invention.
  • monomers selected from ethylene, propylene or an ⁇ -o!efin, or mixtures of these monomers can be oligomerized
  • ethylene is used as the monomer which is subjected to oligomer!zation.
  • the method comprises the step of contacting the monomer(s) to be oligomerized with the complex in accordance with the invention or with an activated complex obtainable by contacting the complex in accordance with the invention with an activator, and optionally a co- activator.
  • the monomers can be contacted first with an activator and optionally a co-activator, and subsequently with the complex of the invention, or the monomers are first contacted with the complex in accordance with the invention, and then with the activator and optionally a co-activator.
  • Scavengers for oligomerization reactions are known in the a t, and generally the same compounds can be used as they are used in polymerization reactions. Examples are aluminium alkyls, such as triisobutylaluminium (TIBA), alumoxanes or combinations thereof.
  • the reaction temperature during the oligomerization reaction is typically in the range of 0°C to 100°C, preferably 20°C to 80 °C and in particular 30 to 70°C. It is an advantage of the complexes in accordance with the invention that they are able to catalyze the oligomerization with a high activity favourably at reduced temperatures.
  • the temperature can also be used to influence the composition of the oiigomerized product. At lower temperatures, the formation of products with a lower degree of oligomerization is favoured, at higher temperatures, a higher ratio of products with a higher degree of oligomerization can be obtained.
  • An exemplary concentration of the monomer to be oiigomerized, especially ethylene, in the reaction vessel ranges from 0.1 to 5 MPa (1 - 50 bar), preferably from 0.2 to 1 .0 MPa (2 - 10 bar) for a concentration of the complex of the invention of 1 ⁇ 10 "5 bis 1 ⁇ 10 "6 M (mol/l).
  • the complex of the invention is preferably used in a catalyst composition comprising a solvent, and the liquid phase of the catalyst composition can be contacted with the gaseous or liquid monomers. Since ethylene is a preferred monomer, the reaction usually proceeds by contact between the liquid catalyst composition and a gaseous monomer.
  • the monomer can be conveniently oiigomerized at an absolute pressure in the reactor (usually provided by the monomer) of 0.10 to 5.0 MPa, preferably 0.15 to 1.0 MPa, and more preferably 0.15 to 0.3 MPa.
  • a high activity is achieved at relatively low pressures.
  • the monomer pressure in the reactor can also be used to influence the composition of the oiigomerized product. At lower pressures, the formation of products with a lower degree of oligomerization is favoured, at higher pressures, a higher ratio of products with a higher degree of oligomerization can be obtained.
  • the complexes and catalyst systems in accordance with the invention allow the production of oligomeric a-olefins with a high selectivity.
  • the products show a narrow product distribution with respect to the number of monomers contained in the oligomers (i.e. the degree of oligomerization).
  • 1 -butene. 1 -hexene and 1 - octene in particular 1 -butene and 1 -hexene can be obtained as main products with a ratio of preferably more than 50 wt% of all oligomers produced. No polymeric side products are obtained. If the distribution of oligomer chain lengths in the product (as determined e.g.
  • the K-value is usually between 0.2 and 0.7, preferably between 0.2 and 0.6.
  • the K-value can be determined as disclosed in "Oligomerization of Ethylene Using New Tridentate Iron Catalysts Bearing alpha-Diimine Ligands with Pendant S and P Donors " , Brooke L. Small, Ray Rios, Eric R. Fernandez, Deidra L. Gerlach, Jason A. Halfen, and Michael J. Carney; Organometallics 2010, 29, 6723-6731.
  • the complexes in accordance with the invention ensure a highly selective oligomerization. No incorporation of a-olefins already formed as products into the growing a-olefin chains has been observed. Thus, in the case of ethylene oligomerization, only linear (non-branched) oligomeric a-olefins are formed. Moreover, no isomerization of the products was observed, i.e. ⁇ -olefins having one double bond are provided with a high yield.
  • the complexes in accordance with the invention can be conveniently prepared according to synthetic methods known in the art.
  • the bidentate ligands containing two coordinating N-Atoms of the complexes in accordance with the invention, such as the aminopyridinato-ligands, are accessible via convenient routes of synthesis at high yields (z.B. Natalie M. Scott. Thomas Schareina, Oleg Tok, Rhett Kempe, Eur. J. Inorg. Chem. 2004, 3297 - 3304 and the literature cited therein).
  • the sterical and electronic properties of such ligands can be easily varied.
  • the preparation of the ligand-metal complexes, such as the aminopyridinato complexes is well documented especially in the field of polymerization catalysts (e.g. R. Kempe, Eur. J. Inorg. Chem.
  • the monodentate ligand J can be prepared by methods known in the art.
  • the synthesis of the iminoimdazoiines is described in DE 2916140 A1 via reaction of the corresponding N. N'-diarylalky!-1 .2-diamine with cyanogene bromide in toluene.
  • the 1 ,2- diamine can be prepared either from the corresponding arylamine and 1 ,2-dibromoethane, or via reduction of an a-diimine, the latter being prepared via condensation reaction between the corresponding arylamine and glyoxal.
  • the synthesis of other ketimide ligands is described, e.g., in US 2004/0192541 and the literature cited therein.
  • Z 1 , L, Z 2 , X 1 and X 2 are defined as above, including preferred embodiments, and X 3 is selected from CI, Br, I, F, H, alkyl, -alkyl-O-alkyl, -a!ky!-O-ary!, a!koxy, aryloxy, aralkyl, -alkyl-SiR a R b R°, and NR R 2 , wherein any alkyl group, alone or as part of another group such as -alkyl-O-alkyl, alkoxy or aralkyl, is optionally substituted by one or more substituents selected from OH, F, CI. Br.
  • Q 3 Q 4 Q 5 p NH (VI b), wherein Q 1 to O 5 are independently defined as above, including preferred embodiments, or with a salt containing an anion of a compound of the formula (Via) or (Vlb) obtained by abstracting the proton indicated these formulae.
  • the molar ratio of the compounds of formula (V) and (Via) or (VIb) in the reaction is about 1 , such as 0.9 to 1 .1 , and is preferably 1.0.
  • the reaction can be conveniently accomplished in a solvent, e.g. an aromatic solvent such as toluene, at moderate temperatures ranging e.g. from 25 to 70 °C, preferably from 40 to 60 °C.
  • X 3 is preferably selected from CI, Br, alkyl, alkoxy, aryloxy, and aralkyl, wherein any alkyl group, alone or as part of alkoxy or aralkyl, is optionally substituted by one or more substituents selected from F, CI, Br N(C1 -8 alkyl) 2 , and any aryl group, alone or as part of another group such as aralkyl or aryloxy, is optionally substituted by one or more substituents selected from CI -8 alkyl. phenyl, C1 -8 alkoxy, F. CI, Br and N(C1 -8 aikyl) 2 . It is more preferred that X 3 selected from CI, Br, alkyl, especially methyl, and aralkyl. especially benzyl. Most preferred is benzyl.
  • the complexes in accordance with the invention can be prepared by reacting a complex precursor of formula (VII):
  • J, X 1 and X 2 are defined as above, including preferred embodiments, and X 4 is selected from CI, Br, I, F, H, alkyl, -alkyi-O-alkyl, -alkyl-O-aryl, alkoxy, aryloxy, aralkyl, -alkyl-SiR a R b R c , and NR 1 R 2 , wherein any alkyl group, alone or as part of another group such as -alkyl-O-alkyl, alkoxy or aralkyl, is optionally substituted by one or more substituents selected from OH, F, CI, Br.
  • a precursor of formula (V) can be conveniently prepared by reacting a compound of formula MX X 2 X J X ' ⁇ wherein X 1 to X 4 are defined as above, including preferred embodiments, with a compound of formula (Villa) or (VI I lb) as defined above, or with a salt containing an anion of a compound of the formula (Villa) or (VI I lb) obtained by abstracting the proton indicated these formulae.
  • M(CH 2 SiMe 3 ). and M(CH 2 SiMe 2 Ph) 4 (M Zr, Hf) (M. R. Collier, M. F. Lappert, R. Pearce, J. Chem. Soc, Dalton Trans. 1973, 445.) and tetrabenzylzirconium as exemplary compounds of formula MX X 2 X 3 X 4 have been long known in literature.
  • a precursor of formula (VII) can be conveniently prepared by reacting a compound of formula MX ' X 2 X : X 4 , wherein X 1 to X " are defined as above, including preferred embodiments, with a compound of formula (Via) or (VI b) as defined above, or with a salt containing an anion of a compound of the formula (Via) or (VI b) obtained by abstracting the proton indicated these formulae.
  • Methylaluminumoxane (MeAIO)., ⁇ (Me 3 AI) 1/3 n ]
  • the H in the abbreviation indicates the parent compound from which the corresponding anionic ligand (e.g. Ap - aminopyridinato ligand) is prepared via abstraction of a proton.
  • anionic ligand e.g. Ap - aminopyridinato ligand
  • GPC Gel permeation chromatography
  • GC analysis was performed with an Agilent 6850 gas chromatograph equipped with an Agilent 19095J-323E capillary column (HP-5; 5 % phenyl methyl siloxane; 30 m; film 1 .5 pm, diameter 0.53 mm) and a flame ionization detector.
  • the ligand precursor 1 .3- bis-(2,6-dimethyl-phenyl)imidazolidin-2-ylideneamine (DE 2916140 A1 , US 2004/0192541 Al ) and Tri-tert-butylphosphoranimine (US 6239061 Bl). and the metal precursors tetrabenzylzirconium (Zucchini, U.; Albizzati, E.; Giannini, U. J. Organomet. Chem.
  • Ph 121.3 (s, 1C, Ph), 125.5 (s, 1C, C), 127.6 (s, 2C, CH), 1281 (s, 4C, Ph), 128.3 (s, 4C, Ph), 128.9 (s, 2C, CH), 129.2 (s, 2C, CH), 129.9 (s, 2C, C), 135.6 (s, 1C, C), 137.5 (s, 6C, C 6 H 3 ), 138.3 (s, 2C, NC), 139.6 (s, 1C, C), 144.0 (s, 1C, C), 145.6 (s, 2C, C), 146.7 (s, 2C.
  • the catalytic ethylene oligomerization reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, precatalyst and activator injection systems. During a oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 h at 80 °C prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with 150 mL of toluene.
  • the catalytic ethylene oligomerization reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, precatalyst and activator injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semibatch experiment, the autoclave was evacuated and heated for 1 h at 80 °C prior to use.
  • the catalytic ethylene oligomerization reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toiuene, precatalyst and activator injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semibatch experiment, the autoclave was evacuated and heated for 1 h at 80 °C prior to use.

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Abstract

L'invention concerne des complexes métalliques de transition de formule (I) fournissant des catalyseurs actifs et sélectifs pour l'oligomérisation d'oléfines, en particulier l'éthylène, ainsi que des procédés pour l'oligomérisation d'oléfines utilisant les complexes métalliques de transition.
PCT/EP2014/054373 2013-03-11 2014-03-06 Complexes pour l'oligomérisation catalytique d'oléfines WO2014139861A1 (fr)

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WO2015094513A1 (fr) * 2013-12-19 2015-06-25 Dow Global Technologies Llc Complexe métal-ligand, catalyseur de polymérisation d'oléfines dérivé de ce dernier et procédé de polymérisation d'oléfines utilisant le catalyseur
WO2017173079A1 (fr) * 2016-03-31 2017-10-05 Dow Global Technologies Llc Systèmes catalyseurs de polymérisation d'oléfine et leurs procédés d'utilisation
WO2017173080A1 (fr) * 2016-03-31 2017-10-05 Dow Global Technologies Llc Systèmes catalyseurs de polymérisation d'oléfine et leurs procédés d'utilisation
WO2020197907A1 (fr) * 2019-03-28 2020-10-01 Dow Global Technologies Llc Catalyseurs de copolymérisation d'oléfine à métal de transition du groupe iv de monobidentate aminopyridine ayant une capacité de poids moléculaire ultra-élevé et une incorporation de comonomère ultra-faible
US11066494B2 (en) 2018-09-20 2021-07-20 Exxonmobil Chemical Patents Inc. Amine bridged anilide phenolate catalyst compounds
WO2024177286A1 (fr) * 2023-02-21 2024-08-29 주식회사 엘지화학 Composé de métal de transition et composition de catalyseur le comprenant
US12104002B2 (en) 2020-03-19 2024-10-01 Dow Global Technologies Llc Monobidentate aminopyridine group IV transition metal olefin copolymerization catalysts with ultra-high molecular weight capability and ultra-low comonomer incorporation

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