EP0896599A1 - PROCEDE DE PREPARATION D'UN COPOLYMERE D'$g(a)-OLEFINE ET D'ETHYLENE - Google Patents

PROCEDE DE PREPARATION D'UN COPOLYMERE D'$g(a)-OLEFINE ET D'ETHYLENE

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Publication number
EP0896599A1
EP0896599A1 EP97919763A EP97919763A EP0896599A1 EP 0896599 A1 EP0896599 A1 EP 0896599A1 EP 97919763 A EP97919763 A EP 97919763A EP 97919763 A EP97919763 A EP 97919763A EP 0896599 A1 EP0896599 A1 EP 0896599A1
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European Patent Office
Prior art keywords
group
transition metal
process according
ligand
groups
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EP97919763A
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German (de)
English (en)
Inventor
Jacob Renkema
Bernardus Johanna Muskens
Johannes Antonius Maria Van Beek
Gerardus Henricus Josephus Van Doremeale
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Koninklijke DSM NV
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DSM NV
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Priority to EP97919763A priority Critical patent/EP0896599A1/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
    • 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
    • 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
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63908—Component covered by group C08F4/62 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
    • C08F4/639—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 invention relates to a process for the preparation of an ethylene and ⁇ -olefin copolymer with an ethylene content of between about 20 and 90 weight % at a temperature range of 100-220°C, with a catalyst composition comprising a transition metal complex and a co-catalyst.
  • a process for the preparation of an ethylene/ ⁇ -olefin copolymer is known from U.S. Patent No. 5,491,207, in which a cyclopentadiene based transition metal complex (in combination with a co ⁇ catalyst) is used to prepare ethylene/ ⁇ -olefin copolymers having an ethylene content in the range of about 20-90 mol%.
  • copolymer means a polymer formed from two types of monomeric constituents: ethylene and one or more ⁇ - olefins.
  • a disadvantage of a process according to U.S. Patent No. 5,491,207 is that it is conducted at relatively low temperatures (-10°C to about 100°C), which cause the process to be less attractive from an economical point of view. There is a need for a process to be conducted at higher temperatures. There is also a need for a higher temperature polymerization process which does not require too high a pressure, otherwise the costs for such a high pressure process could undo the advantages of a high temperature process.
  • this object is obtained by providing a process for the preparation of an ethylene/ ⁇ -olefin copolymer with an ethylene content of between about 20 and 90 weight %, at higher temperatures that range from 100°C to 220°C, with a catalyst composition comprising a transition metal complex and a co-catalyst.
  • Another object of the present invention is the provision of an ethylene/ ⁇ -olefin copolymer obtained by the means of a polymerization process with utilization of the catalyst composition according to the invention.
  • the polymerization of ethylene and at least one [additional] ⁇ -olefin is conducted under effective copolymerization conditions at a temperature of between 100°C and 220°C , under the influence of the present a 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 comple of the catalyst composition of the present invention represented by the following formula (I):
  • X a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S Y(-R t -DR' n ) q ;
  • 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;
  • Ar an electron-donating aryl group;
  • L a monoanionic ligand bonded to the reduced transition metal M, wherein the monoanionic ligand L is not a ligand comprising a cyciopentadienyl, 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
  • m is the number of K ligands, wherein when the K ligand is an anionic ligand m is 0 for M 3+ , m is 1 for M* "1" , and m is 2 for M s+ , and when K is a neutral ligand 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 and (ii) the Y and DR' n groups, wherein
  • a transition metal complex of formula (I) makes it possible to prepare ethylene/ ⁇ -olefin copolymers at temperatures between 100°C and 220°C, whereas other known catalysts for these types of polymerization do not produce copolymers at temperatures above 100°C (they are only active at temperatures well below 100°C; U.S. Patent No. 5,491,207 discloses temperatures between -10°C and 100°C and shows examples with temperatures between 35°C and 50°C).
  • the process according to the present invention is suitable for the preparation of copolymers having an M n (the number-average molecular weight (as determined by SEC-DV (Size Exclusion
  • any ethylene/ ⁇ - olefin copolymer can be made with an M n between about 100 and about 500 , 000 .
  • Copolymers with a molecular weight M n between about 100 and about 30,000 are preferably prepared in a polymerization process at temperatures between about 135 and about 220°C; copolymers with a molecular weight M n between about 20,000 and about 100,000 are preferably prepared in a polymerization process at a temperature between about 115 and about 180°C.
  • the copolymers also have an ethylene content of between about 20 and about 90 weight %.
  • the copolymers can be amorphous, being products with an ethylene content of between about 30 and about 70 weight %, or can be semicrystalline, being products with an ethylene content of between about 70 and about 90 wt %.
  • the pressure at which the polymerization is conducted is preferably below about 100 MPa. Pressures up to 10 MPa are in several cases sufficient enough for a good catalytic activity.
  • CA-A-2 , 11, 057 discloses a process (in comparative experiment 2) for the preparation of an ethylene/butene low molecular weight copolymer at an extreme high pressure of 1,330 bar to cope with the extreme low catalytic activity at normal pressures.
  • 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 _ ⁇ -R t -DR ' n 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 cyciopentadienyl, amido (-NR'-), or phosphido (-PR'-) group. Most preferably, the Y group is a cyciopentadienyl ligand (Cp group).
  • cyciopentadienyl group encompasses substituted cyciopentadienyl 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 -D ' 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.
  • multidentate monoanionic ligand with a Cp group as the Y group include the following (with the (-R t -DR' n ) or (Ar-R t -) substituent on the ring) :
  • the Y group can also be a hetero cyciopentadienyl group.
  • a hetero cyciopentadienyl group means a hetero ligand derived from a cyciopentadienyl group, but in which at least one of the atoms defining the five-member ring structure of the cyciopentadienyl 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.
  • representative hetero ligands of the X group that can be practiced in accordance with the present invention are hetero cyciopentadienyl groups having the following structures, in which the hetero cyciopentadienyl 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 ⁇ * ) s 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 cyciopentadienyl group of formula (III) is the R t -DR' n group or the R t -Ar group.
  • the Y group can a so e 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 - li ⁇
  • 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 -Si ' 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' 5 ), 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 1 to Y ⁇ 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.
  • 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 ⁇ i 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 5 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) :
  • transition metal complexes are described in which a group 4 transition metal in a reduced oxidation state (3+) is present.
  • 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.
  • 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. Examples of 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.
  • trialkyl aluminum compounds such as triethyl aluminum and tri-isobutyl aluminum
  • alkyl aluminum hydrides such as di-isobutyl aluminum hydride
  • alkylalkoxy organoaluminium compounds alkylalkoxy organoaluminium compounds
  • halogen-containing organoaluminium compounds such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
  • 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 foi 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-277,00 , 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)
  • TAA triethyl aluminum
  • 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.
  • 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 process according to the invention is suitable for the preparation of semi-crystalline or of amorphous copolymers based on ethylene and an ⁇ -olefin.
  • the copolymer according to the invention comprises one or more ⁇ -olefins.
  • such an ⁇ -olefin contains 3-25 carbon atoms (although higher ⁇ -olefins are also allowable); more preferably, the ⁇ -olefin contains 3-10 carbon atoms.
  • the ⁇ -olefin has preferably been selected from the group consisting of propylene, butene, isobutene, pentene, 4-methyl pentene, hexene, octene and ( ⁇ - methyl) styrene. More preferably, the ⁇ -olefin is propylene, 1-butene, 1-hexene or 1-octene. Most preferred, the ⁇ -olefin is propylene.
  • the process of the present invention enables the preparation of an ethylene/ ⁇ -olefin copolymer with a broad range of molecular weights M n .
  • An alternative for products with a high molecular weight is the characterisation of the copolymer by its Mooney viscosity (ML 1+4 , 125°C, as per ASTM D1646).
  • the process of the present invention is able to prepare ethylene/ ⁇ -olefin copolymers having an ML 1+4 , 125°C of between 10 and 150.
  • the catalyst composition in the process according to the invention can be used supported or non-supported.
  • the transition metal complex or the co ⁇ catalyst can be supported on a carrier. It is also possible that both the transition metal complex and the co-catalyst are supported on a carrier.
  • the carrier material for the transition metal complex and for the co-catalyst can be the same material or a different material. It is also possible to support the transition metal complex and the co-catalyst on the same carrier.
  • the supported catalyst systems of the invention can be prepared as separate compounds, which can be used as such in polymerization reactions or the supported catalyst systems can be formed in situ by in situ methods just before a polymerization reaction starts.
  • 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, finely divided solid porous support, including, but not limited to, or MgCl 2 , Zeolites, mineral clays, inorganic oxides such as talc, silica (Si0 2 ), alumina (A1 2 0 3 ), silica-alumina, inorganic hydroxides, phosphates, sulphates, and the like, or resinous support materials such as polyolefins, including polystyrene, or mixtures thereof.
  • the carrier may be used as such, or be modified, for example by silanes, aluminium alkyls, aluminoxanes, and others.
  • the catalyst composition may also be prepared by in-situ methods.
  • Polymerization 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, while the quantity of transition metal to be used generally is such that its concentration in the dispersion agent amounts to 10 ⁇ 8 - 10 "3 mol/1, preferably 10" 7 - 10"* mol/1. Any liquid that is inert relative to the catalyst system can be used as a dispersion agent in the polymerization.
  • 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 are suitable for that purpose.
  • 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 a solvent the low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry.
  • the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
  • MAO methyl aluminoxane
  • toluene can be used as solvent 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.
  • the polymerization is carried out under pressure, the yield of polymer can be increased additionally, resulting in an even lower catalyst residue content.
  • Chain regulators can be used to control the molecular weight and the amount of unsaturation of the resulting copolymer. Preference is given to hydrogen as the chain regulator.
  • 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 polymer solution 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 at this point owing to the use of the catalyst system in the process according to the invention.
  • copolymers prepared according to the process of the present invention, can be used in different applications, like impact modifications, use in extrusion coating and wire-and-cable applications. These polymers are also useful in the manufacture of rubber articles and modified rubber articles.
  • the invention will now be elucidated by means of the following non-restrictive examples.
  • Cp means "cyciopentadienyl”
  • Me means “methyl”
  • Bu means "butyl”
  • ' ⁇ pr means "isopropyl”.
  • the carbinol (21.1 g; 0.10 mol) prepared as described under a) was added in a single portion to p- toluenesulphonic acid.H 2 0 (28.5 g; 0.15 mol), dissolved in 200 mL of diethyl ether. After stirring for 30 minutes at room temperature, the reaction mixture was poured out in a solution of 50 g of Na 2 CO 3 *10H 2 O in 250 mL of water. After separation, the water phase was extracted two times with 100 mL of diethyl ether. The combined ether layer was dried (Na 2 S0 4 ), filtered and boiled down. Then the residue was distilled at reduced pressure. The yield was 11.6 g (60%).
  • the THF was removed at reduced pressure.
  • the complex (a green solid) was purified by repeated washing of the solid, followed by filtration and back distillation of the solvent. It was also possible to obtain the pure complex through sublimation.
  • the catalyst is (dimethylaminomethyl)- diisopropyl-cyclopentadienyltitanium-(III) dichloride (CpH 2 i Pr 2 (CH 2 ) 2 NMe 2 TiCl 2 ).
  • GC was used to show that at that instant 92% of di(2- propyl)cyclopentadiene was present in the mixture of di-and tri(2-propyl)cyclopentadiene.
  • the product was distilled at 10 mbar and 70°C. After distillation, 25.35 g of di(2-propyl)cyclopentadiene were obtained. Characterization took place with the aid of GC, GC-MS, 13 C-and -NMR.
  • reaction mixture containing l-(dimethylaminoethyl )-2 , -di (2- propyl )cyclopentadienyltitanium(III ) dichloride was slowly brought to room temperature, after which stirring was continued for a further 18 hours.
  • a number of continuous streams of petrol, propylene, ethylene catalyst and co-catalyst were dosed to a 1-litre reactor.
  • the solution was continuously removed from the reactor.
  • the catalyst was inactivated with the aid of isopropyl alcohol in a flash vessel; the monomers were flashed and the solution was stabilised with the aid of about 1000 ppm of Irganox 1076®.
  • the polymer was analysed after further processing.
  • the composition of the polymers was determined with the aid of Fourier Transform Infrared Spectroscopy (FT-IR).
  • FT-IR Fourier Transform Infrared Spectroscopy
  • the FT-IR results indicate the composition of the various monomers in weight percentages relative to the overall composition.
  • the polymers prepared according to the Examples were analysed by means of SEC-DV. Molecular weight distributions were determined accordinging to the universal calibration principle as known from literature (see Z. Grubistic, R. Rempp, H. Benoit, J. Polym. Sci., part B, 5,753 (1967)).
  • the intrinsic viscosity (IV) was determined in decaline at 135°C.
  • the composition of the polymers was determined with the aid of Fourier Transform Infrared Spectroscopy (FT-IR).
  • FT-IR Fourier Transform Infrared Spectroscopy
  • the FT-IR results indicate the composition of the various monomers in weight percentages relative to the overall composition.
  • the polymers prepared according to the Examples were analysed by means of SEC-DV.
  • Molecular weight distributions were determined according to the universal calibration principle as described in Z. Grubistic, R. Rempp, H. Benoit, J. Polym. Sci., part B,5,753 (1967), the complete disclosure of which is incorporated herein by reference.
  • the intrinsic viscosity (int.vise, or "IV” was determined in decaline at 135°C.
  • Table 1 presents the polymerization conditions of the continuous polymerization of ethylene and propylene for Examples IV-VIII. This Table indicates: the amounts of petrol, propylene and ethylene, the amount of catalyst added, the amount of co-catalyst, the polymerization temperature and the polymerization time.
  • catalyst a is ⁇ Cp(Me) 4 (CH 2 ) 2 NMe 2 ⁇ TiMe 2
  • catalyst b is (Cp(Me) 4 (CH 2 ) 2 NBu 2 ⁇ TiMe 2
  • catalyst c is £CpH 2 i Pr 2 (CH 2 ) 2 NMe 2 ⁇ TiMe 2 (as they are prepared according to Examples I-III).
  • the co-catalyst used in the Examples is dimethylanilinium tetrakispentafluorophenylborate [HMe 2 N-C 6 H 5 ) ] + [ (C 6 F 5 ) 4 B] ⁇
  • the results of the continuous polymerizations according to Examples IV-VIII are summarized in Table 2.

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Abstract

L'invention concerne un procédé de préparation d'un copolymère d'éthylène α-oléfine, ce procédé se déroulant en présence d'un nouveau complexe d'un métal de transition et d'un co-catalyseur. Le procédé se caractérise également en ce que le complexe d'un métal de transition est un complexe d'un métal de transition réduit pouvant être choisi parmi les groupes 4 à 6 de la table périodique des éléments, avec un ligand monoanionique multidenté et avec deux ligands monoanioniques, à une température comprise entre 100 et 220 °C. En particulier, le métal de transition réduit dans le complexe est le titane (Ti (III)).
EP97919763A 1996-05-03 1997-05-01 PROCEDE DE PREPARATION D'UN COPOLYMERE D'$g(a)-OLEFINE ET D'ETHYLENE Withdrawn EP0896599A1 (fr)

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EP97919763A EP0896599A1 (fr) 1996-05-03 1997-05-01 PROCEDE DE PREPARATION D'UN COPOLYMERE D'$g(a)-OLEFINE ET D'ETHYLENE
PCT/NL1997/000243 WO1997042241A1 (fr) 1996-05-03 1997-05-01 PROCEDE DE PREPARATION D'UN COPOLYMERE D'α-OLEFINE ET D'ETHYLENE

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WO2002083754A1 (fr) 2001-04-12 2002-10-24 Exxonmobil Chemical Patents Inc. Polymeres d'ethylene et de propylene et procede de production
JP2002519497A (ja) 1998-07-01 2002-07-02 エクソンモービル・ケミカル・パテンツ・インク 結晶性プロピレンポリマーと結晶化可能プロピレンポリマーとを含んでなる弾性ブレンド
US6403773B1 (en) 1998-09-30 2002-06-11 Exxon Mobil Chemical Patents Inc. Cationic group 3 catalyst system
US6943215B2 (en) 2001-11-06 2005-09-13 Dow Global Technologies Inc. Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
KR100830317B1 (ko) * 2001-12-27 2008-05-16 삼성토탈 주식회사 시클로펜타디엔계열 및 카르보디이미드계열 리간드의 킬레이트 화합물 촉매를 이용한 에틸렌 중합 또는 공중합방법
JP4728643B2 (ja) 2002-10-02 2011-07-20 ダウ グローバル テクノロジーズ エルエルシー 液状およびゲル状の低分子量エチレンポリマー類
US7335696B2 (en) 2002-10-17 2008-02-26 Dow Global Technologies, Inc. Highly filled polymer compositions
ATE455832T1 (de) 2003-08-19 2010-02-15 Dow Global Technologies Inc Interpolymere zur verwendung für schmelzklebstoffe und verfahren zu ihrer herstellung
JP2012176915A (ja) * 2011-02-28 2012-09-13 Ube Industries Ltd アルキルシクロペンタジエン化合物及びその製造方法

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US5278272A (en) * 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5374696A (en) * 1992-03-26 1994-12-20 The Dow Chemical Company Addition polymerization process using stabilized reduced metal catalysts
AU3817595A (en) * 1994-10-31 1996-05-23 Dsm N.V. Catalyst composition and process for the polymerization of an olefin

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BR9709194A (pt) 1999-08-10
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TW370537B (en) 1999-09-21
AU2411997A (en) 1997-11-26

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