WO1997042235A1 - Procede pour la production de polymeres contenant des olefines cycliques - Google Patents

Procede pour la production de polymeres contenant des olefines cycliques Download PDF

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WO1997042235A1
WO1997042235A1 PCT/NL1997/000240 NL9700240W WO9742235A1 WO 1997042235 A1 WO1997042235 A1 WO 1997042235A1 NL 9700240 W NL9700240 W NL 9700240W WO 9742235 A1 WO9742235 A1 WO 9742235A1
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group
transition metal
process according
ligand
groups
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PCT/NL1997/000240
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Maurits Frederik Hendrik Van Tol
Johannes Antonius Maria Van Beek
Paulus Johannes Jacobus Pieters
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Dsm N.V.
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Priority to AU24116/97A priority Critical patent/AU2411697A/en
Publication of WO1997042235A1 publication Critical patent/WO1997042235A1/fr

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    • 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
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912—Component covered by group C08F4/62 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
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392—Component covered by group C08F4/62 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 present invention relates to a process for the production of polymers containing cyclic olefins.
  • the invention relates to a process for producing such polymers showing excellent transparency, excellent electrical insulative properties, high heat deflection temperature, high resistance to polar solvents, very good hydrolytic stability and easy processability. It is known, e.g. from Kaminsky (Catalysis
  • Copolymers of cyclo-alkenes with ethylene, with a relatively high incorporation (above about 14 mol%) of the cyclo-alkene, are amorphous and transparent with a glass transition temperature that allows the use of these materials, for example, for optical disk fabrication or for polymer optical fibre (POF) applications.
  • EP-A-501 370 teaches the polymerisation of polycyclic olefins, in particular norbornene and tetracyclododecene, and the copolymerisation of polycyclic olefins and/or 1-olefins with a very narrow molecular weight distribution (Mw/Mn ⁇ 2 , in particular Mw/Mn ⁇ 1.4) without ring opening, using a stereo- rigid, chiral metallocene in combination with aluminoxane. This process yields however very narrow molecular weight distributions so that the application of the resins produced is limited, due to difficult processing.
  • EP-A-407 870 teaches the polymerisation of polycyclic olefins, without ring opening, using stereo- rigid, chiral metallocene/aluminoxane mixtures, in particular at temperatures up to 70 C.
  • the purpose of the present invention is to provide such a process, furthermore offering the possibility to incorporate very low to very high amounts of cyclic and/or polycyclic olefines in the copolymers.
  • the process described in this invention makes the production of the resins concerned very interesting from a commercial point of view as a consequence of the process' flexibility and low catalyst-system costs.
  • the higher polymerisation temperatures not only result in higher polymerisation rates but also allow the use of cocatalysts other than aluminoxanes, e.g. borates.
  • the process of the invention for the production of polymers containing cyclic olefins by contacting, under polymerisation conditions, at least one cyclic and/or polycyclic olefin, optionally in the presence of ⁇ -olefins, in the presence of the present catalyst composition.
  • the catalyst composition includes at least one complex comprising a reduced valency transition metal (M) selected from groups 4-6 of the Periodic Table of Elements, a multidentate monoanionic ligand (X), two monoanionic ligands (L), and, optionally, additional ligands (K). More specifically, the complex of the catalyst composition of the present invention is represented by the following formula (I):
  • M a reduced transition metal selected from group 4, 5 or 6 of the Periodic Table of Elements
  • X a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S Y(-R t -DR' n ) q ;
  • Y a cyclopentadienyl, amido (-NR'-), or phosphido group (-PR'-), which is bonded to the reduced transition metal M;
  • R at least one member selected from the group consisting of (i) a connecting group between the Y group and the DR' n group and (ii) a connecting group between the Y group and the Ar group, wherein when the ligand X contains more than one R group, the R groups can be identical to or different from each other;
  • D an electron-donating hetero atom selected from group 15 or 16 of the Periodic Table of Elements;
  • R' a substituent selected from the group consisting of a hydrogen, hydrocarbon radical and hetero atom-containing moiety, except that R' cannot be hydrogen when R' is directly bonded to the electron-donating hetero atom D, wherein when the multidentate monoanionic ligand X contains more than one substituent R', the substituents R' can be identical or different from each other;
  • the monoanionic ligand L a monoanionic ligand bonded to the reduced transition metal M, wherein the monoanionic ligand L is not a ligand comprising a cyclopentadienyl, amido (-NR'-), or phosphido (-PR'-) group, and wherein the monoanionic ligands L can be identical or different from each other;
  • K a neutral or anionic ligand bonded to the reduced transition metal M, wherein when the transition metal complex contains more than one ligand K, the ligands K can be identical or different from each other; m the number of the K ligands, wherein when the K ligand is an anionic ligand m is 0, 1, or 2, and when K is a neutral ligand, m increases by one for each neutral K ligand; n the number of the R' groups bonded to the electron-donating hetero atom D, wherein when D is selected from group 15 of the Periodic Table of Elements n is 2, and when D is selected from group 16 of the Periodic Table of Elements n is 1; q,s q and s are the number of (-R t -DR' n ) groups and (Ar-R t -) groups bonded to group Y, respectively, wherein q + s is an integer not less than 1; and t the number of R groups connecting each of (i) the Y and Ar groups
  • FIG. 1 is a schematic view of a cationic active site of a trivalent catalyst complex in accordance with an embodiment of the present invention
  • FIG. 2 is a schematic view of a neutral active site of a trivalent catalyst complex of a dianionic ligand of a conventional catalyst complex according to WO-A-93/19104.
  • transition metal complex Various components (groups) of the transition metal complex are discussed below in more detail.
  • the transition metal in the complex is selected from groups 4-6 of the Periodic Table of Elements. As referred to herein, all references to the Periodic Table of Elements mean the version set forth in the new IUPAC notation found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990, the complete disclosure of which is incorporated herein by reference. More preferably, the transition metal is selected from group 4 of the Periodic Table of Elements, and most preferably is titanium (Ti).
  • the transition metal is present in reduced form in the complex, which means that the transition metal is in a reduced oxidation state.
  • reduced oxidation state means an oxidation state which is greater than zero but lower than the highest possible oxidation state of the metal (for example, the reduced oxidation state is at most M 3+ for a transition metal of group 4, at most M 4+ for a transition metal of group 5 and at most M 5+ for a transition metal of group 6).
  • the X ligand is a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S Y(-R t -DR' n ) q .
  • a multidentate monoanionic ligand is bonded with a covalent bond to the reduced transition metal (M) at one site (the anionic site, Y) and is bonded either (i) with a coordinate bond to the transition metal at one other site (bidentate) or (ii) with a plurality of coordinate bonds at several other sites (tridentate, tetradentate, etc.). Such coordinate bonding can take place, for example, via the D heteroatom or Ar group(s).
  • tridentate monoanionic ligands include, without limitation, Y-R t -DR ' n _ 1 -R t -OR'êt and Y(-R-DR' n ) 2 .
  • R represents a connecting or bridging group between the DR' n and Y, and/or between the electron- donating aryl (Ar) group and Y. Since R is optional, "t" can be zero.
  • the R group is discussed below in paragraph (d) in more detail.
  • the Y group of the multidentate monoanionic ligand (X) is preferably a cyclopentadienyl, amido (-NR'-), or phosphido (-PR'-) group.
  • the Y group is a cyclopentadienyl ligand (Cp group).
  • Cp group cyclopentadienyl ligand
  • the term cyclopentadienyl group encompasses substituted cyclopentadienyl groups such as indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the Cp group is an R t -DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
  • Examples of a multidentate monoanionic ligand with a Cp group as the Y group (or ligand) include the following (with the (-R t -DR' n ) or (Ar-R t -) substituent on the ring) : R R
  • the Y group can also be a hetero cyclopentadienyl group.
  • a hetero cyclopentadienyl group means a hetero ligand derived from a cyclopentadienyl group, but in which at least one of the atoms defining the five-member ring structure of the cyclopentadienyl is replaced with a hetero atom via an endocyclic substitution.
  • the hetero Cp group also includes at least one R t -DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
  • the hetero Cp group encompasses indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the hetero Cp group is an R t -DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the hetero Cp group via an exocyclic substitution.
  • the hetero atom can be selected from group 14, 15 or 16 of the Periodic Table of Elements. If there is more than one hetero atom present in the five- member ring, these hetero atoms can be either the same or different from each other. More preferably, the hetero atom(s) is/are selected from group 15, and still more preferably the hetero atom(s) selected is/are phosphorus.
  • hetero ligands of the X group that can be practiced in accordance with the present invention are hetero cyclopentadienyl groups having the following structures, in which the hetero cyclopentadienyl contains one phosphorus atom (i.e., the hetero atom) substituted in the five-member ring:
  • the transition metal group M is bonded to the Cp group via an h . 5 bond.
  • the other R' exocyclic substituents (shown in formula (III)) on the ring of the hetero Cp group can be of the same type as those present on the Cp group, as represented in formula (II).
  • at least one of the exocyclic substituents on the five- member ring of the hetero cyclopentadienyl group of formula (III) is the R t -DR' n group or the R t -Ar group.
  • the numeration of the substitution sites of the indenyl group is in general and in the present description based on the IUPAC Nomenclature of Organic Chemistry 1979, rule A 21.1. The numeration of the substituent sites for indene is shown below. This numeration is analogous for an indenyl group:
  • the Y group can also be an amido (-NR'-) group or a phosphido (-PR'-) group.
  • the Y group contains nitrogen (N) or phosphorus (P) and is bonded covalently to the transition metal M as well as to the (optional) R group of the (-R t -DR' n ) or (Ar-R t -) substituent.
  • the R group is optional, such that it can be absent from the X group. Where the R group is absent, the DR' n or Ar group is bonded directly to the Y group (that is, the DR' n or Ar group is bonded directly to the Cp, amido, or phosphido group). The presence or absence of an R group between each of the DR' n groups and/or Ar groups is independent.
  • each of the R group constitutes the connecting bond between, on the one hand the Y group, and on the other hand the DR' n group or the Ar group.
  • the presence and size of the R group determines the accessibility of the transition metal M relative to the DR' n or Ar group, which gives the desired intramolecular coordination. If the R group (or bridge) is too short or absent, the donor may not coordinate well due to ring tension.
  • the R groups are each selected independently, and can generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, aryl alkylidene, etc.). Specific examples of such R groups include, without limitation, methylene, ethylene, propylene, butylene, phenylene, whether or not with a substituted side chain.
  • the R group has the following structure:
  • R' groups of formula (IV) can each be selected independently, and can be the same as the R' groups defined below in paragraph (g).
  • the main chain of the R group can also contain silicon or germanium.
  • R groups are: dialkyl silylene (-SiR' 2 -), dialkyl germylene (-GeR' 2 -), tetra-alkyl silylene (-SiR ' 2 -SiR ' 2 -) , or tetraalkyl silaethylene (-SiR ' 2 CR ' 2 -) .
  • the alkyl groups in such a group preferably have 1-4 carbon atoms and more preferably are a methyl or ethyl group.
  • This donor group consists of an electron ⁇ donating hetero atom D, selected from group 15 or 16 of the Periodic Table of Elements, and one or more substituents R' bonded to D.
  • the number (n) of R' groups is determined by the nature of the hetero atom D, insofar as n being 2 if D is selected from group 15 and n being 1 if D is selected from group 16.
  • the R' substituents bonded to D can each be selected independently, and can be the same as the R' groups defined below in paragraph (g), with the exception that the R' substituent bonded to D cannot be hydrogen.
  • the hetero atom D is preferably selected from the group consisting of nitrogen (N), oxygen (0), phosphorus (P) and sulphur (S); more preferably, the hetero atom is nitrogen (N).
  • the R' group is an alkyl, more preferably an n-alkyl group having 1- 20 carbon atoms, and most preferably an n-alkyl having 1-8 carbon atoms. It is further possible for two R' groups in the DR' n group to be connected with each other to form a ring-shaped structure (so that the DR' n group can be, for example, a pyrrolidinyl group).
  • the DR' n group can form coordinate bonds with the transition metal M.
  • the electron-donating group (or donor) selected can also be an aryl group (C 6 R' S ), such as phenyl, tolyl, xylyl, mesityl, cumenyl, tetramethyl phenyl, pentamethyl phenyl, a polycyclic group such as triphenylmethane, etc.
  • the electron-donating group D of formula (I) cannot, however, be a substituted Cp group, such as an indenyl, benzoindenyl, or fluorenyl group.
  • the coordination of this Ar group in relation to the transition metal M can vary from h 1 to ⁇ 6 .
  • the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like as shown in Table
  • alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
  • aryl groups are phenyl, mesityl, tolyl and cumenyl.
  • aryl alkyl groups are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
  • R' groups are halides, such as chloride, bromide, fluoride and iodide, methoxy, ethoxy and phenoxy.
  • two adjacent hydrocarbon radicals of the Y group can be connected with each other to define a ring system?
  • the Y group can be an indenyl, a fluorenyl or a benzoindenyl group.
  • the indenyl, fluorenyl, and/or benzoindenyl can contain one or more R' groups as substituents.
  • R' can also be a substituent which instead of or in addition to carbon and/or hydrogen can comprise one or more hetero atoms of groups 14-16 of the Periodic Table of Elements.
  • a substituent can be, for example, a Si-containing group, such as Si(CH 3 ) 3 .
  • the transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
  • L group ligands which can be identical or different, include, without limitation, the following: a hydrogen atom; a halogen atom; an alkyl, aryl or aryl alkyl group; an alkoxy or aryloxy group; a group comprising a hetero atom selected from group 15 or 16 of the Periodic Table of Elements, including, by way of example, (i) a sulphur compound, such as sulphite, sulphate, thiol, sulphonate, and thioalkyl, and (ii) a phosphorus compound, such as phosphite, and phosphate.
  • the two L groups can also be connected with each other to form a dianionic bidentate ring system.
  • L is a halide and/or an alkyl or aryl group; more preferably, L is a Cl group and/or a C ! -C 4 alkyl or a benzyl group.
  • the L group cannot be a Cp, amido, or phosphido group. In other words, L cannot be one of the Y groups.
  • the K ligand is a neutral or anionic group bonded to the transition metal M.
  • the K group is a neutral or anionic ligand bonded to M.
  • neutral K ligands which by definition are not anionic, are not subject to the same rule. Therefore, for each neutral K ligand, the value of m (i.e., the number of total K ligands) is one higher than the value stated above for a complex having all monoanionic K ligands.
  • the K ligand can be a ligand as described above for the L group or a Cp group (-C S R' 5 ), an amido group (-NR' 2 ) or a phosphido group (-PR' 2 ).
  • the K group can also be a neutral ligand such as an ether, an amine, a phosphine, a thioether, among others.
  • the two K groups can be connected with each other via an R group to form a bidentate ring system.
  • the X group of the complex contains a Y group to which are linked one or more donor groups (the Ar group(s) and/or DR' n group(s)) via, optionally, an R group.
  • the number of donor groups linked to the Y group is at least one and at most the number of substitution sites present on a Y group.
  • One preferred embodiment of the catalyst composition according to the present invention comprises a transition metal complex in which a bidentate/monoanionic ligand is present and in which the reduced transition metal has been selected from group 4 of the Periodic Table of Elements and has an oxidation state of +3.
  • the catalyst composition according to the invention comprises a transition metal complex represented by formula (V):
  • the Y group in this formula (VI) is a hetero atom, such as phosphorus, oxygen, sulfur, or nitrogen bonded covalently to the transition metal M (see p. 2 of WO-A- 93/19104).
  • This means that the Cp a (ZY) b group is of a dianionic nature, and has the anionic charges residing formerly on the Cp and Y groups. Accordingly, the Cp a (ZY) b group of formula (VI) contains two covalent bonds: the first being between the 5-member ring of the Cp group and the transition metal M, and the second being between the Y group and the transition metal.
  • the X group in the complex according to the present invention is of a monoanionic nature, such that a covalent bond is present between the Y group (e.g., the Cp group) and transition metal, and a coordinate bond can be present between the transition metal M and one or more of the (Ar-R t -) and (-R t -DR' n ) groups.
  • a coordinate bond is a bond (e.g., H 3 N-BH 3 ) which when broken, yields either (i) two species without net charge and without unpaired electrons (e.g., H 3 N: and BH 3 ) or (ii) two species with net charge and with unpaired electrons (e.g., H 3 N- + and BH 3 " ).
  • a covalent bond is a bond (e.g., CH 3 -CH 3 ) which when broken yields either (i) two species without net charge and with unpaired electrons (e.g., CH 3 - and CH 3 - ) or (ii) two species with net charges and without unpaired electrons (e.g., CH 3 + and CH 3 : ⁇ ).
  • a discussion of coordinate and covalent bonding is set forth in Haaland et al. (Angew. Chem Int. Ed. Eng. Vol. 28, 1989, p. 992), the complete disclosure of which is incorporated herein by reference.
  • the transition metal complexes described in WO-A- 93/19104 are ionic after interaction with the co ⁇ catalyst.
  • the transition metal complex according to WO-A-93/19104 that is active in the polymerization contains an overall neutral charge (on the basis of the assumption that the polymerizing transition metal complex comprises, a M(III) transition metal, one dianionic ligand and one growing monoanionic polymer chain (POL)).
  • POL monoanionic polymer chain
  • the polymerization active transition metal complex of the catalyst composition according to the present invention is of a cationic nature (on the basis of the assumption that the polymerizing transition metal complex - based on the formula (V) structure - comprises, a M(III) transition metal, one monoanionic bidentate ligand and one growing monoanionic polymer chain (POL)).
  • Transition metal complexes in which the transition metal is in a reduced oxidation state have the following structure:
  • transition metal complex of the present invention are generally not active in co-polymerization reactions. It is precisely the presence, in the transition metal complex of the present invention, of the DR' n or Ar group (the donor), optionally bonded to the Y group by means of the R group, that gives a stable transition metal complex suitable for polymerization.
  • Such an intramolecular donor is to be preferred over an external (intermolecular) donor on account of the fact that the former shows a stronger and more stable coordination with the transition metal complex.
  • the catalyst system may also be formed in situ if the components thereof are added directly to the polymerization reactor system and a solvent or diluent, including liquid monomer, is used in said polymerization reactor.
  • the catalyst composition of the present invention also contains a co-catalyst.
  • the co-catalyst can be an organometallic compound.
  • the metal of the organometallic compound can be selected from group 1, 2, 12 or 13 of the Periodic Table of Elements. Suitable metals include, for example and without limitation, sodium, lithium, zinc, magnesium, and aluminum, with aluminum being preferred. At least one hydrocarbon radical is bonded directly to the metal to provide a carbon-metal bond.
  • the hydrocarbon group used in such compounds preferably contains 1-30, more preferably 1-10 carbon atoms.
  • suitable compounds include, without limitation, amyl sodium, butyl lithium, diethyl zinc, butyl magnesium chloride, and dibutyl magnesium.
  • organoaluminium compounds including, for example and without limitation, the following: trialkyl aluminum compounds, such as triethyl aluminum and tri-isobutyl aluminum; alkyl aluminum hydrides, such as di-isobutyl aluminum hydride; alkylalkoxy organoaluminium compounds; and halogen-containing organoaluminium compounds, such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
  • linear or cyclic aluminoxanes are selected as the organoaluminium compound.
  • the catalyst composition of the present invention can include a compound which contains or yields in a reaction with the transition metal complex of the present invention a non-coordinating or poorly coordinating anion.
  • a non-coordinating or poorly coordinating anion Such compounds have been described for instance in EP-A-426,637, the complete disclosure of which is incorporated herein by reference. Such an anion is bonded sufficiently unstably such that it is replaced by an unsaturated monomer during the co ⁇ polymerization.
  • Such compounds are also mentioned in EP-A-277,003 and EP-A-277,004, the complete disclosures of which are incorporated herein by reference.
  • Such a compound preferably contains a triaryl borane or a tetraaryl borate or an aluminum equivalent thereof.
  • suitable co-catalyst compounds include, without limitation, the following:
  • the transition metal complex is alkylated (that is, the L group is an alkyl group).
  • the reaction product of a halogenated transition metal complex and an organometallic compound such as for instance triethyl aluminum (TEA) can also be used.
  • the molar ratio of the co-catalyst relative to the transition metal complex in case an organometallic compound is selected as the co-catalyst, usually is in a range of from about 1:1 to about 10,000:1, and preferably is in a range of from about 1:1 to about 2,500:1. If a compound containing or yielding a non-coordinating or poorly coordinating anion is selected as co-catalyst, the molar ratio usually is in a range of from about 1:100 to about 1,000:1, and preferably is in a range of from about 1:2 to about 250:1.
  • the transition metal complex as well as the co ⁇ catalyst can be present in the catalyst composition as a single component or as a mixture of several components. For instance, a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight and in particular molecular weight distribution.
  • the polymerization of at least one cyclic and/or polycyclic olefin, with or without ⁇ -olefins is carried out using a catalyst composition as described above.
  • cyclic olefin(s) is/are suitably chosen from the group comprising at least one monomer of formula:
  • n is an integer from 2 to 10.
  • the cyclic olefin is chosen from the group comprising: cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene. More preferably the cyclic olefin is cyclopentene.
  • the polycyclic olefin(s) are in particular chosen from the group comprising at least one monomer of formula:
  • R x , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R ⁇ are the same or different and may represent a hydrogen atom or a C x - C ⁇ alkyl group.
  • the substituent groups in these formulae X to XIII may have different meanings.
  • the polycyclic olefin is chosen from the group comprising norbornene, dimethano- octahydronaphthalene (DMON) , and substituted norbornene. More preferably the polycyclic olefin is dimethano-octahydronaphthalene (DMON) or norbornene.
  • the optional ⁇ -olefin(s) may in particular be chosen from the group comprising ethene, propene, butene, pentene, hexene, heptene, octene and styrene (substituted or non-substituted), mixtures of which may also be used. More preferably, ethene and/or propene and/or octene and/or styrene are used as ⁇ -olefin. Most preferably ethene and/or octene and/or styrene are used as ⁇ -olefin. Mixtures of the above mentioned monomers can also be used.
  • the catalyst composition can be used supported as well as non ⁇ supported.
  • the supported catalysts are used mainly in gas phase and slurry processes.
  • the carrier used may be any carrier known as carrier material for catalysts, for instance Si0 2/ A1 2 0 3 or MgCl 2 . These carriers may be used as such or modified, for example by silanes and/or aluminium alkyles and/or aluminoxane compounds, etc.
  • Polymerization of the olefins can be effected in a known manner, in the gas phase as well as in a liquid reaction medium. In the latter case, both solution and suspension polymerization are suitable. Polymerisation can also be performed in the pure monomer (bulk polymerisation).
  • the quantity of transition metal to be used in case of solution or suspension polymerisation generally is such that its concentration in the dispersion agent amounts to 10 ⁇ 8 - IO -3 mol/1, preferably IO -7 - 10 "4 mol/1.
  • the catalyst system used in accordance with this invention may also be prepared by in-situ methods, e.g. in the polymerisation reactor.
  • the process of the present invention can be conducted as a gas phase polymerisation (e.g. in a fluidized bed reaction), solution or slurry/suspension polymerisation or solid phase powder polymerisation.
  • a gas phase polymerisation no solvents or dispersion media are required.
  • a solvent or a combination of solvents may be employed if desired.
  • Suitable solvents include toluene, ethylbenzene, one or more saturated straight or branched aliphatic hydrocarbons, such as butanes, pentanes, hexanes, heptanes, pentamethyl heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosine or gas oil.
  • a suspension utilizing a perfluorinated hydrocarbon or similar liquid may also be used.
  • Aromatic hydrocarbons for instance benzene and toluene, can be used, but because of their cost as well as on account of safety considerations, it will be preferred not to use such solvents for production on a technical scale. In polymerization processes on a technical scale, it is preferred therefore to use as solvent the low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry. If an aliphatic hydrocarbon is used as solvent, the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
  • methyl aluminoxane (MAO)
  • toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification is desirable if such solvents are used; this can be done without problems by the average person skilled in the art.
  • a suspension polymerization is preferably carried out at temperatures between -100°C and + 250°C;
  • the polymer solution or suspension resulting from the polymerization can be worked up by a method known per se.
  • the catalyst is de-activated at some point during the processing of the polymer.
  • the de-activation is also effected in a manner known per se, e.g. by means of water or an alcohol. Removal of the catalyst residues can mostly be omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal is very low according to the invention.
  • Polymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at elevated pressure of up to 500 MPa, continuously or discontinuously.
  • the polymerization is performed at pressures between 1 KPa and 10 MPa. Higher pressures can be applied if the polymerization is carried out in so-called high-pressure reactors. In such a high-pressure process the process according to the present invention can also be used with good results.
  • the polymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc. may be varied from step to step. In this way it is also possible to obtain products with a wide molecular weight distribution.
  • the invention also relates to a polymer containing cyclic olefins which can be obtained by means of the polymerization process according to the invention.
  • TiCl 3 the esters used and the lithium reagents, 2- bromo-2-butene and 1-chlorocyclohexene were obtained from Aldrich Chemical Company.
  • TiCl 3 .3THF was obtained by heating TiCl 3 for 24 hours in THF with reflux. (THF stands for tetrahydrofurane) .
  • THF stands for tetrahydrofurane
  • 2-Lithium-2-butene was prepared from 2-bromo- 2-butene (16.5 g; 0.122 mol) and lithium (2.8 g; 0.4 mol) as in example I.
  • the ester of a) 7.0 g; 0.031 mol
  • the water layer was separated off and extracted twice with 50 ml of CH 2 C1 2 .
  • the combined organic layer was washed once with 50 ml of water, dried with K 2 C0 3 , filtered and evaporated. The yield was 9.0 g (100%).
  • the complex (a green solid) was purified by repeated washing of the solid, followed by filtration and backdistillation of the solvent. It was also possible to obtain the pure complex through sublimation.
  • the polymerisation was stopped by the addition of methanol to the reaction mixture and the polymer slurry was washed with, respectively, 10% HCl in water, several portions of water, a saturated solution of NaHC0 3 , followed by rinsing of the polymer with water and drying.
  • the polymer formed was studied by wide angle X-ray scattering (WAXS) and solid state NMR and appeared to be polynorbornene having a very high melting temperature (T m ⁇ lt around 600 C).
  • Example II Co-polymerisation of ethene and norbornene using (dibutylaminoethyl)- tetramethylcyclopentadienyltitanium(III) dichloride (C 5 Me 4 (CH 2 ) 2 NBu 2 TiCl 2 ) as catalyst.
  • the copolymer yield was 16.2 kg copolymer/gTi*hour .
  • the copolymer showed a glass transition temperature (Tg) of 148.6°C in the DSC spectrum.
  • the copolymer was analysed with DSC and showed a Tg at 39.6°C.
  • GPC results (conventional calibration) indicated a molecular weight distribution of 6.5, a number averaged molecular weight Mn * of 14 kg/mol and Mw * of 88 kg/mol.
  • Aqueous KOH (50%; 1950g, ca. 31.5 mol in 2.483 1 water) and Adogen 464 (31.5g) were placed in a 3L three-neck flask fitted with a condenser, mechanical stirrer, heating mantle, thermometer, and an inlet adapter.
  • GC and GC-MS analysis showed the product mixture to consist of diisopropylcyclopentadien (iPr 2 -Cp, 40%) and triisopropylcyclopentadien (iPr 3 -Cp, 60%).
  • iPr 2 -Cp and iPr 3 -Cp were isolated by distillation at reduced (20 mmHg) pressure. Yield depending on distillation accuracy (approx. 0.2 mol iPr 2 -Cp (25%) and 0.3 mol iPr 3 -Cp (40%)).
  • Solid TiCl 3 -3THF (18.53g, 50.0 mmol) was added to a solution of of K iPr 3 -Cp in 160 mL of THF at -60 °C at once, after which the solution was allowed to warm to RT. The color changed from blue to green. After all the TiCl 3 .3THF had disappeared the reaction mixture was cooled again to -60 °C after which 2.0 equivalents of MeLi (62.5 ml of a 1.6 M solution in Et 2 0) were added. After warming to RT again, the black solution was stirred for an additional 30 minutes after which the THF was removed at reduced pressure.
  • the copolymer yield was 65 kg/gTi*hour.

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Abstract

Cette invention se rapporte à un procédé qui sert à produire des polymères contenant des oléfines cycliques en mettant en contact, dans des conditions de polymérisation, au moins une oléfine cyclique et/ou polycyclique, éventuellement en présence d'α-oléfines, avec un catalyseur comprenant un complexe de métal de transition et un cocatalyseur. Cette invention se caractérise en ce que le complexe de métal de transition est constitué par un métal de transition réduit, choisi dans les groupes 4 à 6 du tableau périodique des éléments, avec un ligand monoanionique multidenté et avec deux ligands monoanioniques. Le métal de transition réduit est en particulier le titane (Ti).
PCT/NL1997/000240 1996-05-03 1997-05-01 Procede pour la production de polymeres contenant des olefines cycliques WO1997042235A1 (fr)

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Cited By (2)

* 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
CN109843948A (zh) * 2016-12-06 2019-06-04 Sabic环球技术有限责任公司 用于制备具有极性基团的烯属共聚物的方法和由此获得的产物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019104A1 (fr) * 1992-03-26 1993-09-30 The Dow Chemical Company Catalyseurs de polymerisation par addition comportant des complexes metalliques a etat d'oxydation reduit
WO1995014044A1 (fr) * 1993-11-19 1995-05-26 Exxon Chemical Patents Inc. Systemes catalyseurs de polymerisation, production et utilisation de ces systemes
EP0655467A1 (fr) * 1993-11-26 1995-05-31 Idemitsu Kosan Company Limited Catalyseur pour la production de polymère vinylaromatique et procédé de production l'utilisant
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993019104A1 (fr) * 1992-03-26 1993-09-30 The Dow Chemical Company Catalyseurs de polymerisation par addition comportant des complexes metalliques a etat d'oxydation reduit
WO1995014044A1 (fr) * 1993-11-19 1995-05-26 Exxon Chemical Patents Inc. Systemes catalyseurs de polymerisation, production et utilisation de ces systemes
EP0655467A1 (fr) * 1993-11-26 1995-05-31 Idemitsu Kosan Company Limited Catalyseur pour la production de polymère vinylaromatique et procédé de production l'utilisant
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Cited By (3)

* 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
CN109843948A (zh) * 2016-12-06 2019-06-04 Sabic环球技术有限责任公司 用于制备具有极性基团的烯属共聚物的方法和由此获得的产物
CN109843948B (zh) * 2016-12-06 2022-04-29 Sabic环球技术有限责任公司 用于制备具有极性基团的烯属共聚物的方法和由此获得的产物

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