Classifications

• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/02—Iron compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/53—Nitrogen atoms
• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/02—Iron compounds
  • C07F15/025—Iron compounds without a metal-carbon linkage
• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/06—Cobalt compounds
  • C07F15/065—Cobalt compounds without a metal-carbon linkage
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—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
  • 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
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

• the invention relates to bisimidine compounds, a process for their preparation, bisimidinato complexes as catalysts, processes for their preparation and their use in the polymerization of unsaturated compounds.
• transition metal compounds as catalytically active substances for the polymerization of unsaturated compounds has long been known.
• Ziegler-Natta or Phillips catalysts are used commercially for the synthesis of polyolefins.
• metallocenes have been used as polymerization catalysts which are characterized by high activity. With the help of the metallocenes, polymers with a narrow molecular weight distribution and copolymers with uniform comonomer incorporation are accessible.
• the metallocene catalysts have disadvantages for large-scale use. For example, they are very sensitive to impurities in commercially available monomers, in the process gas and the solvents used and to hydrolysis. Furthermore, the price for metallocenes with zircon as the central metal is very high.
• the activities shown in the polymerization of ethylene are far too low for technical applications.
• the object of the present invention is to develop new complexes with a metal from groups 7, 8, 9 and 10 of the periodic table
• This task is divided into the provision of a ligand system for this catalyst, as well as a process for the production of this ligand system and the provision of a process for the production of the corresponding catalyst.
• a non-metal selected from N, S, 0 and P R 1 radicals of the general formula NR 5 R 6 ,
• R 5 and R 6 together with the N atom form a 5-, 6- or 7-membered ring in which one or more of the —CH or —CH 2 groups can be replaced by suitable heteroatom groups, which is saturated, unsaturated and unsubstituted, substituted or fused with further carbacyclic or heterocarbacyclic 5- or 6-membered rings, which in turn can be saturated or unsaturated and substituted or unsubstituted,
• R 7 and R 8 independently of one another are alkyl, aryl or cycloalkyl radicals,
• R 3 , R 4 independently of one another are H, alkyl, aryl or cycloalkyl radicals,
• alkyl radicals are generally to be understood as linear or branched C 1 -C 10 -alkyl radicals, preferably C 1 -C 10 -alkyl radicals, particularly preferably C 1 -C 4 -alkyl radicals. These alkyl radicals can be heteroatom-substituted. Suitable alkyl radicals are, for example, methyl, i-propyl, t-butyl, trifluoroethyl and trimethylsilyl radicals.
• Aryl radicals are generally unsubstituted and substituted C 6 to C 0 aryl radicals (the number of carbon atoms refers to the carbon atoms in the aryl radical), preferably C 6 to C 1 aryl radicals, which are unsubstituted or singly or multiply can be substituted, are very particularly preferred with CT .
• - to C ⁇ -alkyl radicals substituted Cg to Cirj aryl radicals such as 4-methylphenyl, 2, 6-dimethylphenyl, 2,6-diethylphenyl, 2, 6-diisopropylphenyl, 2-tert. Butyl-phenyl,
• aryl residues can also be mixed with heteroatoms, e.g. be substituted with F.
• Cycloalkyl radicals are generally to be understood as meaning C 5 -C 6 -cycloalkyl radicals (the number of carbon atoms relates to the carbon atoms in the cycloalkyl ring), which can be unsubstituted or substituted one or more times by alkyl or aryl radicals or heteroatoms. C 5 to C 6 cycloalkyl radicals are preferred.
• R 5 and R 6 together with the N atom form a 5-, 6- or 7-membered ring in which one or more of the -CH or -CH groups can be replaced by suitable heteroatom groups .
• suitable hetero atom groups are preferably -N or -NH groups. It is particularly preferred that no to 3 -CH or -CH groups are replaced by -N or -NH groups.
• the 5-, 6- or 7-membered ring can be saturated or unsaturated.
• the ring can be unsaturated one or more times.
• Unsaturated 5-membered rings are preferred.
• Unsaturated rings should also be understood to mean, in the case of the 5-membered rings, aromatic rings such as unsubstituted or substituted pyrrole radicals and derivatives thereof, which are particularly preferred.
• the 5-, 6- or 7-membered ring can be unsubstituted, substituted or with other carbacyclic or heterocarbacycll - see 5- or 6-membered rings, which in turn can be saturated or unsaturated and substituted or unsubstituted.
• Carbacyclic rings are understood to mean those rings which have a pure carbon skeleton.
• one or more -CH - or -CH- groups are replaced by heteroatoms, preferably -NH- or -N-groups.
• Carbacyclic rings or heterocarbacyclic rings with a nitrogen atom in the ring system are particularly preferred.
• the substituents in these carbacyclic and heterocarbacycli - see 5- or 6-membered rings are the alkyl, aryl or cycloalkyl radicals mentioned above.
• the rings can be substituted one or more times. 1- to 3-fold substitution is preferred.
• the ring system can furthermore be ortho- or ortho- and peri-fused.
• the system is preferably ortho-fused, with particularly preferably 1 to 2 phenyl radicals fused to the central 5- or 6-ring, such as indole, carbazole and derivatives thereof.
• the ring described by the general formula NR 5 R 6 is 5-membered.
• a non-fused 5-ring in particular a pyrrole radical or a radical derived from pyrrole, in which none, one or more, preferably 0 to 3, particularly preferably 0 or 2 —CH groups in the pyrrole ring have been replaced by nitrogen, is very particularly preferred can. Examples include the pyrrole and triazole systems.
• pyrrole residues or residues derived from pyrrole which are substituted in the 2- and 5-positions with: -C 1 -C 6 -alkyl groups, which can be linear, branched and substituted with heteroatoms - electron-withdrawing residues such as halogen, nitro, sulfonate or trihalomethyl are substituted.
• S0 3 R *, S0 3 Si (R *) 3 , and S0 3 " (HN (R *) 3 ) + are particularly suitable among the sulfonate residues.
• trihalomethyl radicals trifluoro, trichlor and tribromomethyl, in particular trifluoromethyl, are particularly suitable.
• ortho substituents are halogen radicals, such as the fluorine, chlorine, bromine or iodine radical
• Chlorine or bromine radicals are used as ortho substituents, and the respective ortho positions are preferably occupied by identical radicals, aryl groups which are unsubstituted or in turn substituted by C 1 -C 6 -alkyl groups which may be heteroatom-substituted.
• Preferred substituents in the 2- and 5-position of the proline ring or a derivative thereof, preferably triazole are methyl, i-propyl, t-butyl, phenyl, substituted aryl radicals, as defined above.
• R 3 and R 4 in the general formula (I) can independently be H, alkyl, aryl or cycloalkyl radicals, preferred radicals being defined above.
• R 3 and R 4 are very particularly preferably independently of one another H or CH 3 .
• R * can be H, alkyl, aryl or gebalkyl, preferred radicals being defined above.
• R *, CH or H is very particularly preferred.
• the central ring is preferably a 6-membered ring, i.e. n is preferred 2.
• pyridine bisimidine systems are very particularly preferred.
• R 3 , R 4 , R 9 and R 10 independently of one another are C 1 -C 2 o -alkyl radicals which may be linear or branched, preferably C 1 -C 4 -alkyl radicals, particularly preferably C 8 -C 8 -alkyl radicals , These alkyl radicals can be heteroatom-substituted. Suitable alkyl radicals are, for example, methyl, i-propyl, t-butyl, trifluoromethyl and trimethylsilyl radicals.
• the residues R ', R'',R''' and R ''' are H, alkyl, aryl or cycloalkyl as defined above.
• the preferred production process depends on the desired compound of the general formula (I).
• R 5 and R 6 have the meanings given above, prepared with diketo compounds of the general formula (III),
• R 3 , R 4 are independently H, alkyl, aryl or cycloalkyl radicals, and
• A is S, N, O or P, and
• n 1 or 2.
• the process has one stage and is carried out under acidic reaction conditions, preferably with the addition of a mineral acid or an organic acid, particularly preferably formic acid, in alcoholic solvents, preferably in methanol.
• the process can be carried out with aluminum trialkyl catalysis, preferably using trimethylaluminum, in an aprotic solvent, preferably in toluene.
• the ratio of the compound of the general formula (II) to the compound of the general formula (III) is 2: 0.7 to 1.3, preferably 2: 0.9 to 1.1, particularly preferably 2: 1 Reaction under acidic conditions in methanol / formic acid is generally preferred.
• the condensation is carried out at from 0 to 100.degree. C., preferably from 15 to 80.degree. C., particularly preferably from 20 to 40.degree.
• the reaction time is generally 20 minutes to 48 hours, preferably 1 hour to 16 hours, particularly preferably 2 hours to 14 hours.
• the exact reaction conditions depend on the compounds used in each case. In the case of compounds of the general formulas (II) and (III) which only condense slowly to the desired compounds of the general formula (I), a reaction with aluminum trialkyl catalysis in aprotic solvents is preferred.
• the asymmetrical 1,2-diimines of the general formula (I), in which R 1 + R 2 are prepared in a two-stage process in which: a) in a first stage compounds of the general formula (II)
• R 5 and R 6 have the meanings given above,
• R 3 , R 4 are independently H, alkyl, aryl or cycloalkyl radicals, and
• A is S, N, 0 or P
• n 1 or 2
• R 7 and R 8 are independently alkyl, aryl or cycloalkyl radicals, or
• the condensation in stage a) is carried out at temperatures from 0 to 100 ° C., preferably from 15 to 80 ° C., particularly preferably from 20 to 40 ° C.
• the reaction time is generally 20 minutes to 48 hours, preferably 1 hour to 16 hours, particularly preferably 2 hours to 14 hours.
• the exact reaction conditions depend on the compounds used in each case.
• Stage b) is generally carried out at temperatures from 0 to 100 ° C., preferably from 20 to 80 ° C., particularly preferably from 30 to 60 ° C.
• the reaction time is generally 20 minutes to 48 hours, preferably 1 hour to 8 hours, particularly preferably 2 hours to 7 hours.
• the exact reaction conditions depend on the compounds used.
• R 5 and R 6 have the meanings given above,
• Group NR 5 R 6 is a pyrrole radical or a radical derived from pyrrole, which is very particularly preferably in the 2- and 5-position with C 1 -C 6 -alkyl groups, which are linear, branched and substituted with heteroatoms can, and / or aryl groups, which is unsubstituted or in turn substituted with -C ⁇ to C ⁇ -alkyl groups, which may be heteroatom-substituted.
• Preferred substituents in the 2- and 5-position of the pyrrole ring are methyl, i-propyl, t-butyl, phenyl, substituted aryl radicals, as defined above.
• N-amino pyrroles can be obtained, for example, by the following two-step process:
• R 3 , R 4 are independently H, alkyl, aryl or cycloalkyl radicals, preferred radicals being defined above; R 3 and R 4 are very particularly preferably H or CH 3 ; and
• A is S, N, 0 or P, preferably N or S, particularly preferably N, and
• n 1 or 2, preferably 2.
• the central base of the compounds of the general formula (III) is thus preferably a pyridine base which is substituted in the 2- and 6-position.
• the compounds according to the invention are suitable as ligands for catalysts which can be used for the polymerization of unsaturated compounds.
• the compounds according to the invention are ligands for catalysts with a metal of the late transition metals, e.g. with a metal from group 7, 8, 9 and 10 of the periodic table of the elements.
• the present invention therefore furthermore relates to compounds of the general formula (VI)
• R 5 and R 6 together with the N atom form a 5-, 6- or
• R 7 , R 8 independently of one another are alkyl, aryl or cycloalkyl radicals,
• R 3 , R 4 independently of one another are H, alkyl, aryl or cycloalkkyl radicals,
• X is a halide or a Cj . - to C ⁇ -alkyl radical
• n valency of the metal preferably 2 or 3.
• the transition metal M of group 7, 8, 9 or 10 of the periodic table of the elements is preferably Ru, Mn, Co, Fe, Ni or Pd.
• the metals can be used in the following valences: Fe (II), Fe (III), C ⁇ (I), Co (II), Co (III), Ru (II), Ru (III), Ru (IV) , Mn (I), Mn (II), Mn (III), Mn (IV), Ni (II), Pd (II).
• the ligands X can independently of one another be halide or alkyl radicals. It is preferably chloride, bromide or methyl radicals. Particularly preferred as group MX m : MnCl 2 , FeCl 3 , CoCl 3 , PdCl 2 , NiCl 2 or CoCl 2 , FeCl.
• R 1 , R 2 , R 3 and R 4 have the meanings given above.
• R 3 , R 4 independently of one another are H, alkyl or aryl radicals, preferred radicals being defined above,
• R 9 , R 10 , R 11 and R 12 are independently CT . - to C 6 -alkyl radicals, preferred radicals being defined above, and
• R ', R' ', R' '', R '' "are H, alkyl, aryl or cycloalkyl radicals, preferred radicals being defined above,
• MX 2 is MnCl 2 , CoCl or FeCl, particularly preferably FeCl 2 and CoCl 2 .
• the compounds of the general formula (VI) 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 7, 8, 9 and 10 of the periodic table of the elements.
• a compound of the general formula (I) suitable as a ligand is dissolved in an organic solvent, for example tetrahydrofuran (THF) or methylene chloride, with a corresponding metal salt, for example MnCl 2 , FeCl 3 , CoCl, CoCl, NiCl 2 , PdCl, FeCl, FeCl 2 -THF complex combined.
• a metal salt for example MnCl 2 , FeCl 3 , CoCl, CoCl, NiCl 2 , PdCl, FeCl, FeCl 2 -THF complex combined.
• 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 generally stirred at temperatures from room temperature to 50 ° C., preferably from room temperature to 40 ° C., particularly preferably at room temperature for generally 0.5 hours to 16 hours, preferably 1 to 6 hours, particularly preferably 1 to 3 hours ,
• Working up is carried out in the customary 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 diethyl ether, optionally digesting in a non-polar solvent, for example hexane , Filtering, washing and drying.
• the metal complexes of the general formula (VI) according to the invention are easily accessible and are suitable as catalysts for the polymerization of unsaturated compounds. They are characterized by a surprisingly high productivity in the polymerization or copolymerization of unsaturated compounds. Furthermore, a number of the complexes according to the invention are characterized in copolymerization by a high copolymer incorporation rate which can be achieved with them. Even slight variations in the ligand structure of the metal complex open up the production of a wide range of polymers with different properties, so that it is possible to "tailor" a catalyst for a polymer with the desired properties.
• oligomers according to the invention additionally have a large number of unsaturated end groups, which allow their further use as a monomer in polymerizations or also a chemical functionalization.
• polymers By variation of the ligand, e.g. Iron complex with a carbazole substituent, polymers can be obtained that provide shorter-chain oligomers (liquids).
• ligand e.g. Iron complex with a carbazole substituent
• catalyst systems e.g. Co-complexes with carbazole groups provide very short-chain oligomers in a range of generally 6 to 18 carbon atoms, preferably with a maximum of 8 carbon atoms.
• catalysts are therefore available for producing a wide variety of polymers. These catalysts are also characterized by a very high activity, which in many cases exceeds that of comparable systems. Cobalt complexes with extremely high activity were also found. In the case of compounds known from the literature, the activity of the co-complexes is usually at least a power of ten worse than that of analogous Fe complexes (VC Gibson et al., Chem. Commun. 1998, 849-850 and M. Brookhart et al. , J. Am. Chem. Soc. 1998, 120, 4049-4050).
• the present invention therefore furthermore relates to the use of compounds of the general formula (VI) as catalysts in a process for the polymerization of unsaturated compounds, and to a process for the preparation of polyolefin by polymerization of unsaturated compounds in the presence of the catalyst according to the invention and an activator.
• M 'an element of III Main group of the periodic table of the elements, preferably B, Al or Ga, particularly preferably B,
• X 1 , X 2 , X 3 independently of one another are hydrogen, Ci- to Cio-alkyl,
• Cis-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical or fluoride, chloride, bromide or iodide, preference is given to halogenoaryls, particularly preferred pentafluorophenyl.
• R 1 A10 alkylaluminoxane
• R 14 is a C 1 -C 5 -alkyl, preferably a C 1 -C 4 -alkyl radical, particularly preferably a methyl radical (methylaluminoxane) is.
• Suitable ionic compounds with Lewis acid cations are compounds of the general formula (VIII),
• Y is an element of I. to VI. Main group or subgroup I to VIII of the Periodic Table of the Elements,
• Q to Q z are singly negatively charged groups such as C - C -A 28 lkyl, ß - C ⁇ to 5 aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl and 1 to 28 carbonic lenstoffatomen in the alkyl radical, C ⁇ ⁇ to Cio-cycloalkyl, which may optionally be substituted with C ⁇ ⁇ to CiQ-alkyl groups, halide, CT.- to C s-alkoxy, C 6 - to C ⁇ 5 aryloxy, silyl or mercaptyl groups,
• 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 1, 1 '-dimethylferrocenyl cation are to be mentioned. 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 having Brönsted acids as cations and preferably likewise noncoordinating counterions are also mentioned in WO 91/09882, the preferred cation is N, N-Dimethylanili ⁇ nium.
• the amount of activator is preferably 0.1 to 10 equivalents, particularly preferably 1 to 2 equivalents, for borates, based on the catalyst (VI).
• the amount of activator is generally 50 to 1000 equivalents, preferably 100 to 500 equivalents, particularly preferably 100 to 300 equivalents, based on the catalyst (VI).
• the polymerization process according to the invention is suitable for the production of homopolymers or copolymers.
• Unsaturated compounds or combinations of unsaturated compounds which are preferably used are unsaturated compounds selected from ethylene, C - to C 2 o -monoolefins, ethylene and C 3 - to C 20 -monoolefins, cycloolefins, cycloolefins and ethylene and cyclo-olefins and propylene.
• Preferred C 3 to C 2 onoolefins are propylene, butene, hexene and octene and preferred cycloolefins are norbones, norbonadiene and cyclopentene.
• the above monomers can be copolymerized with monomers having a carbonyl group such as esters, carboxylic acids, carbon monoxide and vinyl ketones.
• monomers having a carbonyl group such as esters, carboxylic acids, carbon monoxide and vinyl ketones.
• the following combinations of unsaturated compounds are preferred: ethylene O 01/14391 ig PCT / EPOO / 07 57 and an alkyl acrylate, especially methyl acrylate, ethylene and an acrylic acid, ethylene and carbon monoxide, ethylene, carbon monoxide and an acrylate ester or an acrylic acid, especially methyl acrylate as well as propylene and alkyl acrylate, especially methyl acrylate , Acrylonitrile and styrene are also suitable as comonomers.
• the polymerization is carried out in solution, e.g. as high-pressure polymerization in a high-pressure reactor or high-pressure autoclave, in suspension or in the gas phase (e.g. GPWS polymerization process).
• the corresponding polymerization processes can be carried out as a batch process, semi-continuously or continuously, the procedures being known from the prior art.
• the catalyst systems according to the invention can be used in the form of unsupported catalysts or supported catalysts, depending on the polymerization conditions.
• Finely divided solids are preferably used as carrier materials, the particle diameters of which are generally in the range from 1 to 200 mm, preferably from 30 to 70 mm.
• Suitable carrier materials are, for example, silica gels, preferably those of the formula Si0 2 • a A1 2 0 3 , in which a stands for 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 A1 2 0 3 , in which a stands for 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 thermal treatment preferably being carried out at 80 to 200 ° C., particularly preferably at 100 to 150 ° C.
• the catalysts of the general formula (VI) can be prepared “in situ” and used directly in the polymerization without prior isolation.
• the catalysts can also be prepared “in situ” in the presence of the support material.
• Aprotic organic solvents are particularly suitable as solvents.
• the catalyst system, the monomer (s) 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 polymerization temperatures in solution polymerization are generally in the range from -20 to 350 ° C., preferably from 0 to 350 ° C., particularly preferably from +20 to 180 ° C., very particularly preferably from room temperature to 80 ° C.
• the reaction pressure is generally 0.1 to 5000 bar, preferably 0.1 to 3000 bar, particularly preferably 1 to 200 bar, very particularly preferably 5 to 40 bar.
• the polymerization can be carried out in any apparatus suitable for the polymerization of unsaturated compounds.
• the polymerization can be carried out in the presence of hydrogen gas, which acts as a chain transfer reagent.
• hydrogen gas acts as a chain transfer reagent.
• auxiliaries customary in the corresponding polymerization process can be used.
• the polymerization process according to the invention opens up access to polyolefins with novel structures and properties.
• Another object of the present invention is therefore polymers which can be produced by the process according to the invention.
• Acetonylacetone (1) is commercially available (Aldrich), the ketones, 2-7, were prepared according to literature guidelines (T.Sagegusa, Y.Ito, T.Konsoke, J.Am. Chem. Soc., 97 (1975 ) 2912; H. Stetter, M. Schreckenberger, Chem. Ber., 107 (1974) 2453; H. Stetter, H. Kuhlmann, Chem. Ber., 109 (1976) 3426; H. Stetter, Angew. Chem ., 21 (1976) 695; H. Stetter, F. Jonas, Chem. Ber., 114 (1981) 564).
• toluene 150 ml (or 250 ml) of toluene were introduced into the 25 non-conduit tube. Sufficient ml of a 30% solution of methylaluminoxane (MAO) in toluene was added to this, so that 100 equivalents, based on the catalyst complex added later, were used; if appropriate, 12.5 ml (or 25 ml) of 1-hexene were added. Then were
• Tables 1 and 2 show details of the polymerizations of ethylene with iron (Table 1) and cobalt catalysts (Table 2).
• Tables 3 and 4 show the polymer analysis of the resulting polyethylene (Table 3: Polyethylene with iron catalysts, Table 4 Polyethylene using cobalt catalysts)
• Oligomers Polymerization of ethylene with complex 20
• reaction solution was worked up with methanol / HCl and the aqueous phase was separated from the toluene phase. A small part of the organic phase was examined untreated for its composition. The rest was worked up by removing the solvent in vacuo. 2 g of an oil are obtained. Both the untreated phase and the oil were examined by gas chromatography. Table 7 shows the distribution of the carbon chains.
• the propene polymerization was carried out analogously to the ethylene polymerization, using propylene instead of ethylene.
• Catalyst complex 34, batch size: 50 mmol, polymer discharge: 15 g (oil), activity (gPE / mmolKatxh): 300.

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