WO1997042241A1 - PROCESS FOR THE PREPARATION OF AN ETHYLENE AND α-OLEFIN COPOLYMER - Google Patents
PROCESS FOR THE PREPARATION OF AN ETHYLENE AND α-OLEFIN COPOLYMER Download PDFInfo
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- WO1997042241A1 WO1997042241A1 PCT/NL1997/000243 NL9700243W WO9742241A1 WO 1997042241 A1 WO1997042241 A1 WO 1997042241A1 NL 9700243 W NL9700243 W NL 9700243W WO 9742241 A1 WO9742241 A1 WO 9742241A1
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—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+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Definitions
- the invention relates to a process for the preparation of an ethylene and ⁇ -olefin copolymer with an ethylene content of between about 20 and 90 weight % at a temperature range of 100-220°C, with a catalysr composition comprising a transition metal complex and a co-catalyst.
- transition metal complex in combination with a cocatalyst is used to prepare ethylene/ ⁇ -olefin
- copolymers having an ethylene content in the range of about 20-90 mol%.
- copolymer means a polymer formed from two types of monomeric constituents: ethylene and one or more ⁇ - olefins.
- this object is obtained by providing a process for the preparation of an ethylene/ ⁇ -olefin copolymer with an ethylene content of between about 20 and 90 weight %, at higher
- temperatures that range fro, 100°C to 220°C, with a catalyst composition comprising a transition metal complex and a co-catalyst.
- Another object of the present invention is the provision of an ethylene/ ⁇ -olefin copolymer
- the polymerization of ethylene and at least one [additional] ⁇ -olefin is conducted under effective copolymerization conditions at a temperature of between 100°C and 220°C , under the influence of the present a catalyst composition.
- the catalyst composition includes at least one complex comprising a reduced valency transition metal (M) selected from groups 4-6 of the Periodic Table of Elements, a multidentate monoanionic ligand (X), two monoanionic ligands (L), and, optionally, additional ligands (K). More specifically, the comple of the catalyst composition of the present invention represented by the following formula (I):
- X a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S Y(-R t -DR' n ) q ;
- Y a cyciopentadienyl, amido (-NR'-), or phosphido group (-PR'-), which is bonded to the reduced transition metal M;
- R at least one member selected from the group
- R groups 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
- 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
- the multidentate monoanionic ligand X contains more than one substituent R', the substituents R' can be identical or different from each other;
- the monoanionic ligand L is not a ligand comprising a cyciopentadienyl, amido (-NR'-), or phosphido (-PR'-) group, and wherein the monoanionic ligands L can be identical or different from each other;
- the transition metal complex contains more than one ligand K, the ligands K can be identical or different from each other;
- n 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
- q,s q and s are the number of (-R t -DR' n ) groups and (Ar-R t -) groups bonded to group Y, respectively, wherein q + s is an integer not less than 1; and t the number of R groups connecting each of (i) the Y and Ar groups and (ii) the Y and DR' n groups, wherein t is selected independently as 0 or 1.
- transition metal complex of formula (I) makes it possible to prepare ethylene/ ⁇ -olef in copolymers at temperatures between 100°C and 220°C, whereas other known catalysts for these types of polymerization do not produce copolymers at temperatures above 100°C (they are only active at temperatures well below 100°C; U.S. Patent No. 5,491,207 discloses temperatures between -10°C and 100°C and shows examples with
- the process according to the present invention is suitable for the preparation of copolymers having an M n (the number-average molecular weight (as determined by SEC-DV (Size Exclusion
- any ethylene/ ⁇ - olefin copolymer can be made with an M n between about 100 and about 500 , 000 .
- Copolymers with a molecular weight M n between about 100 and about 30,000 are preferably prepared in a polymerization process at temperatures between about 135 and about 220°C; copolymers with a molecular weight M n between about 20,000 and about 100,000 are preferably prepared in a polymerization process at a temperature between about 115 and about 180°C.
- the copolymers also have an ethylene content of between about 20 and about 90 weight %.
- copolymers can be amorphous, being products with an ethylene content of between about 30 and about 70 weight %, or can be semicrystalline, being products with an ethylene content of between about 70 and about 90 wt %.
- the pressure at which the polymerization is conducted is preferably below about 100 MPa. Pressures up to 10 MPa are in several cases sufficient enough for a good catalytic activity.
- CA-A-2,11,057 discloses a process (in comparative experiment 2) for the
- FIG. 1 is a schematic view of a cationic active site of a trivalent catalyst complex in
- 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
- 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
- Such coordinate bonding can take place, for example, via the D heteroatom or Ar group(s).
- tridentate monoanionic ligands include, without limitation, Y-R t -DR' n _ ⁇ -R t -DR' n and Y(-R-DR' n ) 2 . 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 cyciopentadienyl, amido (-NR'-), or phosphido (-PR'-) group.
- the Y group is a
- cyciopentadienyl ligand Cp group
- the term cyciopentadienyl group encompasses substituted cyciopentadienyl groups such as indenyl, fluorenyl, and benzoindenyl groups, and other
- 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
- 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
- a hetero cyciopentadienyl group means a hetero ligand derived from a cyciopentadienyl group, but in which at least one of the atoms defining the five-member ring
- 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
- 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 cyciopentadienyl groups having the following structures, in which the hetero cyciopentadienyl contains one phosphorus atom (i.e., the hetero atom) substituted in the five-member ring:
- the transition metal group M is bonded to the Cp group via an ⁇ 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 cyciopentadienyl group of formula (III) is the R t -DR' n group or the R t -Ar group.
- the Y group can a so e an amido (-NR'-) group or a phosphido (-PR'-) group.
- the Y group contains nitrogen (N) or phosphorus (P) and is bonded covalently to the transition metal M as well as to the (optional) R group of the (-R t -DR' n ) or (Ar-R t -) substituent.
- the R group is optional, such that it can be absent from the X group. Where the R group is absent, the DR' n or Ar group is bonded directly to the Y group (that is, the DR' n or Ar group is bonded directly to the Cp, amido, or phosphido group). The presence or absence of an R group between each of the DR' n groups and/or Ar groups is independent.
- each of the R group constitutes the connecting bond between, on the one hand the Y group, and on the other hand the DR' n group or the Ar group.
- the presence and size of the R group determines the accsssibility of the transition metal M relative to the DR' n or Ar group, which gives the desired intramolecular
- R group or bridge
- the R groups are each selected
- R groups independently, and can generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, aryl alkylidene, etc.).
- 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
- 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
- R' 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
- 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 tr iphenylmethane, 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 ⁇ 6 .
- the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like as shown in Table
- alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
- aryl groups are phenyl, mesityl, tolyl and cumenyl.
- aryl alkyl groups are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
- R' groups are halides, such as chloride, bromide, fluoride and iodide, methoxy, ethoxy and phenoxy.
- two adjacent hydrocarbon radicals of the Y group can be connected with each other to define a ring system; therefore the Y group can be an indenyl, a fluorenyl or a benzoindenyl group.
- 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
- a hydrogen atom such as: 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
- 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 1 -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 When K is a neutral ligand K may be absent, but when K is
- 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.
- bidentate/monoanionic ligand is present and in which the reduced transition metal has been selected from group 4 of the Periodic Table of Elements and has an oxidation state of +3.
- the catalyst composition according to the invention comprises a transition metal complex represented by formula (V):
- transition metal complexes are described in which a group 4 transition metal in a reduced oxidation state (3+) is present.
- the Y group in this formula (VI) is a hetero atom, such as phosphorus, oxygen, sulfur, or nitrogen bonded covalently to the transition metal M (see p. 2 of WO-A- 93/19104).
- This means that the Cp a (ZY) b group is of a dianionic nature, and has the anionic charges residing formerly on the Cp and Y groups. Accordingly, the
- Cp a (ZY) b group of formula (VI) contains two covalent bonds: the first being between the 5-member ring of the Cp group and the transition metal M, and the second being between the Y group and the transition metal.
- the X group in the complex according to the present invention is of a monoanionic nature, such that a covalent bond is present between the Y group (e.g., the Cp group) and transition metal, and a coordinate bond can be present between the transition metal M and one or more of the (Ar-R t -) and (-R t -DR' n ) groups. This changes the nature of the transition metal complex and consequently the nature of the catalyst that is active in the polymerization. As referred to herein, 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.
- transition metal complexes described in WO-A- 93/19104 are ionic after interaction with the co- catalyst.
- the transition metal complexes described in WO-A- 93/19104 are ionic after interaction with the co- catalyst.
- 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 but have the following structure: Cp - M(III) - L 2 (VII) are generally not active in co-polymerization
- 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
- Such an intramolecular donor is to be any intramolecular donor.
- 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. Preference is given to
- 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
- halogen-containing organoaluminium compounds such as diethyl aluminum chloride
- diisobutyl aluminum chloride and ethyl aluminum sesquichloride.
- aluminoxanes are selected as the organoaluminium compound.
- the catalyst composition of the present invention can include a compound which contains or yields in a reaction with the transition metal complex of the present invention a non-coordinating or poorly
- Such compounds have been described foi instance in EP-A-426, 637, the complete disclosure of which is incorporated herein by reference. Such an anion is bonded sufficiently unstably such that it is replaced by an unsaturated monomer during the co- polymerization. Such compounds are also mentioned in EP-A-277,003 and EP-A-277, 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. Examples of 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.
- organometallic compound is selected as the co-catalyst, usually is in a range of from about 1:1 to about
- 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 cocatalyst can be present in the catalyst composition as a single component or as a mixture of several
- a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight and in particular molecular weight distribution.
- the process according to the invention is suitable for the preparation of semi-crystalline or of amorphous copolymers based on ethylene and an ⁇ -olefin.
- the copolymer according to the invention comprises one or more ⁇ -olefins.
- such an ⁇ -olefin contains 3-25 carbon atoms (although higher ⁇ -olefins are also allowable); more preferably, the ⁇ -olefin contains 3-10 carbon atoms.
- the ⁇ -olefin has preferably been selected from the group consisting of propylene, butene, isobutene, pentene, 4-methyl pentene, hexene, octene and ( ⁇ - methyl) styrene. More preferably, the ⁇ -olefin is propylene, 1-butene, 1-hexene or 1-octene.
- the ⁇ -olefin is propylene.
- ethylene/ ⁇ -olef in copolymer with a broad range of molecular weights M n .
- An alternative for products with a high molecular weight is the characterisation of the copolymer by its Mooney viscosity (ML 1+4 , 125°C, as per ASTM D1646).
- the process of the present invention is able to prepare ethylene/ ⁇ -olefin copolymers having an ML 1+4 , 125°C of between 10 and 150.
- the catalyst composition in the process according to the invention can be used supported or non-supported.
- the transition metal complex or the cocatalyst can be supported on a carrier. It is also possible that both the transition metal complex and the co-catalyst are supported on a carrier.
- the carrier material for the transition metal complex and for the co-catalyst can be the same material or a different material. It is also possible to support the
- the supported catalyst systems of the invention can be prepared as separate compounds, which can be used as such in polymerization reactions or the supported catalyst systems can be formed in situ by in situ methods just before a polymerization reaction starts.
- the supported catalysts are used mainly in gas phase and slurry processes.
- the carrier used may be any carrier known as carrier material for catalysts, for instance, finely divided solid porous support,
- MgCl 2 including, but not limited to, or MgCl 2 , Zeolites, mineral clays, inorganic oxides such as talc, silica (SiO 2 ), alumina (Al 2 O 3 ), silica-alumina, inorganic hydroxides, phosphates, sulphates, and the like, or resinous support materials such as polyolefins,
- the carrier may be used as such, or be modified, for example by silanes, aluminium alkyls, aluminoxanes, and others.
- the catalyst composition may also be prepared by in-situ methods.
- Polymerization can be effected in a known manner, in the gas phase as well as in a liquid
- reaction medium both solution and suspension polymerization are suitable, while the quantity of transition metal to be used generally is such that its concentration in the dispersion agent amounts to 10 -8 - 10 -3 mol/1, preferably 10 -7 - 10 -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 as well as on account of safety considerations, it will be preferred not to use such solvents for production on a technical scale. In polymerization processes, on a technical scale, it is preferred, therefore, to use as a solvent the low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry. If an aliphatic hydrocarbon is used as solvent, the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
- methyl aluminoxane (MAO)
- toluene can be used as solvent 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 can be used to control the molecular weight and the amount of
- the polymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc. may be varied from step to step. In this way it is also possible to obtain products with a wide molecular weight distribution.
- the polymer solution resulting from the polymerization can be worked up by a method known per se.
- the catalyst is de-activated at some point during the processing of the polymer.
- the de- activation is also effected in a manner known per se, e.g. by means of water or an alcohol. Removal of the catalyst residues can mostly be omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal is very low at this point owing to the use of the catalyst system in the process according to the invention.
- copolymers prepared according to the process of the present invention, can be used in different applications, like impact modifications, use in extrusion coating and wire-and-cable applications. These polymers are also useful in the manufacture of rubber articles and modified rubber articles.
- the catalyst is (dimethylaminomethyl)- diisopropyl-cyclopentadienyltitanium-(III) dichloride (CpH 2 i Pr 2 (CH 2 ) 2 NMe 2 TiCl 2 ).
- the conver sion was 97% .
- the dimethylamino- ethyldiisopropylcyclopentadiene was obtained by
- a number of continuous streams of petrol, propylene, ethylene catalyst and co-catalyst were dosed to a 1-litre reactor.
- the solution was continuously removed from the reactor.
- the catalyst was inactivated with the aid of isopropyl alcohol in a flash vessel; the monomers were flashed and the solution was
- composition of the polymers 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.
- the catalysts given in Examples I, II and III were methylated with MeLi in diethylether.
- composition of the polymers was determined with the aid of Fourier Transform Infrared Spectroscopy (FT-IR).
- FT-IR Fourier Transform Infrared Spectroscopy
- the intrinsic viscosity (int. vise, or "IV” was determined in decaline at 135°C.
- Table 1 presents the polymerization conditions of the continuous polymerization of ethylene and propylene for Examples IV-VIII. This Table
- catalyst a is ⁇ Cp(Me) 4 (CH 2 ) 2 NMe 2 ⁇ TiMe 2 ,
- catalyst b is ⁇ Cp(Me) 4 (CH 2 ) 2 NBu 2 ⁇ TiMe 2 , and
- catalyst c is ⁇ CpH 2 1 Pr 2 (CH 2 ) 2 NMe 2 ⁇ TiMe 2
- transition metal complexes useful in the process according to the invention are presented in Table 3.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EA199800977A EA199800977A1 (en) | 1996-05-03 | 1997-05-01 | Method of producing copolymer of ethylene and α-olefin |
AU24119/97A AU2411997A (en) | 1996-05-03 | 1997-05-01 | Process for the preparation of an ethylene and alpha-olefin copolymer |
EP97919763A EP0896599A1 (en) | 1996-05-03 | 1997-05-01 | PROCESS FOR THE PREPARATION OF AN ETHYLENE AND $g(a)-OLEFIN COPOLYMER |
JP9539793A JP2000509741A (en) | 1996-05-03 | 1997-05-01 | Method for producing ethylene and α-olefin copolymer |
BR9709194A BR9709194A (en) | 1996-05-03 | 1997-05-01 | Process for the preparation of a copolymer of ethylene and alphaolefin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96201114.4 | 1996-05-03 | ||
EP96201114 | 1996-05-03 |
Publications (1)
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---|---|
WO1997042241A1 true WO1997042241A1 (en) | 1997-11-13 |
Family
ID=8223923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1997/000243 WO1997042241A1 (en) | 1996-05-03 | 1997-05-01 | PROCESS FOR THE PREPARATION OF AN ETHYLENE AND α-OLEFIN COPOLYMER |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0896599A1 (en) |
JP (1) | JP2000509741A (en) |
KR (1) | KR20000010946A (en) |
AU (1) | AU2411997A (en) |
BR (1) | BR9709194A (en) |
CA (1) | CA2253542A1 (en) |
EA (1) | EA199800977A1 (en) |
ID (1) | ID16857A (en) |
TW (1) | TW370537B (en) |
WO (1) | WO1997042241A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000018808A1 (en) * | 1998-09-30 | 2000-04-06 | Exxon Chemical Patents Inc. | Cationic group 3 catalyst system |
US6943215B2 (en) | 2001-11-06 | 2005-09-13 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
US7335696B2 (en) | 2002-10-17 | 2008-02-26 | Dow Global Technologies, Inc. | Highly filled polymer compositions |
EP1905807A2 (en) | 2003-08-19 | 2008-04-02 | Dow Gloval Technologies Inc. | Interpolymers suitable for use in hot melt adhesives and processes to prepare same |
US7855258B2 (en) | 1998-07-01 | 2010-12-21 | Exxonmobil Chemical Patents Inc. | Propylene olefin copolymers |
US8026323B2 (en) | 2001-04-12 | 2011-09-27 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US8846991B2 (en) | 2002-10-02 | 2014-09-30 | Dow Global Technologies Llc | Liquid and gel-like low molecular weight ethylene polymers |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100830317B1 (en) * | 2001-12-27 | 2008-05-16 | 삼성토탈 주식회사 | Method of polymerization or copolymerization of ethylene using cyclopentadiene and carbodiimde ligand chelated catalyst |
JP2012176915A (en) * | 2011-02-28 | 2012-09-13 | Ube Industries Ltd | Alkylcyclopentadiene compound and method for producing the same |
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EP0416815A2 (en) * | 1989-08-31 | 1991-03-13 | The Dow Chemical Company | Constrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewith |
WO1993008221A2 (en) * | 1991-10-15 | 1993-04-29 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
WO1993019104A1 (en) * | 1992-03-26 | 1993-09-30 | The Dow Chemical Company | Addition polymerization catalysts comprising reduced oxidation state metal complexes |
WO1996013529A1 (en) * | 1994-10-31 | 1996-05-09 | Dsm N.V. | Catalyst composition and process for the polymerization of an olefin |
-
1997
- 1997-04-14 TW TW086104786A patent/TW370537B/en active
- 1997-05-01 CA CA002253542A patent/CA2253542A1/en not_active Abandoned
- 1997-05-01 JP JP9539793A patent/JP2000509741A/en active Pending
- 1997-05-01 AU AU24119/97A patent/AU2411997A/en not_active Abandoned
- 1997-05-01 KR KR1019980709095A patent/KR20000010946A/en not_active Application Discontinuation
- 1997-05-01 WO PCT/NL1997/000243 patent/WO1997042241A1/en not_active Application Discontinuation
- 1997-05-01 BR BR9709194A patent/BR9709194A/en unknown
- 1997-05-01 EA EA199800977A patent/EA199800977A1/en unknown
- 1997-05-01 EP EP97919763A patent/EP0896599A1/en not_active Withdrawn
- 1997-05-02 ID IDP971471A patent/ID16857A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0416815A2 (en) * | 1989-08-31 | 1991-03-13 | The Dow Chemical Company | Constrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewith |
WO1993008221A2 (en) * | 1991-10-15 | 1993-04-29 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
WO1993019104A1 (en) * | 1992-03-26 | 1993-09-30 | The Dow Chemical Company | Addition polymerization catalysts comprising reduced oxidation state metal complexes |
WO1996013529A1 (en) * | 1994-10-31 | 1996-05-09 | Dsm N.V. | Catalyst composition and process for the polymerization of an olefin |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7855258B2 (en) | 1998-07-01 | 2010-12-21 | Exxonmobil Chemical Patents Inc. | Propylene olefin copolymers |
WO2000018808A1 (en) * | 1998-09-30 | 2000-04-06 | Exxon Chemical Patents Inc. | Cationic group 3 catalyst system |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6677441B2 (en) | 1998-09-30 | 2004-01-13 | Exxonmobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6984722B2 (en) | 1998-09-30 | 2006-01-10 | Exxonmobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US8026323B2 (en) | 2001-04-12 | 2011-09-27 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6943215B2 (en) | 2001-11-06 | 2005-09-13 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
US8846991B2 (en) | 2002-10-02 | 2014-09-30 | Dow Global Technologies Llc | Liquid and gel-like low molecular weight ethylene polymers |
US7335696B2 (en) | 2002-10-17 | 2008-02-26 | Dow Global Technologies, Inc. | Highly filled polymer compositions |
EP1964884A1 (en) | 2002-10-17 | 2008-09-03 | Dow Global Technologies Inc. | Highly filled polymer compositions |
US7781510B2 (en) | 2002-10-17 | 2010-08-24 | Dow Global Technologies Inc. | Highly filled polymer compositions |
EP1905807A2 (en) | 2003-08-19 | 2008-04-02 | Dow Gloval Technologies Inc. | Interpolymers suitable for use in hot melt adhesives and processes to prepare same |
Also Published As
Publication number | Publication date |
---|---|
BR9709194A (en) | 1999-08-10 |
CA2253542A1 (en) | 1997-11-13 |
ID16857A (en) | 1997-11-13 |
KR20000010946A (en) | 2000-02-25 |
TW370537B (en) | 1999-09-21 |
JP2000509741A (en) | 2000-08-02 |
EA199800977A1 (en) | 1999-04-29 |
EP0896599A1 (en) | 1999-02-17 |
AU2411997A (en) | 1997-11-26 |
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