EP1401848A1 - Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines - Google Patents

Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines

Info

Publication number
EP1401848A1
EP1401848A1 EP02751045A EP02751045A EP1401848A1 EP 1401848 A1 EP1401848 A1 EP 1401848A1 EP 02751045 A EP02751045 A EP 02751045A EP 02751045 A EP02751045 A EP 02751045A EP 1401848 A1 EP1401848 A1 EP 1401848A1
Authority
EP
European Patent Office
Prior art keywords
group
different
same
integer
alkylaryl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02751045A
Other languages
German (de)
English (en)
Inventor
Jörg Ludwig SCHULTE
Jörg SCHOTTEK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Ventures GmbH
Original Assignee
Celanese Ventures GmbH
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 Celanese Ventures GmbH filed Critical Celanese Ventures GmbH
Publication of EP1401848A1 publication Critical patent/EP1401848A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron 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

Definitions

  • Non-metallocenes processes for their preparation and their use in the polymerization of olefins
  • the present invention relates to a process for the preparation of special transition metal compounds, new transition metal compounds and their use for the polymerization of olefins
  • Metallocenes are used to generate polyolefins with special properties that cannot be achieved with conventional Ziegler catalysts. Metallocenes, optionally in combination with one or more cocatalysts, can be used as a catalyst component for the polymerization and copolymerization of olefins. In particular, as
  • Halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex.
  • non-metallocenes are described in the literature, for example in EP 874 005, which are notable for advantages in the representability and the cost of the educts. The high activities of these complexes represent a further cost-saving factor.
  • numerous compounds known from the literature such as e.g. in J. Organomet. Chem. 1999, 587, 58-66 and Organometallics 2001, 20, 408-
  • Ligands with transition metal compounds provide chiral transition metal complexes that are capable of stereospecifically polymerizing propene. This type of representation represents universal access to these new types of connection. The object underlying the invention is thus achieved by these connections.
  • the present invention relates to compounds of the formula I.
  • M 1 is a metal of III. to XII.
  • Group of the Periodic Table of the Elements in particular Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd or Cu and D 1 is the same or different and a donor atom of the XV and XVI.
  • Group of the Periodic Table of the Elements in particular N, P, As, O, S, Se and Te and D 2 is the same or different and a donor atom of XV and XVI.
  • N is a bridging structural element between the two donor atoms D 1 and X is the same or different and a hydrogen atom, a C C ⁇ o-
  • Hydrocarbon group such as C ⁇ -C ⁇ o-alkyl, C 6 -C ⁇ o-aryl, C 7 -C 2 o-alkylaryl, C 7 - C 20 arylalkyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl or a halogen atom, or OR 6 , SR 6 , OS0 2 R 6 , OSi (R 6 ) 3 , Si (R 6 ) 3 , P (R 6 ) 2 , P (R 6 ) 3 , NCR 6 , N (R 6 ) 3 , B (R 6 ) 4 , substituted or unsubstituted pyridine or N (R 6 ) 2 , and R 1 is the same or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 n-aryl group, a C -C 2 o-alkylaryl group, a C
  • radicals R 1 with one or more radicals R 2 can form a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl , which in turn can be substituted by one or more radicals R 6 , and
  • R 2 is the same or different and a hydrogen atom, a -C 20 alkyl group, a C 6 -C 20 aryl group, a C -C 20 alkylaryl group, a C -C 3 o-arylalkyl group, a C 2 -C 2 o-alkenyl group, a C 2 -C 2 r j: j alkynyl group or a halogen-containing C 1 -C 20 alkyl group, C 6 -C 2 o aryl group, C 7 -C 2 o alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 -
  • Alkynyl group or a heteroatom-containing CC 2 o -alkyl group, C 6 -C 20 aryl group, C 7 -C 20 alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group or Si (R 6 ) 3 means, where one or more radicals R 2 with one or more radicals R 1 and / or R 3 is a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or
  • Isoquinolinyl may form which may itself be substituted by one or more radicals R 6, and R 3 are identical or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 - aralkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group or a halogen-containing C 1 -C 20 alkyl, C 6 -C 20 - Aryl group, C 7 -C 2 o -alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 alkynyl group or a heteroatom-containing C 1 -C 20 alkyl group, C 6 - C 20 - ar l group, C 7 -C 20 alkyla
  • R 4 is the same or different and is a hydrogen atom, a C 1 -C 20 -alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 arylalkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 2 o-alkynyl group or a halogen-containing -C-C 20 alkyl group, C 6 -C 20 aryl group, C -C 2 o- alkylaryl group, C -C 3 o-arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 -
  • Alkynyl group or a heteroatom-containing C- ⁇ -C 2 o alkyl group Ce-C 2 o aryl, C 7 -C 20 -alkylaryl, C 7 -C 30 arylalkyl group, C 2 -C 20 - alkenyl or C 2 -C 20 alkynyl group, and R 5 are identical or different and are a hydrogen atom, a C ⁇ -C 2 o alkyl group, a C 6 -C 2 o-aryl group, a C 7 -C 20 alkylaryl group, a C 7 -C 30 -
  • Arylalkyl group a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group or a halogen-containing C ⁇ -C 20 alkyl, C 6 -C 20 aryl group, C7-C 20 - alkylaryl, C 7 -C 30 - Arylalkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group or a heteroatom-containing C 1 -C 2 rj alkyl group, C6-C20 aryl group, C 7 -C 20 alkylaryl group, C 7 -C 30 arylalkyl group, C2-C 2 0-
  • D 1 -Z 1 (R 5 ) fD 1 are:
  • Transition metal compounds of the formula I in which are preferred are preferred
  • M 1 is a metal of III. to XII.
  • Group of the Periodic Table of the Elements is, in particular Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe., Ru, Co, Rh, Ni, Pd or Cu and D 1 is the same or different and a donor atom of XV. and XVI.
  • Periodic table of the elements in particular N, P, O and S, and D 2 is identical or different and a donor atom of XV. and XVI.
  • Group of the Periodic Table of the Elements, in particular N, P, O and S, and Z is a bridging structural element between the two donor atoms D 1 , in particular formula !!
  • X is the same or different and is a C ⁇ -C ⁇ 0 -hydrocarbon group such as C-Cs alkyl, C 6 -C 10 aryl, CrCu-alkylaryl, C7-Cn aralkyl, C 2 -C ⁇ 0 - Alkenyl, C 2 -C ⁇ 0 - alkynyl or a halogen atom, or OR 6 , SR 6 , OS0 2 R 6 , OSi (R 6 ) 3 , Si (R ⁇ ) 3 , P (R 6 ) 2 , P (R 6 ) 3, NCR 6 , N (R 6 ) 3 , B (R 6 ) 4 , substituted or unsubstituted.es
  • R 1 is identical or different and is a hydrogen atom, a C 10 -C 10 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 8 alkylaryl group, a C -Cn- Ar lalkyl group, a C 2 -C ⁇ 0 alkenyl group, a C 2 -C ⁇ o alkynyl group or a halogen-containing C ⁇ -C ⁇ 0 alkyl group, C 6 -C 10 aryl group, C 7 -Cn-
  • Arylalkyl group a C 2 -C ⁇ 0 alkenyl group, a C 2 -C 10 alkynyl group or a halogen-containing CrCio alkyl group, C 6 -C ⁇ 0 aryl group, C 7 -C ⁇ r alkylaryl group, C 7 -Cn arylalkyl group, C 2 - C 10 alkenyl group, C 2 -C 10 alkynyl group or a hetero atom-containing CrC 10 alkyl group, C 6 -C 10 aryl group, C 7 -Cn alkylaryl group, C 7 -Cn arylalkyl group, C 2 -C ⁇ o-
  • Aryl group, C 7 -C ⁇ -alkylaryl, C7-Cn arylalkyl group, C 2 -C 10 - alkenyl or C 2 -C ⁇ 0 alkynyl group, and R 5 are identical or different and are a hydrogen atom, a G 1 -C 1 1 -
  • Alkylaryl group C -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 -
  • Alkynyl group or a hetero atom-containing C 20 alkyl group C 6 -C 20 -
  • Aryl group, C 7 -C 2 o-alkylaryl group, C 7 -C 30 arylalkyl group, C 2 -C 2 o-alkenyl group, C 2 -C 20 alkynyl group, and a are each the same or different and an integer of 1 to 4 and b are each the same or different and are an integer from 0 to 2 and c are each the same or different and are an integer from 0 to 2 and d are each the same or different and an integer from 0 to 2 and e are the same or different and are an integer from 0 to 2 and f are each the same or different and are an integer from 2 to 20 and g are each the same or different and 1 or 2 and h are each the same or are different and are an integer from 1 to 4 and i are each the same or different and are an integer from 0 to 24 and j are each the same or different and are an integer from 0 to 10,
  • Periodic table of the elements, in particular N, P, O and S, and D 2 is identical or different and a donor atom of XV. and XVI.
  • Periodic table of the elements is, in particular N, P, O and S, and Z corresponds to the formulas II d, II j, II o, II r or II s and X is the same or different and chloride, bromide, iodide, methyl, ethyl Propyl
  • R 1 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
  • a radical R 1 with a radical R 2 forms a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. 6 can be substituted, and R 2 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
  • a radical R 2 with a radical R 1 forms a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. 6 can be substituted, and R 3 is the same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-
  • R 4 is the same or different and is a hydrogen atom, methyl, ethyl, propyl, i-
  • R 5 is the same or different and is a hydrogen atom, methyl, ethyl, propyl, i-
  • R 5 can form a mono- or polycyclic ring system with one another, and R s is identical or different and is a hydrogen atom, fluorine, chlorine, bromine, iodine,
  • the ligands with bisimine structure can be obtained by condensing bisamines with aldehydes or ketones.
  • the bisamine ligands are obtained by reducing the corresponding bisimines or by alkylating bisamines with common alkylation reagents, e.g. Arylalkyl halides, prepared with the addition of bases in a solvent.
  • the reaction of bisimines with transition metal salts e.g. with iron (II) chloride, nickel (II) bromide * DME, cobalt (II) chloride or bisacetonitrile palladium dichloride in a solvent, e.g. Tetrahydrofuran or dichloromethane, provides the corresponding
  • Transition metal complexes The reaction of ligands with a bisamine structure with transition metal compounds, such as, for example, tetrabenzylzircon, tetrakis (dimethylamido) zircon, tetrabenzyltitanium, tetrakis (dimethylamido) titanium, Tetrabenzylhafnium or tetrakis (dimethylamido) hafnium, in a solvent such as benzene, toluene or tetrahydrofuran provides the corresponding transition metal complexes.
  • complexes of this type can be obtained by deprotonation of the bisamine ligand with a base in a solvent, such as toluene or THF, or solvent mixtures, followed by the conversion with
  • Transition metal halide dides such as e.g. Zirconium tetrachloride, titanium tetrachloride, or hafnium tetrachloride can be obtained.
  • the present invention also relates to a catalyst system which contains the chemical compound of the formula I according to the invention.
  • the metal complexes of the formula I according to the invention are particularly suitable as a constituent of catalyst systems for the preparation of polyolefins by polymerizing at least one olefin in the presence of a catalyst which contains at least one cocatalyst and at least one metal complex of the formula I.
  • the cocatalyst which, together with a transition metal complex of the formula I according to the invention, forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with a metal complex, converts the latter into a cationic compound.
  • a compound of the general formula (III) is preferred as the aluminoxane
  • aluminoxanes can e.g. cyclic as in formula (IV)
  • the radicals R in the formulas (III), (IV), (V) and (VI) can be the same or different and a Ci ⁇ rj hydrocarbon group such as a C-
  • the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, where hydrogen or isobutyl or n-
  • Butyl preferably 0.01 to 40% (number of radicals R) are contained.
  • the aluminoxane can be prepared in various ways by known methods.
  • One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminium hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • the C j ⁇ n-carbonaceous groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups, such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.
  • the C j ⁇ n-carbonaceous groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl or trifluoromethyl
  • unsaturated groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p
  • Lewis acids are trimethyl aluminum, triethyl aluminum,
  • Compounds which contain a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 ⁇ , CF3SO3- or CIO4-, are preferably used as ionic cocatalysts.
  • Protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and derivatives, N, N-dimethylcyclohexylamine and derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N- are used as cationic counterions.
  • Trimethylammonium tetra (tolyl) borate Trimethylammonium tetra (tolyl) borate, tributylammonium tetra (tolyl) borate,
  • Triphenylcarbenium tetrakis (phenyl) aluminate Triphenylcarbenium tetrakis (phenyl) aluminate
  • Ferrocenium (pentafluorophenyl) aluminate
  • Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
  • Borane or carborane compounds such as e.g.
  • Combinations of at least one of the amines mentioned above and a support with organic compounds as described in patent WO 99/40129 are also important as cocatalyst systems.
  • P 7 is a hydrogen atom, a halogen atom, a C- ⁇ -C o-koh! Enstoffha! Tige
  • R 17 can also be a -OSiR 18 3 group, in which R 18 are identical or different and have the same meaning as R 17 .
  • cocatalysts are generally compounds which are formed by the reaction of at least one compound of the formula (C) and / or (D) and / or (E) with at least one compound of the formula (F).
  • R 80 is a hydrogen atom or a boron-free C ⁇ -C 40 -group such as C ⁇ -C 20 alkyl, C 6 -C 20 aryl, C 7 -C 40 -Arylalky, C -C 40 -alkylaryl may be, and wherein
  • R1 has the same meaning as above,
  • X 1 is an element of VI.
  • Main group of the Periodic Table of the Elements or an NR group in which R is a hydrogen atom or a C 1 -C 2 -hydrocarbon radical such as C 1 -C 20 alkyl or C 1 -C 20 aryl, D is an element of VI.
  • Main group of the Periodic Table of the Elements or an NR group in which R is a hydrogen atom or a CrC 2 o hydrocarbon radical such as -CC 20 alkyl or C 1 -C 20 aryl, v is an integer from 0 to 3, s is a is an integer from 0 to 3, h is an integer from 1 to 10,
  • B is boron
  • AI is aluminum.
  • the elemental organic compounds are combined with an organometallic compound of the formula III to V and or VII [M ⁇ 0R ⁇ , where M ⁇ 0 is an element of I., II. And III. Main group of the Periodic Table of the Elements is, R19 is the same or different and is a hydrogen atom, a halogen atom, a C-
  • Examples of the cocatalytically active compounds of the formulas A and B are H 3 OC-
  • the organometallic compounds of the formula VII are preferably neutral Lewis acids in which M ⁇ O is lithium, magnesium and / or aluminum, in particular aluminum.
  • Examples of the preferred organometallic compounds of the formula XII are trimethylaluminium, triethylaluminium, triisopropylaluminum, trihexylaluminium, trioctylaluminium, tri-n-butylaluminium, trin-propylaluminium, triisoprenaluminium, dimethylaluminium monochloride, diethylaluminiumaluminiumchloromethylaluminium chloride, diethylaluminiumaluminium chloride, , Dimethylaluminiumhydrid, Diethylaluminiumhydrid, Diisopropylaluminiumhydrid, Dimethylaluminium (trimethylsiloxid), Dimethylaluminium (triethylsiloxid), Phenylalan, Pentafluorphen
  • the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g.
  • Suitable inorganic oxides can be found in the II-VI main group of the periodic table and the III-IV sub-group in the periodic table of the elements.
  • oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures, and hydrotalcites.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZrO 2 , Ti0 2 or B 2 0 3 , to name just a few.
  • the carrier materials used have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 ⁇ m. Carriers with a specific surface area in the range from 50 to 500 ⁇ m, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m are preferred. Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m are particularly preferred.
  • the carrier material used has a naturally low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time with an inert gas blanket (eg nitrogen). The drying temperature is between 100 and
  • the pressure parameter is not critical.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
  • Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane, or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
  • the chemical dehydration or inertization of the carrier material takes place, for example, by suspending the carrier material in a suitable manner with the exclusion of air and moisture Solvent with the inerting reagent in pure form or dissolved in a suitable solvent to react.
  • suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
  • the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
  • the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
  • the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then in an inert gas stream or on
  • Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
  • polyolefin powders e.g. polyethylene, polypropylene or polystyrene
  • At least one of the transition metal compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
  • the preparation so obtained is then mixed with the dehydrated or rendered inert support material, the solvent removed and the resulting supported transition metal compound catalyst system dried to ensure that all or most of the solvent is removed from the pores of the support material.
  • the supported catalyst is obtained as a free flowing powder.
  • a process for the preparation of a free-flowing and optionally prepolymerized transition metal compound catalyst system comprises the following steps: a) preparation of a transition metal compound / cocatalyst mixture in a suitable solvent or suspension medium, the transition metal compound component having one of the structures described above, b) application of the Transition metal compound / cocatalyst mixture on a porous, preferably inorganic, dehydrated support c) removing the majority of the solvent from the resulting mixture d) isolating the supported catalyst system e) optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer (s) to obtain a prepolymerized supported catalyst system.
  • Preferred solvents for the preparation of the transition metal compound / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of transition metal compound and cocatalyst components is soluble in the solvent selected.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene.
  • Toluene is very particularly preferred.
  • the amounts of aluminoxane and transition metal compound used in the preparation of the supported catalyst system can be varied over a wide range.
  • a molar ratio of aluminum to the transition metal in the transition metal compounds of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
  • 30% toluene solutions are preferably used; the use of 10% solutions is also possible.
  • the transition metal compound is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the transition metal compound separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used.
  • the preactivation time is 1 minute to 200 hours.
  • the preactivation can take place at room temperature (25 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 ° C.
  • the preactivated solution or the transition metal compound / cocatalyst mixture is then combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents.
  • the carrier material is preferably used as a powder. The order of addition is arbitrary.
  • Transition metal compound-cocatalyst solution or the transition metal compound-cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution presented.
  • Cocatalyst mixture can 100% of the total pore volume of the used
  • Contact can vary between 0 and 100 ° C. However, lower or higher temperatures are also possible.
  • the solvent is then completely or largely removed from the supported catalyst system, and the mixture can be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed.
  • the solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C.
  • the free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores.
  • the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely.
  • the supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • a low-boiling hydrocarbon such as pentane or hexane
  • the supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before it is used in a polymerization process.
  • the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • an olefin preferably an olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) can be added as a modifying component or an antistatic (as described in US Serial No. 08/365280) during or after the preparation of the supported catalyst system.
  • an olefin for example vinylcyclohexane, styrene or phenyldimethylvinylsilane
  • an antistatic as described in US Serial No. 08/365280
  • Metallocene component compound I is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula VII.
  • polymerization is understood to mean homopolymerization and also copolymerization.
  • Examples of such olefins are 1-olefins with 2 - 20, preferably 2 to 10 C -
  • Atoms such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene , Ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methyl norbornene.
  • Ethene or propene are preferably homopolymerized in the process according to the invention, or propene with ethene and / or with one or more 1-olefins having 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes 4 to 20 carbon atoms, such as 1, 4-butadiene, norbomadiene, ethylidene norbones or ethyl norbornadiene, copolymerized.
  • 1-olefins having 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane
  • dienes 4 to 20 carbon atoms such as 1, 4-butadiene, norbomadiene, ethylidene norbones or ethyl norbornadiene, copolymerized.
  • copolymers examples include ethene / propene copolymers, ethene / norbornene, ethene / styrene or ethene / propene / 1,4-hexadiene terpolymers.
  • the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • the catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one
  • Alkyl compound of the elements from I. to III. Main group of the periodic table, e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
  • the alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. The amount of the alkyl compound added depends on the quality of the monomers used. If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • the catalyst system can be fed to the polymerization system neat or for better dosing with inert components such as paraffins, oils or
  • an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used.
  • the polymers represented by the catalyst system according to the invention have a uniform grain morphology and have no fine grain proportions.
  • Polymerization with the catalyst system according to the invention does not result in deposits or caking.
  • Reaction mixture refluxed for one hour. After cooling 30 ml of water are added to room temperature and the product is extracted with 3 ⁇ 100 ml of dichloromethane. The combined organic phases are dried over magnesium sulfate and that
  • Phases are dried over magnesium sulfate, and the solvent is in
  • a solution of 3.30 g (5.0 mmol) of fraA7s-N, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamine in 60 ml of methanol is mixed with 1.14 g (30 mmol) of sodium borohydride in portions.
  • the solution is refluxed for 24 h and after cooling to room temperature with 20 ml of water are added.
  • the organic phase is extracted 3 times with 50 ml of dichloromethane and the combined organic phases are extracted 2 times with 30 ml of 10% ammonium chloride.
  • Example 12 (N'-P dimethylamino-methylenaminoJ-II 'jbinaphthalenyl ⁇ -yl] - N, N-dimethyl-formamidino) palladium (II) chloride
  • Example 17 (N 2 , N 2 '-Bis-dimethylaminomethyl- [1,1 , ] binaphthalenyl-2,2'-diamido) -dibenzylzircon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un nouveau groupe de composés de métaux de transition spéciaux, connus sous la désignation de </= composés non métallocènes >/= , ainsi que les systèmes catalyseurs fabriqués à partir de ceux-ci. Les systèmes catalyseurs préparés pour la première fois sont appropriés pour la polymérisation des oléfines.
EP02751045A 2001-06-22 2002-06-19 Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines Withdrawn EP1401848A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10130229 2001-06-22
DE10130229A DE10130229A1 (de) 2001-06-22 2001-06-22 Non-Metallocene, Verfahren zur Herstellung von diesen und deren Verwendung zur Polymerisation von Olefinen
PCT/EP2002/006772 WO2003004506A1 (fr) 2001-06-22 2002-06-19 Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines

Publications (1)

Publication Number Publication Date
EP1401848A1 true EP1401848A1 (fr) 2004-03-31

Family

ID=7689134

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02751045A Withdrawn EP1401848A1 (fr) 2001-06-22 2002-06-19 Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines

Country Status (6)

Country Link
US (2) US7148174B2 (fr)
EP (1) EP1401848A1 (fr)
JP (1) JP2004533487A (fr)
CN (1) CN100432084C (fr)
DE (1) DE10130229A1 (fr)
WO (1) WO2003004506A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6689848B2 (en) * 2002-03-04 2004-02-10 Equistar Chemicals, Lp Late transition metal polymerization catalysts
US7304172B2 (en) * 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
EP1982975A1 (fr) * 2007-04-17 2008-10-22 Total Petrochemicals Research Feluy Polymérisation d'éthylène et d'alpha-oléfines avec des systèmes de catalyseur basés sur des ligands dérivés de binam
CA2736482C (fr) 2008-09-08 2018-01-02 Novomer, Inc. Compositions de polycarbonate-polyol et procedes
KR101205474B1 (ko) 2008-10-01 2012-11-27 주식회사 엘지화학 금속 화합물 및 이를 이용한 올레핀 중합체의 제조방법
US8673998B2 (en) 2010-09-22 2014-03-18 Bridgestone Corporation Polymer compositions with improved cold flow
WO2012139994A1 (fr) 2011-04-13 2012-10-18 Basf Se Procédé de couplage d'époxydes et du dioxyde de carbone
CN102952021B (zh) * 2011-08-31 2014-04-16 云南大学 一种3,4-二甲基苯胺的合成方法
JP6360549B2 (ja) * 2013-03-15 2018-07-18 ユニベーション・テクノロジーズ・エルエルシー オレフィン重合触媒用の三座窒素系配位子
SG11201808185XA (en) * 2016-03-31 2018-10-30 Dow Global Technologies Llc Olefin polymerization catalyst systems and methods of use thereof
KR102344637B1 (ko) * 2016-03-31 2021-12-30 다우 글로벌 테크놀로지스 엘엘씨 올레핀 중합 촉매
CN109843949B (zh) * 2016-09-30 2021-08-10 陶氏环球技术有限责任公司 硫代胍iv族过渡金属催化剂和聚合系统
KR102448253B1 (ko) * 2016-09-30 2022-09-28 다우 글로벌 테크놀로지스 엘엘씨 티오우레아 iv군 전이 금속 촉매 및 중합 시스템
CN108359035B (zh) * 2017-01-26 2020-07-24 中国石油化工股份有限公司 一种乙烯与端烯基硅烷/硅氧烷的共聚方法
WO2020028606A1 (fr) 2018-08-02 2020-02-06 Saudi Aramco Technologies Company Compositions polymères durables et procédés
JP7647233B2 (ja) * 2021-03-29 2025-03-18 三菱ケミカル株式会社 オレフィン系共重合体の製造方法
US12195576B2 (en) 2021-06-23 2025-01-14 Saudi Aramco Technologies Company Polyol compositions and methods

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465630A (en) * 1981-08-24 1984-08-14 Asahi Kasei Kogyo Kabushiki Kaisha Tetraazaannulene cobalt complex compounds and method for preparation therefor
AU686576B2 (en) * 1990-05-02 1998-02-12 W.R. Grace & Co.-Conn. Polymer compositions containing oxygen scavenging compounds
US5200539A (en) * 1990-08-27 1993-04-06 Louisiana State University Board Of Supervisors, A Governing Body Of Louisiana State University Agricultural And Mechanical College Homogeneous bimetallic hydroformylation catalysts, and processes utilizing these catalysts for conducting hydroformylation reactions
US5449650A (en) 1992-12-08 1995-09-12 Mitsubishi Petrochemical Company Limited Catalyst components for polymerization of olefins and use thereof
KR100314971B1 (ko) 1993-05-25 2002-07-03 엑손모빌 케미칼 패턴츠 인코포레이티드 올레핀중합을위한지지된메탈로센촉매시스템,그의제조방법및용도
US6211107B1 (en) * 1994-02-04 2001-04-03 Smithkline Beecham P.L.C. Process for expoxidizing prochiral olefins and a catalyst therefor and intermediates for making the catalyst
ATE245665T1 (de) 1995-09-28 2003-08-15 Basell Polyolefine Gmbh Geträgertes katalysatorsystem, verfahren zu seiner herstellung und seine verwendung zur polymerisation von olefinen
DE19606167A1 (de) 1996-02-20 1997-08-21 Basf Ag Geträgerte Katalysatorsysteme
DE19622207A1 (de) 1996-06-03 1997-12-04 Hoechst Ag Chemische Verbindung
ES2160289T3 (es) 1996-08-13 2001-11-01 Basell Polyolefine Gmbh Sistema catalizador soportado, un procedimiento para su obtencion y su empleo para la polimerizacion de olefinas.
ATE325821T1 (de) 1996-08-13 2006-06-15 Basell Polyolefine Gmbh Geträgerte chemische verbindung
TW420693B (en) * 1997-04-25 2001-02-01 Mitsui Chemicals Inc Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers
US5744620A (en) * 1997-07-10 1998-04-28 Bayer Corporation Catalytic oxidation of cyclic olefins
US5981424A (en) * 1997-07-31 1999-11-09 Sunoco, Inc. (R&M) Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant
TW476765B (en) 1997-12-22 2002-02-21 Mitsui Chemicals Inc Catalyst component for ethylenically unsaturated monomer polymerization, catalyst for ethylenically unsaturated monomer polymerization, and process for ethylenically unsaturated monomer polymerization using said catalyst
DE19804970A1 (de) 1998-02-07 1999-08-12 Aventis Res & Tech Gmbh & Co Katalysatorsystem
US7053159B2 (en) * 2000-07-04 2006-05-30 Mitsui Chemicals, Inc. Process for producing polar olefin copolymer and polar olefin copolymer obtained thereby
US6686490B1 (en) * 2000-11-06 2004-02-03 Ramot University Authority For Applied Research & Industrial Development Ltd. Active non-metallocene pre-catalyst and method for tactic catalytic polymerization of alpha-olefin monomers
KR100342659B1 (en) * 2000-12-15 2002-07-04 Rstech Co Ltd Chiral polymer salene catalyst and process for preparing chiral compounds from racemic epoxide using the same
JP3968076B2 (ja) * 2001-06-27 2007-08-29 アールエス テック コーポレイション 新しいキラルサレン化合物、キラルサレン触媒及びこれを利用したラセミックエポキシ化合物からキラル化合物を製造する方法
US6809058B2 (en) * 2001-08-28 2004-10-26 Exxonmobil Research And Engineering Company Multi-dentate late transition metal catalyst complexes and polymerization methods using those complexes
US6730757B2 (en) * 2002-03-08 2004-05-04 Exxonmobil Research And Engineering Company Sulfur-containing and sulfur-nitrogen-containing catalysts for polymerization of olefins and polar monomers
US6897276B2 (en) * 2002-04-24 2005-05-24 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7091292B2 (en) * 2002-04-24 2006-08-15 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
US6781006B2 (en) * 2002-09-17 2004-08-24 Rhodia Pharma Solutions Inc. Active catalysts for stereoselective ring-opening reactions
US7304172B2 (en) * 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03004506A1 *

Also Published As

Publication number Publication date
DE10130229A1 (de) 2003-01-02
US20060135352A1 (en) 2006-06-22
CN1518556A (zh) 2004-08-04
JP2004533487A (ja) 2004-11-04
CN100432084C (zh) 2008-11-12
WO2003004506A1 (fr) 2003-01-16
US20050037918A1 (en) 2005-02-17
US7148174B2 (en) 2006-12-12

Similar Documents

Publication Publication Date Title
EP1133504B1 (fr) Procede de production de monoaryloxy-ansa-metallocenes
EP1074557A2 (fr) Complexes de métaux de transition, ligandes, catalyseurs, et leur utilisation dans la polymérisation d&#39;oléfines
EP1401848A1 (fr) Non-metallocenes, leur production et leur utilisation pour la polymerisation des olefines
DE602004006965T2 (de) Polymerisationskatalysatoren, organische übergangsmetallverbindungen, verfahren zur herstellung von polyolefinen
DE69725675T2 (de) Verfahren zur Herstellung von Metallocenen
DE19908938A1 (de) Übergangsmetallverbindung, Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE60011507T2 (de) Katalysator basierend auf einem Übergangsmetall aus den Gruppen 8, 9 und 10 für die Polymerisation von Olefinen
EP1000073B1 (fr) Procede de fabrication de metallocenes
EP1284981B1 (fr) Procede de preparation de composes de metaux de transition et leur utilisation pour polymeriser des olefines
EP1003757B1 (fr) Procede de fabrication de metallocenes
EP1373283A1 (fr) Non-metallocenes, leur procede de production et leur utilisation dans la polymerisation d&#39;olefines
DE60106277T2 (de) Katalysatoren
DE19922020A1 (de) Übergangsmetallverbindung, Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
EP1334107B1 (fr) Composes non metallocenes, leur procede de production et leur utilisation dans la polymerisation d&#39;olefines
WO2004041796A1 (fr) Catalyseurs a metal de transition pour la (co)polymerisation de monomeres olefiniques
DE60117569T2 (de) Liganden mit wenigstens einem fluorosilizium-substituenten zur herstellung von metallocenen
EP1368385A1 (fr) Compose de metal de transition utilise comme constituant de catalyseur et son utilisation pour produire des polyolefines
EP1992630B1 (fr) Composés non metallocènes fixés de façon covalente, procédé de fabrication de ceux-ci et utilisation pour la polymerisation
EP1523508A1 (fr) Metallocenes a geometrie contrainte&#34;, leur procede de production et leur utilisation pour la polymerisation d&#39;olefines
DE102004032581A1 (de) Polymerisationskatalysatoren, Hauptgruppenkoordinationsverbindungen, Verfahren zur Herstellung von Polyolefinen und Polyolefine
DE19962905A1 (de) Übergangsmetallverbindung, Ligandensystem, Katalysatorsystem und seine Verwendung zur Polymerisation und Copolymerisation von Olefinen
WO2002034758A1 (fr) Composition a base de complexes monofluorometalliques
DE10026786A1 (de) Verfahren zur Herstellung von Übergangsmetallverbindungen und deren Verwendung zur Polymerisation von Olefinen
DE10054649A1 (de) Verfahren zur Herstellung von Übergangsmetallverbindungen und deren Verwendung zur Polymerisation von Olefinen
DE19912576A1 (de) Verfahren zur Herstellung von Monoaryloxy-Ansa-Metallocenen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040122

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SCHOTTEK, JOERG

Inventor name: SCHULTE, JOERG LUDWIG

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SCHOTTEK, JOERG

Inventor name: SCHULTE, JOERG LUDWIG

17Q First examination report despatched

Effective date: 20050908

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070817