WO1997042238A1 - Copolymeres polyolefiniques inverses - Google Patents

Copolymeres polyolefiniques inverses Download PDF

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Publication number
WO1997042238A1
WO1997042238A1 PCT/NL1997/000250 NL9700250W WO9742238A1 WO 1997042238 A1 WO1997042238 A1 WO 1997042238A1 NL 9700250 W NL9700250 W NL 9700250W WO 9742238 A1 WO9742238 A1 WO 9742238A1
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group
transition metal
ligand
olefin
copolymer
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PCT/NL1997/000250
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English (en)
Inventor
Jacob Renkema
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Dms N.V.
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Priority to AU24125/97A priority Critical patent/AU2412597A/en
Publication of WO1997042238A1 publication Critical patent/WO1997042238A1/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
    • 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
    • C08F210/00—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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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 polyolefin copolymer, and in particular, a copolymer comprising between about 20 wt.% and about 90 wt. % ethylene repeat unit, between about 10 wt.% and about 80 wt. % of at least one ⁇ -olefin repeat unit, and optionally between about 0 wt.% and about 30 weight % of at least one diene.
  • Copolymers are known which are prepared from the polymerization of ethylene, an ⁇ -olefin and optionally a diene. These copolymers are generally referred to as "EAM,” “EADM”, or “EA(D)M” (copolymers based on ethylene, ⁇ -olefin, and optionally diene).
  • EAM ethylene
  • EAM EA(D)M
  • a specific copolymer is EPM or EPDM, wherein the ⁇ -olefin is p_ropylene.
  • EA(D)M copolymers are described, for instance, in EP-A-44,119. These copolymers are prepared by a conventional Ziegler-Natta polymerization using vanadium (oxy)halide catalysts. Analysis of the copolymer molecular structure by 13 C-NMR suggests that the ⁇ -olefin is present in the polymer chain in its inverted form in substantial amounts. In other words, a significant amount of "head-to-head” addition is evident in the polymer-chain as well as non-inverted "head-to- tail” addition.
  • Formulas (II) and (IV), which illustrate inverted head-to-head addition, show that the number of carbon atoms between two carbon atoms bearing the side- chain methyl group is even.
  • formulas (I) and (III), which illustrate non-inverted head-to-tail addition have an uneven or odd number of carbon atoms between the carbon atoms bearing the side-chain methyl group. 13 C-NMR analysis allows one to determine a statistical distribution for the number of carbon atom(s) between the carbon atoms bearing side-chains.
  • [IC] 1 carbon atom between two carbons bearing side- chain (e.g., formula I);
  • [2C] 2 carbon atoms between two carbons bearing side- chain (e.g., formula II);
  • [3C] 3 carbon atoms between two carbons bearing side- chain (e.g., formula III);
  • [ 4C ] 4 carbon atoms between two carbons bearing side- chain (e.g., formula IV), and the like for [5C],
  • An object of the present invention is to develop polyolefin copolymers which have reduced amounts of inversion.
  • the polyolefin copolymer of the present invention is characterized in that the copolymer has a Reduced First Inversion Index, RFI, which statisfies the relation (V) :
  • the polyolefin copolymer of the present invention can also be characterized by a Reduced Second Inversion Index, RSI, which satisfies the relation (VI):
  • copolymers of the present invention do not suffer from the above indicated disadvantages associated with polyolefin products made either with a conventional Ziegler-Natta catalyst system or with a metallocene system.
  • the copolymers of the present invention also have ⁇ -olefin triade-sequences in the polymer chain which are at least in part syndiotactic.
  • Copolymers in the prior art show either isotactic or atactic ⁇ -olefin sequences.
  • C carbon to carbon double bonds
  • molecular weight control or chain termination is believed to result from the well- known mechanism in Ziegler-Natta catalysis, ⁇ -hydride elimination. This typically results in vinyl, vinylidene, and vinylene types of unsaturation in the terminal monomer unit.
  • the ethylene is present in an amount of about 20 wt.% to about 90 wt.%.
  • the EAM or EADM can be semicrystalline or amorphous (detectable by Differential Scanning Calorimetry, DSC) but is preferably amorphous. If amorphous, substantially no crystallinity is detectable by DSC at temperatures above 25°C. In general, amorphous copolymers have an ethylene content of between about 30 wt.% and 70 wt.%.
  • the copolymer according to the invention comprises one or more polymerized ⁇ -olefins which form the basis for copolymer repeat unit.
  • such an ⁇ -olefin contains 3-25 carbon atoms (although higher ⁇ -olefins can be used). More preferably, the ⁇ -olefin contains 3-10 carbon atoms.
  • the ⁇ -olefin is preferably selected from the group consisting of propylene, butene, isobutene, pentene, 4-methyl pentene, hexene, octene, styrene and ( ⁇ -methyl) styrene.
  • the ⁇ -olefin is propylene, 1-butene, 1-hexene or l-octene, styrene or ( ⁇ -methyl)styrene. Most preferred is propylene, resulting in the preparation of EP(D)M.
  • the copolymer optionally comprises one or more polymerized dienes which form the basis for a copolymer repeat unit.
  • Examples of such compounds include: 1,3-butadiene, isoprene, 2,3-dimethyl-l,3-butadiene, 2-ethyl-l,3- butadiene, piperylene, myrcene, allene, 1,2-butadiene, 1,4,9-decatrienes, 1,4-hexadiene, 1,5-hexadiene and 4- methyl-1,4-hexadiene.
  • Alicyclic polyunsaturated compounds may be either monocyclic or polycyclic.
  • examples of such compounds include norbornadiene and its alkyl derivatives; the alkylidene norbornenes, and in particular the 5-alkylidene-2- norbornenes, in which the alkylidene group contains 1 to 20, and preferably, 1 to 8 carbon atoms; the alkenyl norbornenes, and in particular the 5-alkenyl-2- norbornenes, in which the alkenyl group contains 2 to 20, and by preference, 2 to 10 carbon atoms, such as for instance vinyl norbornene, 5-(2 '-methyl-2 'butenyl)-2- norbornene and 5-(3 '-methyl-2 'butenyl)-2-norbornene; dicyclopentadiene and the polyunsaturated compounds of bicyclo-(2 ,2,l)-heptane, bicyclo-(2,2,2)-octane, bicyl
  • compounds such as 4,7,8,9-tetrahydroindene and isopropylidene tetrahydroindene can be used.
  • DCPD dicyclopentadiene
  • ENB ethylidene norbornene
  • VNB vinyl norbornene
  • HD hexadiene
  • the diene is present in the polymer in quantities of up to about 30 wt.%. More preferably, diene is present up to about 15 wt.%. Even more preferred is an amount of diene in the copolymer of about 1 wt.% to about 10 wt.%, and specifically between about 2 wt.% and about 8 wt.%.
  • the copolymers of the present invention can have a broad range of molecular weights.
  • the number-average molecular weight M n [as determined by SEC-DV (Size Exclusion Chromatography/Differential Viscometry combination)], can be as low as about 100.
  • the temperature at which the polymerization is performed is one of the parameters to control the value of M n .
  • any copolymer can be made with an M n between about 100 and about 500,000.
  • 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).
  • Copolymers of the present invention have an ML 1+4 , 125°C of ⁇ 1 up to about 150.
  • the polydispersity of the copolymers of the present invention (the ratio between M w and M n ; M rent being the weight average molecular weight, also measured by SEC- DV) generally is between about 1.5 and about 10. More preferably, the polydispersity is between about 1.8 and about 5.
  • compositions can be prepared which comprise the copolymer of the present invention as a pre-mixture ingredient.
  • the copolymer of the present invention may include extender oil.
  • This oil typically of a naphthenic or parafinnic nature, can be present in quantities of normally up to about 250 parts by weight per 100 parts by weight of copolymer. More in particular, between about 15 and about 150 parts by weight of oil per 100 parts by weight of copolymer can be used.
  • the invention also relates to a composition, that is to say a formulated mixture, of which the EA(D)M copolymer constitutes an essential part.
  • Such compositions comprise components which are required in order to ensure desirable end use properties in a final elastomer.
  • a formulated composition usually contains one or more of the following components: fillers, carbon black, stabilizers, antioxidants, pigments, release agents, vulcanization agents, foaming agents, vulcanization inhibitors and accelerators, oil, and the like.
  • An at least partially vulcanized composition based on the copolymer also forms part of the invention.
  • the invention also relates to a process for the preparation of the copolymer of the invention.
  • Such a process comprises the polymerization of ethylene and the ⁇ -olefin, optionally in the presence of a diene, under polymerization conditions which are known per se, under the influence of a catalyst, with or without a co- catalyst.
  • a polymerization can take place in the gas phase as well as in a liquid reaction medium. In the latter case, solution as well as suspension polymerization can be applied.
  • the reaction is preferably carried out continuously, but semi-continuous or batchwise modes of operation are also possible.
  • 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 -) ⁇ 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 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
  • 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 ' 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 ( ⁇ ) 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'. ⁇ -R t -DR 'êt and Y(-R- DR'êt) 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, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the Cp group is an R t - DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
  • 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.
  • 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 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 (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 l") 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 L Group The transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
  • the 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 Cj_- C 4 alkyl or a benzyl group.
  • the L group cannot be a Cp, amido, or phosphido group. In other words, L cannot be one of the Y groups.
  • the K ligand is a neutral or anionic group bonded to the transition metal M.
  • the K group is a neutral or anionic ligand bonded to M.
  • neutral K ligands which by definition are not anionic, are not subject to the same rule. Therefore, for each neutral K ligand, the value of m (i.e., the number of total K ligands) is one higher than the value stated above for a complex having all monoanionic K ligands.
  • the K ligand can be a ligand as described above for the L group or a Cp group (-C 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.
  • One preferred embodiment of the catalyst composition according to the present invention comprises a transition metal complex in which a bidentate/monoanionic ligand is present and in which the reduced transition metal has been selected from group 4 of the Periodic Table of Elements and has an oxidation state of +3.
  • the catalyst composition according to the invention comprises a transition metal complex represented by formula (V) :
  • the Y group in this formula (VI) is a hetero atom, such as phosphorus, oxygen, sulfur, or nitrogen bonded covalently to the transition metal M (see p. 2 of WO-A-93/19104).
  • This means that the Cp a (ZY) b group is of a dianionic nature, and has the anionic charges residing formerly on the Cp and Y groups. Accordingly, the Cp a (ZY) b group of formula (VI) contains two covalent bonds: the first being between the 5-member ring of the Cp group and the transition metal M, and the second being between the Y group and the transition metal.
  • the X group in the complex according to the present invention is of a monoanionic nature, such that a covalent bond is present between the Y group (e.g., the Cp group) and transition metal, and a coordinate bond can be present between the transition metal M and one or more of the (Ar-R t -) and (- R t -DR' n ) groups.
  • a coordinate bond is a bond (e.g., H 3 N-BH 3 ) which when broken, yields either (i) two species without net charge and without unpaired electrons (e.g., H 3 N: and BH 3 ) or (ii) two species with net charge and with unpaired electrons (e.g., H 3 N- + and BH 3 " ).
  • a covalent bond is a bond (e.g., CH 3 - CH 3 ) which when broken yields either (i) two species without net charge and with unpaired electrons (e.g., CH 3 - and CH 3 - ) or (ii) two species with net charges and without unpaired electrons (e.g., CH 3 + and CH 3 : ⁇ ).
  • a discussion of coordinate and covalent bonding is set forth in Haaland et al. (Angew. Chem Int. Ed. Eng. Vol. 28, 1989, p. 992), the complete disclosure of which is incorporated herein by reference.
  • the transition metal complexes described in WO-A-93/19104 are ionic after interaction with the co-catalyst.
  • the transition metal complex according to WO-A-93/19104 that is active in the polymerization contains an overall neutral charge (on the basis of the assumption that the polymerizing transition metal complex comprises, a M(III) transition metal, one dianionic ligand and one growing monoanionic polymer chain (POL)).
  • POL monoanionic polymer chain
  • the polymerization active transition metal complex of the catalyst composition according to the present invention is of a cationic nature (on the basis of the assumption that the polymerizing transition metal complex - based on the formula (V) structure - comprises, a M(III) transition metal, one monoanionic bidentate ligand and one growing monoanionic polymer chain (POL)).
  • Transition metal complexes in which the transition metal is in a reduced oxidation state have the following structure:
  • transition metal complex of the present invention 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 5 N(CH 3 ) 2 H] + [B(C 6 F 5 ) 4 ]";
  • 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 catalyst composition used in the process according to the invention can be used in supported or non-supported form.
  • 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 such as, for instance, Si0 2/ A1 2 0 3 or MgCl 2 .
  • Polymerization can be effected in a known manner including 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 about 10" 8 to about 10 "3 mol/1, and preferably, about 10 "7 to about 10 "4 mol/1.
  • Any liquid that is inert relative to the catalyst system can be used as solvent or suspension 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 not preferred to use such solvents for production on a commercial scale.
  • solvent in polymerization processes on a commercial scale, it is preferred therefore to use as solvent the low-priced aliphatic hydrocarbons, liquid monomers, or mixtures thereof, as marketed by the petrochemical industry.
  • an aliphatic hydrocarbon is used as solvent, the solvent may yet contain minor quantities of aromatic hydrocarbon such as, for instance, toluene.
  • 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. Drying techniques typically practiced by the polyolefin industry can be employed.
  • Chain regulators can be used to control the molecular weight and the amount of unsaturation of the resulting EA(D)M. Preference is given to hydrogen as chain regulator.
  • the polymerization can also be performed in several steps, in series or in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc. can be varied from step to step. In this way, it is also possible to obtain products with a broad molecular weight distribution.
  • Recovery of EA(D)M's from the polymerization process can proceed by methods generally practiced for high mileage polymerization.
  • the catalyst is de-activated at some point during the processing of the polymer. Deactivation can be effected by known techniques e.g. steam, water, alcohol, glycols. Removal of the catalyst residues generally and preferably is omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal, is very low due to the high mileage of these systems.
  • the EA(D)M's prepared according to the process of the present invention can be vulcanized generally most often in the form of a compound, with vulcanizing agents known in the art. Suitable vulcanizing agents include, for example, peroxides, sulfur and sulfur containing compounds, and phenolic resin. EA(D)M's with a controlled low level of crosslinking can be prepared with conventional curing agents.
  • vulcanizing agents include, for example, peroxides, sulfur and sulfur containing compounds, and phenolic resin.
  • EA(D)M's with a controlled low level of crosslinking can be prepared with conventional curing agents.
  • Cp means "cyclopentadienyl”
  • Me means “methyl”
  • Bu means “butyl”
  • iPr means "iso ⁇ propyl”
  • Me- 2 Ind means "an indenyl group, substituted on the 2-position with a methyl group”.
  • Example I Table 1 presents general conditions of the continuous polymerization of ethylene and propylene. This Table indicates: the amounts of petrol, ethylene and propylene, the amount of catalyst (cat.) added, the amount of co-catalyst (co-cat.), the polymerization temperature (pol. temp.) and the polymerization time (pol time). ⁇ Cp(Me) 4 CH 2 CH 2 NMe 2 ⁇ TiMe 2 was the catalyst. The co-catalyst was anilinium tetrakis-pentafluorophenylborate (HMe 2 N-C 6 H 5 + (C 6 F 5 ) 4 B) " .
  • This catalyst from (c) was methylated with methyl lithium in diethyl ether to prepare the final transition metal complex used in Example 1, Cp(Me) 4 CH 2 CH 2 NMe 2 ⁇ TiMe 2 .
  • Table 1 presents general conditions of the continuous polymerization of ethylene and propylene. This Table indicates: the amounts of petrol, ethylene and propylene, the amount of catalyst (cat.) added, the amount of co-catalyst (co-cat.), the polymerization temperature (pol. temp.) and the polymerization time (pol time). (iPr 3 CpCH 2 CH 2 NMe 2 )TiMe 2 was the catalyst.
  • the cocatalyst was anilinium tetrakis-pentafluorophenylborate (HMe 2 N-C 6 H 5 + (C 6 F s ) 4 B-).
  • Catalyst Synthesis a) Reaction of cvclopentadiene with isopropyl bromide
  • Aqueous KOH 50%; 1950g, ca. 31.5 mol in 2.483 1 water
  • Adogen 464 31.5g
  • Freshly cracked cyclopen-tadiene 55.3 g, 0.79 mol
  • isopropyl bromide 364 g, 2.94 mol
  • the mixture turned brown and became warm (50°C).
  • the mixture was stirred vigorously over night, after which the upper layer containing the product was removed. Water was added to this layer and the product was extracted with hexane.
  • dimethylaminoethyl chloride (11.3g, 105 mmol, freed from HCl 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 room temperature after which it was stirred over night. The progress of the reaction was monitored by GC . After addition of water (and pet-ether), the organic layer was separated, dried and evaporated under reduced pressure.
  • Solid TiCl 3 3THF (18.53g, 50.0 mmol) was added to a solution of the potassium salt of iPr 3 -Cp in 160 ml of THF at-60°C at once, after which the solution was allowed to warm to room temperature. The color changed from blue to green. After all the TiCl 3 .3THF had disappeared the reaction mixture was cooled again to -60°C. After warming to room temperature again, the solution was stirred for an additional 30 minutes after which the THF was removed at reduced pressure.
  • This catalyst from (c) was methylated withmethyl lithium in diethyl ether to prepare the final transition metal complex used in Example II.
  • Example II The results of the continuous polymerisation according to Example I and II are summarized in Table 2.
  • This Table indicates: the copolymer production (yield), expressed in grams/hour, the propylene content of the copolymer (%C 3 ) (in wt%) and the occurence of different methylene sequences as determined with 13 C-NMR (as referenced previously).
  • Comparative Experiment A Two comparative ethylene/propylene copolymers were produced according to the procedure of Example I, but with different catalyst systems (see Tables 1 and 2).
  • Comparative Experiment B a copolymer was prepared with a conventional V-catalyst (VOCl 3 /ethylsesquialuminium- chloride).
  • Comparative Experiment B a copolymer was produced with a zirconocene in the form of ⁇ Me- 2 Ind ⁇ 2 - ZrCl 2 and MAO as co-catalyst.

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Abstract

L'invention concerne un copolymère comprenant environ 20-90 % en poids d'éthylène, environ 10-80 % en poids d'une α-oléfine et éventuellement jusqu'à 20 % en poids d'un diène. La quantité des séquences α-oléfines inversées dans la chaîne polymère se trouve à l'intérieur de certaines plages. L'invention concerne également des copolymères ayant une nature syndiotactique dans les pentades d'α-oléfines.
PCT/NL1997/000250 1996-05-03 1997-05-01 Copolymeres polyolefiniques inverses WO1997042238A1 (fr)

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Cited By (1)

* 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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044119A2 (fr) * 1980-07-11 1982-01-20 Stamicarbon B.V. Procédé pour la préparation de copolymères d'éthylène et d'au moins un autre alcène-1
EP0200351A2 (fr) * 1985-03-26 1986-11-05 Mitsui Petrochemical Industries, Ltd. Copolymère d'éthylène statistique liquide, procédé de préparation et son utilisation
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044119A2 (fr) * 1980-07-11 1982-01-20 Stamicarbon B.V. Procédé pour la préparation de copolymères d'éthylène et d'au moins un autre alcène-1
EP0200351A2 (fr) * 1985-03-26 1986-11-05 Mitsui Petrochemical Industries, Ltd. Copolymère d'éthylène statistique liquide, procédé de préparation et son utilisation
WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine

Cited By (1)

* 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

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