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WO1997017379A1 - Catalyseurs de polymerisation - Google Patents

Catalyseurs de polymerisation Download PDF

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Publication number
WO1997017379A1
WO1997017379A1 PCT/GB1996/002743 GB9602743W WO9717379A1 WO 1997017379 A1 WO1997017379 A1 WO 1997017379A1 GB 9602743 W GB9602743 W GB 9602743W WO 9717379 A1 WO9717379 A1 WO 9717379A1
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Prior art keywords
catalyst
group
compound
pyrazol
substituted
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PCT/GB1996/002743
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English (en)
Inventor
Klaus Joachim Jens
Mats Tilset
Andreas Heuman
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Borealis A/S
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Priority to AU75024/96A priority Critical patent/AU7502496A/en
Publication of WO1997017379A1 publication Critical patent/WO1997017379A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • 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
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • This invention relates to compounds useful as polymerization catalysts, and in particular to metal coordination compounds and their use as olefin polymerization catalysts.
  • One group of catalysts of particular interest is that of the metal coordination compounds which provide homogeneous catalysts which can be used as such or can be heterogenized by loading onto a carrier material.
  • polymerization proceeds via olefin approach to a vacant metal coordination site adjacent a metal coordinating organic group, addition of the organic group to the olefin to produce a longer organic group and to vacate a metal coordination site, approach of a further olefin to the vacated site, and so on.
  • the homogeneous catalysts used hitherto have included complexes of metals such as the group 4 metals Ti, Zr and Hf, generally complexed by a polydentate organic complexant which does not itself take part m the polymerization reaction but serves to block off several of the metal coordination sites.
  • Remaining coordination sites may be occupied by organic or inorganic ligands which can be displaceable to vacate a coordination site for the catalysis reaction, or may be organic chain-initiating ligands (i.e. organic groups which may be added to the incoming olefms m the catalysis reaction) , or they may be non-displaceable ligands which, like the polydentate complexants do not take part m the catalysis reaction.
  • CN an organic chain-initiating group
  • a ligand displaceable by such an organic chain-initiating ligand e.g. a halide such as chloride
  • the catalyst may be used with a co-catalyst or activator which serves to produce the organic cham- mitiating group/vacant coordination site configuration. This may typically be achieved by introduction of more than one such organic group followed by removal of one to leave the requisite vacant site
  • the characteristics of the polymerization process may be desirably modified. More particularly, substitution of these organic complexants with a bulky space-filling group adjacent a metal- coordinating atom enables the catalytically active site of the complex to be engineered to modify the molecular weight distribution of the olefin polymerization product. Modification of polymer molecular weight and molecular weight distribution is desirable as it enables the properties of the polymer to be tailored m a desired manner. Thus for example increased molecular weight will lead to increased polymer melt strength which is advantageous in processing the polymer, e.g. m blow moulding.
  • a bimodal molecular weight distribution i.e. a distribution with lower and higher molecular weight peaks
  • catalysts which are able to generate higher molecular weight polymers may be used instead to improve polymer production economics by allowing one to operate at higher reactor temperatures and thus achieve higher production rates. In this way the reduction in molecular weight that occurs in using higher reactor temperatures is offset by the increase in molecular weight achievable with such a catalyst.
  • the invention provides an olefin polymerization catalyst compound comprising a catalytically effective metal complexed by a pyrazol-1- yl group containing complexant, characterised in that said complexant contains a pyrazol-1-yl group substituted in the 3-position by an organic moiety containing at least 3 carbon atoms .
  • the invention also provides a catalyst system comprising (a) a catalyst compound according to the invention and (b) a co- catalyst .
  • MAO co-catalyst (or catalyst activator)
  • MAO may be used as the sole co-catalyst or optionally together with another catalyst activator.
  • other cation complex forming activators may also be used.
  • silver and borane compounds known to the art. What is required of such alternative activators is that they should react with the organometallic catalyst to yield an organometallic cation and a non-coordinating anion (see for example the discussion on non-coordinating anions J " in EP-A-617052
  • Alummoxane co-catalysts are described by Hoechst in WO-A-94/28034. These can be linear or cyclic oligomers having up to 40, preferably 3 to 20, fAl-O]- repeat units (where R is hydrogen, C 1-8 alkyl
  • R is hydrogen, C 1-8 alkyl
  • R (preferably methyl) or C 6 . 18 aryl or mixtures thereof) .
  • the invention also provides a process for catalysed polymerization of olefins, characterised in that as a catalyst is used a catalyst or catalyst system according to the invention.
  • the catalyst of the invention thus may be a compound of formula I
  • M is a transition metal, lanthanide or actinide
  • L is a mono or polydentate, preferably monodentate ligand or a mono or polyvalent non- coordinating anion
  • Cx is a mono or polydentate organic complexant comprising a 3-substituted pyrazol-1-yl group
  • n is a positive integer, preferably 1 or 2, especially 1
  • m is zero or a positive integer
  • the catalyst may be ionic (cationic or anionic) or non-ionic.
  • ionic catalysts compounds with non-coordinating counte ⁇ ons are preferred, and the complex formed with MAO is particularly preferred.
  • the values of n and m will depend upon the mono or polydentate nature and on the mono or polyvalent nature of the complexant Cx and ligands or anions L, as well as on the group to which metal M belongs However, both n and m will generally be 4 or less.
  • the complexant Cx is conveniently a compound of formula II
  • trispyrazolyl compounds m which at least one, and preferably all three pyrazolyl rings are 3-substituted, i.e. compounds of formula X(Pz(R 1 ) q ) 3 , especially HB(PzR 1 ) 3 .
  • the bridging group X may have a carbon skeleton, but alternatively may have as its branching site any appropriate polyvalent atom, such as boron, nitrogen, phosphorus, gallium, etc. Boron is a preferred branching site and trispyrazolylborates are especially preferred as complexants Cx.
  • the 3-substituent on the pyrazole ring may for example be an optionally substituted alkyl, aryl or aralkyl group.
  • alkyl moieties mention may be made of C 3 _ 2 o linear, branched, cyclic or partially cyclic (e.g. cycloalkyl-alkyl) groups, in particular isopropyl, n- butyl, l-butyl, t-butyl, neopentyl, cyclohexyl and n- hexyl .
  • Aryl moieties may be mono or polycyclic and may contain one or more heteroaryl rings, e.g. incorporating N, 0 or S atoms in the aryl ring. Particular mention may be made of phenyl , 2-pyr ⁇ dyl, naphthyl , and anthracenyl groups.
  • alkyl and aryl groups may be substituted, e.g. to enhance their space-filling effects or to hinder rotation whereby to present a spatially restricted catalytically active site (the possible olefin coordination sites) in the catalyst.
  • Substitution with alkyl and aryl in particular is contemplated, e.g. 2,6- dialkyl or 4-phenyl substitution of a phenyl R ⁇ group, e.g. to produce a bisphenyl R x group.
  • the R ⁇ group may be attached to the pyrazolyl ring at both the 3 and 4 positions to yield an annelated structure having for example a benzene, cyclohexane or naphthalene ring fused to the pyrazole ring, and optionally carrying pendant or fused ring substituents, eg. alkyl, aryl, aralkyl and alkylene groups .
  • fused substituents will conveniently comprise one or more cycloalkyl, aryl or heteroaryl rings optionally substituted, e.g. by alkyl or aryl groups.
  • R x groups may thus conveniently comprise one or more, e.g. up to 4, fused or linked rings, each ring containing 5 to 9, preferably 5 to 7, ring atoms of which none, one or two may be ring heteroatoms, preferably 0, N or S atoms.
  • the pyrazole ring may be substituted at the 4 or 5 positions, e.g. to modify the solubility properties of the catalyst or to shield a bridging group X.
  • substitution in this regard may again be by optionally substituted alkyl, aryl or aralkyl groups, halogen atoms, carboxyl or sulphate (S0 3 H) groups (or esters, amides or carboxylate salts thereof) , e.g. phenyl, methyl or haloalkyl groups such as CF 3 .
  • alkyl or alkylene moieties in the compounds of the invention will contain up to 12, preferably up to 6, carbons, cyclic groups will have ring sizes of 5 to 9 ring atoms containing 0, 1 or 2 ring heteroatoms, and polycyclic substituent groups will contain up to 4, preferably 2 or 3, fused or non-fused rings.
  • Examples of preferred 3-substituted pyrazole groups PzR thus include groups of formula
  • R 3 is a linear or branched C 3 _ e alkyl group
  • R 4 is hydrogen alkyl, aryl, fused aryl or COOH or S0 3 H (or salts, esters or amides thereof)
  • R 5 is hydrogen or optionally substituted alkyl or aryl, e.g. CH 3 or CF 3
  • R 6 is a hydrogen or halogen atom or an alkyl, aryl or aralkyl group
  • A is a C 5 or C 6 ring optionally carrying a further 4 to 6 membered fused ring and optionally substituted by R 4 or by alkyl or alkaryl groups, e.g. the groups
  • Examples of preferred complexants Cx include
  • hydridotris (3-propylpyrazol-1-yl)borate hydridotris (3-isopropylpyrazol-l-yl)borate hydridotris (3-tert-butylpyrazol-l-yl)borate hydridotris (3-neopentylpyrazol-l-yl) borate hydridotris (3-phenylpyrazol-1-yl) borate hydridotris (3-mesitylpyrazol-1-yl)borate hydridotris (3-an ⁇ sylpyrazol-1-yl) borate hydridotris (3-m-tolylpyrazol-l-yl) borate hydridotris (3-thienylpyrazol-1-yl) borate hydridotris (3-naphthylpyrazol-1-yl) borate hydridotris (3-anthracy
  • the remaining ligands or non-coordinating anions L may for example be any of the ligands conventionally used in organometallic olefin polymerization catalysts, e.g. aluminoxane (eg. MAO) residues, halide, alkyl or alkaryl such as halide, methyl and benzyl, as described in the above-referenced patent publications, as well as non-coordinating anions such as halogenates, perhalogenates, tetra-substituted borates (e.g.
  • organometallic olefin polymerization catalysts e.g. aluminoxane (eg. MAO) residues, halide, alkyl or alkaryl such as halide, methyl and benzyl, as described in the above-referenced patent publications, as well as non-coordinating anions such as halogenates, perhalogenates, tetra-substituted borates (e.g.
  • tetrafluoroborate tetraphenylborate, tetrakis (p- fluorophenyl)borate, tetrakis (pentaphenyl)borate, tetratolylborate and tetraoctylborate)
  • polyborates tridecahydride-7-carbaundecaborate, bis (1 ,8- dicarbaundecaborate) cobaltate, group 15 halides (e.g. hexafluorophosphate) , heteropolyanions, triflate, etc.
  • Tetra-substituted borates are preferred as non- coordinating anions.
  • the metal M which provides the catalytically active site in the catalysts of the invention is conveniently a lanthanide or actinide or a group 3, 4, 5, 6, 7, 8, 9 or 10 transition metal.
  • Group 4 metals however are preferred, particularly titanium or hafnium and especially zirconium.
  • the use as olefin polymerization catalysts of pyrazolyl complexes of certain metals from groups other than group 4 is novel and forms a further aspect of the invention.
  • the invention provides a method of catalysed polymerization of an olefin using an olefin polymerization catalyst compound comprising a catalytically effective metal complexed by a pyrazol-1-yl group containing complexant, characterised in that said metal is selected from the actinides and lanthanides, Ta, Nb and the group 3, 7, 8, 9 and 10 transition metals, preferably a lanthanide or an actinide.
  • the pyrazolyl group is either unsubstituted or substituted and preferably is 3- substituted as described above. If desired the pyrazolyl groups may carry no substituent or a methyl or ethyl substituent at the 3-position. Examples of such groups include (7R) -4-methyl-7- (1-methyl-1-ethenyl) - 2 , 3- diazabicyclo[3.3.0] -oct-2-yl and 3, 9, 9-trimethyl-4, 5- diazatricyclo [6.1.0.0 2 - 6 ]non-2 (6) , 3-dien-5-yl group containing complexants.
  • the preparation of the pyrazole starting materials for such catalysts is described by Popov et al in Tetrahedron: Asymmetry 5.: 479(1994) and __.: 1013 (1995) .
  • the invention also provides an olefin polymerization catalyst compound comprising a catalytically effective metal complexed by a pyrazol-1-yl group containing complexant, characterised in that said metal is selected from the actinides and lanthanides, Ta, Nb and the group 3, 7, 8, 9 and 10 transition metals, preferably a lanthanide or an actinide.
  • the invention provides a catalyst system comprising d) a co-catalyst and (n) an olefm polymerization catalyst compound comprising a catalytically effective metal complexed by a pyrazol-1-yl group containing complexant, characterised m that said metal is selected from the actinides and lanthanides, Ta, Nb and the group 3, 7, 8, 9 and 10 transition metals, preferably a lanthanide or an actinide.
  • the invention comprises a catalyst system (and the use thereof olefin polymerization) comprising a pyrazoyl-complex catalyst as defined above together with a further olefm polymerization catalyst, e.g. a heterogeneous or homogeneous catalyst such as a metal oxide or organometallic compound, optionally together with a co- catalyst .
  • a catalyst system comprising a pyrazoyl-complex catalyst as defined above together with a further olefm polymerization catalyst, e.g. a heterogeneous or homogeneous catalyst such as a metal oxide or organometallic compound, optionally together with a co- catalyst .
  • Cx 1 is a group Cx or a chiral 4-subst ⁇ tuted-2, 3- diazabicyclo [3.3.0] octan-2-yl or a chiral 4, 5, 6 or 7 substituted ⁇ ndazol-2-yl group, at least one Cx 1 being such a chiral group.
  • Further aspects of the invention include catalyst systems involving catalysts of formula II analagous to those discussed above involving catalysts of formula I, and their use in olefin polymerization.
  • Chiral complexants Cx 1 are conveniently of formula IV or V
  • R 10 is hydrogen, methyl, ethyl, a group R 3 or an R 4 substituted phenyl group
  • R x ⁇ and R 12 are hydrogen or branched or linear optionally unsaturated alkyl (e.g. C 1-6 alkyl or alkylene, e.g. propen-2-yl) or together form an optionally substituted 1 to 5 membered bridging group (e.g. a C 1-5 alkandiyl group such as a propan-2,2- diyl group)
  • R 2i , R 22 ⁇ R 23 an d R 24 are hydrogen, alkyl, or aralkyl or two non-adjacent such groups together from a bridging group, eg. a methylene or propan-2, 2-diyl group.
  • Suitable examples of Cx 1 include the chiral pyrazoles of Popov et al (supra) and the following indazol-2-yl groups:
  • the 3-subst ⁇ tuted-pyrazol-l-yl complexants Cx used in the production of the compounds of the invention may be prepared by conventional procedures, e.g. as described by Trofimenko in Chem Rev _____: 943 (1993) . Ga, C, P and S linked multi pyrazolyl complexants Cz are described by Trofimenko in Prog. Inorg. Chem. 3_4: 115 (1986) and by Tokar et al . in Organometallics __1 : 2737 (1992) .
  • the complexants may conveniently be prepared by conjugating a corresponding 3-substituted- pyrazole to a backbone structure which provides group X. This process forms a further aspect of the present invention.
  • the backbone structure is conveniently an electrophile, such as a boron compound, and particularly preferably a borane or a metal borohydride.
  • electrophile such as a boron compound, and particularly preferably a borane or a metal borohydride.
  • tetrahydride compounds of group 13 metals, with group 1 metal counterions can be used as the electrophile backbone structure.
  • the degree of substitution of the bridging group may be selected as desired. In general, temperatures between 50 and 200°C may be used and the progress of the substitution reaction can be followed by monitoring the volume of hydrogen evolved.
  • Mono, di, tri and tetra-pyrazol-1-yl borates may be prepared by reacting a metal borohydride such as KBH 4 with a pyrazole in the presence of a solvent or an excess of pyrazole.
  • a metal borohydride such as KBH 4
  • a pyrazole By control of the reaction conditions (e.g. temperature, stoichiometry, reaction time, etc) the degree of pyrazole substitution of the boron can be regulated.
  • reaction of KBH 4 with three equivalents of pyrazole in a high boiling point solvent such as anisole yields a trispyrazolyl borate
  • R_ is as described above and R 2 and R 3 are optional substituents on the 4 and 5 positions of the pyrazole.
  • Mixed trispyrazolyl borates can thus conveniently be produced by an initial disubstitution by refluxing with a first pyrazole in N,N dimethylacetamide followed by refluxing in anisole with a second pyrazole.
  • the 3-substituted pyrazoles used in the synthesis of the pyrazolyl borates are either known compounds or may be prepared by procedures known from the literature.
  • One particularly preferred method for the production of 3-substituted-pyrazoles involves ketone :carboxylate ester condensation to yield a diketone
  • 3-substituted pyrazoles can be prepared from ketones via carbonyl-enamines by reaction with N-dimethoxymethyl-N,N-dimethylamine followed by clyclization as above O
  • the catalysts of the invention may be prepared by conventional techniques by reacting the complexant Cx with a compound of the metal, e.g. a chloride, bromide or iodide such as TiCl 4 , TiBr 4 , Til 4 , ZrCl 4 , ZrBr 4 or Zrl 4 (especially preferably TiCl 4 or ZrCl 4 ) .
  • a compound of the metal e.g. a chloride, bromide or iodide
  • TiCl 4 , TiBr 4 , Til 4 , ZrCl 4 , ZrBr 4 or Zrl 4 especially preferably TiCl 4 or ZrCl 4
  • Compounds containing organic ligands L e.g. methyl or benzyl
  • Such techniques form a further aspect of the invention.
  • the catalyst compounds of the invention may be used as catalysts in olefin polymerization on their own or together with a co-catalyst (e.g. MAO or a cation activator) as described in the patent publications referred to above.
  • a co-catalyst e.g. MAO or a cation activator
  • the co-catalyst is a Lewis acid that removes an organic ligand from the catalyst to yield a non-coordinating anion and a catalyst complex having an organic ligand which can serve for chain-initiation and an adjacent vacant coordination site.
  • the co-catalyst desirably also serves to introduce such an organic group, e.g. by displacement of halide ions.
  • Suitable co-catalysts include for example organoaluminium, organotm, organozmc compounds and borohydrides or boron halides.
  • the co-catalyst is an organoaluminium compound, such as an alkylalum oxane, or a cation producer (e.g. a compound of formulae XVI to XIX of EP-A-617052) , and especially preferably it is the tnmethylaluminium:water reaction product known as methylalummoxane (MAO) .
  • organoaluminium compound such as an alkylalum oxane
  • a cation producer e.g. a compound of formulae XVI to XIX of EP-A-617052
  • MAO tnmethylaluminium:water reaction product
  • Such co-catalysts are used conventional quantities relative to the pyrazolyl catalyst, eg. at from 1 to 10 8 , preferably 1 to 10 4 moles aluminium per mole pyrazolyl-complexed metal, or 0 1 to 10 preferably 0.5 to 2 moles cation of cation producer per mole pyrazolyl-complexed metal.
  • the ratio of aluminium to catalytic metal eg. Ti or Zr
  • stoichiometric ratios may be preferred.
  • the catalyst complexes of the invention may be used with or without a support.
  • Heterogeneous catalysts comprising the catalyst compounds of the invention together with a substrate (le carrier or support) form a further aspect of the invention.
  • support or carrier materials include organic and inorganic materials, preferably in pulverulent form, eg. silica, carbon or a metal phosphate or oxide such as alumina, zirconia, titania or magnesium oxide. Catalyst loading levels on such supports will preferably be m the range 0.01 to 30% by weight. Examples of appropriate materials are discussed on page 37 of EP-A-617052. Inorganic supports, and especially predominantly porous silica supports (>90% by weight silica) are preferred.
  • any inorganic carrier material and indeed the metallic components of the catalyst and any co-catalyst, should be selected with the end use of the polymer in mind and where the polymer is to be used for food storage, for example, toxic metals should be avoided.
  • the catalysts of the invention may be used for the polymerization of various olefins.
  • suitable olefins include -olefins such as ethylene, propylene, but-1-ene, pent-1-ene, 4-methyl-pent-1-ene, hex-1-ene, hept-1-ene, oct-1-ene and vinylcyclohexane; vinyl aromatics such as styrene and methyl-styrene; cyclic olefins such as cyclopentene, cyclohexene, cycloheptene and cyclooctene; conjugated dienes such as butadiene, cyclopentadiene and vmyl-1-cyclohexene; uncon ugated dienes and polyenes; and alkynes, such as acetylene, butyne and hexyne.
  • the catalyst can be used for copolymerization of two or more such olefm monomers.
  • the catalyst can optionally be used together with a further olefin polymerization catalyst.
  • selective copolymerization may be effected using a 3-substituted- pyrazolyl catalyst according to the invention together with a further catalyst such as an inorganic metal oxide catalyst, a Ziegler-Natta type catalyst, or a coordination or organometallic catalyst in which the catalytically active site is not constricted by groups pendent from the organic complexant, e.g. complexes of tris 3-unsubstituted-pyrazolyl borate or Cp complexes.
  • a further catalyst such as an inorganic metal oxide catalyst, a Ziegler-Natta type catalyst, or a coordination or organometallic catalyst in which the catalytically active site is not constricted by groups pendent from the organic complexant, e.g. complexes of tris 3-unsubstituted-pyrazolyl borate or Cp complexes.
  • a bulky monomer and a non-bulky monomer such as ethylene will give rise to a molecular aggregate of polymers having
  • hydrogen can optionally be used as an adjuvant to the catalyst.
  • the polymerization can take place in conventional form, eg. in solution, slurry or in the gas phase, using for example slurry tank or loop reactors, fluidized bed or mechanically stirred bed reactors or m high pressure reactors above the melting point of the polymer.
  • Non-polymerizable organic solvents such as alkanes or cycloalkanes may also be used as solvents for the reaction.
  • the reaction temperature may be reduced, ambient or elevated. Temperatures of -50 to 300°C, preferably 50°C to 250°C may be used as may be pressures of 1 to 2000kg/cm 2 G.
  • a preferred polymerization technique is the slurry process in which the temperature is kept below the temperature at which the polymer product dissolves in the reaction solution.
  • reaction temperatures of 50-110°C, preferably 60 to 105°C, are conveniently used.
  • the pyrazolyl-complexed catalyst is used in catalytic quantities.
  • molecular weight and GPC curves were determined using a Waters 150 CV instrument operating with Waters Expert Ease software. Calibration was effected according to SECV PS (Polymer Lab) Narrow standard calibration: column set: 3 x Waters, Linear, Styragel High Temperature, 7.8 x 300 mL. The analyses were run at 140°C with trichlorobenzene (TCB) and 0.25 g/L 2-tert.butyl-4-methylphenol as solvent. The sample concentration was about 0.0005 g samp i e /9 ⁇ _ B with an injection volume of 500 ⁇ L. The dissolution conditions were: 2 hours 140°C + 4 hours 160°C + 4 hours 140°C (atmosphere:air; filtration by mime filter only) .
  • Potassium bis hydrido bis (3 ' -phenyl-pyrazol-1-yl)borate Into a 1L reactor equipped with a magnetic stirrer bar, a cooler and an oil bubbler connected to a graduated expansion vessel is introduced 0.24mol of 3- phenyl-pyrazole and 20mL of freshly distilled N,N- dimethylacetamide. O.llmol KBH 4 is introduced in one portion and the heterogeneous mixture is placed in a bath at 170°C. The progression of the reaction is followed by measuring the volume of hydrogen evolved. After 6 hours' heating, 5L of hydrogen have been evolved and the solvent is distilled off in vacuo. The viscous solid residue is suspended in hot toluene. The white solid which remains is filtered and washed repeatedly with toluene, then pentane, then dried under reduced pressure.
  • the title compound may be prepared by the method of Kouba et al, Inorg Chem lj_ . :2313 (1976) .
  • Potassium hydrido tris (3, 5-dimethyl-pyrazol-1-yl) borate (0.400g, 1.23mmol) is dissolved in 20mL THF and cooled to 0°C. To the cooled solution is added a small excess of TiCl 4 (ca. 0.15mL) . The resulting yellow solution is refluxed overnight during which a colour change to orange occurs. The THF is evaporated off and the product is dissolved in 30mL toluene and filtered. This solution is used in the polymerization experiments reported below.
  • Polymerization tests were performed in a 200ml glass reactor with a heating/cooling jacket, magnetic stirring, a stainless steel thermocouple and a sceptre. The temperature was kept within ⁇ 1°C by circulating water from a thermostated reservoir.
  • the reactor was first evacuated and filled with argon gas. Then toluene was added. When the reactor temperature was constant at the desired temperature, a toluene solution containing the desired amount of the metal complex was added using a syringe. The argon was flushed away and replaced by ethylene.
  • a toluene solution of methylaluminoxane (MAO from AKZO) was added as the last component .
  • the ethylene pressure m the reactor was kept constant at approximately 1 atmosphere by continuously adding ethylene through a mass-flow meter. The amount of ethylene consumed per unit time and the temperature in the reactor could be monitored and sampled on a computer. If desired, a certain amount of argon could be added to the reactor to keep the ethylene pressure lower than 1 atmosphere, or a desired pressure of hydrogen could be added. In some tests, 1ml of 1-hexene was added to the toluene as a co-monomer before the catalyst components were added. At the end of the polymerization, the ethylene flow was closed, the reactor flushed with argon, the catalyst destroyed and the polymer precipitated by adding acidic methanol (1% HC1 in methanol) . The polymer was filtered off, washed with methanol and dried in a heating cupboard at 60°C overnight .
  • the molecular weight distribution of the product of reactor 2 is determined by gel permeation chromatography(GPC) and the GPC curve is shown in Figure 1A of the accompanying drawings.
  • Example 9 The procedure of Example 9 is repeated using 50mg (0.114mmol) of HB(3, 5-Me 2 -Pz) 3 T ⁇ Cl 3 and MAO at an Al/Ti ratio of 84 with the further addition of 1ml 1-hexene in reactor 2. The polymerization was run for 1 hour at 30°C.
  • Two 200mL glass reactors each containing 50mL toluene under an argon atmosphere are each charged with lmL of a slurry of HB(5-Me-3-Ph-Pz) 3 T ⁇ Cl 3 m toluene containing 61mg (0.0957mmol) of HB (5-Me-3-Ph-Pz) 3 T ⁇ Cl 3 .
  • Argon is removed and replaced by ethylene by repeated evacuation.
  • OmL of a solution of MAO in toluene is added to each reactor to provide an Al/Ti ratio of 92.
  • Ethylene is added to the reactors to maintain present constant at about 1 atmosphere during the polymerization reaction.
  • the reactor temperatures are maintained constant at 50°C (reactor 1) and 31°C (reactor 2) using thermostatted baths. After one hour polymerization time, the polymer is precipitated by addition of methanolic HC1. The precipitates are filtered and dried at 60°C.
  • the molecular weight distribution of the product of reactor 1 is determined by GPC and the GPC curve is shown in Figure 1C of the accompanying drawings .
  • the catalyst was prepared by reacting 4ml of the toluene suspension with 10ml MAO/toluene at ambient temperature for 10 minutes. 2.5ml of the catalyst solution was used in polymerization tests at 30°C (reactor 1) and 60°C
  • reactor 2 After 1 hour and 15 minutes polymerization time, 0.220 and 0.012g polyethylene could be precipitated with methanolic HCl from reactors 1 and 2 respectively.
  • Solid Phase Catalyst lOg silica of the type Crossfield EP-10 is calcined at 500°C for 10 hours with nitrogen.
  • the silica is cooled under nitrogen and the pore volume is checked to be in the range 1.6-2 ml/g. All of the following operations are performed under an argon atmosphere m a glove box: a solution of MAO/catalyst is prepared according to one of the earlier examples (e.g. Example 9) 0.196 mol of a hydridotrispyrazolyl : TiCl 3 catalyst being dissolved in 13 ml toluene and combined with 7.2 ml MAO in toluene, giving a solution with an Al/Ti ratio of 87.
  • the title complex was synthesized using a method similar to that of Reger et al . , Inorg. Chem. 2J5: 2046 (1986) using, however, as the starting material (C 5 H s )ZrCl 3 and not the DME adduct .
  • (C 5 H 5 ) ZrCl 3 100 mg, 0.381 mmole) and potassium (bis-hydrogen, bis (3-mesityl-pyrazole) borate) (160 g, 0.379 mmole) was added to 10 ml methylene chloride at -78°C.
  • the reaction mixture was filtered and all volatiles removed under reduced pressure at -10 C C, resulting in pale brown crystals.
  • the NMR data are in accordance with the title product.
  • Formyl tetralone was synthesized by processes (A) or (B) below:

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  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention se rapporte à un nouveau catalyseur de polymérisation, notamment à un composé oléfinique de catalyseur de polymérisation comprenant un métal catalytiquement efficace complexé par un agent complexant renfermant le groupe pyrazol-l-yle. Le catalyseur se caractérise en ce que l'agent complexant contient un groupe pyrazol-l-yle substitué en position 3 par une fraction organique contenant au moins 3 atomes de carbone.
PCT/GB1996/002743 1995-11-08 1996-11-08 Catalyseurs de polymerisation WO1997017379A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029739A1 (fr) * 1997-12-11 1999-06-17 Exxon Chemical Patents Inc. Composes renfermant des metaux de transition faiblement oxydes, utiles comme catalyseurs de polymerisation des olefines
WO2001040322A1 (fr) * 1999-12-03 2001-06-07 Polimeri Europa S.P.A. Dichlorure de borate de tris-(3,5-dimethylpyrazolyl)chrome comme constituant de systemes catalytiques pour la polymerisation d'olefines et procede de polymerisation utilisant ce compose
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization
EP1266911A1 (fr) * 2001-06-13 2002-12-18 Sumitomo Chemical Company, Limited Catalyseur pour polymérisation par addition et procédé de préparation d'un polymère d'addition
WO2004003031A2 (fr) * 2002-06-28 2004-01-08 Univation Technologies, Llc Activateurs de catalyseurs de polymerisation, procede de preparation de ces activateurs et leur utilisation dans des operations de polymerisation
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
JP2007519614A (ja) * 2003-10-30 2007-07-19 メルク パテント ゲーエムベーハー 二座（Ｂｉｐｏｄａｌ）配位子を有する金属錯体
EP1914252A1 (fr) 1999-12-16 2008-04-23 Univation Technologies, LLC Procédé de polymérisation
JP2008248243A (ja) * 2008-03-07 2008-10-16 Mitsui Chemicals Inc オレフィン重合触媒及びオレフィンの重合方法
US7741417B2 (en) 2004-01-07 2010-06-22 Exxonmobil Chemical Patents Inc. Preparation of polymerization catalyst activators utilizing indole-modified silica supports
US8022005B2 (en) 2007-11-08 2011-09-20 Exxonmobil Chemical Patents Inc. Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes
WO2016086039A1 (fr) 2014-11-25 2016-06-02 Univation Technologies, Llc Procédés de commande de l'indice de fluidité de la polyoléfine
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

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EP0482934A1 (fr) * 1990-10-26 1992-04-29 The Dow Chemical Company Utilisation des complexes hétérocycliques de borate-métal comme catalyseurs de coordination pour la polymérisation
WO1994001471A1 (fr) * 1992-07-01 1994-01-20 Exxon Chemical Patents Inc. Metaux de transition utilises comme catalyseurs de polymerisation d'olefines
EP0617052A2 (fr) * 1993-03-23 1994-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Catalyseur de polymérisation d'oléfines possédant un ligand multidenté

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EP0482934A1 (fr) * 1990-10-26 1992-04-29 The Dow Chemical Company Utilisation des complexes hétérocycliques de borate-métal comme catalyseurs de coordination pour la polymérisation
WO1994001471A1 (fr) * 1992-07-01 1994-01-20 Exxon Chemical Patents Inc. Metaux de transition utilises comme catalyseurs de polymerisation d'olefines
EP0617052A2 (fr) * 1993-03-23 1994-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Catalyseur de polymérisation d'oléfines possédant un ligand multidenté

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029739A1 (fr) * 1997-12-11 1999-06-17 Exxon Chemical Patents Inc. Composes renfermant des metaux de transition faiblement oxydes, utiles comme catalyseurs de polymerisation des olefines
US6362294B1 (en) 1997-12-11 2002-03-26 Exxon Mobil Chemical Patents Inc. Reduced oxidation state transition metal compounds useful as olefin polymerization catalysts
KR100592623B1 (ko) * 1997-12-11 2006-06-23 엑손모빌 케미칼 패턴츠 인코포레이티드 올레핀 중합 촉매로서 유용한 산화상태가 감소된 전이금속 화합물
US6294495B1 (en) 1998-05-01 2001-09-25 Exxonmobil Chemicals Patent Inc. Tridentate ligand-containing metal catalyst complexes for olefin polymerization
WO2001040322A1 (fr) * 1999-12-03 2001-06-07 Polimeri Europa S.P.A. Dichlorure de borate de tris-(3,5-dimethylpyrazolyl)chrome comme constituant de systemes catalytiques pour la polymerisation d'olefines et procede de polymerisation utilisant ce compose
EP1914252A1 (fr) 1999-12-16 2008-04-23 Univation Technologies, LLC Procédé de polymérisation
US6881802B2 (en) 2001-06-13 2005-04-19 Sumitomo Chemical Company, Limited Catalyst for addition polymerization and process for producing an addition polymer
EP1266911A1 (fr) * 2001-06-13 2002-12-18 Sumitomo Chemical Company, Limited Catalyseur pour polymérisation par addition et procédé de préparation d'un polymère d'addition
SG98056A1 (en) * 2001-06-13 2003-08-20 Sumitomo Chemical Co Catalyst for addition polymerization and process for producing and addition polymer
WO2004003031A3 (fr) * 2002-06-28 2004-07-08 Univation Tech Llc Activateurs de catalyseurs de polymerisation, procede de preparation de ces activateurs et leur utilisation dans des operations de polymerisation
US6858689B2 (en) 2002-06-28 2005-02-22 Univation Technologies, Llc Polymerization catalyst activators, method of preparing, and their use in polymerization processes
WO2004003031A2 (fr) * 2002-06-28 2004-01-08 Univation Technologies, Llc Activateurs de catalyseurs de polymerisation, procede de preparation de ces activateurs et leur utilisation dans des operations de polymerisation
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
JP2007519614A (ja) * 2003-10-30 2007-07-19 メルク パテント ゲーエムベーハー 二座（Ｂｉｐｏｄａｌ）配位子を有する金属錯体
US7741417B2 (en) 2004-01-07 2010-06-22 Exxonmobil Chemical Patents Inc. Preparation of polymerization catalyst activators utilizing indole-modified silica supports
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
US8022005B2 (en) 2007-11-08 2011-09-20 Exxonmobil Chemical Patents Inc. Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes
JP2008248243A (ja) * 2008-03-07 2008-10-16 Mitsui Chemicals Inc オレフィン重合触媒及びオレフィンの重合方法
WO2016086039A1 (fr) 2014-11-25 2016-06-02 Univation Technologies, Llc Procédés de commande de l'indice de fluidité de la polyoléfine
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

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