EP0896596A1 - Procede de production de polyolefines fonctionnelles - Google Patents

Procede de production de polyolefines fonctionnelles

Info

Publication number
EP0896596A1
EP0896596A1 EP97918423A EP97918423A EP0896596A1 EP 0896596 A1 EP0896596 A1 EP 0896596A1 EP 97918423 A EP97918423 A EP 97918423A EP 97918423 A EP97918423 A EP 97918423A EP 0896596 A1 EP0896596 A1 EP 0896596A1
Authority
EP
European Patent Office
Prior art keywords
group
transition metal
process according
ligand
polar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97918423A
Other languages
German (de)
English (en)
Inventor
Maurits Frederik Hendrik Van Tol
Johannes Antonius Maria Van Beek
Paulus Johannes Jacobus Pieters
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
Original Assignee
DSM NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Priority to EP97918423A priority Critical patent/EP0896596A1/fr
Publication of EP0896596A1 publication Critical patent/EP0896596A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a process for the production of functionalized polyolefins, and particularly of polyolefins which have polar functional groups incorporated in the polymer chain (backbone). These functionalized polyolefins are desirable for their chemical and physical properties such as good adhesion, dyeability, compatibility, permeability and paintability.
  • the present process enables directly incorporating functional monomers in a polyolefin chain using catalyst systems activatable by other non-MAO cocatalysts, such as, for instance, boranes and borates.
  • the present process does not suffer from excessive catalyst deactivation.
  • the present process can also be used to introduce a very broad range of polar monomers into a polyolefin chain.
  • the present process concerns the production of functional polyolefins by copolymerizing at least one polar monomer, and, as the predominant monomer, at least one ⁇ -olefin under effective copolymerization conditions using a catalyst system and a cocatalyst.
  • functional polyolefins result from incorporating polar monomers into a polyolefin chain by copolymerization, using a catalyst system of a transition metal complex and a cocatalyst and in that the polar group(s) to be incorporated is (are) reacted with or coordinated to a protecting compound.
  • 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
  • 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
  • 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 present process concerns the production of functionalized polyolefins by copolymerizing at least one polar monomer and, as a main monomer, at least one ⁇ -olefin, under effective copolymerization conditions, using a catalyst system of a transition metal complex and a cocatalyst.
  • the transition metal complex consists of a transition metal having a reduced valency which can be selected from groups 4-6 of the Periodic Table of the Elements (see IUPAC notation on the inside cover of the Handbook of Chemistry and
  • a polar monomer has at least one polar group and that group is reacted with or coordinated to a protecting compound prior to the copolymerization step.
  • the reduced valency transition metal is titanium (Ti (III)).
  • functionalized polyolefin (sometimes referred to herein a s a funtionalized polymer) means a polyolefin comprising at least one polar group.
  • the polar group(s) comprised in the functionalized polyolefin can still be protected with a protecting compound.
  • transition metal complex Various components (groups) of the transition metal complex are discussed below in more detail.
  • the transition metal in the complex is selected from groups 4-6 of the Periodic Table of Elements. As referred to herein, all references to the Periodic Table of Elements mean the version set forth in the new IUPAC notation found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990, the complete disclosure of which is incorporated herein by reference. More preferably, the transition metal is selected from group 4 of the Periodic Table of Elements, and most preferably is titanium (Ti) .
  • the transition metal is present in reduced form in the complex, which means that the transition metal is in a reduced oxidation state.
  • reduced oxidation state means an oxidation state which is greater than zero but lower than the highest possible oxidation state of the metal (for example, the reduced oxidation state is at most M 3+ for a transition metal of group 4, at most M 4+ for a transition metal of group 5 and at most M 5+ for a transition metal of group 6).
  • the X ligand is a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S Y(-R t -DR' n ) q .
  • a multidentate monoanionic ligand is bonded with a covalent bond to the reduced transition metal (M) at one site (the anionic site, Y) and is bonded either (i) with a coordinate bond to the transition metal at one other site (bidentate) or (ii) with a plurality of coordinate bonds at several other sites (tridentate, tetradentate, etc.). Such coordinate bonding can take place, for example, via the D heteroatom or Ar group(s).
  • tridentate monoanionic ligands include, without limitation, Y-R t -DR' n _ ! -R t -DR' n and Y(-R-DR' n ) 2 .
  • R represents a connecting or bridging group between the DR' n and Y, and/or between the electron- donating aryl (Ar) group and Y. Since R is optional, "t" can be zero.
  • the R group is discussed below in paragraph (d) in more detail.
  • the Y group of the multidentate monoanionic ligand (X) is preferably a cyclopentadienyl, amido (-NR'-), or phosphido (-PR'-) group.
  • the Y group is a cyclopentadienyl ligand (Cp group).
  • Cp group cyclopentadienyl ligand
  • the term 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 h , s bond.
  • the other R' exocyclic substituents (shown in formula (III)) on the ring of the hetero Cp group can be of the same type as those present on the Cp group, as represented in formula (II).
  • at least one of the exocyclic substituents on the five- member ring of the hetero 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 analo group:
  • the Y group contains nitrogen
  • the R group is optional, such that it can be absent from the X group. Where the R group is absent, the DR' n or Ar group is bonded directly to the Y group (that is, the DR' n or Ar group is bonded directly to the Cp, amido, or phosphido group). The presence or absence of an R group between each of the DR' n groups and/or Ar groups is independent.
  • each of the R group constitutes the connecting bond between, on the one hand the Y group, and on the other hand the DR' n group or the Ar group.
  • the presence and size of the R group determines the accessibility of the transition metal M relative to the DR' n or Ar group, which gives the desired intramolecular coordination. If the R group (or bridge) is too short or absent, the donor may not coordinate well due to ring tension.
  • the R groups are each selected independently, and can generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, aryl alkylidene, etc.). Specific examples of such R groups include, without limitation, methylene, ethylene, propylene, butylene, phenylene, whether or not with a substituted side chain.
  • the R group has the following structure:
  • R' groups of formula (IV) can each be selected independently, and can be the same as the R' groups defined below in paragraph (g). In addition to carbon, the main chain of the
  • R group can also contain silicon or germanium.
  • R groups are: dialkyl silylene (-SiR' 2 -), dialkyl germylene (-GeR' 2 -), tetra-alkyl silylene (-SiR ' 2 -SiR ' 2 -) , or tetraalkyl silaethylene (-SiR' 2 CR' 2 - ) .
  • the alkyl groups in such a group preferably have 1-4 carbon atoms and more preferably are a methyl or ethyl group.
  • the DR' n Group This donor group consists of an electron- donating hetero atom D, selected from group 15 or 16 of the Periodic Table of Elements, and one or more substituents R' bonded to D.
  • the number (n) of R' groups is determined by the nature of the hetero atom D, insofar as n being 2 if D is selected from group 15 and n being 1 if D is selected from group 16.
  • the R' substituents bonded to D can each be selected independently, and can be the same as the R' groups defined below in paragraph (g) , with the exception that the R' substituent bonded to D cannot be hydrogen.
  • the hetero atom D is preferably selected from the group consisting of nitrogen (N) , oxygen (0), phosphorus (P) and sulphur (S); more preferably, the hetero atom is nitrogen (N).
  • the R' group is an alkyl, more preferably an n-alkyl group having 1- 20 carbon atoms, and most preferably an n-alkyl having 1-8 carbon atoms. It is further possible for two R' groups in the DR'êt group to be connected with each other to form a ring-shaped structure (so that the DR' n group can be, for example, a pyrrolidinyl group).
  • the DR' n group can form coordinate bonds with the transition metal M.
  • the electron-donating group (or donor) selected can also be an aryl group (C 6 R' 5 ), such as phenyl, tolyl, xylyl, mesityl, cumenyl, tetramethyl phenyl, pentamethyl phenyl, a polycyclic group such as triphenylmethane, etc.
  • the electron-donating group D of formula (I) cannot, however, be a substituted Cp group, such as an indenyl, benzoindenyl, or fluorenyl group.
  • the coordination of this Ar group in relation to the transition metal M can vary from ⁇ 1 to Y ⁇ 6 .
  • the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like as shown in Table
  • alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
  • aryl groups are phenyl, mesityl, tolyl and cumenyl.
  • aryl alkyl groups are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
  • R' groups are halides, such as chloride, bromide, fluoride and iodide, methoxy, ethoxy and phenoxy.
  • Y group can be an indenyl, a fluorenyl or a benzoindenyl group.
  • the indenyl, fluorenyl, and/or benzoindenyl can contain one or more R' groups as substituents.
  • R' can also be a substituent which instead of or in addition to carbon and/or hydrogen can comprise one or more hetero atoms of groups 14-16 of the Periodic Table of Elements.
  • a substituent can be, for example, a Si-containing group, such as Si(CH 3 ) 3 .
  • the transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
  • L group ligands which can be identical or different, include, without limitation, the following: a hydrogen atom; a halogen atom; an alkyl, aryl or aryl alkyl group; an alkoxy or aryloxy group; a group comprising a hetero atom selected from group 15 or 16 of the Periodic Table of Elements, including, by way of example, (i) a sulphur compound, such as sulphite, sulphate, thiol, sulphonate, and thioalkyl, and (ii) a phosphorus compound, such as phosphite, and phosphate.
  • the two L groups can also be connected with each other to form a dianionic bidentate ring system.
  • L is a halide and/or an alkyl or aryl group; more preferably, L is a Cl group and/or a 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 S 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): X
  • the Y group in this formula (VI) is a hetero atom, such as phosphorus, oxygen, sulfur, or nitrogen bonded covalently to the transition metal M (see p. 2 of WO-A- 93/19104).
  • This means that the Cp a (ZY) b group is of a dianionic nature, and has the anionic charges residing formerly on the Cp and Y groups. Accordingly, the Cp a (ZY) b group of formula (VI) contains two covalent bonds: the first being between the 5-member ring of the Cp group and the transition metal M, and the second being between the Y group and the transition metal.
  • the X group in the complex according to the present invention is of a monoanionic nature, such that a covalent bond is present between the Y group (e.g., the Cp group) and transition metal, and a coordinate bond can be present between the transition metal M and one or more of the (Ar-R t -) and (-R t -DR' n ) groups.
  • a coordinate bond is a bond (e.g., H 3 N-BH 3 ) which when broken, yields either (i) two species without net charge and without unpaired electrons (e.g., H 3 N: and BH 3 ) or (ii) two species with net charge and with unpaired electrons (e.g., H 3 N- + and BH 3 ⁇ ).
  • a covalent bond is a bond (e.g., CH 3 -CH 3 ) which when broken yields either (i) two species without net charge and with unpaired electrons (e.g., CH 3 - and CH 3 - ) or (ii) two species with net charges and without unpaired electrons (e.g., CH 3 + and CH 3 : ⁇ ).
  • a discussion of coordinate and covalent bonding is set forth in Haaland et al. (Angew. Chem Int. Ed. Eng. Vol. 28, 1989, p. 992), the complete disclosure of which is incorporated herein by reference.
  • the transition metal complexes described in WO-A- 93/19104 are ionic after interaction with the co ⁇ catalyst.
  • the transition metal complex according to WO-A-93/19104 that is active in the polymerization contains an overall neutral charge (on the basis of the assumption that the polymerizing transition metal complex comprises, a M(III) transition metal, one dianionic ligand and one growing monoanionic polymer chain (POL)).
  • POL monoanionic polymer chain
  • the polymerization active transition metal complex of the catalyst composition according to the present invention is of a cationic nature (on the basis of the assumption that the polymerizing transition metal complex - based on the formula (V) structure - comprises, a M(III) transition metal, one monoanionic bidentate ligand and one growing monoanionic polymer chain (POL)).
  • Transition metal complexes in which the transition metal is in a reduced oxidation state have the following structure:
  • transition metal complex of the present invention are generally not active in co-polymerization reactions. It is precisely the presence, in the transition metal complex of the present invention, of the DR' n or Ar group (the donor), optionally bonded to the Y group by means of the R group, that gives a stable transition metal complex suitable for polymerization.
  • Such an intramolecular donor is to be preferred over an external (intermolecular) donor on account of the fact that the former shows a stronger and more stable coordination with the transition metal complex.
  • the catalyst system may also be formed in situ if the components thereof are added directly to the polymerization reactor system and a solvent or diluent, including liquid monomer, is used in said polymerization reactor.
  • the catalyst composition of the present invention also contains a co-catalyst.
  • the co-catalyst can be an organometallic compound.
  • the metal of the organometallic compound can be selected from group 1, 2, 12 or 13 of the Periodic Table of Elements. Suitable metals include, for example and without limitation, sodium, lithium, zinc, magnesium, and aluminum, with aluminum being preferred. At least one hydrocarbon radical is bonded directly to the metal to provide a carbon-metal bond.
  • the hydrocarbon group used in such compounds preferably contains 1-30, more preferably 1-10 carbon atoms. Examples of suitable compounds include, without limitation, amyl sodium, butyl lithium, diethyl zinc, butyl magnesium chloride, and dibutyl magnesium.
  • organoaluminium compounds including, for example and without limitation, the following: trialkyl aluminum compounds, such as triethyl aluminum and tri-isobutyl aluminum; alkyl aluminum hydrides, such as di-isobutyl aluminum hydride; alkylalkoxy organoaluminium compounds; and halogen-containing organoaluminium compounds, such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
  • trialkyl aluminum compounds such as triethyl aluminum and tri-isobutyl aluminum
  • alkyl aluminum hydrides such as di-isobutyl aluminum hydride
  • alkylalkoxy organoaluminium compounds alkylalkoxy organoaluminium compounds
  • halogen-containing organoaluminium compounds such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
  • the catalyst composition of the present invention can include a compound which contains or yields in a reaction with the transition metal complex of the present invention a non-coordinating or poorly coordinating anion.
  • a non-coordinating or poorly coordinating anion Such compounds have been described for instance in EP-A-426, 637, the complete disclosure of which is incorporated herein by reference.
  • Such an anion is bonded sufficiently unstably such that it is replaced by an unsaturated monomer during the co ⁇ polymerization.
  • Such compounds are also mentioned in EP-A-277,003 and EP-A-277, 004, the complete disclosures of which are incorporated herein by reference.
  • Such a compound preferably contains a triaryl borane or a tetraaryl borate or an aluminum equivalent thereof.
  • suitable co-catalyst compounds include, without limitation, the following: - dimethyl anilinium tetrakis (pentafluorophenyl) borate [C 6 H 5 N(CH 3 ) 2 H] + [B(C 6 F 5 ) 4 ]-; - dimethyl anilinium bis (7 , 8-dicarbaundecaborate)- cobaltate (III); tri (n-butyl)ammonium tetraphenyl borate; - triphenylcarbenium tetrakis (pentafluorophenyl) borate; dimethylanilinium tetraphenyl borate; tris(pentafluorophenyl) borane; and - tetrakis(pentafluorophenyl) borate.
  • 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
  • the molar ratio usually is in a range of from about 1:100 to about
  • 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 polar group of the polar comonomer is protected by reaction with or coordination to a suitable protecting compound.
  • Methods to sterically and/or chemically protect polar groups to be incorporated into polymers are generally available to a person skilled in the art.
  • the polar group to be incorporated in the polyolefin is preferably protected by an organoaluminum compound, an organo zinc compound or an organo magnesium compound.
  • the protection is effected using an organoaluminum compound.
  • Suitable organoaluminum compounds include alkyl aluminum compounds, alkyl aluminum hydrides, alkylalkoxy aluminum compounds, halogen-containing organoaluminum compounds like alkyl aluminum halides, aryl aluminum halides; aryl aluminum compounds, aluminoxanes (preferably methyl aluminoxane) , modified aluminoxanes, modified aluminum alkyls and related compounds that can be chosen by those skilled in the art.
  • the aluminum alkyls are the most preferred compounds to react with or coordinate to the polar compounds to be incorporated in the polyolefin chain.
  • trimethylaluminum, triethylaluminum and triisobutylaluminum are used as a protecting compound.
  • the polar monomer Before the polar monomer is contacted with the catalyst system, the polar monomer is contacted, e.g., reacted or coordinated, with the protecting chemical compound.
  • the contacting of the polar monomer with the protecting the chemical compound should be done with great care, especially in those cases were gas evolution or heat evolution can occur.
  • the contacting is preferably performed at low temperature and/or in diluted solutions. Most preferably the contacting is performed under very controlled conditions at or below 50°C, under rapid stirring and under conditions where the gases that might be formed are allowed to escape from the reaction system without excessive pressure build-up in the reactor system equipment.
  • a person skilled in the art can, however, elect to perform the contacting treatment at temperatures greater than 50°C, if required.
  • the copolymerization of the at least one olefin monomer (s) and the at least one polar monomer is carried out under effective copolymerization conditions using a catalytically effective anionic of the described catalyst composition, Suitable polar monomers copolymerizable with olefinic compounds, alpha-olefins, dienes and the like, are selectable from the class of monomers having the general formula:
  • R is the polar group.
  • the polar group is a group containing next to, or instead of carbon atoms at least one hetero atom from group 15-17 of the Periodic System of the Elements, the hetere atom can be directly bonded to the
  • I H or it can be bonded to this group via a spacer group.
  • the spacer group is, for instance, an alkylene group
  • R can be selected from for instance, primary, secondary or tertiary alcohol, amine or alkyl halide, aldehyde, ⁇ -ketone, ether, amide, imine, thiol, sulfide, disulfide, borane, borate, carboxylic acid, ester, acylhalide, nitrile, nitro- or nitroso-group imide, anhydride, isocyanate, urea, acrylate, sulfone, sulfonic acid, silane, chloro-, bromo- or iodo-silane, silanol, halogen-containing groups, azo-groups, thioether, and urethane, among others.
  • the copolymerizable polar monomer represented by Formula XI may contain any polar group which may be protected in accordance with this invention. The persons skilled in the art will easily understand how to determine such polar groups.
  • the main monomer for the polyolefin chain comprises at least one olefin which can be suitably selected from among ⁇ -olefin, internal olefin, cyclic olefin and di-olefin. Mixtures of these can also be used.
  • the ⁇ -olefin is preferably selected from among ethylene, propane, butene, pentene, hexene, heptene, octene and styrene. Mixtures of any of these may also be used. More preferably, the ⁇ -olefin is at least one from among ethylene, propylene, octene and propene. Most preferably, the ⁇ -olefin is at least one from among ethylene, octene, and styrene.
  • the process according to the invention can also be used to prepare functionalized amorphous or rubber-like copolymers based on ethylene and another ⁇ - olefin.
  • Propylene is preferably used as the other ⁇ - olefin, so that a functionalized EPM rubber is formed.
  • a diene besides ethylene and the other ⁇ -olefin, so that a functionalized ethylene, ⁇ -olefin, diene monomer rubber (a so-called functionalized EADM rubber) is formed.
  • a functionalized ethylene propylene diene rubber (“EPDM") is preferred. In this way functionalized rubbers can be prepared.
  • the catalyst composition can be used as is, or optionally the catalyst can be supported.
  • the supported catalysts are used mainly in gas phase and slurry processes.
  • a suitable carrier, e.g., support includes any known carrier material for catalysts, for instance Si0 2( (silica) A1 2 0 3 (alumina) or MgCl 2 to provide a heterogeneus supported catalyst. These carriers can be used as such, or modified with, for example, by one or more of silanes, aluminum alkyls and/or aluminoxane compounds.
  • the catalyst system used in accordance with the present invention can also be prepared by in-situ methods which are known to those skilled in the art.
  • the process of the present invention will hereafter be elucidated with reference to a polyolefin preparation, which is a representative polymerization.
  • a polyolefin preparation which is a representative polymerization.
  • polar olefins including polar cyclic and vinyl aromatic olefin monomers, as described above, having 3-32 carbon atoms and with an olefin monomer and optionally one or more non-conjugated dienes.
  • the process of the present invention can be conducted as a gas phase polymerization (such as, in a fluidized bed reactor), a liquid phase polymerization, such as a solution or slurry/suspension polymerization, or solid phase powder polymerization.
  • a gas phase polymerization no solvents or dispersion media are required.
  • a solvent or a combination of solvents may be employed if desired.
  • the quantity of transition metal to be used in case of solution or suspension polymerization is such that its concentration in the dispersion agent amounts to IO" 8 - IO -3 mol/1, preferably IO -7 - 10 -4 mol/1.
  • Suitable solvents include toluene, ethylbenzene, 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.
  • a suspension utilizing a perfluorinated hydrocarbon or similar liquid may in particular be used.
  • olefinic monomer may be used as the reaction medium (so-called bulk polymerization processes).
  • Aromatic hydrocarbons such as, for instance, benzene and toluene, can be used, but because
  • the present co-polymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at an elevated pressure of up to 500 MPa, continuously or discontinuously.
  • the polymerization is performed at pressures between about 1 KPa and 35 MPa. Higher pressures can be applied if the polymerization is carried out in so-called high- pressure reactors.
  • the present process can yield good results when practiced using such high pressure reactors.
  • the co-polymerization can also be performed in several steps, in series, or in parallel. If required, process parameters, such as, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, or the like, may be varied from step to step. In this way it is also possible to obtain products with a wide molecular weight distribution.
  • the present invention also relates to a functionalized polymer which can be obtained by means of the co-polymerization process according to the invention.
  • TiCl 3 the esters used and the lithium reagents, 2-bromo-2-butene and 1-chlorocyclohexene were obtained from Aldrich Chemical Company.
  • TiCl 3 .3THF was obtained by heating TiCl 3 for 24 hours in THF with reflux. (THF stands for tetrahydrofuran).
  • 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.
  • the resulting mixture was stirred during one minute.
  • the polymerization reaction was started by addition of the catalyst/cocatalyst mixture to the stainless steel reactor.
  • the polymerization reaction was stopped by closing the ethylene supply.
  • the resulting polymer slurry was drained from the reactor and the polymer was recovered.
  • the polymerization activity was 167 kg copolymer produced per gramme Ti per hour (polymer yield 167 kg/gTi*hour) .
  • the polymer was studied by SEC- DV using conventional calibration. Mw was found to be 10.7 kg/mol, Mn was found to amount to 1.7 kg/mol.
  • the hexenol content in the polymer chain was found with ⁇ -NMR to be 5 wt.%.
  • 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.
  • the polymer yield was 0,55 kg/gZr.hour.
  • the polymer was studied by ⁇ -NMR and DSC and was found to contain 4 mole % of hexenol, incorporated in the polymer chain. The OH-groups were clearly resolved.
  • This percentage of 5-hexen-l-ol incorporated in the polymer chain shows the advantage of the method described in the present invention: it is almost 4 times as high as described so far in literature.
  • the activity of this catalyst system in which the transition metal is in its highest formal oxidation state is, however, low.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un procédé de production de polyoléfines fonctionnalisées par copolymérisation d'au moins un monomère polaire et d'au moins une oléfine dans des conditions efficaces de copolymérisation à l'aide d'un système catalyseur contenant un complexe d'un métal de transition et un cocatalyseur. L'oléfine utilisée peut être le monomère prédominant formant la chaîne polyoléfinique fonctionnalisée. Le complexe de métal de transition comprend un métal de transition ayant une valence réduite qui peut être sélectionnée dans les groupes 4 à 6 de la table périodique des éléments, avec un ligand monoanionique multidenté et deux ligands monoanioniques. Un monomère polaire possède au moins un groupe polaire qui réagit ou est coordonné avec un composé de protection avant l'étape de copolymérisation. En particulier, le métal de transition à valence réduite est le titane (Ti(III)).
EP97918423A 1996-05-03 1997-05-01 Procede de production de polyolefines fonctionnelles Withdrawn EP0896596A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97918423A EP0896596A1 (fr) 1996-05-03 1997-05-01 Procede de production de polyolefines fonctionnelles

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP96201113 1996-05-03
EP96201113 1996-05-03
PCT/NL1997/000249 WO1997042236A1 (fr) 1996-05-03 1997-05-01 Procede de production de polyolefines fonctionnelles
EP97918423A EP0896596A1 (fr) 1996-05-03 1997-05-01 Procede de production de polyolefines fonctionnelles

Publications (1)

Publication Number Publication Date
EP0896596A1 true EP0896596A1 (fr) 1999-02-17

Family

ID=8223922

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97918423A Withdrawn EP0896596A1 (fr) 1996-05-03 1997-05-01 Procede de production de polyolefines fonctionnelles

Country Status (4)

Country Link
EP (1) EP0896596A1 (fr)
JP (1) JP2000513761A (fr)
AU (1) AU2653097A (fr)
WO (1) WO1997042236A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19757830C2 (de) 1997-12-24 2003-06-18 Clariant Gmbh Brennstofföle mit verbesserter Schmierwirkung
CN1149229C (zh) 1998-05-01 2004-05-12 埃克森美孚化学专利公司 用于烯烃聚合的含三齿配体的金属催化剂配合物
ES2276731T3 (es) * 2000-09-07 2007-07-01 Mitsui Chemicals, Inc. Copolimero de olefina que contiene un grupo polar, procedimiento para preparar el mismo, composicion de resina termoplastica que contiene el copolimero y usos de los mismos.
JP2002293818A (ja) * 2001-03-30 2002-10-09 Sumitomo Chem Co Ltd オレフィン重合用触媒、およびオレフィン重合体の製造方法
JP5184769B2 (ja) * 2005-09-06 2013-04-17 日本曹達株式会社 活性水素を含有するモノマーを用いた重合体の製造方法
EP3034546B1 (fr) 2014-12-17 2019-10-16 SABIC Global Technologies B.V. Procédé de préparation d'un copolymère bloc comprenant un premier bloc de polyoléfine et un second bloc de polymère
EP3034544B1 (fr) 2014-12-17 2019-10-16 SABIC Global Technologies B.V. Procédé de préparation d'un copolymère greffé comprenant une chaîne de polyoléfine principale et une ou plusieurs chaînes latérales polymères
EP3034545B1 (fr) 2014-12-17 2020-11-04 SABIC Global Technologies B.V. Procédé de préparation d'un copolymère greffé comprenant une chaîne de polyoléfine principale et une ou plusieurs chaînes latérales de polymères et produits obtenus à partir de ce dernier
EP3034547B1 (fr) 2014-12-17 2019-10-09 SABIC Global Technologies B.V. Procédé de préparation d'un copolymère bloc comprenant un premier bloc de polyoléfine et d'un second bloc polymère
EP3037438A1 (fr) 2014-12-23 2016-06-29 SABIC Global Technologies B.V. Procédé pour la préparation d'une polyoléfine ramifiée
EP3037437A1 (fr) 2014-12-23 2016-06-29 SABIC Global Technologies B.V. Procédé pour la préparation d'une polyoléfine présentant une ou plusieurs branches à extrémité fonctionnalisée
EP3387046B1 (fr) 2015-12-09 2019-12-25 SABIC Global Technologies B.V. Procédé de préparation de copolymères greffés à base de polyoléfine fonctionnalisée comprenant un premier bloc de polyoléfine ramifié à chaîne courte et une ou plusieurs chaînes latérales de polymères
WO2017097568A1 (fr) 2015-12-09 2017-06-15 Sabic Global Technologies B.V. Procédé pour la préparation de copolymères greffés à base de polyoléfine comprenant une première séquence polyoléfine ramifiée à longue chaîne et une ou plusieurs chaînes latérales polymères
CN109843948B (zh) 2016-12-06 2022-04-29 Sabic环球技术有限责任公司 用于制备具有极性基团的烯属共聚物的方法和由此获得的产物
WO2019122455A1 (fr) 2017-12-22 2019-06-27 Sabic Global Technologies B.V. Procédé de préparation d'une forme amorphe de copolymère d'oléfine fonctionnalisée
EP3728346B1 (fr) 2017-12-22 2024-05-08 SABIC Global Technologies B.V. Procédé de préparation d'ionomères polyoléfiniques semi-cristallins
WO2020212129A1 (fr) 2019-04-16 2020-10-22 Sabic Global Technologies B.V. Capteur basé sur une matrice de polyoléfine et un composé de détection

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1198651A (en) * 1967-01-31 1970-07-15 Ici Ltd Olefine Copolymers Containing Polar Groups and Process for Their Preparation.
US5374696A (en) * 1992-03-26 1994-12-20 The Dow Chemical Company Addition polymerization process using stabilized reduced metal catalysts
AU3817595A (en) * 1994-10-31 1996-05-23 Dsm N.V. Catalyst composition and process for the polymerization of an olefin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9742236A1 *

Also Published As

Publication number Publication date
AU2653097A (en) 1997-11-26
WO1997042236A1 (fr) 1997-11-13
JP2000513761A (ja) 2000-10-17

Similar Documents

Publication Publication Date Title
RU2135522C1 (ru) Каталитическая композиция и способ полимеризации олефинов
EP0993464B1 (fr) Catalyseur pour la production de polymeres olefiniques
MXPA97008182A (en) S $! azaborolinilo metallic complexs as olefi polymerization catalysts
WO1997042236A1 (fr) Procede de production de polyolefines fonctionnelles
EP0896593A1 (fr) PROCEDE DE POLYMERISATION D'$g(a)-OLEFINES
US6831187B2 (en) Multimetallic catalyst compositions for the polymerization of olefins
WO1997042239A1 (fr) PROCEDE DE PREPARATION D'UN TERPOLYMERE D'ETHYLENE, UNE α-OLEFINE ET UN DIENE
WO1997042241A1 (fr) PROCEDE DE PREPARATION D'UN COPOLYMERE D'α-OLEFINE ET D'ETHYLENE
EP0896589A1 (fr) Composition de catalyseur sur support et procede pour la polymerisation de monomeres d'olefines
US20020002256A1 (en) Catalyst composition for the polymerization of olefins
US6383968B1 (en) Process for the polymerization of olefins
WO1997042237A1 (fr) Procede pour fabriquer des polyolefines ayant des repartitions larges des poids moleculaires
EP1028983B1 (fr) Composition catalytique comprenant un complexe de metal de transition reduit et un cocatalyseur
JP3858372B2 (ja) オレフィン重合用触媒およびそれを用いたポリオレフィンの製造方法
KR102001965B1 (ko) 폴리올레핀 촉매 및 이를 이용한 폴리올레핀 제조방법
WO1997042235A1 (fr) Procede pour la production de polymeres contenant des olefines cycliques
JP3887905B2 (ja) オレフィン重合用触媒およびそれを用いたポリオレフィンの製造方法
KR100209859B1 (ko) 폴리에틸렌 공중합체의 제조방법
US6489261B1 (en) Catalyst composition comprising a reduced transition metal complex and a cocatalyst
WO1997042240A1 (fr) Procede pour la copolymerisation d'une olefine et d'un monomere aromatique de vinyle
CA2219816C (fr) Complexes metalliques d'azaborolinyle utilises comme catalyseurs de polymerisation d'olefines
WO1997042233A1 (fr) Procede de polymerisation de monomeres aromatiques de vinyle
WO1997042238A1 (fr) Copolymeres polyolefiniques inverses
MXPA98009115A (en) Procedure for the co-polymerization of an olefine and an aromat vinyl monomer
MXPA98009110A (en) Composition of supported catalyst and procedure for the polymerization of olef monomers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981013

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17Q First examination report despatched

Effective date: 19990301

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20001201