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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
  • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
• • 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
  • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
  • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/46—Titanium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/48—Zirconium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/62—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron

Definitions

• a new transition metal complex its preparation as well as a catalyst system comprising based thereupon and its use for the polymerization of olefins
• the invention relates to a triaza transition metal complex having the formula (1)
• each L is independently a multidentate ligand
• M is the central atom which is a metal selected from Groups 4-8 of the Periodic Table of the Elements (IUPAC 1990)
• each X is independently a unidentate organic or halogen ligand
• m is the coordination number or number of coordination sites on the central atom M
• n is the number of the ligands L which is an integer from 1 to m.
• the complex may also be ionic.
• the invention also relates to a process for the preparation of a transition metal complex of the above type. Further, the invention relates to another new complex, which can be used in the preparation of the above mentioned transition metal complex. Finally, the invention relates to a polymerization catalyst system comprising the above mentioned transition metal complex, and the use of such a catalyst system for the polymerization of ethylenically unsaturated compounds.
• each of the ligands L and X can be connected by bivalent L-L, X-X or L-X bridges.
• Such bridges are e.g. al ylene bridges as well as silylene and other heteroatomic bridges.
• aza complexes could be prepared, in which the ligand was bound to the central atom in a totally new way.
• the new triaza transition metal complexes could be used in the polymerization of olefins.
• the above mentioned transition metal complex according to formula (1) it was found possible to prepare and use for polymerization complexes, in which at least one of the ligands L of the above formula (1) has the formula (2) wherein each of R R ⁇ is independently selected from hydrogen and organic groups having from 1 to 10 carbon atoms.
• This ligand is coordinated to the central atom M by one, two, three or four of the three nitrogen atoms and/or the carbon atom of the ligand L according to the formula (2). Note especially the fact that the carbon atom connecting the three nitrogen atoms is three-valent and thus gives rise to a carbanion or the like.
• RpR ⁇ can be hydrogen or any organic group with or without heteroatoms.
• RpR ⁇ are independently selected from hydrogen, C ⁇ -C 1 alkyls, CpC 12 alkenyls, C 6 -C 18 aryls and silyls such as tri- C ⁇ -C 1 alkylsilyls.
• adjacent groups selected from Ri-R ⁇ of the ligand may be interconnected to form rings.
• some or all of the pairs: R t and R 2 , R 3 and t , and R 5 and R ⁇ 5 may form ring structures.
• at least one of the pairs: R 2 and R 3 , R 4 and R 5 , and Rg and R t are interconnected to form a ring structure.
• These ring structures may be substituted further or fused with other rings. If the ring structures are substituted, typical substituents are C C ⁇ 2 alkyls, C ⁇ -C ⁇ 2 alkenyls, C 6 -C 18 aryls and silyls.
• the ring structure may be fused with a further aliphatic or aromatic ring.
• the ring structures of the ligand may also contain other heteroatoms than the nitrogen atoms of formula (2).
• the groups of all of the pairs: R 2 and R 3 , R and R 5 , as well as Re and Ri of the above defined L ligand are interconnected to form bridge structures which are selected from 2 carbon and 3 carbon chains.
• the ligands L of the claimed complex may e.g. have the following formulas:
• any of the ring structures may independently from the other ring structures contain a ⁇ bond in any position.
• the most preferred ligands N are l,5,9-triazatricyclo[7.3.1.0] ' tridecanyl (1) and l,4,7-triazatricyclo[5.2.1.0 4 10 ] decanyl (2).
• Said ligand N is a tetradentate ligand and according to formulas (l)and (2) coordinated by four adjacent atoms to a transition metal M belonging to any of Groups 4 to 8 of the Periodic Table of the Elements (IUPAC 1990).
• the transition metal M is selected from iron Fe, chromium Cr, titanium Ti and zirconium Zr.
• L of the complex of formula (1) have the general formula (2).
• Other ligands may be present, as well, as long as at least one of the L ligands fulfill the definition given in formula (2).
• Such other L ligands may e.g. be ⁇ -bonded alkenes and polyenes, as well as ⁇ - bonded charged aromatic rings such as the cyclobutadiene dianion and the cyclo- pentadienide ion (cyclopentadienyl anion). They are well-known as multidentate ligands for transition metal complexes.
• ligand L of formula (2) which is a multidentate ligand by adjacent cooordinating atoms (3 N + 1 C)
• another type of ligand is also bound to the transition metal M, namely the unidentate organic or halogen ligand X.
• X is an organic ligand, it may or may not contain a heteroatom. It may also form a bridge to another ligand X or to at least one of the ligands L, in which case it preferably is an amino bridge.
• Typical non-bridge organic ligands X are alkyls and alkylamido groups, preferably C C 3 alkyls such as methyl.
• the ligand X is a halogen, most preferably chlorine Cl.
• the ligands L may alone saturate the central atom M coordinatively. However, it is preferable, if the complex also has an X ligand coordinated thereto. Most preferably, the number n of ligands L is selected from 1 and 2, whereby the number of X ligands exceeds 1.
• the number n of ligands L is selected from 1 and 2, whereby the number of X ligands exceeds 1.
• examples of preferred transition metal complexes according to the present invention is given. Any of the one, two, three or four atoms (one C and three N atoms) may be coordinated to the transition metal.
• the complex may be a l,5,9-triazatricyclo[7.3.1.0] ' tridecanyl chromium dichloride of the formula (3):
• Typical complex structures are l-5,9-triazatricyclo[7.3.1.0] " tridecanyl chromium trichloride l,5,9-triazatricyclo[7.3.1.0] tridecanyl iron trichloride l,5,9-triazatricyclo[7.3.1.0] 5 13 tridecanyl iron dichloride l,5,9-triazatricyclo[7.3.1.0] tridecanyl chromium dichloride l,5,9-triazatricyclo[7.3.1.0] 5 13 tridecanyl titanium trichloride l,4,7-triazatricyclo[5.2.1.0 4 10]decanyl chromium trichloride l,4,7-triazatricyclo[5.2.1.0 4 10]decanyl iron trichloride l,4,7-triazatricyclo[5.2.1.0 4 10]decanyl iron trichloride l,4,7-triazatricyclo[5.2.1.0 4 10]decan
• the invention also relates to a process for the preparation of the transition metal complex described above.
• the preparation process is characerized by reacting a triaza compound of the formula (9)
• R is an organic group such as a hydro carbyl, a silyl or a siloxy or a hydrogen, and each of Ri-R ⁇ is the same as above (see formula (2)), a transition metal compound of the formula (10)
• M, X and m are the same as above (see formula (1)), and a strong base, in the sequence (triaza compound + transition, metal compound) + strong base, or the order (triaza compound + strong base) + transition metal compound, to give said transition metal complex.
• R is preferably a C C 6 alkyl, a tri-CrC ⁇ alkylsilyl or a hydrogen.
• the triaza compound and the transition metal compound are reacted into an intermediate, which is in this connection called a precursor complex.
• the precursor complex is reacted with the strong base to form the claimed triaza transition metal complex.
• a complexing agent is used to facilitate the formation of the precursor complex.
• the triaza compound is reacted with the transition metal compound and a complexating electron donor compound to form said precursor complex comprising said triaza compound, said transition metal compound and said complexating electron donor compound.
• the triaza compound is reacted with a starting complex of said transition metal compound and said complexating electron donor compound.
• a suitable complexating electron donor compound is e.g. tetrahydrofurane.
• R, R R ⁇ , M, X, m and n are as defined above (see formulas (1), (2) and (9)), CED is said complexating electron donor and p is an integer 1 to 3.
• the strong base may be any base which is capable of removing the substituent R from the carbon atom connected with all three nitrogen atoms, see above.
• it is an organoalkali compound having the formula R'A, wherein R' is a C C 12 hydrocarbyl and A is an alkali metal.
• R' is a C C 12 hydrocarbyl and A is an alkali metal.
• R' is a C C 12 hydrocarbyl and A is an alkali metal.
• R' is a C C 12 hydrocarbyl
• A is an alkali metal.
• benzyl potassium is benzyl potassium.
• a transition metal complex having a tri-N-uni-C-dentate ligand as at least one of the ligands L was described. During the synthesis of that complex, another new useful compound was found. As an immediate reaction product between the triaza compound (9) and the transition metal compound (10), a transition metal complex having a tri-N-dentate ligand was formed. See the precursor complex (11) above. The triaza compound was coordinated to the transition metal through the three nitrogen atoms without losing the substituent on its central carbon. With some metals, this product was formed spontaneously and could be isolated.
• the present invention also relates to a transition metal complex containing a tri-N-dentate triaza ligand (within brackets) of the formula (12) wherein the R of the triaza ligand within brackets is an organic group or hydrogen, each of R R ⁇ is independently selected from organic groups having from 1 to 10 carbon atoms, M is a central atom which is a metal selected from Groups 4-8 of the Periodic Table of the Elements, each X is independently an unidentate organic or halogen ligand, CED is a complexating dectron donor, m is the coordination number or number of coordination sites on the central atom M, n is the number of the triaza ligands, and p is an integer 1 to 3.
• the R of the triaza ligand within brackets is an organic group or hydrogen
• each of R R ⁇ is independently selected from organic groups having from 1 to 10 carbon atoms
• M is a central atom which is a metal selected from Groups 4-8 of the Periodic Table of the Elements
• R may be any organic group such as an alkyl, aryl, silyl or siloxy group. Typically R is a C C 6 alkyl or a trialkyl silyl group. Most preferably, R is hydrogen.
• said organic groups of at least one of the pairs: R 2 and R 3 , R-j and R 5 , and Re and R. are preferably interconnected to form a bridge structure.
• the groups of all of the pairs: R 2 and R 3 , R-t and R 5 , R ⁇ and Ri are most preferably interconnected to form bridge structures which are selected from 2 carbon and 3 carbon chanis.
• M of formula (12) is preferably selected from chromium Fe, Cr, titanium Ti and zirconium Zr.
• X is preferably selected from a C C 3 alkyl and a halogen, most preferably from methyl and chlorine Cl.
• the integer n of formula (12) is preferably 1 or 2.
• the complex of formula (12) is preferably an intermediate when preparing the complex according to formula (1). Under proper reaction conditions the complex of formula (12) may react further to form a complex of the formula (1) and RX may then be bound to the complex of formula (1) or they may escape from the system.
• the invention also relates to a catalyst system for the polymerization of ethylenically unsaturated compounds. It comprises a transition metal complex according to the above description and a cocatalyst selected from an aluminoxane having one of the following formulas (13)
• each R" is independently selected from a Ci-Cio alkyl and q is an integer between 1 and 40, and an organic compound having the formula (14)
• R"' is a CpCio hydrocarbyl
• X is a halogen
• r is 1, 2 or 3
• s is the valency of M'
• M' is a metal selected from Groups 1 to 3 and 13 of the Periodic Table of the Elements (IUPAC 1990)
• t is 1 or 2.
• Said organic compound also called an ionic catalyst activator
• said cocatalyst is a C ⁇ -C 10 aluminoxane, preferably a C C 6 aluminoxane, most preferably methyl aluminoxane.
• the invention relates to the use of the above described catalyst system for the polymerization of one or several ethylenically unsaturated compounds.
• at least one polymerizable ethylenically unsaturated compound is under polymerization conditions contacted with a catalyst system of the above described type.
• the atomic ratio Al/M or M'/M is preferably between 10 and 10000, most preferably between 100 and 2000.
• the polymerizable ethylenically unsaturated compound is preferably selected from ethylene, a C 3 -C 20 - ⁇ -olefin, a conjugated C -C 12 diene and a C 5 -C 1 - ⁇ - ⁇ -diolefin and polymerizable combinations thereof. Most preferably, it is ethylene.
• FeCl 3 (Merck) and TiCL t (Aldrich) were used without further purification.
• CrCl 3 (Merck) was converted into CrCl 3 -3 (THF) prior to use.
• the ⁇ -NMR spectra were recorded using a JEOL JNM-EX 270 Mhz FT NMR spectrometer with tetramethylsilane (TMS) as an internal reference.
• the MS spectra were recorded by a VG Quadrupole TRIO 2 electronic ionization method and direct probe 70 eV spectrometer.
• the polymerization tests were carried out using MAO, 30% solution in toluene purchased from Albermarle. Test polymerizations were carried out in pentane at 80 °C with no hydrogen present using an Al/Zr ratio of 1000 unless otherwise stated.
• a Buchi 2 L stirred reactor with mantle heating was used for the polymerization tests.
• the CrCl 3 (THF) 3 solution was then added dropwise during 2 hours at -78 °C into the triazatricyclotridecane solution and stirred overnight at -30 °C to give a dark green solution and a green precipitate.
• the solid green product was filtered and washed with more THF. All solvents were removed in a vacuum and the green solid product was analyzed. The yield was 20%.
• Polymerizations were carried out in a 2 1 stainless steel autoclave reactor equipped with a paddle stirred and a continuous supply of ethylene. Hydrogen and comonomer, if used were fed to the reactor simultaneously with ethylene. MFR's of the produced polymers were measured according to the ISO-1133 method. GPC was used to determine the average molecular weights and molecular weight distributions of the produced polymers. Polymerization temperature was 80 °C and ethylene pressure 10 bar. The amount of substances and the polymerization results are shown in Table 1. Table 1

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