EP0896592A1 - Compose de cyclopentadiene a anion non coordinateur - Google Patents

Compose de cyclopentadiene a anion non coordinateur

Info

Publication number
EP0896592A1
EP0896592A1 EP97919751A EP97919751A EP0896592A1 EP 0896592 A1 EP0896592 A1 EP 0896592A1 EP 97919751 A EP97919751 A EP 97919751A EP 97919751 A EP97919751 A EP 97919751A EP 0896592 A1 EP0896592 A1 EP 0896592A1
Authority
EP
European Patent Office
Prior art keywords
precursor
group
bound
derivative
catalyst
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Withdrawn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
EP97919751A
Other languages
German (de)
English (en)
Inventor
Rutgerus Antonie Jacobus Postema
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 NV filed Critical DSM NV
Publication of EP0896592A1 publication Critical patent/EP0896592A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the invention relates to a precursor for a catalyst, comprising a transition metal or lanthanide with a ligand system in which at least one Cp
  • a disadvantage of the known precursors is that their activation in the way described above may result in byproducts being formed that may have an adverse effect on the polymerization process or, if they exhibit catalytic activity themselves, may give rise to the formation of undesired byproducts. Moreover, the anion or a derivative thereof remains behind in the reaction mixture. In the process
  • N-N- dimethylaniline a toxic substance, which ends up in the polymer formed and limits its applicability, for instance in food packagings. That is why there is a need for precursors that can be activated in situ without the above-mentioned adverse effects occurring.
  • the precursor contains a non- coordinating A- anion which can stabilize a catalyst obtained by activation of the precursor and which is bound to a cationic group of the Cp derivative or is bound to a cationic group forming part of or being bound to a bridge bound to the Cp derivative within the precursor, the cationic group containing a subgroup that is capable of reacting which a metal-bound alkyl, benzyl, or phenyl group.
  • the precursor according to the invention can simply be activated by contacting it with only an alkylating compound, upon which the anion stabilizes the metal that has become cationic on activation without affecting the capability of the cationic metal complex to act as catalyst. For this reason the anion must be labile enough to be replaced by a monomer to be polymerized. Although the inventor does not want to be bound by any theoretical explanation, the following seems to be a plausible description of the mechanism that occurs.
  • the reaction with the alkylating compound causes two or more of the non-Cp ligands on the metal to be replaced by an alkyl group, of which at least one subsequently reacts in turn with the subgroup bound to the cationic group which is capable of reacting with a metal-bound alkyl, benzyl, or phenyl group.
  • This causes the metal to become cationic, while also the non- coordinating anion is liberated.
  • the non-coordinating anion then stabilizes the cationic metal complex.
  • a catalyst is formed which, apart from the presence of a neutral residue of the cationic group, corresponds to the known precursor described above after it has been activated with a non-coordinating anion, if necessary in the presence of an alkylating compound, to yield a catalyst.
  • the precursor according to the invention differs from the known precursors in that it already contains the non-coordinating anion, so that this anion is always available in the right amount, and in that the addition of an alkylating compound directly results in its conversion into the active catalyst, without the formation of undesirable byproducts.
  • any compound can be used in which a transition metal or lanthanide with a ligand system containing at least one Cp derivative is present and which can be activated to yield a catalyst by a non- coordination anion, if necessary in the presence of an alkylating agent.
  • a great many of such compounds are known.
  • the precursor according to the invention differs from these known compounds in that it contains a cationic group that is bound to the Cp derivative or a cationic group that forming part of or being bound to a bridge bound to the Cp derivative within the precursor, the cationic group containing a group that is capable of reacting with a metal-bound alkyl, benzyl or phenyl group.
  • the precursor according to the invention also exists in a great many variants.
  • Examples of basic forms of compounds, known per se, which can serve as precursor according to the invention if they contain a non-coordinating anion bound to a cationic group at one of the positions specified above are:
  • R n Cp is a cyclopentadienyl derivative, in which Cp is a cyclopentadienyl group or a group derived from such a group, for example an indenyl group or a fluorenyl group, including the corresponding compounds which contain at least one hetero atom in the Cp ring, chosen from group 15 or 16 of the Periodic System of the
  • R groups each separately are hydrogen, a hydrocarbon radical with 1-20 C-atoms, for example alkyl, aryl, aralkyl, or a corresponding group which instead of carbon or hydrogen contains one or more hetero atoms from group 15 or 16 of the Periodic
  • M is a transition metal chosen from group 4, 5 or 6 of the Periodic System of the Elements or a lanthanide, preferably titanium, zirconium or hafnium, which may be either in its highest valence state or in a reduced valence state;
  • R 1 is a mono-anionic ligand, excluding a Cp derivative or a group from such a derivative and excluding an alkyl group.
  • R 1 may be subject to other limitations and preferences. These will be specified when the cationic group is discussed.
  • n ranges from 0 up to and including the number of positions that are free for substitution on Cp and m is the valence state of M minus 1.
  • Such compounds are known, for example, from EP-A- 420.134. wherein R, R 1 , Cp, n and M are as defined above, m is the valence of M minus 2 and Z forms a bridge between Cp and Y.
  • Such compounds are known from US-A-5.272.236 and Z and Y here have the same meaning as in said patent specification.
  • the precursor according to the invention differs from said compounds in that a cationic group X + is present in the precursor. Also, a non-coordinating anion A- is bound to this cationic group X + .
  • the precursor therefore contains a group of the form -X + A-, while in all complexes mentioned, (I)-(IV), X may take the place of a group R.
  • X may take the place of a group R.
  • X may also be bound to Y or Z or X may also form part of Z.
  • X may also form part of the bridge A' or be bound to it.
  • the cationic group X+ preferably has the form -Q-D + (R 2 ) k (R 3 ) (V) wherein 0 may be absent or be a hydrocarbon group with 1-20 C atoms, for example alkylidene, arylidene, arylalkylidene, optionally with a substituted side chain.
  • Q-groups which instead of carbon or hydrogen contains one or more hetero atoms from group 15-16 of the Periodic System.
  • Q-groups then are dialkylsililene, dialkylgermylene, tetraalkyl- disilylene, tetraalkylsiliethylene.
  • the alkyl groups in such a Q-group preferably have 1-4 C-atoms and are more preferably a methyl or ethyl group.
  • D is a hetero atom chosen from group 15 or 16
  • R 2 is a hydrocarbon radical with 1-20 C-atoms
  • alkyl for example alkyl, aryl, aralkyl, or a corresponding substituent which instead of carbon or hydrogen
  • R 3 is a group that is capable of reacting with a metal-bound alkyl, benzyl or phenyl group and preferably H
  • k is the valence of D minus 1 when X is bound to Cp, Cp' or to a bridge and equal to the valence of D minus 2, when X forms part of a bridge.
  • the group R 1 described above must not be
  • R 1 reactive with R 3 and preferably R 1 is a halogen, more preferably chlorine.
  • the cationic group X+ can be formed in these compounds by a compound of a group R 3 .
  • M is Ti(III) and m consequently 2.
  • the presence of the -QD(R 2 ) k group is essential for the catalytic action of these
  • precursors according to the invention based on the known precursors according to formulas I-IV and differing therefrom by the presence of a cationic group according to formula V and a non- coordinating anion bound thereto are the following:
  • the anion A- is a non-coordinating anion and can stabilize a catalyst obtained by activation of the precursor.
  • A- preferably contains at least an element from group 13.
  • halocarbyl radical or a hydrocarbyl- or halocarbyl- substituted organometalloid radical which each, but not more than one at a time, may be a halide radical.
  • the charge of the anion equals the number of radicals minus the formal valence of the metal or metalloid.
  • suitable metalloids are B, P and Si.
  • Suitable B-containing compounds are, for example, tetra (phenyl)borate, tetra(p-tolyl)borate, tetra(o- tolyl)borate, tetra(pentafluorphenyl)borate, tetra(o,p- dimethylphenyl) borate, tetra (m,m-dimethylphenyl)borate and tetra(p-trifluoromethylphenyl)borate.
  • tetra (pentafluorophenyl)borate is used.
  • the precursors according to the invention are prepared in a way that is analogous with the
  • a compound having the form - QD(R 2 ) k is bound to one of the constituent parts, from which according to a process known for this a
  • the R 3 group is bound to the -QD(R 2 ) k group, the entire compound being
  • the last and the penultimate step can be combined and A- can be combined with the - QD(R 2 ) k group in a single step, it being understood that in that case the R 3 group in de precursor is hydrogen.
  • the invention also relates to a process for the polymerization of ⁇ -olefines, diolefines and other ethylenically unsaturated monomers in the presence of a catalyst comprising a transition metal or lanthanide with a ligand system in which at least one Cp
  • a drawback of this known process is that besides the desired catalyst byproducts may be formed, as described in US-A-5.198.401, that may have an adverse effect on the polymerization process or, if they display catalytic activity themselves, may give rise to the formation of undesired byproducts.
  • the aim of the invention is to provide a process in which this drawback is eliminated or
  • the catalyst is formed by contacting a
  • the non-coordinating anion is already present, being bound one to one to the precursor, and there is no need to add it in complex form, so that the formation of foreign components in the polymerization mixture is avoided.
  • the precursors described above can be used.
  • One skilled in the art will choose the suitable precursor on the basis of his knowledge of the suitability of the catalyst formed in the activation with the alkylating compound for the intended polymerization.
  • Suitable alkylating compounds are compounds meeting the general formula M'R 5 k-m X' m , wherein M' is an element from group 1, 2, 12 or 13 of the Periodic
  • k is the oxidation state of M'
  • R 5 is a hydrocarbon radical with 1-20 carbon atoms
  • X' is a halogen atom or an alkoxy group with 1-20 carbon atoms
  • Oligomeric organo- aluminium compounds with linear and cyclic structures such as for example MAO (methylaluminoxane), are also suitable.
  • suitable alkylating compounds are methyllithium, butyllithium, phenyllithium,
  • trioctylaluminium ethylaluminiumsesquichloride, ethylaluminiumdichloride, diethylaluminiumethoxide, dioctylaluminiumiodide, diethylaluminiumhydride, methylaluminoxane, ethylaluminoxane, triethylboron and dimethylboronbromide.
  • trioctylaluminium or methylaluminoxane are used as alkylating compound.
  • dimethylaminohydrochloride-ethylcyclopentadienyltitaniumtrichloride was obtained in the form of an orange powder (quantitative).
  • precursors A The compounds synthesized in Examples I and II hereinafter to be referred to as precursors A
  • Example II Example II
  • a 1.3 litre reactor was charged with 400 ml of pentamethylheptane and ethylene and heating took place up to the polymerization temperature of 160 °C; the pressure eventually was 2 MPa. Subsequently, an amount of a solution of an alkylating agent and a precursor slurry in toluene were successively pre-mixed at room temperature for 1 minute, after which the mixture was fed to the reactor.
  • the catalyst metering vessel was flushed with 100 ml pentamethylheptane.
  • the reactor pressure was kept constant by supplying
  • the reactor temperature was kept at 160 ⁇ 5 °C by cooling. After a certain time the polymerization was stopped and the polymer formed was recovered from the reaction mixture by draining the latter from the reactor and drying it under vacuum at 50 °C.
  • the precursors and alkylating agents used and the data recorded for the polymers obtained are presented in Table 1.
  • active catalysts can be prepared from the precursors according to the invention by addition of a relatively small amount of alkylating agent, in other words, at a very favourable (low) Al/transition metal ratio.
  • a certain amount of N,N-dimethylaniline remains behind in the polymer formed, as a consequence of which this polymer is in principle unsuitable for food packaging applications.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Précurseur de catalyseur comportant un lanthanide ou un métal de transition et un système de ligands dans lequel est présent au moins un dérivé Cp et dans lequel le précurseur renferme un anion non coordinateur A-, apte à stabiliser un catalyseur obtenu par l'activation du précurseur, et lié à un groupe cationique du dérivé Cp, ou à un groupe cationique faisant partie d'un pont lié au dérivé Cp à l'intérieur du précurseur, ou lié à un tel pont. Le groupe cationique renferme un sous-groupe apte à réagir avec un groupe alkyle, benzyle ou phényle lié à un métal. On décrit également un procédé de polymérisation d'oléfines en présence d'un catalyseur préparé par la mise en contact d'un tel précurseur avec un composé d'alkylation.
EP97919751A 1996-05-03 1997-04-28 Compose de cyclopentadiene a anion non coordinateur Withdrawn EP0896592A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1003020A NL1003020C2 (nl) 1996-05-03 1996-05-03 Cyclopentadieenverbinding met een niet-coördinerend anion.
NL1003020 1996-05-03
PCT/NL1997/000231 WO1997042231A1 (fr) 1996-05-03 1997-04-28 Compose de cyclopentadiene a anion non coordinateur

Publications (1)

Publication Number Publication Date
EP0896592A1 true EP0896592A1 (fr) 1999-02-17

Family

ID=19762792

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97919751A Withdrawn EP0896592A1 (fr) 1996-05-03 1997-04-28 Compose de cyclopentadiene a anion non coordinateur

Country Status (5)

Country Link
EP (1) EP0896592A1 (fr)
JP (1) JP2000509739A (fr)
AU (1) AU2410897A (fr)
NL (1) NL1003020C2 (fr)
WO (1) WO1997042231A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5153157A (en) * 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
RU2118203C1 (ru) * 1990-06-22 1998-08-27 Экксон Кэмикал Пейтентс Инк. Каталитическая система для получения полиолефинов и композиция, используемая для полимеризации олефинов
US6008307A (en) * 1994-04-28 1999-12-28 Exxon Chemical Patents Inc Process for producing olefin polymers using cationic catalysts
DE19506557A1 (de) * 1995-02-24 1996-08-29 Basf Ag Metallocenkomplexe mit kationischer Brücke

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9742231A1 *

Also Published As

Publication number Publication date
AU2410897A (en) 1997-11-26
WO1997042231A1 (fr) 1997-11-13
NL1003020C2 (nl) 1997-11-06
JP2000509739A (ja) 2000-08-02

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