DE19757218A1 - Production of elastomer with low glass transition temperature, higher crystallinity peak and good green elasticity - Google Patents

Abstract

In the production of (un)saturated elastomers by (co)polymerization of 2-8 C alpha -olefins, open-chain, monocyclic and/or polycyclic 4-15 C dienes and/or styrene, using catalysts that can be activated by cocatalysts, the catalysts are metallocenes of subgroup III, IV, V or VI metals, including the lanthanides and actinides or pi -complex compounds. The process concerns the production of (un)saturated elastomers, which, in addition to the amorphous structure and a low glass transition temperature, Tg, have melt peak(s), including at least one peak maximum at a Tm above +40 deg C, as determined by differential scanning calorimetry (DSC). It involves (co)polymerization of monomers selected from 2-8 C alpha -olefins, open-chain, monocyclic and/or polycyclic 4-15 C dienes and styrene in bulk, solution, high temperature solution, slurry or gas phase in the presence of organometallic catalysts that can be activated by cocatalysts. The novelty is that the organometallic catalysts are metallocene compounds of formula (I) or pi -complex compounds and especially metallocene compounds of formula (II): CpI, CpII = carbanions with structure containing cyclopentadienyl; D = a donor atom; A = an acceptor atom; M = a sub-group III, IV, V or VI transition metal, including the lanthanides and actinides; X = an anion equivalent; n = 0-4, depending on the charge on M; pi I, pi II = charged or electrically neutral pi -systems

Description

The present invention relates to the use of π systems or metallocene compounds in which a transition metal is complexed with two π systems, in particular with aromatic π systems, such as anionic cyclopentadienyl ligands (carbanions), and the two Systems are reversibly connected by at least one bridge of a donor and an acceptor, as organometallic catalysts in a process for producing saturated or unsaturated elastomers, which in addition to the amorphous structure and a low glass transition temperature Tg in the DSC measurement (DSC = differential Scanning calorimetry) have a crystallinity peak with a melting temperature above + 40 ° C, by (co) polymerizing monomers from the group of the C ₂ -C ₈ -α-olefins, the open-chain, monocyclic and / or polycyclic C ₄ -C ₁₅ -Diolefins and styrene. The coordinative bond between the donor atom and the acceptor atom creates a positive (partial) charge in the donor group and a negative (partial) charge in the acceptor group:

Metallocenes and their use as catalysts in the polymerization of olefins have long been known (EP-A 129 368 and the literature cited therein). Out EP-A '368 is also known that metallocenes in combination with aluminum alkyl / water as cocatalysts effective systems for the polymerization of Represent ethylene (for example, 1 mol of trimethylaluminum and 1 mol Water methylaluminoxane = MAO formed; other stoichiometric ratios nisse have already been used successfully (WO 94/20506)). They are already me Tallocenes known whose cyclopentadienyl frameworks are linked by a bridge are covalently linked. As an example of the numerous patents and applications in this area EP-A 704 461 may be mentioned, in which the link mentioned therein Creation group a (substituted) methylene group or ethylene group, a silylene group, a substituted silylene group, a substituted germylene group or a  represents substituted phosphine group. Also in EP '461 are the bridged metallo cene provided as polymerization catalysts for olefins. Despite the numerous Patents and applications in this area continue to be requested improved catalysts, which are characterized by high activity, so that the Amount of catalyst remaining in the polymer can be set low, and which, for example, for the polymerization and copolymerization of olefins Thermoplastics and to elastomeric products as well as for polymerization and Copolymerization of diolefins, optionally with olefins, are suitable.

It has now been found that particularly advantageous catalysts bridged π-complex compounds and especially metallocene compounds can be produced in which the bridging of the two π systems by a two or three reversible donor-acceptor bond (s) is made in which a coordinative or between the donor atom and the acceptor atom So-called dative bond arises, which is at least formally an ionic bond is superimposed and in which one of the donor or acceptor atoms is part of the respective associated π system can be. The reversibility of the donor-acceptor bond leaves next to the one bridged by the arrow between D and A State also the unbridged state, in which the two π systems due to the inherent rotational energy, for example, around 360 Can turn degrees of angle against each other or deflect by a smaller angle and can swing back without compromising the integrity of the metal complex is abandoned. After deflection or even complete rotation the "snaps" Donor-acceptor binding again. If there are several donors and / or Such "snap-in" can be accepted even after passing less than 360 degrees. Π systems to be used according to the invention, e.g. B. Metallocenes can therefore be identified by a double arrow and the formula parts (Ia) and Represent (Ib) or (XIIIa) and (XIIIb) to encompass both states.

The invention accordingly relates to a process for the production of saturated or unsaturated elastomers which, in addition to the amorphous structure and a deep glass transition temperature Tg in the DSC measurement, have one or more melting peaks, at least one of which has its peak maximum at a melting temperature (T _m ) above + 40 ° C, preferably above 50 ° C, the half-width of at least one melting peak preferably being at most 30 ° C, by (co) polymerizing monomers from the group of the C ₂ -C ₈ -α-olefins, the open-chain, monocyclic and / or polycyclic C ₄ -C ₁₅ diolefins and styrene in the bulk, solution, high-temperature solution, slurry or gas phase in the presence of organometallic catalysts which can be activated by cocatalysts is characterized in that as metal organic catalysts metallocene compounds of the formula

in the
CpI and CpII represent two identical or different carbanions with a cyclopentadienyl-containing structure, in which one to all H atoms are replaced by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ alkyl, the 1-fold to complete can be substituted by halogen, 1 to 3 times by phenyl and 1 to 3 times by vinyl, C ₆ -C ₁₂ aryl, haloaryl with 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl and 1- or can be substituted twice by D and A,
D denotes a donor atom which can additionally carry substituents and which has at least one lone pair of electrons in its respective bond state,
A denotes an acceptor atom which can additionally carry substituents and which has an electron pair gap in its respective bond state,
where D and A are linked by a reversible coordinative bond such that the donor group assumes a positive (partial) charge and the acceptor group a negative (partial) charge,
M for a transition metal of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements (Mendeleev) including the lanthanides and actinides,
X represents an anion equivalent and
n is the number zero, one, two, three or four, depending on the charge of M,
or π-complex compounds and in particular metallocene compounds of the formula

in the
πI and πII represent differently charged or electrically neutral π systems, which can be condensed once or twice with unsaturated or saturated five or six rings,
D denotes a donor atom which is a substituent of πI or part of the π system of πI and which has at least one lone pair of electrons in its respective bond state,
A denotes an acceptor atom which is a substituent of πH or part of the π system of πII and which has an electron pair gap in its respective bond state,
where D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive (partial) charge and the acceptor group takes on a negative (partial) charge and at least one of D and A is part of the respective π system,
where D and A can in turn bear substituents,
wherein each π system or each fused ring system can contain one or more D or A or D and A and
where in πI and πII in the uncondensed or in the condensed form, independently of one another, one to all H atoms of the π system by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ alkyl, the 1-fold to complete can be substituted by halogen, 1 to 3 times by phenyl and 1 to 3 times by vinyl, C ₆ -C ₁₂ aryl, haloaryl with 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl and mono- or can be substituted twice by D and A, so that the reversible coordinative D → A bond (i) between D and A, which are both parts of the respective π system or the fused ring system, or (ii) of which D or A is part of the π system or of the fused-on ring system and the other substituent of the uncondensed π system or of the fused-on ring system is,
M and X have the above meaning and
n, depending on the charges of M and those of π-I and π-II, means the number zero, one, two, three or four,
be used.

Π systems according to the invention are substituted and unsubstituted ethylene, Allyl, pentadienyl, benzyl, butadiene, benzene, the cyclopentadienyl anion and the by replacing at least one carbon atom with a heteroatom-producing species. Among the species mentioned, the cyclic ones are preferred. The type of coordination such ligands (π systems) to the metal can be of the σ type or of the π type.

Such metallocene compounds of the formula (I) to be used according to the invention can be prepared by either using a compound of the formulas (II) and (III)

or a compound of the formulas (IV) and (V)

or a compound of the formulas (VI) and (VII)

with the escape of M'X in the presence of an aprotic solvent or a compound of the formulas (VIII) and (III)

or a compound of the formulas (IV) and (IX)

or a compound of the formulas (X) and (VII)

with the escape of E (R ¹ R ² R ³ ) X and F (R ⁴ R ⁵ R ⁶ ) X in the absence or in the presence of an aprotic solvent
CpI, CpII, D, A, M, X and n have the above meaning,
CpIII and CpIV represent two identical or different uncharged parts of the molecule with a structure containing cyclopentadiene, but are otherwise identical to CpI and CpII,
M 'represents a cation equivalent of an (earth) alkali metal or Tl,
E and F independently of one another represent one of the elements Si, Ge or Sn and
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another for straight-chain or branched C ₁ -C ₂₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkyl-C ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryl C ₁ -C ₆ alkyl, vinyl, allyl or halogen,
where furthermore in the formulas (VIII), (IX), (X) instead of E (R ¹ R ² R ³ ) and F (R ⁴ R ⁵ R ⁶ ) hydrogen and in this case X can also be an amide anion from Type R ₂ N ^θ or a carbanion of the type R ₃ C ^θ or an alcoholate anion of the type RO ^θ , and it is furthermore possible to use compounds of the formulas (II) or (VIII) in the presence of compounds of the formulas (V) or (IX) to react directly with a transition metal compound of the formula (VII).

In the reaction of (VIII) with (III) or (IV) with (IX) or (X) with (VII), the structure (I) is formed in the latter variant with the exit of amine R ₂ NH or R ₂ NE (R ¹ R ² R ³ ) or R ₂ NF (R ⁴ R ⁵ R ⁶ ) or a hydrocarbon compound of the formula R ₃ CH or R ₃ CE (R ¹ R ² R ³ ) or R ₃ CF (R ⁴ R ⁵ R ⁶ ) or an ether ROE (R ¹ R ² R ³ ) or ROF (R ⁴ R ⁵ R ⁶ ), in which the organic radicals R are identical or different and are independent of one another C ₁ -C ₂₀ - Are alkyl, C ₆ -C ₁₂ aryl, substituted or unsubstituted allyl, benzyl or hydrogen. Examples of escaping amine or hydrocarbon, ether, silane, stannane or German are, for example, dimethylamine, diethylamine, di (n-propyl) amine, di (isopropyl) amine, di (tertiary butyl) amine, tertiary butylamine, Cyclohexylamine, aniline, methylphenylamine, di- (allyl) amine or methane, toluene, trimethylsilylamine, trimethylsilyl ether, tetra methylsilane, hexamethyldisilazane and the like.

It is also possible to use compounds of the formulas (II) or (VIII) in the presence of Compounds of the formulas (V) or (IX) directly with a transition metal Implement compound of formula (VII).

π complex compounds of the formula (XIII) in which the π systems are cyclic and aromatic (metallocenes) can be prepared analogously, the following compounds being used analogously:

The production of non-cyclic π-complex compounds takes place according to the expert known processes incorporating donor and acceptor groups.

According to the invention, the polymerization in the bulk, solution, high-temperature solution, slurry or gas phase at -60 to 250 ° C, preferably 0 to + 200 ° C and 1 to 65 bar and in the presence or absence of saturated or aromatic hydrocarbons or of saturated or aromatic halogenated hydrocarbons and in the presence or absence of hydrogen, the metallocene compounds or the π-complex compounds as catalysts in an amount of 10 ¹ to 10 ¹² mol of all monomers per mol of metallocene or the π-complex compounds are used and it is also possible to work in the presence of Lewis acids, Brönstedt acids or Pearson acids or additionally in the presence of Lewis bases.

Such Lewis acids are, for example, boranes or alanes, such as aluminum alkyls, Aluminum halides, aluminum alcoholates, bororganyles, boron halides, boron acid esters or boron or aluminum compounds, both halide and Contain alkyl or aryl or alcoholate substituents, as well as mixtures thereof or the triphenylmethyl cation. Aluminoxanes or are particularly preferred Mixtures of aluminum-containing Lewis acids with water. All acids work according to current knowledge as ionizing agents that contain a metallocenium cation form, which compensates for charge by a bulky, poorly coordinating anion becomes.  

According to the invention, the reaction products of such ionizing agents with metallocene compounds of the formula (I) or π-complex compounds of the formula (XIII) can also be used. They can be described by formulas (XIa) to (XId)

or

respectively.

or

in which
Anion for the entire bulky, poorly coordinating anion and base for a Lewis base.

Examples of such poorly coordinating anions are e.g. B.

B (C ₆ H ₅ ) ₄ ^⊖ , B (C ₆ F ₅ ) ₄ ^⊖ , B (CH ₃ ) (C ₆ F ₅ ) ₃ ^⊖ ,

or sulfonates, such as tosylate or triflate, tetrafluoroborates, hexafluorophosphates or antimonates, perchlorates, and voluminous cluster molecular anions of the carborane type, for example C ₂ B ₉ H ₁₂ ^θ or CB ₁₁ H ₁₂ ^θ . If such anions are present, metallocene compounds can act as highly effective polymerization catalysts even in the absence of aluminoxane. This is especially the case when an X ligand represents an alkyl group, allyl or benzyl. However, it can also be advantageous to use such metallocene complexes with bulky anions in combination with aluminum alkyls, such as (CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ Al, (n- / i-propyl) ₃ Al, (n - / t-Butyl) ₃ Al, (i-butyl) ₃ Al, the isomeric pentyl, hexyl or octyl aluminum alkyls, or lithium alkyls, such as methyl-Li, benzyl-Li, butyl-Li or the corresponding Mg-organic Add compounds such as Grignard compounds or Zn organyls. Such metal alkyls on the one hand transfer alkyl groups to the central metal, on the other hand they catch water or catalyst poisons from the reaction medium or monomer in polymerization reactions. Metal alkyls of the type described can also advantageously be used in combination with aluminoxane cocatalysts, for example in order to reduce the amount of aluminoxane required. Examples of boron compound games using such anions are:
Triethylammonium tetraphenylborate,
Tripropylammonium tetraphenylborate,
Tri (n-butyl) ammonium tetraphenylborate,
Tri (t-butyl) ammonium tetraphenylborate,
N, N-dimethylanilinium tetraphenylborate,
N, N-diethylanilinium tetraphenylborate,
N, N-dimethyl (2,4,6-trimethylanilinium) tetraphenylborate,
Trimethylammonium tetrakis (pentafluorophenyl) borate,
Triethylammonium tetrakis (penta fluorophenyl) borate,
Tripropylammonium tetrakis (pentafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,
Tri (sec-butyl) ammonium te trakis (pentafluorophenyl) borate,
N, N-dimethylanilihium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentaflurophenyl) borate,
N, N-dimethyl (2,4,5-trimethyl anilinium) tetrakis (pentafluorophenyl) borate,
Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tripropylmmonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Dialkylammonium salts such as:
Di (i-propyl) ammonium tetrakis (pentafluorophenyl) borate and
Dicyclohexylammonium tetrakis (pentafluorophenyl) borate;
Tri-substituted phosphonium salts, such as:
Triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate,
Tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate,
Tritolylmethyl tetrakis (pentatluorophenyl) borate,
Triphenylmethyl-tetraphenylborate (trityl-tetraphenylborate),
Trityl tetrakis (pentafluorophenyl) borate,
Silver tetrafluoroborate,
Tris (pentafluorophenyl) borane,
Tris (trifluoromethyl) borane and the analog Al compounds.

Other fluorinated, otherwise analogous boron and aluminum compounds with 1 up to 3 fluorine substituents are possible.

Other poorly coordinating anions can be made from diboranyl or dialanyl compounds of the type
or be formed.

The metallocene compounds to be used according to the invention or the π complex Compounds can be used in isolation as pure substances for (co) polymerization become. However, it is also possible to use them in situ in the (co) polymerization reactor to generate and use in a manner known to those skilled in the art.

The first and second carbanions CpI and CpII with a cyclopentadienyl skeleton or πI and πII, if they are a cyclopentadienyl skeleton, can be the same or different. The cyclopentadienyl skeleton can be, for example, one from the group of cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene. Substituents 1 to 4 per cyclopentadiene or fused benzene ring may be mentioned. These substituents can be C ₁ -C ₂₀ alkyl, such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl, C ₁ -C ₂₀ alkoxy, such as methoxy , Ethoxy, propoxy, isopropoxy, butoxy or iso-butoxy, hexoxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, halogen, such as fluorine, chlorine or bromine, C ₆ -C ₁₂ aryl, such as phenyl, C ₁ - C ₄ -alkylphenyl, such as tolyl, ethylphenyl, (i-) propylphenyl, (i-, tert-) butylphenyl, xylyl, halophenyl, such as fluoro-, chloro-, bromophenyl, naphthyl or biphenylyl, triorganylsilyl, such as trimethylsilyl ( TMS), ferrocenyl and D or A as defined above. Fused aromatic rings can also be partially or fully hydrogenated, so that only the double bond remains, in which both the fused ring and the cyclopentadiene ring have a share. Furthermore, benzene rings, as in indene or fluorene, can contain one or two further fused benzene rings. Furthermore, the cyclopentadiene or cyclopentadienyl ring and a fused-on benzene ring can together contain a further fused benzene ring.

Such cyclopentadiene skeletons are excellent ligands in the form of their anions for transition metals, each cyclopentadienyl carbanion of the named, optionally substituted form a positive charge of the central metal in the com plex compensated. Individual examples of such carbanions are: cyclopentadienyl, Methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopenta dienyl, indenyl, phenylindenyl, 1,2-diethyl-cyclopentadienyl, tetramethyl-cyclopenta dienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl, β- Phenylpropyl-cyclopentadienyl, tetrahydroindenyl, propyl-cyclopentadienyl, t-butyl-cyclo pentadienyl, benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl, tri methylgermyl-cyclopentadienyl, trimethylstannyl-cyclopentadienyl, trimethylstannyl cyclopentadienyl, trifluoromethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, Pentamethylcyclopentadienyl, fluorenyl, tetrahydro- or octahydro-fluorenyl, am Six-ring benzo-fused fluorenyls and indenyls, N, N-dimethylamino-cyclo pentadienyl, dimethylphosphino-cyclopentadienyl, methoxy-cyclopentadienyl, Di methylboranyl-cyclopentadienyl, (N, N-dimethylaminomethyl) -cyclopentadienyl.

In addition to the obligatory first donor-acceptor bond between D and A, further donor-acceptor bonds can be formed if additional  D and / or A as substituents of the respective cyclopentadiene systems or Substituents or parts of the π systems are present. All donor-acceptor bonds are characterized by their reversibility shown above. In the event of several D and A can take up various of these positions. The The invention accordingly comprises both the bridged molecular states (Ia) and (XIIIa) as well as the unbridged states (Ib) and (XIIIb). The number of D Groups can be the same or different from the number of A groups. In CpI and CpII or πI and πII are preferably via only one donor Linked acceptor bridge.

In addition to the D / A bridges according to the invention, covalent bridges can also be present. In this case, the D / A bridges increase the stereo rigidity and the thermal stability of the catalyst. When changing between closed and open D / A binding are sequence polymers in copolymers with different chemical additives compositions accessible.

The π complex compounds are also characterized by the presence of at least one coordinative bond between donor atom (s) D and acceptor atom (s) A. Both D and A can be substituents of their respective π systems πI or πII or part of the π system, but at least one of D and A is always part of the π system. The π system is understood here to mean the entire π system, which may be condensed once or twice. This results in the following embodiments:

• - D is part of the π system, A is a substituent of the π system;
• - D is a substituent of the π system, A is part of the π system;
• - D and A are part of their respective π system.

Examples include the following heterocyclic ring systems in which D or A are part of the ring system:

Important heterocyclic ring systems are those with (a), (b), (c), (d), (g), (m), (n) and (o) designated systems; particularly important are those designated by (a), (b), (c) and (m).

In the event that one of D and A is a substituent of its associated ring system the ring system 3-, 4-, 5-, 6-, 7- or 8-membered with or without electric charge, which in can be further substituted and / or condensed in the manner indicated. Are preferred 5- and 6-membered ring systems. The negatively charged cyclo is particularly preferred pentadienyl system.  

The first and the second π system πI and πII, if it is designed as a ring system, In the event that one of D and A is a substituent of the ring system, CpI or CpII correspond.

Possible donor groups are, in particular, those in which the donor atom D is an element of the 5th, 6th or 7th, preferably the 5th or 6th main group of the Periodic Table of the Elements (Mendeleev) and has at least one lone pair of electrons and wherein the donor atom is in the case of elements of the 5th main group in a binding state with substituents and can be in the case of elements of the 6th main group; Donor atoms of the 7th main group have no substituents. This is illustrated using the example of phosphorus P, oxygen O and chlorine Cl as donor atoms as follows, where "Subst." such mentioned substituents and "-Cp" represent the bond to the cyclopentadienyl-containing carbanion, a dash with an arrow, the meaning given in formula (I) has a coordinative bond and other dashes mean existing electron pairs:

Acceptor groups are primarily those whose acceptor atom A occurs Element from the 3rd main group of the Periodic Table of the Elements (Mendeleev), such as boron, aluminum, gallium, indium and thallium, are in a bond state with substituents and has an electron gap.

D and A are linked by a coordinative bond, with D a positive (Partial) charge and A assume a negative (partial) charge.

It is accordingly between the donor atom D and the donor group or between distinguished the acceptor atom A and the acceptor group. The coordinative Bond D → A is between the donor atom D and the acceptor atom A manufactured. The donor group means the unit from the donor atom D, the  any substituents and electron pairs present; accordingly, the acceptor group means the unit from the acceptor atom A, Substituents and the existing electron gap.

The bond between the donor atom or the acceptor atom and the cyclopentadienyl-containing carbanion can be interrupted by spacer groups in the sense of D-spacer-Cp or A-spacer-Cp. In the third of the above formula examples, = C (R) - represents such a spacer between O and Cp. Examples of such spacer groups are:
Dimethylsilyl, diethylsilyl, di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, di-t-butyl silyl, di-n-hexylsilyl, methylphenylsilyl, ethylmethylsilyl, diphenylsilyl, di- (pt-butylphenethylsilylmyl), n- Cyclopentamethylene silyl, cyclotetra methylene silyl, cyclotrimethylene silyl, dimethylgermanyl, diethylgermanyl, phenylamino, t-butylamino, methylamino, t-butylphosphino, ethylphosphino, phenylphosphino, methylene, dimethylmethylene (i-propylidene), diethylmethylene, ethylene, dimethyl, ethylene, dimethyl, ethylene, dimethyl Dimethylpropylene, diethylpropylene, 1,1-dimethyl-3,3-dimethylpropylene, tetramethyldisiloxane, 1,1,4,4-tetramethyldisilylethylene, diphenylmethylene.

D and A are preferably without a spacer on the cyclopentadienyl-containing Carbanion bound.

D and A can independently on the cyclopentadiene (yl) ring or a fused benzene ring or fused heterocycle or another Substitutes of CpI or CpII or πI / πII sit. In the case of several D or A can take various of the above positions.

Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te and on the acceptor atoms B, Al, Ga, In and Tl are, for example: C ₁ -C ₁₂ (cyclo) alkyl, such as Methyl, ethyl, propyl, i-propyl, cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, the isomeric heptyls, octyls, nonyls, decyls, undecyls, dodecyls; the corresponding C ₁ -C ₁₂ alkoxy groups; Vinyl, butenyl, allyl; C ₆ -C ₁₂ aryl, such as phenyl, naphthyl or biphenylyl, benzyl, which are substituted by halogen, 1 or 2 C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, nitro or haloalkyl groups, C ₁ -C ₆ - Alkyl-carboxy, C ₁ -C ₆ -alkyl-carbonyl or cyano can be substituted (e.g. perfluorophenyl, m, m'-bis (trifluoromethyl) phenyl and analogous substituents familiar to the person skilled in the art); analog aryloxy groups; Indenyl; Halogen such as F, Cl, Br and I, 1-thienyl, disubstituted amino such as (C ₁ -C ₁₂ alkyl) ₂ amino, diphenylamino, (C ₁ -C ₁₂ alkyl) (phenyl) amino, (C ₁ -C ₁₂ - alkylphenyl) amino, tris (C ₁ -C ₁₂ alkyl) silyl, NaSO ₃ aryl such as NaSO ₃ phenyl and NaSO ₃ tolyl, C ₆ H ₅ -C∼C-; aliphatic and aromatic C ₁ -C ₂₀ silyl, the alkyl substituents of which may be octyl, decyl, dodecyl, stearyl or eicosyl in addition to the abovementioned and the aryl substituents which may be phenyl, tolyl, xylyl, naphthyl or biphenylyl; and those substituted silyl groups which are bonded to the donor atom or the acceptor atom via -CH ₂ -, for example (CH ₃ ) ₃ SiCH ₂ -, C ₆ -C ₁₂ aryloxy with the above-mentioned aryl groups, C ₁ -C ₈ - Perfluoroalkyl, perfluorophenyl. Preferred substituents are C ₁ -C ₆ alkyl, C ₅ -C ₆ cycloalkyl, phenyl, tolyl, C ₁ -C ₆ alkoxy, C ₆ -C ₁₂ aryloxy, vinyl, allyl, benzyl, perfluorophenyl, F, Cl , Br, di (C ₁ -C ₆ alkyl) amino, diphenylamino.

Donor groups are those in which the lone pair of electrons is located at N, P, As, Sb, Bi, O, S, Se, Te, F Cl, Br, I; N, P, O, S are preferred thereof. Examples of donor groups are: (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (C ₃ H ₇ ) ₂ N-, (C ₄ H ₉ ) ₂ N-, (C ₆ H ₅ ) ₂ N-, (CH ₃ ) ₂ P-, (C ₂ H ₅ ) ₂ P-, (C ₃ H ₇ ) ₂ P-, (iC ₃ H ₇ ) ₂ P-, (C ₄ H ₉ ) ₂ P-, (t- C ₄ H ₉ ) ₂ P-, (cyclohexyl) ₂ P-, (C ₆ H ₅ ) ₂ P-, CH ₃ O-, CH ₃ S -, C ₆ H ₅ S-, -C (C ₆ H ₅ ) = O, -C (CH ₃ ) = O, -OSi (CH ₃ ) ₃ , -OSi (CH ₃ ) ₂ -t-butyl, in which N and P each carry a free electron pair and O and S each carry two free electron pairs and where in the last two examples the double bonded oxygen is bonded via a spacer group, and systems such as the pyrrolidone ring, the ring members other than N also being used act as a spacer.

Acceptor groups are those in which there is an electron pair gap at B, Al, Ga, In or Tl, preferably B, Al or Ga; Examples include: (CH ₃ ) ₂ B-, (C ₂ H ₅ ) ₂ B-, H ₂ B-, (C ₆ H ₅ ) ₂ B-, (CH ₃ ) (C ₆ H ₅ ) B-, (Vinyl) ₂ B-, (Ben cyl) ₂ B-, Cl ₂ B-, (CH ₃ O) ₂ B-, Cl ₂ Al-, (CH ₃ ) Al-, (iC ₄ H ₉ ) ₂ Al- , (Cl) (C ₂ H ₅ ) ₂ Al-, (CH ₃ ) ₂ Ga, (C ₃ H ₇ ) ₂ Ga, ((CH ₃ ) ₃ Si-CH ₂ ) ₂ Ga, (vinyl) ₂ Ga, (C ₆ H _{5) 2} Ga, (CH _{3) 2} In, ((CH _{3) 3} Si-CH _{2) 2} Germany, (cyclopentadienyl) ₂ home. Furthermore, of the species mentioned are those in which 1 or more H atoms have been replaced by fluorine.

Donor and acceptor groups which contain chiral centers or in which 2 substituents form a ring with the D or A atom are also suitable. Examples include

Preferred donor-acceptor bridges between CpI and CpII are for example the following:

One or both π systems πI and πII can be present as a heterocycle in the form of the above ring systems (a) to (r). D is preferably an element of the 5th or 6th main group of the Periodic Table of the Elements (Mendeleev); A is preferred here boron. Individual examples of such hetero-π systems, especially heterocycles, are:

R, R '= H, alkyl, aryl, alkaryl z. B. methyl, ethyl, t-butyl, phenyl, o, o'-di- (i- Propyl) phenyl.

Examples of heterocycles are: pyrrolyl, methylpyrrolyl, dimethylpyrrolyl, tri methylpyrrolyl, tetramethylpyrrolyl, t-butylpyrrolyl, di-t-butylpyrrolyl, indolyl, Me thylindolyl, dimethylindolyl, t-butylindolyl, di-t-butylindolyl, tetramethylphospholyl, Tetraphenylphospholyl, triphenylphospholyl, trimethylphospholyl, phosphaindenyl, Dibenzophospholyl (phosphafluorenyl), dibenzopyrrolyl.

Preferred donor-acceptor bridges between πI and πII are, for example, the following: N → B, N → Al, P → B, P → Al, O → B, O → Al, Cl → B, Cl → Al, C = O → B, C = O → Al, whereby both atoms of these donor-acceptor bridges are parts of a hetero Systems can be or an atom (donor or acceptor) is part of a π system and the other substituent of the second π system is or where both atoms are substituents of their respective ring and one of the rings additionally contains a hetero atom.

The two ligand systems πI and πII can, as shown above, by a two or three donor-acceptor bridges are linked. This is possible because According to the invention, the formula (Ia) contains the D → A bridge shown, the ligand Systems πI and πII but other D and A as substituents or hetero π centers can wear; the number of resulting additional D → A bridges is Zero, one or two. The number of D or A substituents on πI or πII can be the same or different. The two ligand systems πI and πII can additionally be covalently bridged. (Examples of covalent bridges are above as Spacer groups are described.) However, preference is given to compounds without covalent ones  Bridge in which πI and πII are linked by only one donor-acceptor bridge are.

M stands for a transition metal from the 3rd, 4th, 5th or 6th subgroup of the Periodic table of the elements (Mendeleev), including the lanthanides and Actinides; Examples include: Sc, Y, La, Sm, Nd, Lu, Ti, Zr, W Th, V, Nb, Ta, Cr. Ti, Zr, Hf, V, Nb are preferred.

When the metallocene structure or the π-complex structure is formed, a positive charge of the transition metal M is compensated for by a cyclopentadienyl-containing carbanion. Any remaining positive charges on the central atom M are saturated by further, mostly monovalent anions X, of which two identical or different anions can also be linked to one another, for example monovalent or divalent negative radicals of the same or different, linear or branched, saturated or unsaturated hydrocarbons, Amines, phosphines, thio alcohols, alcohols or phenols. Simple anions such as CR ₃ ⁻, NR ₂ ⁻, PR ₂ ⁻, OR⁻, SR⁻ etc. can be connected by saturated or unsaturated hydrocarbon or silane bridges, whereby dianions arise and the number of bridge atoms 0, 1, 2 , 3, 4, 5, 6, 0 to 4 bridge atoms are preferred, particularly preferably 1 or 2 bridge atoms. In addition to H atoms, the bridge atoms can also carry further KW substituents R. Examples of bridges between the simple anions are about -CH ₂ -, -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, CH = CH, - (CH = CH) ₂ -, -CH = CH-CH ₂ -, CH ₂ -CH = CH-CH ₂ -, -Si (CH ₃ ) ₂ -, C (CH ₃ ) ₂ -. Examples of X are: hydride, chloride, methyl, ethyl, phenyl, fluoride, bromide, iodide, the n-propyl radical, the i-propyl radical, the n-butyl radical, the amyl radical, the i-amyl radical, the hexyl radical, the i- Butyl radical, the heptyl radical, the octyl radical, the nonyl radical, the decyl radical, the cetyl radical, methoxy, ethoxy, propoxy, butoxy, phenoxy, dimethylamino, diethylamino, methylethylamino, di-t-butylamino, diphenylamino, diphenylphosphino, dicyclohexylphosphino, methyl denimophosphino , Ethylidene, propylidene, the ethylene glycol dianion. Examples of dianions are 1,4-diphenyl-1,3-butadiene diyl, 3-methyl-1,3-pentadiene diyl, 1,4-dibenzyl-1,3-butadiene endiyl, 2,4-hexadiene diyl, 1,3-pentadiene diyl , 1,4-ditolyl-1,3-butadiene diyl, 1,4-bis (tri methylsilyl) -1,3-butadiene diyl, 1,3-butadiene diyl. 1,4-Diphenyl-1,3-butadienediyl, 1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 3-methyl-1,3-pentadienediyl are particularly preferred. 1,4-ditolyl-1,3-butadiene diyl and 1,4-bis (trimethylsilyl) -1,3-butadiene diyl. Other examples of dianions are those with heteroatoms, such as structure
respectively. ,
where the bridge has the meaning given. In addition, weak or non-coordinating anions of the type mentioned above are particularly preferred for charge compensation.

Activation by such voluminous anions is achieved, for example, by Implementation of the D / A π complex compounds, especially the D / A metallocenes with tris (pentafluorophenyl) borane, triphenyl borane, triphenyl aluminum, trityl tetra kis (pentafluorophenyl) borate or N, N-dialkylphenylammonium tetrakis (penta fluorophenyl) borate and the corresponding alanes and alanates or the ent speaking phosphonium or sulfonium salts of borates or alanates or (Earth) alkali, thallium or silver salts of borates, alanates, carboranes, Tosylates, triflates, perfluorocarboxylates, such as trifluoroacetate, or the corresponding ones the acids. D / A metallocenes, their anion, are preferably used Equivalent X = alkyl, allyl, aryl, benzyl groups. Such derivatives can also be made "in situ" by combining D / A metallocenes with others Anion equivalents such as X = F, Cl, Br, OR etc. previously with aluminum alkyls, lithium organylene or Grignard compounds or zinc or lead alkylene. The reaction products obtainable therefrom can be used without prior isolation above boranes, borates, alanes or alanates are activated.

Depending on the charge of M, the index n takes the value zero, one, two, three or four, preferably zero, one or two. The above-mentioned subgroup metals can namely, depending on their belonging to the subgroups, valences / charges from two to six, before accepting two to four, of which two are compensated for by the carbanions of the metallocene compound. In the case of La ³⁺ , the index n takes on the value one and in the case of Zr ⁴⁺ the value two. with Sm ²⁺ n = zero.

To prepare the metallocene compounds of the formula (I), either one compound each of the above formulas (II) and (III) or one compound each of the above formulas (IV) and (V) or one compound each of the above formulas (VI ) and (VII) or a compound of the above formulas (VIII) and (III) or a compound of the above formulas (IV) and (IX) or a compound of the above formulas (X) and (VII) with or without leaving Elimination of alkali metal X, alkaline earth metal X ₂ , silyl X, germyl X, stannyl X or HX compounds in an aprotic solvent at temperatures from -78 ° C. to + 120 ° C., preferably from -40 ° C to + 70 ° C and in a molar ratio of (II): (III) or (IV): (V) or (VI): (VII) or (VIII): (III) or (IV): (IX) or (X): (VII) of 1: 0.5-2, preferably 1: 0.8-1.2, particularly preferably 1: 1, react with one another. In the cases where (VIII) is reacted with (III) or (IV) with (IX) or (X) with (VII), it is possible to dispense with an aprotic solvent if (VIII), (IX) or (X) is liquid under the reaction conditions. Examples of such leaking or cleaved compounds are: TlCl, LiCl, LiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl ₂ MgBr ₂ , CaCl ₂ , CaF ₂ , trimethylchlorosilane, triethylchlorosilane, tri- (n-butyl) -chloro silane, triphenylchlorosilane, trimethylchloro-german, trimethylchloro-stannane, dimethylamine, diethylamine, dibutylamine and other compounds which can be recognized by the person skilled in the art from the substitution pattern mentioned above.

Compounds of the formula (II) or (IV) are therefore carbanions with a cyclopentadienyl skeleton or a heterocyclic skeleton which contain 1 to 3 donor groups used for D / A bridging covalently bonded or incorporated as heterocyclic ring members and as counterions to the negative ones Charge of the cyclopentadienyl skeleton have a cation. Compounds of the formula (VIII) are uncharged cyclic structures with 1 to 3 donor groups also used for D / A bridging, but with easily removable leaving groups E (R ¹ R ² R ³ ), such as silyl, germyl or stannyl groups or hydrogen, in place of the ionic groups.

The second component for the formation of the metallocene compounds to be used according to the invention, namely the compound of the formula (III) or (V) likewise represents a carbanion with a cyclopentadienyl skeleton which is the same as the cyclopentadienyl skeleton of the compound (II) or (IV) or is different from it, but carries 1 to 3 acceptor groups instead of the donor groups. Correspondingly, compounds of the formula (IX) are uncharged cyclopentadiene skeletons with 1 to 3 acceptor groups and likewise easily removable leaving groups F (R ⁴ R ⁵ R ⁶ ).

Compounds of the formulas (VI) and (X) exhibit in a completely analogous manner materials with a pre-formed D → A bond, the carbanion countercations Compounds or uncharged cyclopentadiene frameworks with a total of 1 possible to 3 mean D → A bonds and by reaction with compounds of the formula (VII) the metallocene compounds (I) result.

Both starting materials of the manufacturing process, namely (II) and (III) or (IV) and (V) or (VI) and (VII) or (VIII) and (III) or (IV) and (IX) or (X) and (VII) react spontaneously when they are combined, with the simultaneous formation of the donor-acceptor group -D → A- or the complexation of the metal cation M with the escape of M'X and E (R ¹ R ² R ³ ) X or F (R ⁴ R ⁵ R ⁶ ) X or HX. In the illustration of the donor-acceptor group, the substituents on D and A have been omitted for the sake of clarity.

M 'is a cation equivalent of an (earth) alkali metal such as Li, Na, K, ½ Mg, ½ Ca, ½ Sr, ½ Ba, or thallium.

In the manner indicated above, the compounds of the formula (XIII a + b) manufactured.

Solvents for the manufacturing process are aprotic, polar or non-polar Solvents such as aliphatic and aromatic hydrocarbons or aliphatic and aromatic halogenated hydrocarbons. In principle, there are more aprotic solvents as are known to the person skilled in the art; in question, however  because of the easier processing, those with too high boiling points less prefers. Typical examples are: n-hexane, cyclohexane, pentane, heptane, Petroleum ether, toluene, benzene, chlorobenzene, methylene chloride, diethyl ether, Tetrahydrofuran, ethylene glycol dimethyl ether.

The starting materials of formulas (II), (III), (IV) and (V) can be according to literature known methods or can be produced analogously to these. So you can at for example analogous to J. of Organometallic Chem. (1971), 29, 227, the marketable Trimethylsilyl-cyclopentadiene first with butyl lithium and then with trimethyl Convert silyl chloride to bis (trimethylsilyl) cyclopentadiene. This in turn can be done with Boron trichloride can be converted to trimethylsilyl-cyclopentadienyl-dichloroborane (analog to J. of Organometallic Chem. (1979), 169, 327), which finally analog to J. of Organometallic Chem. (1979), 169, 373 with titanium tetrachloride for Dichloroboryl-cyclopentadienyl-titanium trichloride can be implemented. This last the compound mentioned already represents a prototype of the compounds of the formula (III) dar; the latter compound can continue to be selective with trimethyl aluminum be implemented, the two chlorine atoms connected to the boron atom are replaced by methyl groups and another compound of Formula (III) is shown. Analogous to the process descriptions in J. Am. Chem. Soc. (1983) 105, 3882 and Organometallics (1982) 1, 1591 may be the marketable Cyclopentadienyl thallium with chloro-diphenylphosphine and further with butyl lithium be implemented, whereby a prototype of compounds of formula (II) receives. Another example is the formation of dimethylstannyl diphenyl phosphine indene by reacting indene initially with butyl lithium, as above already mentioned, and then named with chlorodiphenylphosphine; the further Implementation, first again with butyl lithium and then with chloro-tributyl tin the compound mentioned, which after further reaction with zirconium tetrachloride Diphenylphosphino indenyl zirconium trichloride as a representative of compounds of the formula (IV). Such syntheses and production methods are on the Specialist in the field of organometallic and organic chemistry common and published in numerous references, only a few of which are listed above were given as examples.  

The examples below show how such heterocyclic precursors or catalysts of the invention are accessible. So pyrrolyl lithium (Formula II) can be prepared from pyrrole by reaction with butyl lithium, such as in J. Amer. Chem. Soc. (1982), 104, 2031. Trimethylstannyl phosphole (formula VIII) is obtained by reacting 1-phenylphosphole with Lithium, followed by aluminum trichloride, whereby phospholyl lithium (formula II) arises, which in turn with trimethylchlorostannan to trimethylstannyl phosphol reacted further. See: J. Chem. Soc. Chem. Comm. (1988), 770. This Compound can be converted into phospholyl titanium trichloride (Formula IV) with titanium tetrachloride be implemented.

10 ¹ to 10 ¹² mol of comonomers are reacted per mole of π-complex compounds or metallocene compounds. The π-complex compounds or metallocene compounds can be used together with cocatalysts. The quantitative ratio between metallocene compound or π complex compound and cocatalyst is 1 to 100,000 mol cocatalyst per mol metallocene or π complex compound. Cocatalysts are, for example, aluminoxane compounds. These include those of the formula

understood in the
R represents C ₁ -C ₂₀ alkyl, C ₆ -C ₁₂ aryl or benzyl and
n is a number from 2 to 50, preferably 10 to 35.

It is also possible to use a mixture of different aluminoxanes or a mixture of their precursors (aluminum alkyls) in combination with water (in gaseous, liquid, solid or bound form, such as water of crystallization). The  Water can also be the (residual) moisture of the polymerization medium, the monomer or a carrier such as silica gel. Those analogous to formula (XII) Boron compounds are also suitable.

The bonds protruding from the square brackets of formula (XII) contain R groups or AlR ₂ groups as end groups of the oligomeric aluminoxane. Such aluminoxanes are generally present as a mixture of several of them with different chain lengths. The fine examination has also revealed aluminoxanes with an annular or cage-like structure. Aluminoxanes are common compounds. In the special case of R = CH ₃ , one speaks of methylaluminoxanes (MAO).

Other cocatalysts are aluminum alkyls, lithium alkyls or organic Mg Compounds such as Grignard compounds or partially hydrolyzed bororganyls. Be preferred cocatalysts are aluminoxanes.

The activation with the cocatalyst or the generation of the voluminous non- or weakly coordinating anions can be in the autoclave or in a separate reaction vessel (preforming) can be carried out. The activation can be in the presence or absence of the monomer (s) to be polymerized respectively. The activation can be in an aliphatic or aromatic or halogenated solvents or suspending agents are carried out.

The π-complex compounds or metallocene compounds and the aluminoxanes can be used both as such in homogeneous form and individually or together in heterogeneous form on supports. The carrier material can be inorganic or organic in nature, such as silica gel, Al ₂ O ₃ , B ₂ O ₃ , MgCl ₂ , NaCl, polysiloxanes, cellulose derivatives, starch derivatives and other polymers. In this case, both the π-complex compound or metallocene compound and also the aluminoxane can be placed on the support and the other component can then be added. Equally, however, one can also activate the π-complex compound or metallocene compound in homogeneous or heterogeneous form with the aluminoxane and then apply the activated metallocene compound to the support.

Carrier materials are preferably thermally and / or chemically pretreated in order to adjust the water content or the OH group concentration in a defined manner or to keep it as low as possible. Chemical pretreatment can e.g. B. In order to implement the support with aluminum alkyl. Inorganic carriers are usually heated to 100 ° C to 1000 ° C for 1 to 100 hours before use. The surface area of such inorganic supports, in particular of silica (SiO ₂ ), is between 10 and 1000 m ² / g, preferably between 100 and 800 m ² / g. The particle diameter is between 0.1 and 500 micrometers (µ), preferably between 10 and 200 µ.

Examples of olefins and diolefins to be reacted by (co) polymerization are Ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, 3-methyl-butene-1, 4- Methyl-pentene-1, 4-methyl-hexene-1, 1,4-hexadiene, 1,5-hexadiene and 1,6-octadiene, 1,7-octadiene, branched, non-conjugated dienes and others to those skilled in the art known. Such olefins and diolefins can furthermore be substituted, for example with phenyl or substituted phenyl; Such connections are for example styrene, vinylsilane, trimethylallylsilane. Preferred monomers are: Ethylene, propylene, butene, hexene, octene, 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene and methyl substituted octadienes with a terminal double bond, such as 7-methyl-1,6-octadiene.

In addition, α-olefins with up to 20 C atoms are fundamentally possible. In cases where α-olefins with 2 to 4 C atoms are involved, along with higher α-olefins, dienes or other comonomers, the C ₂ -C ₄ -α-olefins are present in a proportion of 25 to 95% by weight, preferably 30 up to 80 wt .-%, based on the total weight. In contrast, about 1-octene is present in an amount of 5 to 35% by weight, preferably 7.5 to 25% by weight. Furthermore, 0.1 to 20% by weight of one or more of the diolefins mentioned is present.

In addition to the dienes mentioned, they are wider than open-chain, mono- and polycyclic called the following: 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene; Cyclo pentadiene, 1,4-hexadiene, 1,5-cyclooctadiene; Tetrahydroinden, methyl tetrahydro inden, dicyclopentadiene, bicyclo- (2,2,1) -heptadiene (2,5), norbornenes with substi tuenten such as alkenyl, alkylidene, cycloalkenyl, cycloalkylidene, such as 5-methylene-2-nor boron (MNB), 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-nor borne; Allylcyclohexene, vinyl cyclohexene.

Other preferred monomers in addition to the above are: dicyclopentadiene, 1,4-hexadiene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-nor borne. Mixtures of several of these can of course be used.

The process according to the invention is carried out in bulk, solution, high temperature Solution, slurry or gas phase performed, depending on whether a soluble or a insoluble catalyst of the type described above is used. The solution phase or the slurry phase can be obtained from the comonomers alone, i.e. H. without use formation of an additional solvent. In the event that a If solvents are used, inert solvents are used for example aliphatic or cycloaliphatic hydrocarbons, such as propane, Butane, pentane, hexane, cyclohexane, propene (which is also a (co) monomer), Gasoline or diesel oil fractions (if necessary after a hydrogenation), toluene, Chlorobenzene, o-dichlorobenzene or chloronaphthalene in question. With solvents with low boiling point can be achieved by applying sufficient reaction pressure for compliance with the liquid phase must be ensured; such relationships are the Known specialist. According to the invention, one or more reactors or Reaction zones, e.g. B. in reactor cascades, worked under different Polymerization conditions can be worked.

The temperatures and pressures mentioned above are used. For the Bulk, solution and slurry procedures are temperatures in the range of about 0 to 150 ° C, for the high temperature liquid procedure 40 to 200 ° and for the gas phase, about 20 to 100 ° C applied. The pressures exceed economic reasons often not the value of 30 bar, preferably 20 bar. He  According to the invention in one or more reactors or reaction zones, for. B. in a reactor cascade, worked; in the case of several reactors, different ones Polymerization conditions can be set.

Elastomers which can be produced according to the invention are, for example, those of the type Ethylene-propylene copolymer (EPM), ethylene-butene copo (EBM), ethylene-pentene Copo, ethylene-hexene copo (EHM), ethylene-heptene copo, ethylene-octene copo (EOM), ethylene-propylene-butene copo which does not contain any crosslinking monomers, as well as ethylene-propylene-diene copo (EPDM), ethylene-butene-diene copo (EBDM), Ethylene-hexene (or octene) -diene copo (EHDM or EODM) with crosslinker monomers such as with ethylidene norbornene; the proportion of crosslinking monomers, e.g. B. of diene is up to 20% by weight of all comonomers, e.g. B. 0.1 to 20% by weight, preferably 1 to 12% by weight, particularly preferably 2 to 8% by weight. Preferred Elastomers are those of the EPM and EPDM types.

Such elastomers are distinguished by good elasticity even at low temperatures, by at least partially amorphous structure (moderate or low crystallinity, such a degree of crystallinity of less than 30%, preferably less than 20%, particularly preferably less than 10%, measured according to those known in the art Methods, especially DSC) with a low glass transition temperature Tg. Tg is preferably below -20 ° C, particularly preferably below -40 ° C. They have molar masses M _w of greater than 10 kg / mol, preferably greater than 100 kg / mol, particularly preferably greater than 200 kg / mol. M _w values of up to 10,000 kg / mol, in particular up to 5,000 kg / mol, can be achieved. According to the invention, it is in particular possible to achieve the high molecular weights mentioned and to achieve a uniform distribution of the comonomers. The uniform distribution enables high quality crosslinking during vulcanization in the case of dienes or other crosslinkable comonomers. It is also possible to obtain long-chain branched products. All elastomers that can be produced according to the invention are primarily characterized by one or more melting peaks. At least one of these melting peaks has its peak maximum at a melting temperature T _m above + 40 ° C, preferably above + 50 ° C, particularly preferably above + 60 ° C. Such melting peaks are further characterized by their full width at half maximum. At least one of the melting peaks preferably has a full width at half maximum of at most 30 ° C. The elastomers which can be produced according to the invention have an improved green strength.

The π-complex compounds to be used according to the invention, especially those Metallocene compounds enable a through the donor-acceptor bridge defined opening of the two cyclopentadienyl frameworks in the manner of a beak, in addition to high activity, controlled selectivity, controlled Molecular weight distribution and a uniform incorporation of (co) monomers are guaranteed. Due to a defined beak-like opening there is also space for voluminous (co) monomers. A high uniformity in molecular weight Distribution continues to result from the uniform and defined location of the Polymerization (Single Site Catalyst).

The molecular weight distribution can be specifically changed (broadened) by you use several D / A catalysts at the same time in order to Property profile. Accordingly, it is also possible to use one or several D / A catalysts in combination with other metallocenes that do not contain D / A Show bridge to use.

The D / A structure can be an extra stabilization of the catalysts up to high Cause temperatures, so that the catalysts even in the high temperature range from 80 to 250 ° C, preferably 80 to 200 ° C, can be used. The possible thermal dissociation of the donor-acceptor bond is reversible and does this self-organization process and self-repair mechanism too special high-quality catalyst properties.

It was also observed that metallocene compounds to be used according to the invention show different copolymerization behavior as a function of the temperature. This phenomenon has not yet been fully investigated, but could be consistent with the observation that coordinative bonds overlaid by an ionic bond, such as the donor-acceptor bonds in the metallocene compounds of the invention, show increasing reversibility at higher temperatures . In ethylene-propylene copolymerization, for example, it has been observed that with the same offer of both comonomers, a copolymer containing high propylene is formed at a low copolymerization temperature, while the propylene content decreases with increasing polymerization temperature, until finally at high temperature, predominantly ethylene-containing polymers are formed. The reversible dissociation and association of the D / A structure and the resulting possible rotation of the Cp frameworks against each other can be represented schematically as follows:

Another valuable property of the D / A π complex compound according to the invention dung, for example D / A metallocene compounds, is the possibility of Self-activation and thus a waiver of expensive catalysts, especially in the Case of Dianionic

Here, the acceptor atom A in the opened form of the D / A-π-complex compounds, for example D / A-metallocene compound, binds an X ligand, for example one side of a dianion, with the formation of a zwitterionic metallocene structure and thus generates a positive charge for the transition metal, while the acceptor atom A assumes a negative charge. Such self-activation can take place intramolecularly or intermolecularly. The intramolecular mechanism is illustrated using the example of the preferred linkage of two X ligands to form a chelate ligand, namely the butadiene diyl derivative:

The binding site between the transition metal M and H or substituted or unsubstituted C, substituted C in the molded example of the butadiene diyl shown Dianions is then the site for the olefin insertion for polymerization.

Fig. 1a-e show examples of DSC measurements of the 2nd heating on EPDM samples of the present invention. Fig. 1a represents an amorphous EPDM type with a small melting peak above 50 ° C and a melting enthalpy of only 2-3 J / g corresponding to a crystallinity ≦ 1%. Fig. 1b shows a partially crystalline type with a pronounced melting peak above 90 ° C and a melting enthalpy of approx. 29 J / g corresponding to a crystallinity of approx. 10%.

Fig. 1c embodies a semi-crystalline type with low-temperature crystallinity (T _m1 = -10 ° C, ΔH _m = 15 J / g) and a discrete melting peak T _{m2 according} to the invention at 126 ° C. Fig. 1d shows a semi-crystalline material with a low glass transition temperature T _g = -54 ° C and a discrete melting peak at 100 ° C, which represents about 3% crystallinity (ΔH _m = 8 J / g). Fig. 1e shows a rubber with T _g = -52 ° C with a high temperature crystallinity of approx. 4% and T _m = 112 ° C.

Fig. 1f relates to the EPDM from Example 7.

Examples

All reactions were carried out under strictly anaerobic conditions and using Schlenk techniques or the high vacuum technique. The solvents used were dry and saturated with argon. Chemical shifts δ are given in ppm, relative to the respective standard: ¹ H (tetramethylsilane), ¹³ C (tetramethylsilane), ³¹ P (85% H ₃ PO ₄ ), ¹¹ B (boron trifluoride etherate δ = -18.1 ppm ). Negative signs mean a shift to a higher field.

example 1 (Bis (trimethylsilyl) cyclopentadiene, compound 1)

14.7 g (0.106 mol) of trimethylsilylcyclopentadiene (obtained from Fluka) and 150 ml of tetrahydrofuran (THF) were placed in a reaction flask and cooled to 0.degree. 47.4 ml of a solution of butyl lithium in n-hexane (2.3 molar; total amount 0.109 mol) were added dropwise over the course of 20 minutes. After the addition was complete, the yellow solution was stirred for a further hour; the cold bath was then removed. The solution was stirred at room temperature for a further hour and then cooled to -20 ° C. Then 14.8 ml (0.117 mol) of trimethylsilyl chloride were added dropwise over 10 minutes and the reaction mixture was stirred at -10 ° C. for two hours. The cooling bath was then removed and the reaction solution was warmed to room temperature and stirred for a further hour. The reaction mixture was filtered through Celite; the filter was washed with hexane and the hexane was removed from the combined filtrates in vacuo. The crude product, when distilled at 26 ° C. under 0.4 mbar, gave 19 g of pure product of compound 1 (85% of the theoretical yield). Boiling point and NMR data correspond to the literature data (J. Organometallic Chem. 29 (1971), 227; ibid. 30 (1971), C 57; J. Am. Chem. Soc, 102 (1980), 4429; J. Gen. Chem. USSR, Eng. Transl. 43 (1973), 1970; J. Chem. Soc., Dalton Trans. 1980, 1156).
¹ H NMR (400 MHz, C ₆ D ₆ ): δ = 6.74 (m, 2H), 6.43 (m, 2H), -0.04 (s, 18H).

Example 2 (Trimethylsilyl-cyclopentadienyl-dichloroborane, compound 2)

16 g (0.076 mol) of compound 1 were placed in a round-bottom flask equipped with a dry ice cooling bath. 8.9 g (0.076 mol) of BCl ₃ were condensed in a Schlenk tube at -78 ° C. and then added dropwise to the round-bottom flask over a period of 5 minutes. The reaction mixture was slowly warmed to room temperature over 1 hour and then held at 55-60 ° C for an additional 2 hours. All volatile compounds were removed in vacuo (3 mm Hg = 4 mbar). The subsequent distillation at 39 ° C. and 0.012 mbar gave 14.1 g of compound 2 (85% of the theoretical yield). The ¹ H-NMR agrees with the literature and showed that a number of isomers had been produced (see J. Organometallic Chem. 169 (1979), 327). ¹¹ B NMR (64.2 MHz, C ₆ D ₆ ): δ = +31.5.

Example 3 (Tributylstannyl-diphenylphosphino-indene, compound 3)

10 g (0.086 mol) of indene were placed in a round bottom flask, diluted with 200 ml of diethyl ether and cooled to -20 ° C. 36 ml of a 2.36 molar solution of butyl lithium (0.085 mol) in n-hexane were added to this solution, the solution immediately taking on a yellow color. The cold bath was removed and the reaction mixture was allowed to warm to room temperature and the reaction mixture was stirred for an additional hour. The reaction mixture was then cooled back to 0 ° C and 19 g (15.9 ml, 0.086 mol) of diphenylchlorophosphine was added to form a precipitate. The cold bath was removed again and the solution was allowed to warm to room temperature while stirring was continued for another hour. The solution was then cooled again to -20 ° C. and 36 ml (0.085 mol) of butyl lithium in n-hexane were added dropwise. After the addition had ended, the cooling bath was removed again and the temperature rose to room temperature; the solution was stirred for a further 1.5 hours. The slurry was then cooled again to 0 ° C and 28 g (0.086 mol) tributyltin chloride was added dropwise. The resulting slurry was warmed to room temperature and stirred for an additional 1.5 hours, then filtered through a frit and the solvent removed in vacuo. 46.9 g of compound 3 (92% of the theoretical yield) remained as a heavy yellow oil.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.5-7.3 (m, 6H), 7.28 (br s, 6H), 7.14 (pseudo-d t, 7.3 Hz / 1.0 Hz, 1H), 7.08 (t, J = 7.3 Hz, 1H), 6.5 (br m, 1H), 4.24 (br s, 1H), 1.4-1 , 25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J = 7.2 Hz, 9H), 0.53 (t, J = 8 Hz, 6H) , ³¹ P NMR (161.9 MHz, CDCl ₃ ): δ = -20.6.

Example 4 (Diphenylphosphino indenyl zirconium trichloride, compound 4)

A solution of 37 g (0.0628 mol) of compound 3 in 300 ml of toluene was converted into a slurry of 14.6 g of ZrCl ₄ (99.9%, 0.0628 mol, obtained from Aldrich) for 3 hours. placed in 100 ml of toluene at room temperature. The solution immediately turned red and slowly turned orange and finally yellow. After stirring for 4 hours, the yellow precipitate was filtered off and washed with toluene and then with hexane. The solid was dried in vacuo to give 15.3 g (50% of the theoretical yield) of Compound 4 as a free flowing yellow powder. The yield could easily be increased to over 70% when working at a lower temperature, e.g. B. 30 min at -30 ° C and 5 hours at 0 ° C. The product could be further purified by washing out the remaining tin compound using pentane in a Soxhlet extractor (extraction time: 8 hours).

Example 5 ((C ₆ H ₅ ) ₂ P-BCl ₂ -bridged indenyl-cyclopentadienyl-zirconium di chloride, compound 5)

4.43 g (0.0089 mol) of the purified compound 4 and 100 ml of toluene were placed in a Schlenk tube. To this slurry was added 1.95 g (0.0089 mol) of compound 2. The yellow slurry was stirred at room temperature for 6 hours; a pale white precipitate formed during this time. This precipitate (4.1 g, 75% of the theoretical yield) was collected by filtration and found to be essentially pure material.
¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 7.86 (pseudo ddd, J = 8.5 / 2.5 / 1 Hz, 1H), 7.75-7.55 (m, 10H ), 7.35 (pseudo ddd, J = 8.5 / 6.9 / 0.9 Hz, 1H), 7.32 (br t, J = 3.1 Hz, 1H), 7.22 (pseudo ddd , J = 8.8 / 6.8 / 1.1 Hz, 1H), 7.06 (pseudo ddd, J = 3.4 / 3.4 / 0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H), 6.61 (pseudo q, J = 2.3 Hz, 1H), 6.53 (br d, 8.7 Hz , 1H); ³¹ P NMR (161.9 MHz, CD ₂ Cl ₂ ): δ = 6.2 (br, m); ¹¹ B NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = -18 (br).

Example 6 (Catalyst alkylation)

11 mg (corresponding to 18.10 ^-6 mol) of the donor-acceptor metallocene 5 were weighed into a dry Schlenk vessel under argon and dissolved in 1.8 ml of toluene which contained 1.8 mmol of triisobutylaluminum (TIBA) and stirred for 30 minutes at room temperature . The yellow-brown solution was then diluted with 10 ml of toluene which contained 0.05 mmol of TIBA. An aliquot of this solution, namely 0.65 ml, was used for the polymerization.

Example 7 (EPDM synthesis)

100 ml of dry toluene distilled under inert gas, 1 g of ethylidene norbornene (ENB) distilled over sodium (ENB), 0.1 mmol of TIBA and 10 g of propene were introduced into a dry, oxygen-free 300 ml of V4A steel autoclave and stirred at 80 ° C. with magnetic stirring heated. The internal pressure of approx. 7 bar reached was raised by 2 bar to 9 bar with ethene. Using a pressure lock, 1.10 ^-6 mol of the alkylated D / A metallocene 5 in 0.65 ml of the solution from Example 6 was transferred to the autoclave and the polymerization immediately afterwards by adding 4.10 ^-6 mol (3.2 mg ) N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate in 3.7 ml of argon-saturated chlorobenzene, which had been distilled over calcium hydride, started.

The inside temperature rose to 82 ° C. After 30 minutes of polymerization, the reaction was stopped by adding ethanol, the polymer was precipitated in 500 ml of ethanol / concentrated hydrochloric acid (90/10) and stirred for 1 hour, then filtered off, washed with ethanol and in a vacuum drying cabinet at 90 ° C. until Weight constant dried.
EPDM yield: 3.6 g
Catalyst activity: 7.2 t EPDM per mol catalyst and hour
Intrinsic viscosity (ortho-dichlorobenzene, 140 ° C): 1.08 dl / g
Chemical composition according to FT-IR analysis:
64% by weight ethene
32% by weight propene
4 wt% ENB
DSC (2nd heating):
Freezing temperature: T _e = -53 ° C
Glass temperature: T _g = -47 ° C
Melting temperature: T _m1 = + 18 ° C
T _m2 = + 111 ° C
Width of the 2nd melting peak at half height (half-width): 11 ° C
Enthalpy of fusion ΔH _m = 38 J / g.

Claims (16)

1. A process for the production of saturated or unsaturated elastomers which, in addition to the amorphous structure and a low glass transition temperature Tg, have one or more melting peaks in the DSC measurement, at least one of which has its peak maximum at a melting temperature (T _m ) above + 40 ° C has, by (co) polymerizing monomers from the group of the C ₂ -C ₈ -α-olefins, the open-chain, monocyclic and / or polycyclic C ₄ -C ₁₅ diolefins and styrene in bulk, solution, high Temperature-solution, slurry or gas phase in the presence of organometallic catalysts which can be activated by cocatalysts, characterized in that metallocene compounds of the formula are used as organometallic catalysts
in the
CpI and CpII represent two identical or different carbanions with a cyclopentadienyl-containing structure, in which one to all H atoms by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ alkyl, the 1-fold to completely by halogen , Can be substituted 1 to 3 times by phenyl, and 1 to 3 times by vinyl, C ₆ -C ₁₂ aryl, haloaryl having 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl and 1- or Can be substituted twice by D and A,
D denotes a donor atom which can additionally carry substituents and which has at least one lone pair of electrons in its respective bond state,
A denotes an acceptor atom which can additionally carry substituents and which has one electron pair gap in its respective bond state,
where D and A are linked by a reversible coordinative bond in such a way that the donor group assumes a positive (partial) charge and the acceptor group a negative (partial) charge,
M for a transition metal of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements (Mendeleev) including the lanthanides and actinides,
X represents an anion equivalent and
n is the number zero, one, two, three or four, depending on the charge of M,
or
π complex compounds and in particular metallocene compounds of the formula
in the
πI and πII represent differently charged or electrically neutral π systems which can be condensed once or twice with unsaturated or saturated five or six rings,
D denotes a donor atom which is a substituent of πI or part of the π system of πI and which has at least one lone pair of electrons in its respective bond state,
A denotes an acceptor atom which is a substituent of πII or part of the π system of πII and which has an electron pair gap in its respective bond state,
where D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive (partial) charge and the acceptor group takes on a negative (partial) charge and at least one of D and A is part of the respective π system,
where D and A can in turn bear substituents,
wherein each π system or each fused ring system can contain one or more D or A or D and A and
where in πI and πII in the uncondensed or in the condensed form, one to all H atoms of the π system, independently of one another, by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ -alkyl, the 1-fold to complete can be substituted by halogen, 1 to 3 times by phenyl and 1 to 3 times by vinyl, C ₆ -C ₁₂ aryl, haloaryl with 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl and mono- or can be substituted twice by D and A, so that the reversible coordinative D → A bond (i) between D and A, which are both parts of the respective π system or the fused ring system, or (ii) of which D or A is part of the π system and the other substituent of the uncondensed π system or of the fused ring system or (iii) both D and A are such substituents, in the case of (iii) at least one additional D or A or both Parts of the π system or the condensed ring system is (are) formed,
M and X have the above meaning and
n is the number zero, one, two, three or four, depending on the charges of M and those of πI and πII,
be used. 2. The method according to claim 1, characterized in that the metallocene compounds or the π-complex compounds are used as catalysts in an amount of 10 ¹ to 10 ¹² mol of monomers per mol of metallocene or π-complex compound . 3. The method according to claims 1 and 2, characterized in that at Presence of solvents from the group of saturated and aromatic hydrocarbons or of saturated or aromatic Halogenated hydrocarbons are used. 4. The method according to claims 1 to 3, characterized in that in the metallocene compounds the carbanions CpI and CpII or the π system πI a cyclopentadienyl skeleton from the group of cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene mean in each of which cyclopentadiene or condensed with a benzene ring from 1 to 4 substituents from the group of C ₁ - C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, halogen, C ₆ -C ₁₂ aryl, halophenyl, D and A are present, where D and A have the meaning given in claim 1 and wherein fused aromatic rings can be partially or completely hydrogenated. 5. The method according to claims 1 to 4, characterized in that in the Metallocene compounds as donor atoms D elements from the group N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, I, preferably N, P, O, S, are present. 6. The method according to claims 1 to 5, characterized in that in the Metallocene compounds as acceptor atoms A, elements from group B, Al, Ga, In, Tl, preferably B, Al, Ga are present. 7. The method according to claims 1 to 6, characterized in that in the metallocene compounds or π-complex compounds donor-acceptor bridges from the group of
N → B, N → Al, P → B, P → Al, O → B, O → Al, Cl → B, Cl → Al, C = O → B, C = O → Al
available. 8. The method according to claims 1 to 7, characterized in that in the Metallocene compounds M for Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf, Th, V, Nb, Ta, Cr, preferably stands for Ti, Zr, W V, Nb or Ta. 9. The method according to claims 1 to 8, characterized in that the metal locen compounds or the π complex compounds together with a Aluminoxane, alan or alanate, a borane or borate and optionally  with further cocatalysts and / or metal alkyls as the catalyst system be used. 10. The method according to claims 1 to 9, characterized in that levy tion products of metallocene compounds or π-complex compounds according to claim 1 under self-activation, in which after opening the D / A- Binding the acceptor atom A forms an X ligand zwitterionic metallocene complex structure or π complex structure det, with the transition metal M a positive charge and the acceptor atom A generates a negative charge and is another X ligand Represents H or substituted or unsubstituted C in its bond to the transition metal M the olefin insertion for the polymerization takes place, whereby preferably 2 X ligands are linked to form a chelate ligand become. 11. The method according to claims 1 to 1 0, characterized in that π complex Compounds according to claim 1, in which one of the atoms D or A is part of the Ring of the associated π system, preferably D part of the ring of the supplied π system is used. 12. The method according to claims 1 to 11, characterized in that reaction products of the formula (XI) or (XIa) of ionizing agents with metallocene compounds or π complexes according to formula (I) or (XIII)
or
in which
Anion represents the entire bulky, poorly coordinating anion and base represents a Lewis base,
be used. 13. The method according to claims 1 to 12, characterized in that the Metallocene compounds or π-complex compounds on a support as uses heterogeneous catalysts.   14. The method according to claims 1 to 13, characterized in that it is based on the Manufacturing of EPM and EPDM is targeted. 15. The method according to claims 1 to 14, characterized in that the melting temperature T _{m of} at least one melting peak is above + 50 ° C. 16. The method according to claims 1 to 15, characterized in that the half value range of at least one melting peak is at most 30 ° C.