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WO2004078765A2 - Catalyseurs pour la polymerisation du styrene - Google Patents

Catalyseurs pour la polymerisation du styrene Download PDF

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Publication number
WO2004078765A2
WO2004078765A2 PCT/EP2004/002179 EP2004002179W WO2004078765A2 WO 2004078765 A2 WO2004078765 A2 WO 2004078765A2 EP 2004002179 W EP2004002179 W EP 2004002179W WO 2004078765 A2 WO2004078765 A2 WO 2004078765A2
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group
transition metal
radicals
different
polymerization
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PCT/EP2004/002179
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German (de)
English (en)
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WO2004078765A3 (fr
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Jun Okuda
Klaus Möller
Valentine Reimer
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Basf Aktiengesellschaft
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Publication of WO2004078765A3 publication Critical patent/WO2004078765A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to novel ligand systems containing bridged heteroatoms, which have no cyclopentadienyl ligands, transition metal compounds containing these ligand systems, catalyst systems containing the transition metal compounds according to the invention and a cocatalyst, a process for the preparation of polymers by polymerization or copolymerization of at least one unsaturated compound in the presence of the catalyst system according to the invention and the Use of a transition metal compound according to the invention or a catalyst system according to the invention for the production of isotactic polystyrene.
  • these catalysts are highly active in the polymerization of ethylene and propylene. Polypropylene is obtained with a high molecular weight but low stereoregularity. Furthermore, the catalysts are suitable for the polymerization of styrene, with highly hydrolytic polystyrene being obtained. The copolymerization of styrene with ethylene is also possible, forming strictly alternating polymers with isotactic polystyrene units.
  • heterogeneous Ziegler-Natta catalysts are generally used to produce highly isotactic polystyrene.
  • Hiorns et al., Polymer 43 (2002) 3365-3369 relates to a process for the production of highly isotactic (> 99%) polystyrene with a high molecular weight and narrow molecular weight distribution.
  • a classic Ziegler-Natta system is used as the catalyst.
  • Ultrasound is used in the synthesis of the polymers.
  • Liao et al., Polymer 42 (2001) 4087-4090 relates to the production of isotactic polystyrene with heterogeneous modified Ziegler-Natta systems. With some systems, isotacticities of> 90% are achieved.
  • D, D ' can be the same or different and represents oxygen, sulfur, selenium, tellurium, an NR 11 group or PR ⁇ group,
  • Y, Y ' can be the same or different and represents oxygen, sulfur, selenium, tellurium, an NR 1 ⁇ group or PR 1 ⁇ group,
  • R, R can be the same or different and are hydrogen or a Ci-C ⁇ - carbon-containing radical, or two radicals R 1 and R 2 together with the carbon atom connecting them or, if q> 1, two radicals R 1 together form a cyclic or polycyclic ring system with the C atoms connecting them, which in the ring system can contain, in addition to carbon atoms, one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si,
  • R to R may be the same or different and are hydrogen or a -C-C 40 - carbon-containing radical, or two adjacent radicals R 3 to R 10 together with the atoms connecting them form a cyclic or polycyclisch.es ring system which in addition to the ring system
  • Carbon atoms can contain one or more, identical or different heteroatoms selected from the group consisting of the elements N, O, S and Si.
  • R 11 is hydrogen or a C ⁇ . -C 40 -Carbon residue.
  • the ligand system according to the invention is suitable for the production of transition metal compounds based on nonmetallocenes, which are suitable as a component of catalyst systems for polymerizing unsaturated compounds.
  • D, D ' are the same or different and are preferably oxygen, sulfur, an NR U group or a PR 11 group, particularly preferred is at least D or D' oxygen, very particularly preferably both D and D 'are oxygen.
  • Bis (phenol) compounds are therefore very particularly preferred as ligand systems of the formula I.
  • Y, Y ' are the same or different and are preferably oxygen, sulfur, an NR ⁇ group or a PR ⁇ group, at least Y or Y' is particularly preferred, both Y and Y 'being very particularly preferred.
  • p is 0 or 1. If p is 1, these are symmetrical complexes which are particularly suitable for the preparation of transition metal compounds which are suitable for the preparation of isotactic styrene or copolymers which contain isotactic polystyrene units. If p is 0, these are unsymmetrical complexes which are particularly suitable for the polymerization of further unsaturated compounds.
  • R 1 , R 2 are, independently of one another, hydrogen or a Ci-Cio-, particularly preferably C to C 3 -, very particularly preferably Ci- to C 2 - carbon-containing radical or two radicals R 1 and R 2 together form the C atom connecting them or, if q> 1, two radicals R 1 together with the C atoms connecting them form a cyclic ring system which, in addition to carbon atoms, contains a hetero atom in the ring system, selected from the group consisting of the elements N, O and P may contain.
  • carbon-containing radicals are to be understood as meaning aliphatic, cycloaliphatic and aromatic radicals which may optionally contain heteroatoms such as N, O, S and Si, provided that these do not impair the polymerization with transition metal compounds prepared from the ligand system according to the invention.
  • the aliphatic radicals can be branched or unbranched and the cycloaliphatic radicals can be substituted with further radicals, for example aliphatic C to C 10 , preferably Ci to C 4 , particularly preferably C to C 2 radicals or aromatic radicals.
  • the aliphatic and cycloaliphatic radicals can optionally be unsaturated, provided that these do not impair the polymerization with transition metal compounds prepared from the ligand system according to the invention.
  • the carbon-containing radicals are particularly preferably branched or unbranched alkyl radicals having 1 to 10, preferably 1 to 4, particularly preferably 1 to 2
  • R 1 , R 2 independently of one another are particularly preferably hydrogen or a Cr to Cio, preferably Cr to C 3 , particularly preferably Cr to C 2 alkyl radical.
  • R 1 and R 2 are very particularly preferably independently of one another hydrogen or methyl.
  • both R 1 and R 2 are hydrogen.
  • R 3 to R 10 are, independently of one another, hydrogen or a Ci-Cio, particularly preferably Cr to C 4 , very particularly preferably Cr to C 2 carbon-containing radical, or two adjacent radicals R 3 to R 10 together form a cyclic ring system with the atoms connecting them, which in addition to carbon atoms can contain a heteroatom selected from the group consisting of the elements N and O in the ring system.
  • radicals R 3 to R 6 are preferably hydrogen and 0 to 3, preferably 1 or 2 of the radicals R to R are a radical other than hydrogen, particularly preferably a branched or unbranched Cr to C 10 -, preferably Cr to C alkyl radical. 0 to 3, preferably 1 or 2 of the radicals R 3 to R 6 are very particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl radicals. The same applies to the radicals R 7 to R 10 .
  • At least one of the radicals R 3 to R 6 and at least one of the radicals R 7 to R 10 is very particularly preferably a radical other than hydrogen, preferably a branched or unbranched Cr to C 10 -, particularly preferably Cr to C 4 -alkyl radical particularly preferably a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl radical.
  • R 3 , R 5 , R 7 and R 9 are a radical other than hydrogen, preferably a branched or unbranched Cr to C 10 -, particularly preferably Cr to C 4 -alkyl radical, very particularly preferably a methyl -, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
  • R 11 is preferably hydrogen or a CrC 10 -, particularly preferably Cr to C -, very particularly preferably Cr to C 2 -carbon-containing radical.
  • R 11 is particularly preferably hydrogen or a methyl, ethyl, n-propyl, i- Propyl, n-butyl or t-butyl.
  • D 'oxygen, Y, Y' sulfur, and q are very particularly preferably an integer from 1 to 5, preferably 1 to 3.
  • the radicals R 3 and R 7 , R 4 and R 8 , R 5 and R 9 , R 6 and R 10 each have the same radical
  • R 3 and R 7 , and R 5 and R 9 each represents the same radicals other than hydrogen, preferably branched or unbranched Cr to C 10 -, particularly preferably Cr to C 4 -alkyl radicals, very particularly preferably methyl, ethyl, n-propyl, i-propyl, n- Butyl, i-butyl or t-butyl radicals on and R 4 and R 8 , and R 6 and R 10 are hydrogen.
  • the preparation of the ligand system according to the invention can be carried out by all methods known to the person skilled in the art.
  • the compounds of the formula F are reacted with a base, for example NaOH, generally in alcoholic solution, and then a reaction with a bisfunctional compound of the formula X 1 - (CR 1 R 2 ) q -X 2 , in which q and R 1 and R 2 have the meaning given for the ligand system of the formula I and X 1 and X 2 are in general independently of one another in each case a halogen radical, preferably Br.
  • q is 2 or 3 and X 1 - (CR ⁇ q -X 2 is 1,2-dibromoethane or 1,3-dibrornopropane.
  • the compound of the formula P is generally approximately twice molar amount to the compound X 1 - (CR 1 R 2 ) (1 -X 2) .
  • the symbols R 7 , R 8 , R 9 , R 10 , D 'and Y' have the same meaning as the corresponding symbols R 3 , R 4 , R 5 , R 6 , D and Y in formula 1 '.
  • radicals R 7 to R 10 differs from the radicals R 3 to R 6 of the compound of the formula P, with a bisfunctional compound of the formula X 1 - (CR R) q -X.
  • the radicals R to R have the meanings already mentioned in formula I.
  • the compounds of the formulas P and Ia ' are generally used in approximately equimolar amounts.
  • asymmetrically bridged ligand systems of the formula I are also prepared by reacting a compound of the formula P with a compound of the formula I "
  • the ligand system of formula I according to the invention is suitable for the production of transition metal compounds.
  • the present application therefore furthermore relates to a transition metal compound of the formula (11)
  • M is an element of the 3rd, 4th, 5th, 6, 7th, 8th, 9th or 10th group of the
  • Periodic table of the elements or an element of the lanthanides is
  • X, X ' can be the same or different and is an organic or inorganic anionic ligand, ol, o2 may be the same or different and are 0 or 1, where ol + o2 + 2 corresponds to the oxidation number of M,
  • D, D ' can be the same or different and represents oxygen, sulfur, selenium, tellurium, an NR 11 group or PR 1 group,
  • Y, Y ' can be the same or different and represents oxygen, sulfur, selenium, tellurium, an NR 1 ⁇ group or PR 1 ⁇ group,
  • p 0 or 1
  • R 1 , R 2 can be the same or different and are hydrogen or a Cr C 40 - carbon-containing radical, or two radicals R and R together with the carbon atom connecting them or, if q> 1, two radicals R 1 together with the carbon atoms connecting them form a cyclic or polycyclic ring system which, in addition to carbon atoms, may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si in the ring system,
  • q is an integer from 1 to 10
  • R 3 to R 10 may be the same or different and are hydrogen or a CrC 0 - carbon-containing radical, or two adjacent radicals R 3 to R 10 together with the atoms connecting them form a cyclic or polycyclic ring system which contains one or more carbon atoms in the ring system may contain several identical or different heteroatoms selected from the group consisting of the elements N, O, S and Si,
  • R 11 is hydrogen or a CrC 4 o-carbon-containing radical. After activation with an activator (cocatalyst), these transition metal compounds are very active in the polymerization of unsaturated compounds.
  • M is preferably an element of the 4th, 5th, 8th, 9th or 10th group of the Periodic Table of the Elements, very particularly preferably an element of the 4th group of the Periodic Table of the Elements, in particular Ti, Zr or Hf.
  • X, X ' are preferably each independently an organic ligand selected from the group consisting of CrC t o-alkyl, C 2 -C 10 alkenyl, C 6 -C 14 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6 to 14 carbon atoms in the aryl radical, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 14 carbon atoms in the aryl radical, NR'R "- and OR '", where R' and R "are C to C 10 -, preferably C to C 3 Alkyl radicals, particularly preferably Cr to C 2 alkyl radicals and R '"is a C to C 10 , preferably Cr to C 3 alkyl radical, particularly preferably an i-propyl radical, or a halide radical, preferably selected from chloride and bromide.
  • X and X ' are particularly preferably independently of one another benzyl,
  • ol, o2 are independently 0 or 1, where ol + o2 + 2 corresponds to the oxidation number of M. If M is a transition metal from Group 4 of the Periodic Table of the Elements and has the oxidation state IV, preferably Ti (IV), Zr (IV), Hf (IV), then both ol and o2 are 1.
  • M is an element of the 4th group of the Periodic Table of the Elements, X, X 'independently of one another are a halide, CrCio-alkyl, C 2 -C 1 o-alkenyl, C 6 -C 1 aryl, alkylaryl or arylalkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 14 carbon atoms in the aryl radical, NR' R "- and OR '", wherein R' and R "are Crbis Cio, preferably Cr to C 3 alkyl, particularly preferably C ⁇ - to C 2 alkyl and R""is a Crbis C 10 -, preferably Cr bis C 3 alkyl radical, particularly preferably an i-propyl are particularly preferred X and X 'are independently i-propyl or halide radicals, preferably selected from chloride and bromide,
  • q is an integer from 1 to 5, preferably 1 to 3.
  • the transition metal compounds of the formula II according to the invention are particularly preferably C2-symmetrical. Such C2-symmetrical transition metal compounds are suitable for the production of highly isotactic polystyrene or copolymers containing highly isotactic polystyrene.
  • transition metal compounds according to the invention can be prepared from the ligand systems according to the invention by customary methods known to the person skilled in the art
  • the transition metal compound is through Implementation of a ligand system according to the invention or a dianion prepared therefrom with a transition metal compound.
  • transition metal compounds of the formula II according to the invention are usually prepared by reacting the corresponding compounds of the general formula I with transition metal salts of metals from groups 3, 4, 5, 6, 7, 8, 9 or 10 of the periodic table of the elements or an element of the lanthanides. Preferred metals are mentioned above.
  • a suitable ligand system of the general formula I is in an organic solvent, for example toluene, tetrahydrofuran (THF) or methylene chloride, with a corresponding metal salt, for example titanium tetraisopropoxide, titanium, zirconium or hafnium tetrachloride, titanium, zirconium or hafnium tetrabenzyl , combined in the same organic solvent at temperatures of generally -90 ° C to + 35 ° C, preferably -80 ° C to 30 ° C.
  • the molar ratio of ligand to metal salt is generally 1.5: 1 to 1: 1.5, preferably 1.2: 1 to 1: 1.2, particularly preferably approximately 1: 1.
  • the reaction mixture is then generally at temperatures from 20 to 50 ° C, preferably from 20 to 40 ° C, particularly preferably at room temperature for generally 15 minutes to 16 hours, preferably 0.5 hours to 6 hours, particularly preferably 0.5 Stirred up to 2 hours.
  • Working up is carried out in a conventional manner, for example by removing the solvent in vacuo, washing the residue with a solvent in which the residue (product) is largely insoluble, for example with pentane, hexane or diethyl ether, optionally digesting in a non-polar solvent, for example hexane 'Filtering, washing and drying'.
  • the transition metal compound can be precipitated out of the reaction mixture by concentration in vacuo and / or addition of a non-polar solvent, for example hexane and / or cooling to, for example, from -40 ° C. to -10 ° C. It is then filtered off, washed and dried by methods known to those skilled in the art. It is also possible to convert the ligand system of the formula I according to the invention first into the corresponding dianion by reaction with a strong base, for example n-butyllithium, and to convert this dianion with the metal salts mentioned above. The process conditions are known to the person skilled in the art.
  • transition metal compounds of formula II according to the invention are easily accessible and - together with a cocatalyst - are suitable as catalysts for the polymerization of unsaturated compounds.
  • Another object of the present application is therefore a catalyst system for the polymerization of unsaturated compounds containing at least one transition metal compound of the formula II and at least one cocatalyst.
  • M 'an element of III Main group of the periodic table of the elements, preferably B, Al or Ga, particularly preferably B, Q 1 , Q 2 , Q 3 independently of one another hydrogen, Cr to Cio-alkyl, C 6 - to C 15 -aryl, alkylaryl, arylalkyl, haloalkyl or Halogenaryl with 1 to 10 each
  • R ⁇ AlO alkylaluminoxane
  • R 11 is a C to C 25 -alkyl, preferably a Cr to C 4 -alkyl radical, particularly preferably a methyl radical (methylaluminoxane) ,
  • Suitable ionic compounds with Lewis acid cations are compounds of the general formula (IV)
  • Y is an element of I. to VI. Main group or the I. to VIII. Subgroup of the periodic table of the elements,
  • Ti to T z simply negatively charged radicals such as Cr to C 28 alkyl, C 6 to C 5 aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, each with 6 to 20
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the l, l'-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular Boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.
  • Ionic compounds with Bronsted acids as the cation and preferably also non-coordinating counterions are also mentioned in WO 91/09882, the preferred cation is N, N-dimethylanilinium.
  • Methylaluminoxane, aluminum alkyl compounds and aryl borates such as tetrakis (pentafluorophenyl) borate are particularly preferably used as cocatalysts.
  • the amount of cocatalyst (activator) is preferably 0.1 to 10 equivalents, based on the transition metal compound II.
  • the amount of cocatalyst (activator) is generally 50 to 1000 equivalents, preferably 100 to 500 equivalents, particularly preferably 100 to 300 equivalents, based on the transition metal compound II.
  • the catalyst systems according to the invention can be used in the form of unsupported catalysts or supported catalysts, depending on the polymerization conditions.
  • the catalyst systems according to the invention When the catalyst systems according to the invention are used, they are homogeneously dissolved in the solution during solution polymerization.
  • the catalyst systems according to the invention can be prepared “in situ” and used directly in the polymerization without prior isolation.
  • the catalyst systems according to the invention are generally prepared by adding the transition metal compound according to the invention to a solution of the cocatalyst and the unsaturated compound to be polymerized or optionally a mixture of two or more unsaturated organic compounds in an organic solvent, other addition orders are also possible.
  • Another object of the present application is a catalyst system according to the invention which additionally contains a support.
  • Finely divided solids are preferably used as carrier materials, the particle diameters of which are generally in the range from 1 to 200 ⁇ m, preferably from 30 to 70 ⁇ m.
  • Suitable carrier materials are, for example, silica gels, preferably those of the formula Si0 2 • a Al 2 O 3; wherein a is a number in the range from 0 to 2, preferably from 0 to 0.5; it is therefore alumosilicates or silicon dioxide.
  • silica gels preferably those of the formula Si0 2 • a Al 2 O 3; wherein a is a number in the range from 0 to 2, preferably from 0 to 0.5; it is therefore alumosilicates or silicon dioxide.
  • Such products are commercially available, for example Silica Gel 332 from Grace or ES 70x from Crosfield.
  • carrier materials can be subjected to a thermal or chemical treatment or calcined to remove adsorbed water, a treatment preferably being carried out at 80 to 200 ° C., particularly preferably at 100 to 150 ° C.
  • inorganic compounds such as Al 2 O 3 or MgCl 2 or mixtures containing these compounds can also be used as carrier materials.
  • the catalysts can also be prepared “in situ” in the presence of support material. However, it is also possible to prepare and isolate the catalyst system according to the invention comprising a support. The catalyst system can then be used for the polymerization of unsaturated compounds.
  • the catalyst systems according to the invention are prepared by processes known to those skilled in the art.
  • the catalyst systems according to the invention are suitable for use in the polymerization of unsaturated compounds.
  • Another object of the present application is a process for the preparation of polymers by polymerization or copolymerization of at least one unsaturated compound in the presence of a catalyst system according to the invention.
  • Suitable unsaturated compounds are, for example, vinyl aromatic monomers, ethylene, C 3 - to C 20 -, preferably C 3 - to C 8 -monoolefins and cycloolefins.
  • Preferred C 3 - to C 8 - mono-olefins are propylene, 1-butene, 1-hexene and 1-octene.
  • Preferred cycloolefins are norbornene, norbonadiene and cyclopentene.
  • Suitable vinylaromatic monomers are, for example, styrene and styrene e, preferably styrene, ⁇ -methylstyrene or p-methylstyrene, substituted one to three times with CrC 4 alkyl or halogen in the ⁇ position and / or at the core.
  • a particularly preferred vinyl aromatic monomer is styrene.
  • the unsaturated compounds mentioned can be used to prepare homopolymers or copolymers composed of at least two unsaturated compounds.
  • the process according to the invention gives polymers, in particular polymers and copolymers, composed of vinylaromatic monomers, in particular styrene, with a narrow molecular weight distribution M w / M n of generally ⁇ 3, preferably ⁇ 2.5, particularly preferably ⁇ 2.
  • Vinyl aromatic compounds preferably styrene, ⁇ -methylstyrene, p-methylstyrene, ethylene or C 3 - to C 8 -monoolefins such as propylene, 1-butene, 1-hexene and 1-octene are preferably used as unsaturated compounds in the homopolymerization.
  • At least one vinylaromatic compound is preferably used in the copolymerization, styrene and ethylene, styrene and propylene and styrene and butylene are particularly preferably used.
  • the present application also relates to a process in which at least one vinylaromatic compound, preferably styrene, ⁇ -methylstyrene or p-methylstyrene, particularly preferably styrene, is used as the unsaturated compound.
  • at least one vinylaromatic compound preferably styrene, ⁇ -methylstyrene or p-methylstyrene, particularly preferably styrene
  • styrene is polymerized or copolymerized in the process according to the invention. It has surprisingly been found that when C2-symmetrical transition metal compounds of the formula II are used, highly isotactic polystyrene or copolymers which contain highly isotactic polystyrene units are obtained in the homo- or copolymerization of styrene.
  • highly isotactic polystyrene or highly isotactic polystyrene units are understood to be polystyrene which is composed of at least 80%, preferably at least 85%, particularly preferably at least 90% of m-diads.
  • the proportion of m-diads is determined using ⁇ -N E.
  • Another object of the present application is thus the use of a transition metal compound according to the invention or a catalyst system according to the invention for the production of isotactic polystyrene.
  • Preferred transition metal compounds and catalyst systems have already been mentioned above.
  • the catalyst system according to the invention is used as the catalyst system in the process according to the invention.
  • Preferred catalyst systems are mentioned above.
  • the use of C2-symmetrical transition metal compounds in the catalyst system according to the invention is preferred. It is also possible to use the catalyst system according to the invention not alone, but in conjunction with other catalyst systems of the same type or with other polymerization catalysts (such as Phillips, Ziegler, metallocene catalysts).
  • the polymerization is carried out under generally customary conditions in solution, for example as high-pressure polymerization in a high-pressure reactor or high-pressure autoclave, in suspension or in the gas phase (for example GPWS polymerization process). Polymerization in solution is preferred.
  • the corresponding polymerization processes can be carried out as a batch process, semi-continuously or continuously, the procedures being known from the prior art.
  • Aprotic organic solvents are particularly suitable as solvents.
  • the catalyst system, the monomer (unsaturated compound) and the polymer can be soluble or insoluble in these solvents, but the solvents should not participate in the polymerization.
  • Suitable solvents are alkanes, cycloalkanes, selected halogenated hydrocarbons and aromatic hydrocarbons.
  • Preferred solvents are hexane, toluene and benzene, toluene is particularly preferred.
  • the polymers were examined by NMR on a Bruker ARX 300, with C2D2CI 4 serving as the solvent.
  • DSC measurements to determine T g and T m were carried out on a Seiko DSC 6200 at a heating rate of lOK / min.
  • Wide-angle X-ray scattering (WAXS) on iPS was carried out using a Siemens D500 powder diffractometer equipped with a temperature-controlled sample holder.
  • GPC measurements were carried out in 1,2,4-trichlorobenzene (TCB) at 140 ° C with TR detection and PS calibration.
  • Titanium (rV) chloride in 700 ml of toluene was slowly added to 67.52 g (0.5 mol) at 5 ° C.
  • Example 1 a Analogously to the synthesis in Example 1 a), starting from 6-tert-butyl-4-methoxyphenol, the compound 2,2'-dithiobis (6-tert-butyl-4-methoxyphenol) was introduced as an orange powder in
  • Example C1 4-dithiabutanediyl-2,2'-bis (4,6-di-tert-butylphenol) (C)
  • 0.84 g (55%) of the ligand (C) was obtained in the form of colorless crystals.
  • the bisphenolate (D) was prepared by reacting 3,5-di-tert-butyl-2-hydroxybenzenethiol (3) from Example (3) with 1,3-dibromopropane in 28% yield.
  • EI-MS: M / z (rel. Int.%) 516 (100, *), 460 (11, M ⁇ C 4 H 8 ), 279 (23, C 17 H 27 OS 2 + ), 279 (31 , C 17 H 27 OS + ), 56 (30, C 4 H 8 + ).
  • Compound (XV) was prepared in analogy to, for example, XTV starting from ligand (D) in quantitative yield.
  • the compound (XIX) was prepared according to the method described in Example XVIII from 46 mg (242 ⁇ mol) TiCl 4 in 5 mL CH 2 C1 2 and 100 mg (242 ⁇ mol) bisphenolate ligand (F) in 5 L CH 2 C1 2 . Yield: quantitative.
  • the compound (XX) was prepared as described in Example XVIII from 61 mg (321 ⁇ mol) TiCl; in 5 mL CH 2 C1 2 and 115 mg (307 ⁇ mol) of the bisphenolate ligand (G) in 5 mL CH 2 C1 2 . Yield: quantitative.
  • the compound was prepared according to the same method as Example XXI from 69 mg (215 ⁇ mol) HfCl 4 in 5 L CH 2 C1 2 and 80 mg (215 ⁇ mol) ligand (E) in 5 L CH 2 C1 2 . Yield: 120 mg (193 ⁇ mol, 90%).
  • the compound was prepared from 110 mg (202 ⁇ mol) of Hf (CH 2 Ph) 4 in 10 ml of toluene and 75 mg (201 ⁇ mol) of ligand (E) in 10 ml of toluene using the same method as in Example XXV.
  • the product was obtained in quantitative yield as a colorless solid.
  • Example P4 Polymerization of styrene
  • the polymerization was carried out at 25 ° C. in a Büchi mini-clave glass autoclave (200 ml).
  • the reactor was filled with toluene and 18 mmol methylaluminoxane as MAO solution (10% in toluene) were added.
  • the reactor was then filled with ethylene until the reaction mixture was saturated with monomer gas.
  • the polymerization was started by adding a solution of 12 ⁇ mol of the transition metal compound (XII) in 10 ml of toluene.
  • the ethene pressure was 6 bar.
  • the volume of the reaction mixture was 150 mL.
  • the gas pressure was released and 10 ml of 2-propanol were added.
  • the polymerization was carried out analogously to Example 5. Instead of the transition metal compound (XII), 12 ⁇ mol of the compound (II) was used. 2.9 g of polyethylene were obtained.
  • the reactor with 4 mg (8.1 ⁇ mol) of the transition metal compound (XVIII) was evacuated three times and filled with ethene. 40 ml of toluene and 10.8 g were then passed through a septum
  • the ethene pressure was then increased to 4 bar and kept constant during the reaction. After 15 minutes the reaction was stopped by releasing the ethene pressure.
  • Example P9 Polymerization of ethylene The polymerization was carried out analogously to Example P8. 4 mg (7.5 ⁇ mol) of the transition metal compound (XLX) and 10.1 g (37.5 mmol) of MAO solution were used as the catalyst system. 604 mg of polymer were obtained.
  • the polymerization was carried out analogously to Example P8. 4 mg (8.1 ⁇ mol) of the transition metal compound (XX) and 10.8 g (40.5 mmol) of MAO solution were used as the catalyst system. 706 mg of polymer were obtained.
  • the polymerization was carried out analogously to Example P8. 4 mg (7.5 ⁇ mol) of the transition metal compound (XXI) and 10.1 g (37.5 mmol) of MAO solution were used as the catalyst system. 948 mg of polymer were obtained.
  • the polymerization was carried out analogously to Example P8. 5 mg (8.0 ⁇ mol) of the transition metal compound (XXII) and 10.7 g (40.5 mmol) of MAO solution were used as the catalyst system. 568 mg of polymer were obtained.
  • the polymerization was carried out in a Buchi mini-glass autoclave (200 ml) at 25 ° C.
  • the reactor was filled with toluene and 18.9 ml (165 mmol) styrene and 22.5 mmol memylalumoxane was added as a MAO solution (10% in toluene). J following the reactor was filled with ethylene until the reaction mixture was saturated with monomer gas.
  • the polymerization was started by adding 15 ⁇ mol of the transition metal compound (XII) dissolved in 10 ml of toluene.
  • the ethene pressure was " 2 bar.
  • the volume of the reaction mixture was 150 mL.

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Abstract

Systèmes de ligands bisphénolate et composés apparentés, composés de métaux de transition qui possèdent les systèmes de ligands selon la présente invention, système catalyseur pour la polymérisation de composés non saturés contenant au moins un composé de métaux de transition selon la présente invention et au moins un cocatalyseur, procédé de production de polymères par polymérisation ou copolymérisation d'au moins un composé non saturé en présence d'un système catalyseur selon la présente invention et utilisation d'un composé de métaux de transition selon la présente invention ou d'un système catalyseur selon la présente invention pour la production de polystyrène isotactique.
PCT/EP2004/002179 2003-03-05 2004-03-04 Catalyseurs pour la polymerisation du styrene WO2004078765A2 (fr)

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Cited By (2)

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US7705157B2 (en) 2004-12-16 2010-04-27 Symyx Solutions, Inc. Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts
EP2359930A1 (fr) 2005-12-16 2011-08-24 Dow Global Technologies LLC Polymers préparé en presence des complexes metalliques avec des ligandes polydentates heteroatomiques

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BR112017022689B1 (pt) 2015-04-24 2021-06-15 Pirelli Tyre S.P.A. Pneu para rodas de veículo, copolímero, e processo de copolimerização de estireno e butadieno com um ou mais monômeros diênicos
CN106317282B (zh) * 2016-08-19 2018-10-23 东华大学 超高分子量乙烯/苯乙烯类共聚物的制备方法
CN115697722A (zh) * 2020-06-09 2023-02-03 倍耐力轮胎股份公司 高性能轮胎

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US3161612A (en) * 1959-04-15 1964-12-15 Bayer Ag Alkylated amino phenols protecting rubber goods against ozone
US3149933A (en) * 1960-08-25 1964-09-22 Bayer Ag Process for stabilizing liquid fuels
US6333423B1 (en) * 1999-09-10 2001-12-25 Ramot University Authority For Applied Research And Industrial Development Ltd. Ultra-high activity non-metallocene pre-catalyst and method for catalytic polymerization of alpha-olefin monomers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7705157B2 (en) 2004-12-16 2010-04-27 Symyx Solutions, Inc. Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts
EP2359930A1 (fr) 2005-12-16 2011-08-24 Dow Global Technologies LLC Polymers préparé en presence des complexes metalliques avec des ligandes polydentates heteroatomiques

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