WO1997042163A1 - Compose de pentadiene substitue - Google Patents

Compose de pentadiene substitue Download PDF

Info

Publication number
WO1997042163A1
WO1997042163A1 PCT/NL1997/000237 NL9700237W WO9742163A1 WO 1997042163 A1 WO1997042163 A1 WO 1997042163A1 NL 9700237 W NL9700237 W NL 9700237W WO 9742163 A1 WO9742163 A1 WO 9742163A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound according
substituent
groups
hetero atom
Prior art date
Application number
PCT/NL1997/000237
Other languages
English (en)
Inventor
Gerardus Johannes Maria Gruter
Gerardus Henricus Josephus Van Doremaele
Henricus Johannes Arts
Original Assignee
Dsm N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU24113/97A priority Critical patent/AU2411397A/en
Publication of WO1997042163A1 publication Critical patent/WO1997042163A1/fr

Links

Classifications

    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/25—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
    • 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
    • C07F17/00—Metallocenes
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • 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
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • 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
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/845—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond

Definitions

  • the invention relates to a substituted pentadiene compound (pd compound) according to the formula
  • R 1 " 2 are substituents and at least one R 2 substituent has the form RDR' n , where
  • D is a hetero atom from group 15 or 16 of the Periodic System of the Elements
  • R' is a substituent on the hetero atom, R is a linking group.
  • pentadiene will be abbreviated as 'pd'.
  • the same abbreviation will be used for a pentadienyl group if it is clear, from the context, whether pentadiene itself or its anion is meant.
  • Unsubstituted pentadiene compounds are known.
  • the pd compounds according to the invention prove to be able to stabilize highly reactive intermediates such as organometal hydrides, organometal boron hydrides, organometal alkyls and organometal cations. If, for example, a mono-pd-substituted metal complex is obtained from metals in a lower valency state than the highest possible, in which the pd- containing ligand is mono-anionic, then it has a strongly stabilizing effect without blocking the active sites of the complex, so that the complexes have an excellent catalytic activity. From said publication it is impossible for one skilled in the art to deduce that the compounds according to the invention have such a specific activity. Similar complexes, in which the pd compound is not substituted in the indicated manner, prove to be unstable or, if they are stabilized in another way, have poorer catalytic properties than the complexes with substituted pd compounds according to the invention.
  • Organometal complexes of the pd compounds according to the invention further prove to be suitable as stable and volatile precursors for use in Metal Chemical Vapour Deposition.
  • a substituted pd compound is understood to be a pentadiene substituted with at least a group having the form RDR' n .
  • the R 1 groups may be the same as the R 2 groups to be defined below.
  • the R 1 groups may also be joined, so that a ring is formed.
  • the R 1 groups are joined to form a dimethylmethylene group.
  • the R 1 groups may each separately be hydrogen or a hydrocarbon radical containing 1 - 20 carbon atoms (such as alkyl, aryl, arylalkyl and the like). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. Two adjacent R 2 hydrocarbon radicals may also be joined in a ring system. This may even occur twice, so that, when two R 1 groups also form a ring, the pd compound eventually contains 3 rings. Such a group, too, may contain one or more R 2 groups as substituents.
  • R 2 may also be a substituent which contains one or more hetero atoms from groups 14 - 16 of the Periodic System of the Elements in addition to or instead of carbon and/or hydrogen.
  • a substituent may be a group containing N, 0 and/or Si.
  • One R 2 may also be a cyciopentadienyl group or pd group.
  • the R group forms the link between the pd and the DR' n group.
  • the length of the shortest link between the pd and D hereinafter referred to as the main chain of R, is critical to the extent that it determines the accessibility of the metal in the metal complex for the DR' n group in order thus to achieve the desired intramolecular coordination. If the R group (or bridge) is too short, ring tension may cause the donor to be unable to coordinate well.
  • the R group may be a hydrocarbon group containing 1 - 20 carbon atoms (such as alkylidene, arylidene, arylalkylidene and the like). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, optionally having a substituted side chain.
  • the R group has the following structure:
  • R 4 groups are as defined for R 2 .
  • the main chain of the R group may thus contain silicon or germanium besides carbon.
  • R groups are: dialkylsilylene, dialkylgermylene, tetra-alkyldisilylene or tetraalkylsilaethylene (-SiR' 2 CR' 2 -) .
  • the alkyl groups in such a group preferably have 1-4 C atoms and are, more preferably, a methyl or ethyl group.
  • the DR' n group comprises a hetero atom D chosen from group 15 or 16 of the Periodic System of the Elements and one or more substituent(s) R f bound to D.
  • the hetero atom D is chosen from the group comprising nitrogen (N) , oxygen (0), phosphorus (P) or sulphur (S); more preferably, the hetero atom is nitrogen (N).
  • the R' groups may be the same or different and may be chosen from the same groups as defined for R 2 , with the exception of hydrogen.
  • the R' group is preferably an alkyl, more preferably an n-alkyl group containing 1-20 C atoms.
  • the R' group is an n-alkyl containing 1-10 C atoms.
  • Another possibility is that two R' groups in the DR' n group are joined to form a ring-type structure (so that the DR' n group may be a pyrrolidinyl group) .
  • the DR' n group may bond coordinatively to a metal.
  • the DR' n group may also be an aryl group, for example phenyl, tolyl, xylyl, mesitylyl, cumyl, tetramethylphenyl, pentamethylphenyl.
  • a pd substituted with an aryl group as described above is used as ligand on a metal, the coordination of this group on the metal may vary from h. 1 tot ⁇ 6 .
  • the substituted pd compounds according to the invention are found to yield compounds having a good stability and a good catalytic activity.
  • the invention therefore also relates to this application. These compounds, for that matter, also give good results when used as ligands on metals which are in their highest valency state. In that case as well, active catalysts are obtained, which in many cases give better results in a specific application than the known pd-containing ligands.
  • Metal complexes which are catalytically active if one of their ligands is a compound according to the invention are the metals from groups 4-12 of the Periodic System and rare earths. Particularly suitable for the polymerization of olefins are such metal complexes in which the metal is chosen from the group consisting of Ti, Zr, Hf, V, Co, Pd and Cr.
  • the invention therefore also relates to the metal complexes thus composed and their application as catalysts, in particular for the polymerization of olefins, of linear as well as branched and cyclic olefins and optionally conjugated dienes and mixtures thereof.
  • complexes of metals from groups 4 and 5 of the Periodic System of the Elements are preferably used as a catalyst component for polymerizing olefins; complexes of metals from groups 6 and 7 of the Periodic System of the Elements in addition also for metathesis and ring-opening metathesis polymerizations, and complexes of metals from groups 8-10 of the Periodic System of the Elements for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations.
  • a group of the form RDR' n can be attached, for example via the following synthesis route.
  • a substituted pd compound is deprotonated by reaction with a base, sodium or potassium.
  • organolithium compounds R s Li
  • organomagnesium compounds R s MgX
  • R 5 is an alkyl, aryl, or aralkyl group
  • X is a halide
  • n- butyllithium or i-propylmagnesium chloride n- butyllithium or i-propylmagnesium chloride.
  • Potassium hydride, sodium hydride, tertiary amines such as pyridine and triethylamine
  • inorganic bases such as NaOH and KOH
  • alcoholates of Li, K and Na can also be used as base.
  • Mixtures of the above-mentioned compounds can also be used.
  • strong bases are used, such as the mixture of n-butyllithium and potassium-t-butoxide.
  • This reaction can be carried out in a polar dispersing agent, for example an ether.
  • a polar dispersing agent for example an ether.
  • suitable ethers are tetrahydrofuran (THF) or dibutyl ether.
  • THF tetrahydrofuran
  • Nonpolar solvents such as for example toluene, can also be used.
  • the pentadienyl anion obtained reacts with a compound of the formula (DR' n -R-Y) or (X-R-Sul), where D, R, R' and n are as defined in the foregoing and Y is a halogen atom (X) or a sulphonyl group (Sul).
  • Halogen atom X may be, for example, chlorine, bromine and iodine.
  • the halogen atom X is preferably a chlorine or bromine atom.
  • the sulphonyl group has the form -OS0 2 R 6 , where R 6 is a hydrocarbon radical containing 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene and naphthalene. R 6 may also contain one or more hetero atoms from groups 14-17 of the Periodic System of the Elements, such as N, 0 or F, in addition to or instead of carbon and/or hydrogen. Examples of sulphonyl groups are: phenylmethanesulphonyl, benzenesulphonyl, 1-butane- sulphonyl, 2,5-dichlorobenzenesulphonyl,
  • 5-dimethylamino-l-naphthalenesulphonyl pentafluoro- benzenesulphonyl, p-toluenesulphonyl, trichloromethane- sulphonyl, trifluoro-methanesulphonyl, 2,4,6- triisopropylbenzenesulphonyl, 2,4,6- trimethylbenzenesulphonyl, 2-mesitylenesulphonyl, methanesulphonyl, 4-methoxybenzenesulphonyl, 1- naphthalenesulphonyl, 2-naphthalenesulphonyl, ethane- sulphonyl, 4-fluorobenzenesulphonyl and 1-hexadecane- sulphonyl.
  • the sulphonyl group is p- toluenesulphonyl or trifluoromethanesulphonyl.
  • the compound according to the formula (DR' n -R-Y) is formed in situ by reaction of an aminoalcohol compound (R' 2 NR-0H) with, successively, a base (such as described above), potassium or sodium and a sulphonyl halide (Sul-X).
  • the second reaction step can also be carried out in a polar solvent as described for the first step.
  • the temperature at which the reaction is carried out is -60 to 80°C.
  • Reactions with X-R-Sul and with DR' n -R-Y where Y is Br or I are usually carried out at a temperature between -20 and 20°C.
  • Reactions with DR' n - R-Y where Y is Cl are usually carried out at a higher temperature (10 to 80°C).
  • the upper limit for the temperature at which the reactions are carried out is determined in part by the boiling point of the solvent.
  • a reaction with LiDR' n or HDR' n is carried out to replace X by a DR' moment functionality. This is done by means of a reaction carried out at 20 to 80°C, optionally in a similar solvent as mentioned above.
  • the polymerization of ⁇ -olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and with dienes, can be carried out in the presence of the metal complexes with the cyclo- pentadienyl compounds according to the invention as ligand.
  • Particularly suitable for this purpose are the complexes of transition metals, not in their highest valency state, in which just one of the cyciopentadienyl compounds according to the invention is present as ligand and in which the metal is cationic during the polymerization.
  • Said polymerizations can be carried out in the manner known for the purpose and the use of the metal complexes as catalyst component does not necessitate any essential adaptation of these processes.
  • the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization.
  • An organometallic compound is normally used as co-catalyst, the metal being chosen from groups 1, 2, 12 or 13 of the Periodic System of the Elements.
  • the polymerizations are carried out at temperatures between -50°C and +350°C, more particularly between 25 and 250°C.
  • the pressures used are generally between atmospheric pressure and 250 MPa, for bulk polymerizations more particularly between 50 and 250 MPa, and for the other polymerization processes between 0.5 and 25 MPa.
  • dispersants and solvents use may be made of, for example, hydrocarbons, such as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated, hydrocarbons are also suitable.
  • the monomer to be used in the polymerization may also be used as dispersant or solvent.
  • GC type Hewlett Packard 5890 Series II, provided with autosampler type HP6890 Series Injector, integrator type HP3396A and HP Crosslinked Methyl Silicon Gum (25 m x 0.32 mm x 1.05 ⁇ m) column with one of the following temperature programmes: 50°C (5 min), rate: 7.5°C/min, 250°C (29 minutes) or 150°C (5 min), rate: 7.5°C/min. 250°C (29 minutes).
  • the products were characterized using GC-MS (type
  • Example Ia Preparation of 6,6-dimethyl-l,3- cyclohexadiene 200 mL of dry diethylether was added to 50.7 g of dimedon (0.36 mol), followed by cooling to O'C. To the suspension thus obtained a suspension of lithium aluminiumhydride (12.8 g; 0.337 mol) in dry diethylether was added. Then the ice bath was removed and stirring took place for 2 hours at room temperature, after which another slurry, of 7.5 g lithiumaluminiumhydride in diethylether, was added. Subsequently, refluxing took place for 2 hours.
  • This fraction consisting of a clear, colourless top layer and a grey, turbid bottom layer, was diluted with 150 mL of diethylether and extracted with, successively, 100 mL of Na 2 C0 3 (10 %) and 2x 100 mL of water. Then the diethylether layer was dried over magnesium sulphate. After the drying agent had been filtered off, the filtrate was evaporated down on the rotation evaporator, at 45 * C and at atmospheric pressure. A colourless, clear residue was obtained, which was distilled under vacuum at room temperature. In a cold trap a colourless, clear liquid was collected.
  • Example lb Preparation of 3-(dimethylaminoethyl)-6,6- dimethyl-l,4-cyclohexadiene 6.9 g of potassium-tertiary-butoxide (62 mmol) was dissolved in 100 mL of dry diethylether and cooled to -70'C. Subsequently, 6,5 g of crude 6,6- dimethyl-1,3-cyclohexadiene was added. 37.0 mL of BuLi in hexane, 1.6 M (59 mmol) was added dropwise to this reaction mixture. After the reaction mixture had reach room temperature, it had turned into a yellow suspension.
  • Example lc Preparation of 3-(dimethylaminoethyl)-6,6- dimethylcyclohexadienyltitaniumdichloride 0.31 g of potassium-tertiary-butoxide (2.8 mmol) was dissolved in 10 mL of dry THF, followed by cooling to -70'C. Then, 0.5 g (2.79 mmol) of 3- (dimethylaminoethyl)-6,6-dimethyl-l,3-cyclohexadiene was added. To this reaction mixture 1.75 mL of n-BuLi in hexane (1.6 M, 2.8 mmol) was added dropwise. After the reaction mixture had reached room temperature, stirring was continued for another hour.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

Cette invention se rapporte à un composé de pentadiène substitué ayant la formule (I) ou (II), où R1-2 représentent des substituants et au moins un substituant R2 se présente sous la forme RDR'¿n?, où D représente un atome hétéro choisi dans le groupe 15 ou 16 du système périodique des éléments, R' représente un substituant sur l'atome hétéro et R représente un groupe de liaison. Cette invention se rapporte également à un procédé pour la synthèse d'un composé de pentadiène substitué. Des complexes métalliques, dans lesquels au moins l'un de ces composés de cyclopentadiène est présent comme ligand, sont utiles comme catalyseurs pour la polymérisation des alpha-oléfines.
PCT/NL1997/000237 1996-05-03 1997-04-29 Compose de pentadiene substitue WO1997042163A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24113/97A AU2411397A (en) 1996-05-03 1997-04-29 Substituted pentadiene compound

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1003016A NL1003016C2 (nl) 1996-05-03 1996-05-03 Gesubstitueerde pentadieenverbinding.
NL1003016 1996-05-03

Publications (1)

Publication Number Publication Date
WO1997042163A1 true WO1997042163A1 (fr) 1997-11-13

Family

ID=19762787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1997/000237 WO1997042163A1 (fr) 1996-05-03 1997-04-29 Compose de pentadiene substitue

Country Status (3)

Country Link
AU (1) AU2411397A (fr)
NL (1) NL1003016C2 (fr)
WO (1) WO1997042163A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466162A (en) * 1966-02-25 1969-09-09 Hoffmann La Roche Process for control of algae growth using compositions containing diamines and/or derivatives thereof
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette
JPH06279478A (ja) * 1993-03-24 1994-10-04 Mitsui Petrochem Ind Ltd シクロペンタジエニル基含有ケイ素化合物またはシクロペンタジエニル基含有ゲルマニウム化合物の製造方法
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine
EP0728769A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0728770A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Procédé de préparation de composants solides de catalyseur pour la polymérisation d'oléfines
EP0728724A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466162A (en) * 1966-02-25 1969-09-09 Hoffmann La Roche Process for control of algae growth using compositions containing diamines and/or derivatives thereof
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette
JPH06279478A (ja) * 1993-03-24 1994-10-04 Mitsui Petrochem Ind Ltd シクロペンタジエニル基含有ケイ素化合物またはシクロペンタジエニル基含有ゲルマニウム化合物の製造方法
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine
EP0728769A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0728770A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Procédé de préparation de composants solides de catalyseur pour la polymérisation d'oléfines
EP0728724A1 (fr) * 1995-02-21 1996-08-28 Montell North America Inc. Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
B. HASIAK: "Évolution thermique de sels et hydroxydes de N-diméthyl pipéridinium alpha-substituées. III. Pyrolyse de sels et d'hydroxydes de diméthyl-1,1 alcényl-2 pipéridinium", BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE, no. 9-10, 1976, PARIS FR, pages 1526 - 1530, XP002020387 *
BENSLEY, DENNIS M., JR. ET AL: "Synthesis of [C5(CH3)4H]CH2CH2CH2P(C6H5)2: a novel heterodifunctional ligand possessing both a tetramethylcyclopentadiene and a remote diphenylphosphine functionality", J. ORG. CHEM. (1988), 53(18), 4417-19 CODEN: JOCEAH;ISSN: 0022-3263, 1988, XP002020381 *
CHEMICAL ABSTRACTS, vol. 123, no. 13, 25 September 1995, Columbus, Ohio, US; abstract no. 169881, KISO, YOSHIHISA ET AL: "Preparation of cyclopentadienylsilicon or -germanium compounds" XP002020388 *
CHUNG, R. H. ET AL: "1-Isopropyl-4-methylenebicyclo[3.1.0]hex-2-ene. Synthesis and reactions", J. AMER. CHEM. SOC. (1972), 94(7), 2183-7 CODEN: JACSAT, 1972, XP002020385 *
G. KRESZE ET AL.: "Substitierte Cyclopentadiene und ihre Diels-Alder-Reaktionen", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 666, 1963, WEINHEIM DE, pages 45 - 53, XP002020383 *
J. SZYMONIAK ET AL.: "New Heterodifunctional Ligands for Organotransiton-Metal Chemistry: Ph2P(CH2)nC5Me4H (n=0,2)", JOURNAL OF ORGANIC CHEMISTRY, vol. 55, 1990, EASTON US, pages 1429 - 1432, XP000601947 *
K. HAFNER ET AL.: "Synthesen und Reaktionen von Fulvenaldehyden", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 661, 1963, WEINHEIM DE, pages 52 - 75, XP002020382 *
KRUT'KO, D. P. ET AL: "Tetramethyl(2-methylthioethyl)cyclopentadienyl complexes of zirconium(IV). Synthesis, crystal structure, and dynamic behavior in solutions", RUSSIAN CHEMICAL BULLETIN, vol. 45, no. 4, April 1996 (1996-04-01), pages 940 - 949, XP002020384 *
MU, YING ET AL: "Use of Alkane Elimination in the One-Step Synthesis of Organoscandium Complexes Containing a New Multidentate Cyclopentadienyl Ligand", ORGANOMETALLICS (1996), 15(14), 2720-2726 CODEN: ORGND7;ISSN: 0276-7333, 1996, XP000612366 *
P.V. BALAKRISHNAN ET AL.: "(Pentamethylcyclopentadiene)palladium complexes", J. CHEM. SOC. A (1971), (11), 1721-5 CODEN: JCSIAP, 1971, XP002020380 *
SIEMELING, ULRICH: "C5Me4(CH2)3(OCH2CH2)3OMe: a tentacle-bearing cyclopentadienyl ligand and its use in complex chemistry", J. CHEM. SOC., CHEM. COMMUN. (1992), (18), 1335-6 CODEN: JCCCAT;ISSN: 0022-4936, 1992, XP002020386 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

Also Published As

Publication number Publication date
AU2411397A (en) 1997-11-26
NL1003016C2 (nl) 1997-11-06

Similar Documents

Publication Publication Date Title
KR19980703435A (ko) 전이금속화합물, 올레핀중합용 촉매 및 올레핀계 중합체의 제조방법
CN100390116C (zh) α-烯烃的三聚方法
US20060135352A1 (en) Process for polymerizing olefins with non-metallocene catalysts
US6825296B2 (en) Catalyst component for olefin polymerization
WO1997042145A1 (fr) Procede de transformation d'un cyclopentadiene a substitution geminale
CN107406535B (zh) 复合负载型催化剂体系及使用其制备聚烯烃的方法
US6072067A (en) Cyclopentadiene compound substituted with a hetero atom-containing group
KR102165484B1 (ko) 올레핀 중합 촉매용 전이금속 화합물 및 이를 포함하는 올레핀 중합 촉매
KR100961079B1 (ko) 올레핀 중합용 촉매 및 이를 이용한 올레핀의 중합방법
WO1997042163A1 (fr) Compose de pentadiene substitue
US6063948A (en) Process for cyclopentadiene substitution with groups differing from each other
US6124488A (en) Cyclopentadiene compound substituted with branched alkyl groups
US20060052620A1 (en) Preparation of substituted indenes
EP1225179B1 (fr) Catalyseurs de polymerisation d'olefines
KR100834889B1 (ko) 전이금속 화합물, 프로필렌 중합용 촉매, 및 상기 촉매를이용한 프로필렌 중합체의 제조방법
WO1997042151A1 (fr) Compose de cyclopentadiene substitue par des groupes chiraux
US6117811A (en) Cyclopentadiene compound substituted with linear groups
WO1997042162A1 (fr) Compose de cyclopentadiene substitue avec des groupes alkyle ramifies
WO1997042161A1 (fr) Compose de cyclopentadiene substitue par des groupes lineaires
KR101178996B1 (ko) 1-헥센 제조용 촉매 및 이를 이용한 1-헥센의 제조방법
WO1997042164A1 (fr) Indene substitue par un groupe comportant un heteroatome
WO1997042149A1 (fr) Compose de cyclopentadiene substitue par des groupes tertiaires
WO1997042165A1 (fr) Fluorene substitue par un groupe comportant un heteroatome
WO1997042147A1 (fr) Compose de cyclopentadiene substitue par des groupes aralkyle
CN100420700C (zh) 桥联茂金属异双核催化剂及其制备方法与应用

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE GE HU IL IS JP KP KR LC LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK TR TT UA US UZ VN YU AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97539787

Format of ref document f/p: F

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase