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WO1997042240A1 - Procede pour la copolymerisation d'une olefine et d'un monomere aromatique de vinyle - Google Patents

Procede pour la copolymerisation d'une olefine et d'un monomere aromatique de vinyle Download PDF

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Publication number
WO1997042240A1
WO1997042240A1 PCT/NL1997/000239 NL9700239W WO9742240A1 WO 1997042240 A1 WO1997042240 A1 WO 1997042240A1 NL 9700239 W NL9700239 W NL 9700239W WO 9742240 A1 WO9742240 A1 WO 9742240A1
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group
transition metal
process according
ligand
groups
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PCT/NL1997/000239
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English (en)
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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 EP97919759A priority Critical patent/EP0896598A1/fr
Priority to EA199800978A priority patent/EA199800978A1/ru
Priority to JP09539789A priority patent/JP2000513760A/ja
Priority to AU24115/97A priority patent/AU2411597A/en
Priority to BR9709144A priority patent/BR9709144A/pt
Publication of WO1997042240A1 publication Critical patent/WO1997042240A1/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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • 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 co-polymerization of an olefin, especially ethylene, and a vinyl aromatic monomer.
  • the present invention relates to the co-polymerization process conducted in the presence of a catalyst composition comprising a transition metal complex and a co-catalyst.
  • a process for the co-polymerization of ethylene and a vinyl aromatic monomer is disclosed in EP-A-416,815, in which a so-called constrained-geometry catalyst is applied.
  • the catalysts disclosed in this reference have had success, to some extent, in co-polymerizing vinyl aromatic monomers with ethylene.
  • a disadvantage of the process disclosed in this reference is the unfavorable molecular weights of the co-polymers obtained and the insufficient percentage of vinyl aromatic monomers incorporated into the resultant co-polymers under a given set of polymerization conditions. It is known to enhance this ratio by lowering the polymerization temperature; however, the lowering of the polymerization temperature leads to decreased catalyst activity and an inferior co-polymer yield.
  • 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 -) B 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;
  • 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 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 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 4 *, and m is 2 for M 5+ , 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 - A -
  • n 1; q,s q and s are the number of (-R t -DR' n ) groups and (Ar-
  • the co-polymer prepared in accordance with the process of the present invention also has a higher concentration of vinyl aromatic monomers incorporated into the co-polymer than could be obtained for a co-polymer, of the same molecular weight, prepared in accordance with the above-mentioned known process conducted under similar process conditions.
  • Another object of the present invention is the provision of a copolymer of at least one ⁇ -olefin and at least one vinyl aromatic monomer obtained by means of the above-mentioned polymerization process with utilization of the catalyst composition according to the invention.
  • 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.
  • 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 'êt) 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 - ⁇ R ' n and Y(-R- DR' n ) 2 . It is noted, however, that heteroatom(s) or aryl substituent(s) can be present on the Y group without coordinately bonding to the reduced transition metal M, so long as at least one coordinate bond is formed between an electron-donating group D or an electron donating Ar group and the reduced transition metal M.
  • 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. Most preferably, the Y group is a cyclopentadienyl ligand (Cp group).
  • cyclopentadienyl group encompasses substituted cyclopentadienyl groups such as indenyl, fiuorenyl, 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'êt 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 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, fiuorenyl, 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 ⁇ 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 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
  • 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.
  • the DR' n 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 fiuorenyl group.
  • the coordination of this Ar group in relation to the transition metal M can vary from h 1 to I") 6 .
  • the R ' Group 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 1).
  • alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
  • aryl groups are phenyl, mesityl, tolyl and cumenyl.
  • Examples of 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; therefore the Y group can be an indenyl, a fiuorenyl or a benzoindenyl group.
  • the indenyl, fiuorenyl, 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 CI 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.
  • K is a neutral ligand
  • 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):
  • M(III) is a transition metal selected from group 4 of the Periodic Table of Elements and is in oxidation state 3+.
  • 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. 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 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 present invention relates to a process for the co-polymerization of one or more ⁇ -olefins and one or more vinyl aromatic monomers.
  • the term "monomer” as encompasses dimers, trimers, and oligomers.
  • the ⁇ -olefin is preferably at least one member selected from the group consisting of ethylene, propylene, butene, pentene, heptene and octene, and any combination thereof. More preferably, at least one member selected from the group consisting of ethylene and propylene is selected as the ⁇ -olefin.
  • Suitable vinyl aromatic monomers which can be polymerized in the process of the present invention include, without limitation, those represented by the formula:
  • each R 2 in formula (VIII) is, for example, independently selected as one of the following: hydrogen; an aliphatic, cycloaliphatic or aromatic hydrocarbon group having from 1 to 10 carbon atoms, more suitably from 1 to 6 carbon atoms, most suitably from 1 to 4 carbon atoms; and a halogen atom.
  • exemplary vinyl aromatic monomers include, without limitation, styrene, chlorostyrene, n- butyl styrene, and p-vinyl toluene. Especially preferred is styrene.
  • the amount of vinyl aromatic monomer incorporated in the copolymers of the present invention is at least 0.1 mol%. Additional olefin monomers can be co ⁇ polymerized in the same process to thereby yield ter ⁇ polymers and higher polymers (which are also referred to herein as being encompassed by the term "co-polymer” and made by the "co-polymerization process").
  • olefin monomers include, by way of example and without limitation, ethylene, propylene, butene, pentene, hexene, heptene, octene and dienes such as 1,4-hexadiene, 1,7- octadiene, dicyclopentadiene (DCPD) , 5-vinylidene-2- norbornene, 5-ethylidene-2-norbornene, and 5-methylene-2- norbornene, and polyenes such as polybutadiene.
  • DCPD dicyclopentadiene
  • the process according to the invention is also suitable for the preparation of rubber-like copolymers based on an ⁇ -olefin, a vinyl aromatic monomer and a third monomer. It is preferred to use a diene as the third monomer. Suitable dienes for preparing rubber-like copolymers include those specified above.
  • the catalyst can be used as is, or optionally the catalyst can be supported on a suitable support or carrier, such as alumina, MgCl 2 or silica, to provide a heterogeneous supported catalyst.
  • a suitable support or carrier such as alumina, MgCl 2 or silica
  • the transition metal complex or the co-catalyst can be supported on the carrier. It is also possible to support both the transition metal complex and co-catalyst on the same or different carriers. Where more than one carrier is provided, the carriers can be the same or different from each other.
  • the supported catalyst systems of the invention can be prepared separately before being introduced into the co-polymerization reaction, or can be formed in situ, for example, before the co-polymerization reaction commences.
  • the co-polymerization reaction can be conducted under solution or slurry conditions, in a suspension utilizing a perfluorinated hydrocarbon or similar liquid, in the gas phase (for example, by utilizing a fluidized bed reactor), or in a solid phase powder polymerization.
  • a catalytically effective amount of the present catalyst and co-catalyst are any amounts that successivefully 97/42240 PC NL97
  • the quantity of transition metal complex to be used generally can be such that the concentration of the transition metal in the solution or dispersion agent is about IO -8 mol/1 to about IO -3 mol/1 , and preferably about 10 ⁇ 7 mol/1 to about IO "4 mol/1.
  • transition metal complex described herein undergoes various transformations or forms intermediate species prior to and during the course of co-polymerization.
  • other catalytically active species or intermediates formed from the metal complexes described herein and other metal complexes (precursors) than those described herein that achieve the same catalytic species as the complexes of the present invention are herein envisioned without departing from the scope or the present invention.
  • any liquid that is inert relative to the catalyst system can be used as a dispersion agent in the co-polymerization process.
  • Suitable inert liquids that can be selected as the dispersion agent include, without limitation, the following: one or more saturated, straight or branched aliphatic hydrocarbons, including, without limitation, butane, pentane, hexane, heptane, pentamethyl heptane, and any combination thereof ? and/or one or more mineral oil fractions, including, without limitation, light or regular petrol, naphtha, kerosine, gas oil, and any combination thereof.
  • Aromatic hydrocarbons for instance benzene, ethylbenzene and toluene, can be also used; however, due to the high cost associated with aromatic hydrocarbons, as well as safety considerations, it is generally preferred not to use such solvents for production on a technical (or commercial) scale. In polymerization processes on a technical (or commercial) scale, it is, therefore, preferred to use as the solvent the low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry.
  • Excess vinyl aromatic or olefin monomers can also be applied in so-called bulk polymerization processes.
  • the solvent can yet contain minor quantities of aromatic hydrocarbons such as, for instance, toluene.
  • toluene can be used as the solvent for the MAO in order to dissolve the MAO into solution and supply the solution to the polymerization reactor. Drying or purification of the solvents is desirable if such solvents are used; this can be done without undue experimentation by the skilled artisan.
  • the polymerization is preferably carried out at temperatures well above the melting point of the polymer to be produced. Suitable temperatures generally include, without limitation, temperatures in a range of from about 120°C to about 260°C. In general, suspension or gas phase polymerization takes place at lower temperatures, that is, temperatures well below the melting temperature of the polymer to be produced. Generally, temperatures suitable for suspension or gas phase polymerization are below about 105°C.
  • 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 generally be omitted, since the quantity of catalyst in the co-polymer, in particular the content of halogen and transition metal in the co-polymer, is very low due to the use of the catalyst system according to the invention.
  • Co-polymerization can be effected at sub- atmospheric, atmospheric and elevated pressure, and under conditions where at least one of the monomers is a liquid, which can be realized by application of suitable combinations of pressure and temperature, continuously or discontinuously. If the co-polymerization is carried out under pressure, the polymer yield can be increased substantially, resulting in an even lower catalyst residue content.
  • the co-polymerization is performed at pressures in a range of from about 0.1 MPa to about 25 MPa. Higher pressures, typically but not limited to 100 MPa and above, can be applied if the polymerization is carried out in so-called high-pressure reactors. In such a high-pressure process, the catalyst according to the present invention can also be used with good results.
  • the co-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., or any combination thereof can be varied from step to step. In this way, products having a wide molecular weight distribution can be obtained.
  • TiCl 3 the esters, the lithium reagents, 2- bromo-2-butene and 1-chlorocyclohexene each were supplied by Aldrich Chemical Company.
  • TiCl 3 -3THF was obtained by heating TiCl 3 for 24 hours in THF with reflux.
  • THF refers to tetrahydrofuran
  • Me refers to methyl
  • (t)Bu refers to (tertiary) butyl
  • Ind refers to indenyl
  • Flu refers to fiuorenyl
  • iPr refers to iso-propyl.
  • Examples I-IV set forth non-limiting processes for preparing embodiments of the transition metal complexes of the present invention.
  • the solution was cooled to -100°C and then TiCL 3 -3THF (0.85 g; 2.3 mmol) was added in a single portion. After stirring for 2 hours at room temperature, the THF was removed at reduced pressure. After addition of special boiling point gasoline (i.e., a C 6 hydrocarbon fraction with a boiling range of 65-70°C, obtainable from Shell or Exxon, 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.
  • special boiling point gasoline i.e., a C 6 hydrocarbon fraction with a boiling range of 65-70°C, obtainable from Shell or Exxon
  • Synthes is of ( dibutylaminoethyl ) tetramethyl- cyclopentadienylt itanium ( III ) dichlor ide (C 5 Me 4 ( CH 2 ) 2 NBu 2 TiCl 2 ) .
  • 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 Example I ⁇ (a) (7.0 g; 0.031 mol) was added with reflux over the course of approximately 5 minutes, followed by stirring for about 30 minutes. Then (200 ml) of water was carefully added dropwise. 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 boiled down. The yield was 9.0 g (100%).
  • (didecylaminoethyl)tetramethyl-cyclopentadienyl- titanium(III) dichloride (C 5 Me 4 (CH 2 ) 2 N(C 10 H 21 ) 2 TiCl 2 ) was prepared in an analoguous way as described in Example I, the difference being that the corresponding di-decyl- amino-propionate was applied in place of the ethyl-3-(N,N- dimethylamino)propionate.
  • iPr 2 -Cp diisopropylcyclopentadiene
  • iPr 3 -Cp triisopropylcyclopentadiene
  • iPr 2 -Cp and iPr 3 -Cp were isolated by distillation at reduced (20 mmHg) pressure. Yield depended on distillation accuracy (approx. 0.2 mol iPr 2 -Cp (25%) and 0.3 mol iPr 3 -Cp (40%)).
  • Examples V-XVII set forth non-limiting processes for preparing copolymers with the transition metal complexes of the present invention. Polymerization experiments were carried out according to the procedure described in general terms below. Unless otherwise indicated, the conditions specified in Example V were applied in each of the individual examples. Example V
  • Styrene was distilled from CaH 2 under vacuum. 600 ml of an alkane mixture was introduced as a solvent into a stainless steel reactor with a volume of 1.5 liters under a dry N 2 atmosphere. Then, the required amount of dry styrene was introduced into the reactor. The reactor was heated to 80°C, while stirring, at an absolute ethylene pressure of 800 kPa.
  • the product was analyzed by means of SEC-DV, X H-NMR and DSC.
  • the formed polymer was a copolymer with an Mw of 250,000 g/mol and a maximum melting temperature (as determined via DSC) of 93°C.
  • the copolymer formed had an Mw (as determined by means of SEC-DV) of 180,000 g/mol.
  • the styrene content was determined by means of ⁇ -H-NMR and found to be 6.3 mol.%.
  • Example IX A co-polymerization process was carried out using the transition metal compound (C 5 ME 4 (CH 2 ) 2 NMe 2 TiCl 2 (Example I) under the conditions described in Example VII.
  • the copolymer formed contained 8.6 mol.% styrene, as determined by means of ⁇ -NMR.
  • the polymer had an Mw of 130,000 g/mol (SEC-DV).
  • the polymer formed (6.2 g) was found to have an Mw of 82,000 g/mol (as determined by means of SEC- DV) and to contain 4.2 mol.% styrene.
  • a catalyst on a carrier was synthesised by adding 10 ml of dry toluene to 1.453 g of Si0 2 (Grace/Davidson W952, dried for 4 hours at 400°C under dry N 2 ). Then 16 ml of MAO (Witco, 30% by weight in toluene) was added over the course of 10 minutes, with stirring, at 300 K. The sample was dried for 2 hours in a vacuum, with stirring, after which 25 ml of an alkane mixture was added and the resultant mixture was stirred for 12 hours at
  • Example II a suspension of IO "4 mol (C 5 Me 4 (CH 2 ) 2 NMe 2 TiCl 2 (Example I) was added, with stirring. After drying, the catalyst was found to contain 27.9 wt.% Al and to have an Al/Ti ratio of 328.
  • a co-polymerization experiment was carried out using the supported catalyst described above, under conditions comparable with those of Example VI. 45 g of styrene was added to the reactor. Then 20 micromol (based on Ti) of supported catalyst was introduced into the reactor. The co-polymerization reaction was carried out at an ethylene pressure of 8 bar, at 80°C. The formed polymer (1450 kg/mol Ti.hour) was analyzed by means of SEC-DV. The Mw was found to be 490,000 g/mol at a styrene content of 3.1 mol.% (as determined via X H-NMR).
  • a stainless steel reactor with a volume of 1.5 liters was filled with 600 ml of a mixed high-boiling alkane solvent (with a boiling range starting at 180°C) for a solution polymerization. The temperature was raised to 150°C while stirring. Then the reactor was saturated with ethylene and the ethylene pressure was brought to 21 bar. 45 g of dried styrene was introduced into the reactor. Next, 0.4 mmol aluminium alkyl (triethylaluminium) was introduced into the reactor as a scavenger.
  • the reaction mixture was drained from the reactor, quenched with methanol and stabilized with antioxidant (Irganox 1076 (TM) ) . After drying in a vacuum, the product was analyzed by means of SEC-DV. The product was found to have a molecular weight of 82,000 g/mol. The product also contained 2.7 mol.% styrene as determined by means of X H-NMR and the DSC curve indicated a maximum melting temperature of 127°C.
  • Example VII A co-polymerization reaction was carried out as described in Example VII, with the exception that the transition metal complex was (C 5 Me 4 (CH 2 ) 2 NBu 2 TiMe 2 , obtained by methylating the compound of Example II according to the method described in Example IVc.
  • Example VI A co-polymerization reaction was carried out as described in Example VI, except that the transition metal complex was EtCp(iPr ) 3 NMe 2 TiMe 2 , obtained by methylating the compound of Example IV.
  • Example XIV A co-polymerization reaction was carried out as described in Example VI, with the difference being that 3.0 ml of dried 1,7-octadiene was additionally introduced into the reactor as a third monomer after the styrene had been introduced (terpolymerization) . Then the co-polymerization was carried out in exactly the same manner as described in Example VI.
  • the polymer formed contained 1.6 mol.% styrene and 0.6 mol.% octadiene, both as determined by means of 13 C-NMR and 1 H- NMR, at a polymer yield of 12,000 kg/mol Ti.hour.
  • Example XV A co-polymerization reaction was carried out as described in Example VI, with the difference being that 3.0 ml of dried 1,7-octadiene was additionally introduced into the reactor as a third monomer after the styrene had been introduced (terpolymerization) . Then the co-polymerization was carried out in
  • Example VI An ethylene/styrene co-polymerization process was carried out as described in Example VI, only now 225 g of styrene was co-polymerized at an ethylene pressure of 600 KPa.
  • the product formed was purified and analyzed by means of SEC-DV. The Mw was found to be 100 kg/mol and the Mn 53,000 g/mol. ⁇ -H-NMR analysis showed that the polymer contained 19.9 mol.% styrene.
  • Example XII A co-polymerization experiment was carried out as described in Example XII, with the exception that the transition metal compound was EtCp(iPr ) 3 NMe 2 TiCl 2 (Example

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Abstract

Cette invention se rapporte à un procédé pour la copolymérisation d'au moins une α-oléfine et d'au moins un monomère aromatique. Cette copolymérisation est effectuée en présence d'une composition de catalyseur renfermant au moins un cocatalyseur et un complexe de métal de transition réduit. Le complexe de métal de transition réduit contient un métal de transition réduit choisi dans les groupes 4 à 6 du tableau périodique des éléments, un ligand monoanionique multidenté, et au moins deux ligands monoanioniques. Dans un mode de réalisation, le métal de transition réduit qui est choisi est le titane.
PCT/NL1997/000239 1996-05-03 1997-05-01 Procede pour la copolymerisation d'une olefine et d'un monomere aromatique de vinyle WO1997042240A1 (fr)

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EP97919759A EP0896598A1 (fr) 1996-05-03 1997-05-01 Procede pour la copolymerisation d'une olefine et d'un monomere aromatique de vinyle
EA199800978A EA199800978A1 (ru) 1996-05-03 1997-05-01 Способ сополимеризации олефина и винилового ароматического мономера
JP09539789A JP2000513760A (ja) 1996-05-03 1997-05-01 オレフィンおよびビニル芳香族モノマーの共重合法
AU24115/97A AU2411597A (en) 1996-05-03 1997-05-01 Process for the co-polymerization of an olefin and a vinyl aromatic monomer
BR9709144A BR9709144A (pt) 1996-05-03 1997-05-01 Processo para co-polimerização de uma olefina e um monômero aromático vinílico

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WO2000049059A1 (fr) * 1999-02-17 2000-08-24 The Dow Chemical Company Copolymere aromatique d'alpha-olefine/vinyle ou vinylidene et procede d'elaboration a plusieurs systemes catalytiques
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization

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EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
WO1992012112A1 (fr) * 1990-12-31 1992-07-23 Exxon Chemical Patents Inc. Composes chiraux d'alliage organometallique et leur preparation par creation d'un centre chiral par transfert enantioselectif d'hydrures
WO1992012117A1 (fr) * 1991-01-02 1992-07-23 Exxon Chemical Patents Inc. Composes chiraux d'alliages organometalliques et leur preparation par fixation d'un centre chiral
WO1993008221A2 (fr) * 1991-10-15 1993-04-29 The Dow Chemical Company Polymeres olefiniques elastiques sensiblement lineaires
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
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

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Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
WO1992012112A1 (fr) * 1990-12-31 1992-07-23 Exxon Chemical Patents Inc. Composes chiraux d'alliage organometallique et leur preparation par creation d'un centre chiral par transfert enantioselectif d'hydrures
WO1992012117A1 (fr) * 1991-01-02 1992-07-23 Exxon Chemical Patents Inc. Composes chiraux d'alliages organometalliques et leur preparation par fixation d'un centre chiral
WO1993008221A2 (fr) * 1991-10-15 1993-04-29 The Dow Chemical Company Polymeres olefiniques elastiques sensiblement lineaires
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
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

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* 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
WO2000049059A1 (fr) * 1999-02-17 2000-08-24 The Dow Chemical Company Copolymere aromatique d'alpha-olefine/vinyle ou vinylidene et procede d'elaboration a plusieurs systemes catalytiques
US6552148B1 (en) 1999-02-17 2003-04-22 The Dow Chemical Company α-olefin/vinyl or vinylidene aromatic interpolymer product and process for making same using multiple catalyst systems

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