Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT 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
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

• the invention relates to a process for the preparation of a terpolymer of ethylene, an ⁇ -olefin and a diene, with an ethylene content of between about 20 and about 90 weight %, and a diene content of up to 30 weight %, with a catalyst composition comprising a transition metal complex and a co-catalyst.
• the terpolymer will also be referred to as to "EADM” (ethylene ⁇ -olefin diene monomer) polymer; in case the ⁇ -olefin is propylene, the terpolymer will also be referred to as to "EPDM" (ethylene propylene diene monomer ) .
• EP-A-347, 129 A process for the preparation of an EADM is known from EP-A-347, 129, in which a cyclopentadiene based transition metal complex (in combination with a co-catalyst) is used as a catalyst.
• a disadvantage of a process according to EP-A-347,129 is that it has to be conducted at relatively low temperatures, which causes 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; on the other hand the pressure should preferably not be too high as otherwise the costs for such a high pressure process could undo the advantages of a high temperature process.
• Another object of the present invention is the preparation of such terpolymers having an average molecular weight of as low as lOg/mol.
• the process according to the invention is characterized in that the polymerization is conducted at a temperature of between about -10°C to about 220°C, and preferably between about 75°C and about 220°C, under the influence of a transition metal complex of the structure shown below in Formula (I).
• 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): X ( 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
• 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 s+ , 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
• 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. — o —
• a transition metal complex of formula (I) is capable of facilitating preparation of EADM's at the indicated temperature level, whereas other known catalysts for these types of polymerisation do not produce those polymers at this temperature level (they are only active at temperatures well below 100°C; see the examples in the referenced EP-A- 347,129).
• the process according to the present invention is suitable for the preparation of EADM's having an M n (the number-average molecular weight as determined by SEC-DV (Size Exclusion Chromatography/Differential Viscometry combination)), of as low as 100 (g/mol).
• the temperature at which the polymerization is performed is one of the parameters to control the value of M n .
• any EADM can be made with an M n between about 100 and about 500,000.
• the polymers also have an ethylene content generally of between about 20 and about 90 weight %.
• the polymers can be amorphous, being products with an ethylene content of between 30 and 70 weight %, or can be semicrystalline.
• EADM's with a molecular weight M n between 100 and 30,000 are prepared in a polymerization process at temperatures between 135 and 220°C; EADM's with a molecular weight M n between 20,000 and 100,000 are preferably prepared in a polymerization process at a temperature between 115 and 180°C.
• the pressure at which the polymerization is conducted is in general below 100 MPa. Pressures up to 10 MPa are. in several cases sufficient enough for a good catalytic activity.
• the process according to the invention is suitable for the preparation of low molecular weight semi-crystalline or of amorphous polymers based on ethene, an ⁇ -olefin and a diene. It is also suitable, and preferably used for the preparation of high molecular weight EADM's; that is to say, polymers with a M n of at least about 50,000 or with a Mooney viscosity (ML 1+4 , 125°C, according to ASTM D1646) of 10-150. Besides the ethylene, the polymer according to the invention comprises one or more ⁇ -olefins.
• such an ⁇ -olefin contains 3-25 carbon atoms (although higher ⁇ - olefines are also allowable); more preferably, the ⁇ -olefin contains 3-10 carbon atoms.
• the ⁇ -olefine has preferably been selected from the group consisting of propylene, butene, isobutene, pentene, 4-methyl pentene, hexene, octene and ( ⁇ - methyl) styrene. More preferably, the ⁇ -olefine is propylene, l-butene, 1-hexene or 1-octene, styrene, or ( ⁇ - methyl)styrene. Most preferred is the ⁇ -olefin propylene, resulting in the preparation of EPDM.
• the polymer also comprises one or more dienes.
• Examples of such compounds are: 1,3-butadiene, isoprene, 2,3-dimethyl butadiene-1,3, 2-ethyl butadiene-1,3, piperylene, myrcene, allenes, 1,2-butadiene, 1,4,9-decatrienes, 1,4-hexadiene, octadiene, 1,5-hexadiene and 4-methyl hexadiene-1,4.
• Alicyclic polyunsaturated compounds may be either monocyclic or polycyclic.
• examples of such compounds are norbornadiene and its alkyl derivatives; the alkylidene norbornenes, in particular the 5-alkylidene norbornenes-2 , in which the alkylidene group contains 1 to 20, by preference 1 to 8 carbon atoms; the alkenyl norbornenes, in particular the 5- alkenyl norbornenes-2, in which the alkenyl group contains 2 to 20, by preference 2 to 10 carbon atoms, for instance vinyl norbornene, 5-(2 '-methyl-2 'butenyl)-norbornene-2 and 5-(3'- methyl-2 'butenyl )-norbornene-2 ; dicyclopentadiene and the polyunsaturated compounds of bicyclo-(2,2,l)-heptane, bicyclo-(2 ,2 ,2 , )-octane, bicylco
• compounds such as 4,7,8,9- tetrahydroindene and isoproylidene tetrahydroindene can be used.
• dicyclopentadiene, ethylidene norbornene, vinyl norbornene, or hexadiene are used. Mixtures of the compounds mentioned in the foregoing may also be used.
• the diene is present in the polymer in quantities of up to 30 weight %, typically however up to 10-15 weight %. Even more preferred is an amount of diene in the copolymer of 1-10 weight %, specifically between 2 and 8 weight %.
• transition metal complex Various components (groups) of the transition metal complex are discussed below in more detail.
• the Transition Metal (M) 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 -DRVi-R t -DR' n and Y(-R-DR' n ) 2 .
• 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
• 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, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the Cp group is an R t -DR'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, 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 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 Y ⁇ 5 bond.
• the other R' exocyclic substituents (shown in formula (III)) on the ring of the hetero Cp group can be of the same type as those present on the Cp group, as represented in formula (II).
• at least one of the exocyclic substituents on the five-member ring of the hetero cyclopentadienyl group of formula (III) is the R t -DR' n group or the R t -Ar group.
• the numeration of the substitution sites of the indenyl group is in general and in the present description based on the IUPAC Nomenclature of Organic Chemistry 1979, rule A 21.1. The numeration of the substituent sites for indene is shown below. This numeration is analogous for an indenyl group:
• the Y group can also be an amido (-NR'-) group or a phosphido (-PR'-) group.
• the Y group contains nitrogen (N) or phosphorus (P) and is bonded covalently to the transition metal M as well as to the (optional) R group of the (-R t -DR' n ) or (Ar-R t -) substituent.
• the R group is optional, such that it can be absent from the X group. Where the R group is absent, the DR' n or Ar group is bonded directly to the Y group (that is, the DR' n or Ar group is bonded directly to the Cp, amido, or phosphido group). The presence or absence of an R group between each of the DR' n groups and/or Ar groups is independent.
• each of the R group constitutes the connecting bond between, on the one hand the Y group, and on the other hand the DR' n group or the Ar group.
• the presence and size of the R group determines the accessibility of the transition metal M relative to the DR 'êt or Ar group, which gives the desired intramolecular coordination. If the R group (or bridge) is too short or absent, the donor may not coordinate well due to ring tension.
• the R groups are each selected independently, and can generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, aryl alkylidene, etc.). Specific examples of such R groups include, without limitation, methylene, ethylene, propylene, butylene, phenylene, whether or not with a substituted side chain.
• the R group has the following structure:
• R' groups of formula (IV) can each be selected independently, and can be the same as the R' groups defined below in paragraph (g).
• the main chain of the R group can also contain silicon or germanium.
• R groups are: dialkyl silylene (-SiR' 2 -), dialkyl germylene (-GeR' 2 -), tetra-alkyl silylene (-SiR ' 2 -SiR ' 2 -) , or tetraalkyl silaethylene (-SiR' 2 CR ' 2 - ) .
• the alkyl groups in such a group preferably have 1-4 carbon atoms and more preferably are a methyl or ethyl group.
• This donor group consists of an electron-donating hetero atom D, selected from group 15 or 16 of the Periodic Table of Elements, and one or more substituents R' bonded to D.
• the number (n) of R' groups is determined by the nature of the hetero atom D, insofar as n being 2 if D is selected from group 15 and n being 1 if D is selected from group 16.
• the R' substituents bonded to D can each be selected independently, and can be the same as the R' groups defined below in paragraph (g), with the exception that the R' substituent bonded to D cannot be hydrogen.
• the hetero atom D is preferably selected from the group consisting of nitrogen (N) , oxygen (O) , 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 h. 1 to ⁇ 6 .
• the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like as shown in Table 1).
• alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
• aryl groups are phenyl, mesityl, tolyl and cumenyl.
• aryl alkyl groups are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
• R' groups are halides, such as chloride, bromide, fluoride and iodide, methoxy, ethoxy and phenoxy.
• two adjacent hydrocarbon radicals of the Y group can be connected with each other to define a ring system; therefore the Y group can be an indenyl, a fluorenyl or a benzoindenyl group.
• the indenyl, fluorenyl, and/or benzoindenyl can contain one or more R' groups as substituents.
• R' can also be a substituent which instead of or in addition to carbon and/or hydrogen can comprise one or more hetero atoms of groups 14-16 of the Periodic Table of Elements.
• a substituent can be, for example, a Si-containing group, such as Si(CH 3 ) 3 .
• the transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
• L group ligands which can be identical or different, include, without limitation, the following: a hydrogen atom; a halogen atom; an alkyl, aryl or aryl alkyl group; an alkoxy or aryloxy group? a group comprising a hetero atom selected from group 15 or 16 of the Periodic Table of Elements, including, by way of example, (i) a sulphur compound, such as sulphite, sulphate, thiol, sulphonate, and thioalkyl, and (ii) a phosphorus compound, such as phosphite, and phosphate.
• the two L groups can also be connected with each other to form a dianionic bidentate ring system.
• L is a halide and/or an alkyl or aryl group; more preferably, L is a Cl group and/or a C L -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 K may be absent, but when K is monoanionic, the following holds for
• 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' S ), 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.
• 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 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.
• the donor optionally bonded to the Y group by means of the R group.
• 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: dimethyl anilinium tetrakis (pentafluorophenyl) borate [C 6 H S N(CH 3 ) 2 H] + [B(C ⁇ F s ) 4 ]-j - dimethyl anilinium bis (7,8-dicarbaundecaborate)- cobaltate (III);
• 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 catalyst composition used in the process according to the invention can be used supported as well as non-supported.
• the supported catalysts are used mainly in gas phase and slurry processes.
• the carrier used may be any carrier known as carrier material for catalysts, for instance Si0 2 , Al 2 0 3 or MgCl 2 , zeolites, mineral clays, inorganic oxides such as talc, silica-alumina, inorganic hydroxides, phosphates, sulphates, etc. or resinous support materials such as polyolefins, including polystyrene, or mixtures thereof.
• Suitable brands of silane carriers are MA0/Si0 2 from Witco, based on PQMS3040 Si0 2 and Si0 2 Grace Davison under code W952.
• the carrier may be used as such, or be modified, for example by silanes, aluminiumalkyls, 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 ⁇ - IO "3 mol/1, preferably IO -7 - IO -4 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 and environmental hazards it is preferred not to use such solvents for production on a commercial scale.
• the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
• MAO methyl aluminoxane
• toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification is desirable if such solvents are used; this can be done without problems by the average person skilled in the art.
• Chain regulators such as hydrogen or diethyl zinc
• 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 polymer can be isolated by solution polymerization by methods known in the art.
• 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 be omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal is very low now owing to the use of the catalyst system in the process according to the invention.
• Suitable vulcanizing agents are e.g. peroxides, sulphur and sulphur containing compounds, phenolic resins.
• the EADM's of the present invention can also be used in unvulcanized form, e.g. in blends with other polymeric products. They are useful in rubberized compounds. They are also useful in thermoplastic vulcanizates (blends of a plastic and an at least partially cured EADM).
• the invention will now be elucidated by means of the following non-restrictive examples.
• GC and GC-MS analysis showed the product mixture to consist of diisopropylcyclopentadiene (iPr 2 -Cp, 40%) and triisopropylcyclopentadiene (iPr 3 -Cp, 60%).
• iPr 2 -Cp and iPr 3 -Cp were separated and isolated by distillation at reduced (20 mmHg) pressure. Yield: iPr 2 -Cp: 25% and iPr 3 -Cp: 40%.
• dimethylaminoethyl chloride (11.3 g; 105 mmol; freed from HCI (by the method of Rees W.S. Jr. & Dippel K.A. in OPPI BRIEFS vol 24, No. 5, 1992) was added via a dropping funnel in 5 minutes. The solution was allowed to warm to roomtemperature after which it was stirred over night. The progress of the raction was monitored by GC . After addition of water (and pet-ether), the organic layer was separated, dried and evaporated under reduced pressure.
• composition of the terpolymers was determined with the aid of Fourier Transform Infrared Spectroscopy (FT ⁇ IR).
• FT ⁇ IR Fourier Transform Infrared Spectroscopy
• the intrinsic viscosity (IV) was determined in decaline at 135°C.
• a terpolymer of ethylene, propylene and ENB has been obtained.
• the polymer contained 49 wt% propylene and 9 wt% ENB.
• the intrinsic viscosity of the polymer was 1.29.
• the activity of the catalyst system was 1440 kg EPDM/mol transition metal * 10 min.
• ESDM's ethylene/styrene/diene terpolymers
• Styrene was vacuum distilled over CaH 2 . 600 ml of a dry alkane solvent (boiling range 65-70°C at 100 kPa pressure) was introduced into a 1.5 1 stainless steel reactor. 45 g dried styrene was introduced in the reactor, followed by 3 ml dried 1,7-octadiene. Then the reaction mixture was heated to 80°C under an ethylene pressure of 800 kPa, followed by an equilibration period under stirring.
• a dry alkane solvent boiling range 65-70°C at 100 kPa pressure
• Example V In a catalyst dosing vessel with a volume of 100 mL, 25 mL of the same solvent as present in the reactor was introduced at room temperature, followed by 20 mmol MAO (on Al-basis, Methyl Aluminoxane by Witco, 10 weight % in toluene) and 10 micromoles of the transition metal complex of Example II. After one minute of mixing, the catalyst/co- catalyst mixture was introduced into the reactor, thus starting the polymerisation reaction. The polymerisation was performed isothermally. After 6 minutes of polymerisation the reaction was stopped, the reaction mixture drained from the reactor, followed by quenching with methanol.
• MAO on Al-basis, Methyl Aluminoxane by Witco, 10 weight % in toluene
• the polymer was stabilised using 1000 ppm of Irganox 1076® as anti-oxidant and was dried during 24 hours under vacuum at 70°C.
• the polymer was analysed using 13 C-NMR and ⁇ -NMR and was found to contain 1.6 mol% styrene and 0.6 mol% octadiene.
• the ESDM yield was 12,000 kg/mol transition metal * hour.
• Example VI A polymerisation was performed under the conditions described in Example V but using the transition metal complex of Example III. The polymer was found to contain 3.5 mol% styrene and 0.5 mol% octadiene; the ESDM yield was 860 kg/mol transition metal * hour.

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