Organoboron compound, its production method, the catalytic system, the method of obtaining the olefin polymer and the polyolefin

 

(57) Abstract:

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, p is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3. The invention relates also to a method for producing this chemical compound, catalyst system, process for the preparation of polyolefins. 5 s and 5 C. p. F.-ly.

The invention relates to the organoboron compound, which may be neutral or ionic structure. In combination with metallization olefins. You can renounce the use of alumination, for example methylaluminoxane (MAO), as socializaton and nevertheless to achieve high catalyst activity.

The role of cationic complexes in the polymerization Ziegler-Natta with metallocene widely recognized (M. Bochmann, Nachr. Chem.Lab.Techn. in 1993, 41, 1220). Methylaluminoxane far the most effective socialization has the disadvantage that it must be used in a large excess. The use of cationic alilovic complexes opens up prospects for the use of catalysts that are free from methylaluminoxane with comparable activity.

Synthesis of cationic alilovic complexes possible through

a) protolith metallocene compounds, for example, weakly acidic ammonium salts are very stable, not alkaline anion Tetra(pentafluorophenyl)- borate (e.g., [PhMe2NH]+[B(C6F5)4-)

b) removal of one group of alkyl of metallocene compounds with strong Lewis acids, as Lewis acids can serve as salt type (Ph3C+BR4-), and a strong, neutral salts Lewis, for example, In(C6F5)3,

(C) the oxide is C "casinobodog" metallocene catalysts for polymerization described in J. Am.Chem.Soc. 1991, 113, 3623. According to this source the removal of alkyl of connection metallocene is performed using Tris(pentafluorophenyl)borane. In EP 427 697 described the synthesis and the corresponding catalyst system consisting of neutral metallocene (for example, Cp2ZrMe2), Lewis acid (for example, IN(C6F5)3and aluminiumteilen. The method of obtaining salts of General formula LMX+XA-according to the principle described above is described in EP 520 732.

In EP 558 158 described zwitterion catalytic systems, which are derived from compounds metallocenes of dialkyl and salts of the formula [R3NH]+BPh4]-. In the reaction of exchange of such salts, for example, with Cp2*ZrMe2get through protolith with the removal of methane intermediate zircono-cemetery cation. The latter reacts by activating C-H with zwitterions Cp2*Zr+-m - C6H4-BPh3-. While the Zr atom is covalently bonded to a carbon atom of the phenyl ring and stable eroticheskoe hydrogen bond.

According to the mechanism of the reaction after protolith metallocenes dealkylase group with perfluorinated salt [R3NH]+[B(C6F2Zr-R-R H]+[B(C6F5)4l-. In the US 5 348 299 describes the appropriate system, with salt dimethylaniline used with perfluorinated tetraphenylborate.

The disadvantage of this system is that after protolith of the ammonium salts formed amine, which is coordinated with a strong acid cation Lewis and therefore not active in the polymerization.

In EP 426 637 described a technique in which the used cation CP h3+the Lewis acid. Weakly coordinating anion is a B(C6F5)4-. This has the advantage that after you remove the group CH3the resulting CH3CPh3does not have more coordination properties. Therefore, from a sterically unhindered metal centers can also be obtained cationic complexes.

In WO 95/14044 described carborane as components of catalytic systems.

DIBORANE connected by a hydrogen atom and alkyl group described in WO 95/24269. These systems have the disadvantage that they contained N-sour functions do not exclude interaction with cationic system.

The task of the invention consists in the floors of the prior art.

Thus, the present invention relates to an organoboron compound, and method of its production. Further, the invention relates to a catalytic system containing at least one metallocene and at least one organoboron compound according to the invention as socializaton. Furthermore, it describes a method of producing polyolefins.

Organoboron compound according to the invention correspond to General formula

[RjM - Xd- MRj]a-bAc+,

where R are, independently of one another, identical or different and signify a group containing C1-C40carbon atoms,

X are, independently of one another, identical or different and signify a group containing C1-C40carbon atoms,

M are, independently of one another, identical or different and denote an element IlIa, IVa or Va group of the periodic system of elements, provided that one M is boron,

and is an integer from 0 to 10, b is an integer from 0 to 10, p is an integer from 0 to 10, and a = b c,

d is 1,

j is an integer from 1 to 3, and

A is a cation of an element Ia, IIa IIIa groups of the Periodic Jerusalem.

If a = 0, that is neutral connection; and if 1 is negatively charged connection with b cations ANDc+as counterion.

Structural unit X connects with each other the elements of M by covalent bonds, X represents a linear, cyclic or branched carbon structure.

R represents a hydrocarbon residue, C1-C40that can be galogenidov, preferably perhalogenated by halogen, for example fluorine, chlorine, bromine or iodine, in particular, halogenated, in particular, perhalogenated C1-C30is an alkyl group, such as trifluoromethyl, pentachlorphenol, heptafluoroisopropyl or monitorsobol, or a halogenated, in particular, perhalogenated C6-C30-aryl group such as pentafluorophenyl, heptachlorinated, heptapteridae, 1,2,3 - tryptophanyl, 1,3,5-tryptophanyl, heptapteridae, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-Tris(trifluoromethyl) phenyl or 2,2- (acceptor)biphenyl.

Preferably, X represents a C6-C30- Allenova or group WITH2-C30-alkynylamino group, halogenated, in particular, perhalogenated.

Mainly 5, if M is an element of group Va.

Particularly preferably, M represents a boron as an element of group IlIa.

Preferably a,b or C is 0, 1 or 2.

As the preferred ions of carbene (R2C+or Quaternary ammonium ions with acid function H (R3NH+). The most preferred Quaternary ammonium salts with acidic function H.

If a 1 and all M is boron, preferably the number of boron atoms 4, particularly preferably the number of atoms of boron equal to 2.

Examples of the organoboron compounds according to the invention are given in the end of the text.

Instead cation N,N-dimethylaniline [C6H5N (CH6)2H]+can alternatively be used as the cation CPh3.

Getting organoboron compounds according to the invention can be carried out, for example, according to the scheme given in the end of the text.

where X represents a carbon-containing group, a C1-C40as, for example, WITH2-C40-alkylen,6-C40-halogen-Allen,

Y are, independently of one another, identical or different and signify a group to delete, preferably alertstatus group C1-C40as, for example, WITH1-C40-alkyl, C6-C40-aryl, C6-C40- halogenared,7-C40-arylalkyl or C6-C40- halogenosilanes,

Bs is a base, preferably organolithium compound or compound Grignard,

M is identical or different and denotes an element of group IlIa, IVa or Va of the periodic system of elements,

A is a cation of group la, lla, IlIa of the periodic system of elements, cation of carbene, hydronium or sulfone or Quaternary compound ammonium.

Organoboron compound according to the invention may in conjunction with metallocene be used as the catalytic system. Metallocene contain at least one Central metal atom, which is bound at least one ligand, such as cyclopentadienyls. Preferred are chiral metallocene. In addition, with the Central metal atom can be linked to other substituents such as halogen, alkyl, alkoxy or aryl. The Central metal atom can be element III, IV, V or VI of the side group of the Periodic system of elements, such as Ti, Zr or Hf. Under cyclopentadienylsodium follows Enciklopedija, indenyl, 2-methylindenyl, 2-methyl-4 - phenylindane, tetrahydroindene, octahedrite, benzo - indenyl, fluorenyl, benzofuranyl, tetrahydrofluorene and octahydronaphthalene. - Ligands, such as cyclopentadienylsodium, can be connected or not connected by bridges, with simple and multiple bridge connection, including through the ring system. The concept of metallocen also covers compounds with more than one metallocene fragment, the so-called multi-core metallocene. They may have any circuit, and ways of bridge connections. Fragments of such multi-core metallocenes can be identical or different from each other. Examples of such multi-core metallocenes described, for example, in EP-A-632063, JP-A - 04/80214, JP-A-04/85310, EP-A-654476.

Especially preferred are namashikaye and bridge metallocene formula II

< / BR>
in which M1 is a metal III, IV, V or VI of the side group of the Periodic system of elements, such as Zr or Hf.

R1are the same or different and represent a hydrogen atom, SiR3where R3is the same or different and represents a hydrogen atom is aralkyl, C1-C10-alkoxy, C6-C20-aryl, C6-C10- ferril, C6-C10-aryloxy,2-C10alkenyl,7-C40-arylalkyl, Cp7-C40-alkylaryl or C8-C40- arylalkyl, or carbon-containing group, a C1-C30as, for example, C1-C25-alkyl, for example methyl, ethyl, tert.-butyl, cyclohexyl or octyl,2-C25alkenyl,3-C15-alkylaryl, C6-C24-aryl, C2-C24- heteroaryl, such as pyridyl, furyl or chenail,7-C30-arylalkyl,7-C30- alkylaryl, fluorinated C1-C25-alkyl, fluorinated C6-C24-aryl, fluorinated C7-C30- arylalkyl, fluorinated C7-C30-alkylaryl or1-C12-alkoxy, or two or more residues R1can be connected to each other that the residues R1and connecting atoms cyclopentadienyls ring form a ring system WITH4-C24that in turn can be substituted.

R2are the same or different and represent a hydrogen atom, SiR3where R3are the same or different and represent-alkyl, C1- C10-foralkyl,1-C10-alkoxy, C6-C14-aryl, C6-C10-ferril,6-C10-aryloxy,2-C10alkenyl,7-C40-arylalkyl, C7-C40-alkylaryl or C8-C40-arylalkyl, or carbon-containing C1-C30the group, as, for example, WITH1-C25-alkyl, for example methyl, ethyl, tert.-butyl, cyclohexyl or octyl,2-C25alkenyl,3-C15-alkylaryl, C6-C24-aryl, C5-C24-heteroaryl, such as pyridyl, furyl or chenail, C7-C30-arylalkyl,7-C30-alkylaryl, fluorinated C1-C25-alkyl, fluorinated C6-C24-aryl, fluorinated C7-C30-arylalkyl, fluorinated C7-C30-alkylaryl or C1-C12-alkoxy, or two or more residues R2can be connected to each other that the residues R2and connecting atoms cyclopentadienyls ring form a ring system WITH4-C24that in turn may be substituted,

n = 5 for g = 0, and n = 4 for q = 1,

m is equal to 5 for g = O, and m = 4 for g = 1.

L are identical or different and denote an atom UB>20alkenyl,1-C20-alkoxy, C6-C14-aryloxy or C6-C40-aryl,

k is an integer from 1 to 4, and in the case of M1 = Ti, Zr or Hf, preferably equal to 2,

Z means bridging structural element between the two cyclopentadienyl rings, and q is O or 1.

Examples of Z are groups M2R4R5in which M2is carbon, silicon, germanium or tin, and R4and R5are identical or different and denote a hydrocarbon group, C1-C20for example , C1-C10-alkyl or C6-C14-aryl.

Z preferably is CH2CH2CH2CH(CH3)CH2CH(C4H9) C(CH3)2, (CH3)2(CH3)2Si (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5) (CH3)Si, (C6H5)2Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2o-C6H4or 2,2' -(C6H4)2z may also be formed with one or more residues R1and/or R2mono - or polycyclic system.

Preferred are chiral mo substituted so, they form ingenernoe ring. Ingenernoe ring is preferably substituted, in particular, in position 2, 4, 2,4,5, 2.4.6, 2.4.7, or 2.4.5.6 hydrocarbon groups C1-C20for example, C1-C10-alkyl or C6-C20-aryl, with two or more substituents ingenering ring may together form a ring system.

The following examples metallocene illustrate the present invention but are not restrictive:

bis(cyclopentadienyl)zirconocenes,

bis(indenyl)zirconocenes,

bis(fluorenyl)zirconocenes,

(indenyl) (fluorenyl) zirconocenes,

(3-methyl-5-naphthylidine) (2,7-di-tertbutylphenyl) zirconocenes,

(3-methyl-5-naphthylidine) (3,4,7-trimethoxyphenyl)zirconocenes,

(pentamethylcyclopentadienyl) (tetrahydroindene) zirconocenes,

(cyclopentadienyl) (1-octene-8-enciklopediey) zirconocenes,

(indenyl) (1-butene-4-enciklopediey) zirconocenes,

[1,3-bis (trimethylsilyl) cyclopentadienyl] (3, 4 - benzofuranyl) zirconocenes,

bis (cyclopentadienyl) titanimeteen,

dimethylselenide (indenyl) zirconocenes,

dimetridazole,

dimethylselenide (2-methylindenyl) zirconocenes,

dimethylselenide (2-ethylidene) zirconocenes,

dimethylselenide (2-methyl-4,5-benzhydryl) zirconocenes,

dimethylselenide (2-ethyl-4,5-benzhydryl) zirconocenes,

dimethylselenide (4, 5-dihydro-8-methyl-7H-cyclopent[f] acenaphthylen-7 - ilidene) zirconocenes,

dimethylsilanol (2-methyl-4, 5-benzhydryl) (2-methyl-4-phenylin-Denis) zirconocenes,

dimethylsilanol (2-ethyl-4,5-benzhydryl) (2-methyl-4-phenylindane) zirconocenes,

dimethylsilanol (2-methyl-4, 5 - benzhydryl) (2-ethyl-4-phenylindane) zirconocenes,

dimethylsilanol (2-ethyl-4, 5-benzhydryl) (2-ethyl-4-naphthylidine) zirconocenes,

dimethylsilanol (2-methylindenyl) (4 - phenylindane) zirconocenes,

dimethylselenide (2-methyl-4 - phenylindane) zirconocenes,

dimethylselenide (2-ethyl-4 - phenylindane) zirconocenes,

dimethylselenide (2-methyl-4,6-diisopropylphenol) zirconocenes,

dimethylselenide (2-ethyl-4,6-diisopropylphenol) zirconocenes,

dimethylselenide (2-methyl-4-naphthalenyl) zirconocenes,

dimethylselenide (2-ethyl-4-naphthylidine) zirconocene enyl) zirconocenes,

methylphenylethylamine (tetrahydroindene) zirconocenes,

methylphenylethylamine (2-methylindenyl) zirconocenes,

methylphenylethylamine (2-ethylidene) zirconocenes,

methylphenylethylamine (2-methyl-4, 5-benzhydryl) zirconocenes,

methylphenylethylamine (2-ethyl-4,5-benzhydryl) zirconocenes,

methylphenylethylamine (4,5-dihydro-8-methyl-7H - cyclopent [e] acenaphthylen-7-ilidene)zirconocenes,

methylphenylsulfonyl (2-methyl-4,5-benzhydryl) (2-methyl-4-phenylindane) zirconiated,

methylphenylsulfonyl (2-ethyl-4,5 - benzhydryl) (2-methyl-4-phenylindane) zirconocenes,

methylphenylsulfonyl (2-methyl-4,5-benzhydryl) (2-ethyl-4-phenylindane) zirconocenes,

methylphenylsulfonyl (2-ethyl-4,5 - benzhydryl) (2-ethyl-4-naphthylidine) zirconocenes,

methylphenylsulfonyl (2-methylindenyl) (4-phenylindane) zirconocenes,

methylphenylethylamine (2-methyl-4-phenylindane) zirconocenes,

methylphenylethylamine ((2-ethyl-4-phenylindane) zirconocenes,

methylphenylethylamine (2-methyl-4,6 - diisopropylphenol) zirconocenes,

methylphenylethylamine (2-ethyl-4,6 - diisopropylphenol) zirconocenes,

methylphenylsiloxane the dimethyl,

diphenylsilanediol (indenyl) zirconocenes,

diphenylsilanediol (2-methylindenyl) zirconocenes,

diphenylsilanediol (2-ethylidene) zirconocenes,

diphenylsilanediol (cyclopentadienyl) (indenyl) zirconocenes,

diphenylsilanediol (2-methyl-4,5-benzhydryl) zirconocenes,

diphenylsilanediol (2-ethyl-4,5-benzhydryl) zirconocenes,

diphenylsilanediol (2-methyl-4,5-benzhydryl) (2-methyl-4-phenylindane) zirconocenes,

diphenylsilanediol (2-ethyl-4,5 - benzhydryl) (2-methyl-4-phenylindane) zirconocenes,

diphenylsilanediol (2-methyl-4,5-benzhydryl) (2-ethyl-4-phenylindane) zirconocenes,

diphenylsilanediol (2-ethyl-4,5 - benzhydryl) (2-ethyl-4-naphthylidine) zirconocenes,

diphenylsilanediol (2-methylindenyl) (4-phenylindane) zirconocenes,

diphenylsilanediol (2-methyl-4-phenylindane) zirconocenes,

diphenylsilanediol (2-ethyl-4-phenylindane) zirconocenes,

diphenylsilanediol (2-methyl-4,6 - diisopropylphenol) zirconocenes,

diphenylsilanediol (2-ethyl - 4,6-diisopropylphenol) zirconocenes,

diphenylsilanediol (2-methyl-4-naphthylidine) zirconocenes,

diphenylsilanediol (2-ethyl-4-naftalin is(2-methylindenyl) zirconocenes,

1-silacyclopentane-1,1-bis(2-ethylidene) zirconocenes,

1-silacyclopentane-1,1-bis(2-meth yl-4, 5 - benzhydryl) zirconocenes,

1-silacyclopentane-1,1-bis(2 - ethyl-4,5-benzhydryl) zirconocenes,

1-silacyclopentane-1-(2 - methyl-4, 5-benzhydryl)-1-(2-methyl-4-phenylindane) zirconocenes,

1-silacyclopentane-1-(2-ethyl-4,5-benzhydryl) - 1-(2-methyl-4-phenylindane) zirconocenes,

1-silacyclopentane - 1-(2-methyl-4,5-benzhydryl)-1-(2-ethyl-4-phenylindane) zirconocenes,

1-silacyclopentane-1-(2-ethyl-4,5-benzhydryl) - 1- (2-ethyl-4-naphthylidine) zirconocenes,

1-silacyclopentane-1- (2-methylindenyl)-1-(4-phenylindane) zirconocenes,

1-silacyclopentane-1,1-bis(2-methyl-4-phenylindane) zirconocenes,

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindane) zirconocenes,

1-silacyclopentane-1,1-bis(2-methyl-4,6 - diisopropylphenol) zirconocenes,

1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylphenol) zirconocenes,

1-silacyclopentane-1,2-bis(2-methyl-4-naphthylidine) zirconocenes,

1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylidine) zirconocenes, bis (cyclopentadienyl) titanimeteen,

ethylene-1,2-bis (indenyl) zirconocenes,

ethylene-1,2-bis (tetrahydroindene) C is-2-(2-indenyl) zirconocenes,

the ethylene-1-cyclopentadienyl-2-(2-methyl-1-indenyl) zirconocenes,

the ethylene-1, 2-bis (2-methylindenyl) zirconocenes,

ethylene-1,2-bis (2-ethylidene) zirconocenes,

ethylene-1,2-bis (2-methyl-4,5-benzhydryl) zirconocenes,

ethylene-1,2-bis(2 - ethyl-4,5-benzhydryl) zirconocenes,

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7 - ilidene,) zirconocenes,

the ethylene-1-(2-methyl-4,5-benzhydryl)-2- (2-methyl-4-phenylindane) zirconocenes,

the ethylene-1-(2-ethyl-4, 5 - benzhydryl)-2-(2-methyl-4-phenylindane) zirconocenes,

the ethylene-1-(2-methyl-4,5-benzhydryl)-2-(2-ethyl-4-phenylindane) zirconocenes,

the ethylene-1-(2-ethyl-4,5-benzhydryl)-2-(2-ethyl - 4-naphthylidine) zirconocenes,

the ethylene-1-(2-methylindenyl)-2-(4-phenylindane) zirconocenes,

ethylene-1,2-bis(2-methyl-4 - phenylindane) zirconocenes,

ethylene-1,2-bis(2-ethyl-4-phenylindane) zirconocenes,

ethylene-1,2-bis(2-methyl-4,6 - diisopropylphenol) zirconocenes,

ethylene-1,2-bis(2-ethyl-4,6 - diisopropylphenol) zirconocenes,

ethylene-1,2-bis(2-methyl-4-naphthylidine) zirconocenes,

ethylene-1,2-bis(2-ethyl-4-naphthylidine) zirconocenes,

propylene-2,2-bis(indenyl) zirconocenes,

propylene-2-CEC is Tyl,

propylene-2-cyclopentadienyl-2-(9-fluorenyl) zirconocenes,

propylene-2 - cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl) zirconocenes,

propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl) zirconocenes,

propylene-2-cyclopentadienyl-2-(2,7-dibromo-9 - fluorenyl) zirconocenes,

propylene-2-cyclopentadienyl-2-(2,7 - diphenyl-9-fluorenyl) zirconocenes,

propylene-2-cyclopentadienyl - 2- (2, 7-dimethyl-9-fluorenyl) zirconocenes,

propylene-2-(3 - methylcyclopentadienyl)-2-(2,7-dibutil-9-fluorenyl) zirconocenes,

propylene-2-(3-tert-butylcyclopentadienyl) -2- (2, 7-dibutil-9-fluorenyl) zirconocenes,

propylene-2-(3-trimethylsilylethynyl)-2- (3,6-di-tert-butyl-9-fluorenyl) zirconocenes,

propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl] zirconocenes,

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl) zirconocenes,

propylene-2,2-bis(tetrahydroindene) zirconocenes,

propylene-2,2-bis(2-methylindenyl) zirconocenes,

propylene-2,2-bis(ethylidene) zirconocenes,

propylene-2,2-bis (2-methyl-4, 5-benzhydryl) zirconocenes,

propylene-2,2-bis (2-ethyl-4, 5-benzhydryl) zirconocenes,

propylene-2,2-bis(4,5-di-methyl-4-phenylindane) zirconocenes,

propylene-2-(2-ethyl-4,5-benzhydryl)-2-(2 - methyl-4-phenylindane) zirconocenes,

propylene-2-(2-methyl-4,5 - benzhydryl)-2-(2-ethyl-4-phenylindane) zirconocenes,

propylene-2-(2-ethyl-4,5-benzhydryl)-2-(2-ethyl-4-naphthylidine) zirconocenes,

propylene-2-(2-methylindenyl)-2-(4 - phenylindane) zirconocenes,

propylene-2,2-bis (2-methyl-4 - phenylindane) zirconocenes,

propylene-2,2-bis (2-ethyl-4 - phenylindane) zirconocenes,

propylene-2,2-bis (2-methyl-4,6 - diisopropylphenol) zirconocenes,

propylene-2,2-bis (2-ethyl-4, 6-diisopropylphenyl) zirconocenes,

propylene-2,2-bis (2-methyl - 4-naphthylidine) zirconocenes,

propylene-2,2-bis (2-ethyl-4 - naphthylidine) zirconocenes,

1,6-bis [metalsilver (2-methyl - 4-phenylindane) zirconocenes]hexane,

1,6-bis [metalsilver (2-methyl-4,5-benzhydryl) zirconocenes]hexane,

1,6-bis [metalsilver (2-ethyl-4-phenylindane) zirconocenes] hexane,

1,6-bis[metalsilver (2-methyl-4-naphthylidine) zirconocenes]hexane,

1,6-bis [metalsilver (2-methyl-4, 6 - diisopropylphenyl) zirconocenes] hexane,

1,6-bis [methylsilyl (2-methyl-4-phenylindane)(4,5-benzhydryl) zirconocenes] hexane,

1-[metalsilver (tetrahed the power-1,1,6,6-tetramethyl-1,6-bis [metalsilver (2-methyl-4-phenylindane) zirconocenes]hexane,

1,4-disil-1,4-bis[metalsilver(2-methyl-4-phenylindane) zirconocenes]cyclohexane,

[1,4-bis-(1-indenyl)-1,1,4,4-tetramethyl-1,4-disrepute]bis (pentamethylcyclopentadienyl),

[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disrepute] bis (cyclopentadienylzirconium),

[1,4-bis(1-indenyl) -1,1,4, 4-tetramethyl-1,4-disrepute] bis(cyclopentadienylzirconium),

[1-(1-indenyl)-6-(2-phenyl-1 - indenyl-1,1,6,6-tetraethyl-1,6-disil-4-oxacin]bis (tert-butylcyclopentadienyl),

[1,10-bis-(2,3 - dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10 - dharmarajan]bis (2-methyl-4-vinylidenechloride),

(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7 - chlorofluoride) zirconocenes,

(4,7-dichlorinated) (3,6-dimetilfuranom) zirconocenes, bis (2,7-di-tert-butyl-cyclohexylphenol) zirconocenes,

(2,7-dimetilfuranom) [2,7-bis (1-naphthyl)fluorenyl] zirconocenes,

dimethylsilane (fluorenyl) zirconocenes,

dibutylaniline(2-methylfluorene) zirconocenes,

1,1,2,2-tetramethyldisilane(2-methylindenyl)(4-phenylfluorene) zirconocenes,

propylene-1-(2-indenyl)-2-(9-fluorenyl) zirconocenes,

1,1-dimethyl-1-silatranes(fluorene pentadienyl)-4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydrofuran)] zirconocenes,

[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl) (7-vinyltetrahydrofuran)] zirconocenes,

[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl (6,6-diethylacrylamide)] zirconocenes,

[4-(3-tert-butylcyclopentadienyl) - 4,7,7-trimethyl (tetrahydroindene)] zirconocenes,

[4-(1-indenyl)-4,7,7-trimethyl (tetrahydroindene)] zirconocenes,

bis (cyclopentadienyl) garrigill,

bis (indenyl) vandivner,

bis (fluorenyl) scandigital,

(indenyl) (fluorenyl) liabililty,

(2-methyl-7-naphthylidine) (2,6-di-tert-butylfluorene) titanimeteen,

(pentamethylcyclopentadienyl)(tetrahydroindene) gerribrimmer,

(cyclopentadienyl) (1-octene-8-enciklopediey) garrigill,

(indenyl) (1-butene-4-enciklopediey) titanimeteen,

[1,3-bis(trimethylsilyl) cyclopentadienyl] 3, 4 - benzofuranyl) liabililty,

bis(cyclopentadienyl)titanimeteen,

dimethylselenide(indenyl) titanimeteen,

dimethylselenide (tetrahydroindene) garrigill,

dimethylsilanol(cyclopentadienyl) (indenyl) titanimeteen,

dimethylselenide(2-methylindenyl) garrigill,

dimethylselenide(2-ethylidene) scandigital,

di is tendinitis,

dimethylselenide(4,5-dihydro-8-methyl-7H-cyclopent[f] acenaphthylen-7-ilidene) titanimeteen,

dimethylsilanol(2-methyl-4,5 - benzhydryl) (2-methyl-4-phenylindane) titanimeteen,

dimethylsilanol (2-ethyl-4,5-benzhydryl) (2-methyl-4-phenylindane) garrigill,

dimethylsilanol (2-methyl-4,5-benzhydryl) (2-ethyl-4-phenylindane) scandigital,

dimethylsilanol (2-ethyl - 4, 5-benzhydryl) (2-ethyl-4-naphthylidine) titanimeteen,

dimethylsilanol (2 - methylindenyl) (4-phenylindane) garrigill,

dimethylselenide (2-methyl-4-phenylindane) liabililty,

dimethylselenide (2-ethyl-4-phenylindane) vandivner,

dimethylselenide (2-methyl-4,6-diisopropylphenol) garrigill,

dimethylselenide (2-ethyl-4,6-diisopropylphenol) vandivner,

dimethylselenide (2-methyl-4-naphthylidine) garrigill,

dimethylselenide (2-ethyl-4-naphthylidine) titanimeteen,

methylphenylethylamine (indenyl) titanimeteen,

methylphenylsulfonyl (cyclopentadienyl) (indenyl) garrigill,

methylphenylethylamine (tetrahydroindene) garrigill,

methylphenylethylamine (2-methylindenyl) titanimeteen,

methylphenylethylamine (2-stor is nilsanders (2-ethyl-4,5-benzhydryl) vandivner,

methylphenylethylamine (4,5-dihydro-8-methyl-7H-cyclopent[f] acenaphthylen-7-ilidene) titanimeteen,

methylphenylsulfonyl (2-methyl-4, 5-benzhydryl) (2-methyl-4-phenylindane) titanpanel,

methylphenylsulfonyl (2-ethyl-4,5-benzhydryl) (2-methyl-4-phenylindane) titanimeteen,

methylphenylsulfonyl (2-methyl-4,5 - benzhydryl) (2-ethyl-4-phenylindane) garrigill,

methylphenylsulfonyl (2-ethyl-4,5-benzhydryl) (2-ethyl-4-naphthylidine) garrigill,

methylphenylsulfonyl (2-methylindenyl) (4 - phenylindane) titanimeteen,

methylphenylethylamine (2-methyl-4 - phenylindane) garrigill,

methylphenylethylamine (2-ethyl-4 - phenylindane) vandivner,

methylphenylethylamine (2-methyl-4, 6-diisopropylphenyl) titanimeteen,

methylphenylethylamine (2 - ethyl-4,6-diisopropylphenol) garrigill,

methylphenylethylamine (2-methyl-4-naphthylidine) garrigill,

methylphenylethylamine (2-ethyl-4-naphthylidine) titanimeteen,

diphenylsilanediol (indenyl)titanimeteen,

diphenylsilanediol (2-methylindenyl)garrigill,

diphenylsilanediol (2-ethylidene)titanimeteen,

diphenylsilanediol (cyclopentadienyl)(indenyl)garrigill,

diphenylamine,

diphenylsilanediol (2-methyl - 4,5-benzhydryl) (2-methyl-4-phenylindane)garrigill,

diphenylsilanediol (2-ethyl-4, 5-benzhydryl) (2-methyl-4-phenylindane)titanimeteen,

diphenylsilanediol (2-methyl-4, 5-benzhydryl) (2-ethyl-4-phenylindane)garrigill,

diphenylsilanediol (2-ethyl - 4, 5-benzhydryl) (2-ethyl-4-naphthylidine)titanimeteen,

diphenylsilanediol (2-methylindenyl) (4-phenylindane)titanimeteen,

diphenylsilanediol (2-methyl-4-phenylindane)titanimeteen,

diphenylsilanediol (2-ethyl-4-phenylindane)garrigill,

diphenylsilanediol (2-methyl-4,6-diisopropylphenol) garrigill,

diphenylsilanediol (2-ethyl-4,6-diisopropylphenol) garrigill,

diphenylsilanediol (2-methyl-4-naphthylidine) garrigill,

diphenylsilanediol (2-ethyl-4-naphthylidine) titanimeteen,

1-silacyclopentane-1, 1-bis (indenyl)garrigill,

1-silacyclopentane-1,1-bis (2-methylindenyl)garrigill,

1-silacyclopentane-1,1-bis (2-ethylidene)garrigill,

1-silacyclopentane-1,1-bis (2-methyl-4,5-benzhydryl)titanimeteen,

1-silacyclopentane-1, 1-bis (2-ethyl-4, 5-benzhydryl) garrigill,

1-silacyclopentane-1-(2-methyl-4, 5-benzhydryl) - 1- (2-methyl-4-phenylindane) stilettopoints-1-(2-methyl-4,5-benzhydryl) - 1-(2-ethyl-4-phenylindane) titanimeteen,

1-silacyclopentane-1-(2-ethyl-4,5-benzhydryl)-1-(2-ethyl - 4-naphthylidine)garrigill,

1-silacyclopentane-1-(2 - methylindenyl)-1-(4-phenylindane)garrigill,

1-silacyclopentane-1,1-bis(2-methyl-4-phenylindane) garrigill,

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindane) titanimeteen,

1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylphenol) titanimeteen,

1-silacyclopentane-1,1-bis(2-ethyl-4,6 - diisopropylphenol) titanimeteen,

1-silacyclopentane-1,1-bis(2 - methyl-4-naphthylidine) scandigital,

1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylidine) garrigill,

bis (cyclopentadienyl) titanimeteen,

ethylene-1,2-bis (indenyl) scandigital,

ethylene-1,2-bis (tetrahydroindene) titanimeteen,

the ethylene-1-cyclopentadienyl-2-(1-indenyl) garrigill,

the ethylene-1-cyclopentadienyl-2- (2-indenyl) titanpanel,

the ethylene-1-cyclopentadienyl-2-(2-methyl-1 - indenyl) garrigill,

ethylene-1,2-bis(2-methylindenyl) garrigill,

ethylene-1,2-bis (2-ethylidene) garrigill,

ethylene-1,2-bis (2-methyl-4,5-benzhydryl) garrigill,

ethylene-1,2-bis (2-ethyl-4,5-benzhydryl) titanimeteen,

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-C is titanimeteen,

the ethylene-1-(2-ethyl-4,5 - benzhydryl)-2-(2-methyl-4-phenylindane) titanimeteen,

the ethylene-1-(2-methyl-4, 5-benzhydryl)-2-(2-ethyl-4-phenylindane) scandigital,

the ethylene-1-(2-ethyl-4,5-benzhydryl) -2- (2-ethyl-4 - naphthylidine) garrigill,

the ethylene-1-(2-methylindenyl)-2-(4 - phenylindane) titanimeteen,

ethylene-1,2-bis(2-methyl-4 - phenylindane) garrigill,

the ethylene-1, 2-bis(2-ethyl-4 - phenylindane) garrigill,

ethylene-1,2-bis(2-methyl-4,6 - diisopropylphenol) garrigill,

ethylene-1,2-bis(2-ethyl-4,6 - diisopropylphenol) titanimeteen,

ethylene-1,2-bis(2-methyl-4 - naphthylidine) titanimeteen,

ethylene-1,2-bis(2-ethyl-4 - naphthylidine) garrigill,

propylene-2,2-bis(indenyl) garrigill,

propylene-2-cyclopentadienyl-2-(1-indenyl)titanimeteen,

propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)titanimeteen,

propylene-2-cyclopentadienyl-2-(9-fluorenyl) garrigill,

propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9 - fluorenyl) garrigill,

propylene-2-cyclopentadienyl-2-(2,7-di - tert-butyl-9-fluorenyl) garrigill,

propylene-2-cyclopentadienyl-2-(2,7 - dibromo-9-fluorenyl) titanimeteen,

propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9 - fluorenyl) garrigill,

propylene-2 is l-9-fluorenyl) garrigill,

propylene-2-(3-tert-butylcyclopentadienyl)-2-(2, 7-dibutil-9-fluorenyl) titanimeteen,

propylene-2-(3-trimethylsilylethynyl)-2-(3,6-di-tert-butyl-9 - fluorenyl) titanimeteen,

propylene-2-cyclopentadienyl-2-[2,7-bis (3-butene-1-yl)-9-fluorenyl] garrigill,

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl) titanimeteen,

propylene-2,2-bis(tetrahydroindene) garrigill,

propylene-2,2-bis(2-methylindenyl) garrigill,

propylene-2,2-bis(2-ethylidene) titanimeteen,

propylene-2,2-bis(2-methyl-4,5-benzhydryl) titanimeteen,

propylene-2,2-bis(2-ethyl-4,5-benzhydryl) garrigill,

propylene-2,2-bis(4,5-dihydro-8 - methyl-7H-cyclopent [f] acenaphthylen-7-ilidene)garrigill,

propylene-2-(2-methyl-4,5-benzhydryl)-2-(2-methyl-4 - phenylindane) garrigill,

propylene-2-(2-ethyl-4, 5 - benzhydryl)-2-(2-methyl-4-phenylindane) titanimeteen,

propylene-2-(2-methyl-4,5-benzhydryl)-2-(2-ethyl-4-phenylindane) garrigill,

propylene-2-(2-ethyl-4,5-benzhydryl) -2- (2-ethyl-4-naphthylidine) titanimeteen,

propylene-2-(2-methylindenyl)-2-(4-phenylindane) garrigill,

propylene-2,2-bis(2-methyl-4-phenylindane) titanimeteen,

propylene-2,2-bis(2 - ethyl-4-phenylindane) garrigill,

propylene-2,2-bis(2-methyl-4 - naphthylidine) titanimeteen,

propylene-2,2-bis(2-ethyl-4 - naphthylidine) titanimeteen,

1,6-bis[metalsilver(2-methyl-4-phenylindane) garrigill] hexane,

1,6-bis [metalsilver (2 - methyl-4,5-benzhydryl) titanimeteen] hexane,

1,6-bis[metalsilver(2-ethyl-4-phenylindane) garrigill] hexane,

1,6-bis[metalsilver(2-methyl-4-naphthylidine) titanimeteen]hexane,

1,6-bis[metalsilver(2-methyl-4,6-diisopropylphenol) garrigill]hexane,

1,6-bis[methylsilyl (2-methyl-4 - phenylindane)(4,5-benzhydryl)titanimeteen]hexane,

1-[metalsilver(tetrahydroindene) garrigill] -6-athelstane (cyclopentadienyl)-fluorenyl) titanimeteen]hexane,

1,6-disil-1,1,6,6-tetramethyl-1,6-bis[metalsilver (2-methyl-4-phenylindane) garrigill] hexane,

1,4-disil-1,4-bis[metalsilver (2-methyl-4-phenylindane) garrigill] cyclohexane,

1,4-bis-(1-indenyl)-1,1,4,4-tetramethyl-1,4-disrepute]bis (pentamethylcyclopentadienyl),

1,4-bis-(9-fluorenyl)-1,1,4,4-tetramethyl-1,4 - disrepute] bis (cyclopentadienylmanganese),

[1,4-bis-(1-indenyl) -1,1,4,4-tetramethyl-1,4-disrepute] bis (cyclopentadienylmanganese),

[1-(1-indenyl)-6-(2-phenyl-1 - indenyl)-1,1,6,6 Nile)-1,1,10,10-tetramethyl-1,10-dharmadasa]bis(2-methyl-4 - phenylenedimaleimide),

(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluoride) titanimeteen,

(4,7-dichlorinated) (3,6-dimetilfuranom) titanimeteen, bis(2,7 - di-tert-butyl-cyclohexylphenol) garrigill,

(2,7-dimetilfuranom) [2,7-bis (1-naphthyl) fluorenyl] garrigill, dimethyllysine (fluorenyl) titanimeteen, dibutylaniline (2 - methylfluorene) garrigill,

1,1,2,2-tetramethyldisilane (2 - methylindenyl) (4-phenylfluorene) titanimeteen,

propylene-1-(2-indenyl)-2-(9-fluorenyl) garrigill,

1,1-dimethyl-1-silatranes (fluorenyl) titanimeteen,

[4-(cyclopentadienyl)-4,7-trimethyl(tetrahydroindene)]titanimeteen,

[4-(cyclopentadienyl)-4,7-dimethyl-7-phenyl (5,6 - dimethyltetrahydrofuran)] garrigill,

[4-(cyclopentadienyl) -4,7 - dimethyl-7-(1-naphthyl) (7-vinyltetrahydrofuran)] titanimeteen,

[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl (6,6-diethylacrylamide)] garrigill,

[4-(3-tert-butylcyclopentadienyl)-4, 7,7-trimethyl (tetrahydroindene)] garrigill,

[4-(1-indenyl)-4,7,7-trimethyl (tetrahydroindene) titanimeteen,

bis(cyclopentadienyl) zirconiated,

bis(indenyl) zirconiated,

bis(fluorenyl) zirconiated,

(indenyl) zirconiated,

dimethylselenide (tetrahydroindene) zirconiated,

dimethylsilanol (cyclopentadienyl) (indenyl) zirconiated,

dimethylselenide (2-methylindenyl) zirconiated,

dimethylselenide (2-ethylidene) zirconiated,

dimethylselenide (2-methyl-4,5-benzhydryl) zirconiated,

dimethylselenide (2-ethyl-4,5-benzhydryl) zirconiated,

dimethylselenide (2-methyl-4-phenylindane) zirconiated,

dimethylselenide (2-ethyl-4-phenylindane) zirconiated,

dimethylselenide (2-methyl-4,6-diisopropylphenol) zirconium dichloride,

ethylene-1,2-bis (indenyl) zirconiated,

ethylene-1,2-bis(tetrahydroindene) zirconiated

ethylene-1,2-bis (2-methylindenyl) zirconiated,

the ethylene-1, 2-bis (2-ethylidene) zirconiated,

ethylene-1,2-bis (2-methyl-4,5-benzhydryl) zirconiated,

ethylene-1,2 - bis (2-methyl-4-phenylindane) zirconiated,

ethylene-1,2-bis (2 - ethyl-4-phenylindane) zirconiated,

ethylene-1,2-bis (2-methyl-4, 6-diisopropylphenyl) zirconiated,

propylene-2,2-bis (indenyl)zirconiated,

propylene-2,2-(cyclopentadienyl) (indenyl) zirconiated,

propylene-2,2
bis(methylcyclopentadienyl) (4- butadiene) zirconium,

bis(n-butyl-cyclopentadienyl) (4- butadiene) zirconium,

bisinger (4- butadiene) zirconium,

(rubs. butylamide) dimethyl (tetramethyl- 5- cyclopentadienyl) silane- (4- butadiene) zirconium,

bis (2-methylbenzhydryl) (4- butadiene) zirconium,

dimethylselenide (2-methyl-indenyl) (4- butadiene) zirconium,

dimethylchlorosilane (4- butadiene)zirconium,

dimethylselenide (2-methylbenzhydryl) (4- butadiene) zirconium,

dimethylsilanol(2-methylbenzhydryl) (2 - methyl-indenyl) (4- butadiene) zirconium,

dimethylsilanol (2-methylbenzhydryl) (2-methyl-4-phenylindane) (4- butadiene) zirconium,

dimethylsilanol (2-methylindenyl) (4-phenylindane) (4- butadiene) zirconium,

dimethylselenide (2-methyl-4-phenyl-indenyl) (4- butadiene)zirconium,

dimethylselenide (2-methyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

dimethylselenide (2-methyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

isopropylidene (cyclopentadienyl) (fluorenyl) (4- butadiene) zirconium,

isopropylidene (cyclopentadienyl) (indenyl) (- butadiene) zirconium,

dimethylselenide (2-methyl-indenyl) (4-butadiene) zirconium,

dimethylchlorosilane (4- butadiene) zirconium,

dimethylselenide (2-methylbenzhydryl) (4-butadiene) zirconium,

dimethylsilanol (2-methylbenzhydryl) (2-methyl-indenyl) (4- butadiene) zirconium,

dimethylsilanol (2-methylbenzhydryl) (2-methyl-4-phenylindane) (4-butadiene) zirconium,

dimethylsilanol(2-methylindenyl)(4-phenylindane) (4-butadiene)zirconium,

dimethylselenide (2-methyl-4-phenyl-indene) (4- butadiene)zirconium,

dimethylselenide (2-methyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

dimethylselenide(2-methyl-indenyl) (4- butadiene)zirconium,

dimethylchlorosilane (4-butadiene)zirconium,

dimethylselenide(2-methylbenzhydryl) (4- butadiene) zirconium,

dimethylsilanol(2-methylbenzhydryl)(2-methyl-indenyl) (4-butadiene) zirconium,

dimethylsilanol(2-methylbenzhydryl)(2-methyl-4-phenylindane) (4-butadiene)zirconium

dimethylsilanol(2-methylindenyl) (4-phenylindane) (4- butadiene) zirconium

dimethylselenide(2-methyl-4-phenyl-indenyl) (4
dimethylselenide(2-methyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

dimethylselenide(2-methyl-indenyl) (4- butadiene) zirconium,

dimethylchlorosilane (4- butadiene) zirconium,

dimethylselenide(2-methylbenzhydryl)(4- butadiene) zirconium,

dimethylsilanol(2-methylbenzhydryl) (2-methyl-indenyl) (4- butadiene) zirconium,

dimethylsilanol(2-methylbenzhydryl) (2-methyl-4-phenylindane) (4- butadiene) zirconium,

dimethylsilanol(2-methylindenyl) (4-phenylindane) (4- butadiene) zirconium,

dimethylselenide(2-methyl-4-phenyl-indenyl) (4- butadiene) zirconium,

dimethylselenide(2-methyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

dimethylselenide(2-methyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

methylphenylamine-(fluorenyl) (cyclopentadienyl) (4- butadiene) zirconium,

diphenylmethylene-(fluorenyl) (cyclopentadienyl) (4- butadiene)zirconium,

isopropylidene-(3-methylcyclopentadienyl) (fluorenyl) (4- butadiene)zirconium,

(dimethylsilanol-(3-tert.-butylcyclopentadienyl) (fluorenyl) (4- butadiene) zirconium,

defenseunder-(3-trimethylsilyl) cyclopcedia) zirconium,

phenylethylenediamine (4- butadiene) zirconium,

phenylethylenediamine (2-methyl-4,5-benzhydryl) (4- butadiene) zirconium,

phenylmethylsulfonyl(2-methyl-4,5-benzhydryl) (2-methyl-indenyl) (4- butadiene) zirconium,

phenylmethylsulfonyl(2-methyl-4,5-benzhydryl) (2-methyl-4-phenylindane) (4- butadiene) zirconium,

phenylmethylsulfonyl(2-methylindenyl) (4-phenylindane) (4- butadiene) zirconium,

phenylethylenediamine(2-methyl-4-phenyl-indenyl) (4- butadiene) zirconium,

phenylethylenediamine(2-ethyl-4-phenyl-indenyl) (4- butadiene) zirconium,

phenylethylenediamine(2-methyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

phenylethylenediamine(2-methyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

ethylenebis(2-methyl-indenyl) (4- butadiene) zirconium,

ethylenevinyl (4- butadiene) zirconium,

ethylenebis(2-methyl-4,5-benzhydryl) (4- butadiene) zirconium,

ethylene(2-methyl-4,5-benzhydryl) (2-methyl-indenyl) (4- butadiene) zirconium,

ethylene(2-methyl-4,5-benzhydryl) (2-methyl-4-phenylindane) (4- butadiene) zirconium,

ethylene(2-methylindenyl) (4-phenylindane) (4- butadiene) zirconium,
< 4
- butadiene) zirconium,

ethylenebis(2-methyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

ethylenebis(2-methyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

ethylenebis(2-ethyl-4-phenyl-indenyl) (4- butadiene) zirconium,

ethylenebis(2-ethyl-4,6-aminobutiramida indenyl) (4- butadiene) zirconium,

ethylenebis(2-ethyl-4-naphthyl-indenyl) (4- butadiene) zirconium,

dimethylselenide(2-ethyl-4-phenyl-indenyl) (4- butadiene) zirconium,

dimethylselenide(2,3,5-trimethylcyclopentanone) (4- butadiene) zirconium,

1,6-{bis[methylsilyl-bis (2-methyl-4-phenyl-indenyl) (4- butadiene)zirconium]}hexane,

1,6-{bis[methylsilyl-bis(2-ethyl-4-phenyl-indenyl) (4- butadiene) zirconium] }hexane,

1,6-{ bis[methylsilyl-bis(2-methyl-4-nafti l-indenyl) (4- butadiene) zirconium]}hexane,

1,6-{ bis [methylsilyl-bis(2-methyl-4,5-benzhydryl) (4- butadiene-Zirconia]}hexane,

1,6-{bis[methylsilyl-(2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (4- butadiene) zirconium]}hexane,

1,2-{ bis[methylsilyl-bis(2 - methyl-4-phenyl-indenyl) (4- butadiene) zirconium]}ethane,

1,2-{bis[methylsilyl-bis(2-ethyl-4-phenyl-indenyl) (4- butadiene)zirconium]} ethane,

1,2-{ bis[methylsilyl-bis (2-methyl-4-Nabataean) zirconium]}ethane,

1,2-{ bis[methylsilyl-(2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (4- butadiene) zirconium]}ethane.

The present invention relates also to a catalyst containing at least one transition metal compound according to the invention as socializaton and at least one metallocene, and a method of producing olefin polymer by polymerization of at least one olefin in the presence of the catalyst according to the invention. The polymerization may be Homo - or copolymerization.

Preferably will polimerizuet olefins of the formula R-CH=CH-Rin which Rand Rthe same or different and mean a hydrogen atom, halogen atom, alkoxy group, hydroxy, alkylperoxy, aldehyde, carboxyl or ester group or a saturated or unsaturated hydrocarbon residue with 1-20 carbon atoms, in particular with 1-10 C-atoms which may be substituted by alkoxy group, hydroxy, alkylperoxy, aldehyde, carboxyl or ester group, or Rand Rtogether with the atoms connecting them form one or more rings. Examples of such olefins are 1-olefins, neprimerimogo, tetracyclinea, ethylidenenorbornene, diene, such as 1,3-butadiene or 1,4-hexadiene, bicyclopentadiene or methyl ester of methacrylic acid.

In particular, homopolymerization subjecting propylene and ethylene, the ethylene will copolymerized with one or more3-C20-1-olefins, in particular propylene, and/or one or more4-C20-danami, in particular 1,3-butadiene? or will copolymerized with norbornene or ethylene.

The polymerization is conducted preferably at a temperature of from -60 to 300oC, particularly preferably from 30 to 250oC. the Pressure is from 0.5 to 2500 bar, preferably from 2 to 1500 bar. The polymerization is conducted continuously or periodically, in one or several stages, in solution, in suspension, in gas phase or in a supercritical medium.

The connection according to the invention can be applied to media alone or with metallocene. Suitable media are, for example, silica gel, alumina or other inorganic materials, for example magnesium chloride. Suitable carrier is a powder, fine polyolefin.

System of a carrier in powder form or with the remnants of the solvent can LASS="ptx2">

Using the catalyst according to the invention can be terpolymerization. For terpolymerization preferably used used for the polymerization of olefins or one of them.

To obtain olefin polymers with a wide distribution of molecular weight is used preferably catalytic systems that contain two or more different metallocene.

Removal present in the olefin catalyst poisons carried out mostly clean with trimethylaluminum, triethylaluminum or triisobutylaluminum. This cleaning can be carried out either directly in the polymerization system, or prior to being fed into the polymerization system, olefin is brought into contact with the connection of aluminum and then share.

As molecular weight regulator and/or to improve the activity if necessary add hydrogen. The total pressure in the polymerization system is from 0.5 to 2500 bar, preferably 2 to 1500 bar. This corresponds to the invention the connection is used in a concentration, in terms of the transition metal, preferably equal to 10-3-10-8mainly 10-4-10-7mole of the transition metal is firs to get as chemical compounds according to the invention, and the catalytic system according to the invention are aliphatic or aromatic solvents, such as hexane or toluene, ether solvents such as tetrahydrofuran or diethyl ether, or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons, such as o-dichlorobenzene.

Before applying the catalytic system, in particular catalytic system with media (containing at least one relevant to the invention the connection of at least one metallocene, media and/or powdered polyolefin in fine condition), you can optionally type in the reactor other alkylamine compound, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylamine or isoprenaline to ensure inertness polymerization system (for example, for offices present in the olefin catalyst poisons). Connection at a concentration of 100-0,01 mmol A1 / kg content of a polymerization reactor system. Preferably the application of triisobutylaluminum and triethylaluminum in concentrations of 10-0,1 mmol per kg of the contents of the reactor. Due to this, during the synthesis of catalytics shall serve for a more detailed description of the invention.

General data: acquisition and subsequent operation of ORGANOMETALLIC compounds is carried out without contact with air and moisture in the atmosphere of argon (technology Selenka). All the necessary solvents before use absolutetruth through many hours of boiling over appropriate drying agent and subsequent distillation under argon.

EXAMPLE 1: 1,4 - bis(debentureholders)-2,3,5,6-tetrafluorobenzene

1.54 g (5 mmol) of dibromotetrafluoroethane dissolved in 40 ml of n-hexane and cooled to -78oC. To this solution slowly drops serves to 6.4 ml of n-BuLi (10 mmol) and stirred for 1 hour. Then 1,90 g (5 mmol) of bis pentafluorophenyl of bacillaria dissolved in 40 ml of n-hexane and serves drops to the above solution. The resulting suspension is slowly heated to room temperature, thus there is a white precipitate. It is separated by filtration and the resulting filtrate is vacuum concentrated. The output obtained as a yellow oil 1,4-bis (debentureholders)-2,3,5,6-tetrafluorobenzene is 81%.

19F-NMR (C6D6): -134,8 ppm (m, 4F, o-B(C6F5)2, -150,3 ppm (m, 2F, n-(C6F5)2); -161,0 ppm (m, 4F,6F4); -162 ppm (m, 4F, m-B(C6F5)2)
oC. To this solution slowly drops serves 1,90 g (5 mmol) of bis(pentafluorophenyl)-bacillaria in 40 ml n-hexane. Stirred for 1 hour at a temperature of -78oC and then slowly warmed to room temperature. The solvents and the resulting clear removed in high vacuum. The remaining yellow oil is then fractionary distillation. Thus obtain 2.2 g of bis (departuresarrivals)-acetylene (output 61.7 per cent).

19F-NMR (C6D6): -132,7 ppm (m, 4F, o-(C6F5)2); -158,1 ppm (m, 2F, n-(C6F5)2); -159,8 ppm (m, 4F, m-(C6F5)2)

EXAMPLE 3: [(debentureholder) ethinyl] trimethylsilane

1.12 g (5 mmol) (jodatime)trimethylsilane dissolved in 40 ml of tetrahydrofuran and cooled to -78oC. To this solution slowly drops serves 3.2 ml n-BuLi (5 mmol, 1.6 M in hexane) and stirred for 2 hours. Then 1,90 g (5 mmol) of bis(pentafluorophenyl)bacillaria dissolved in 40 ml of tetrahydrofuran and added in drops to the above solution. The resulting suspension is slowly heated to room temperature, thus there is a white precipitate, which is separated by filtration. From the obtained filtrate under vacuum to remove the solvent. This is B>): -133,7 ppm (m, 4F, o-(C6F5)2); -155,1 ppm (m, 2F, n-(C6F5)2); -160,4 ppm(m, 4F, m-(C6F5)2)

1H-NMR (C6D6): 0.5 ppm(s, 9H, Si(CH3)3)

EXAMPLE 4: [(diphenylphosphino) ethinyl]-debentureholders

of 1.05 g (5 mmol) of diphenyl-getinifopen dissolved in 40 ml of diethyl ether and cooled to -78oC. To this solution slowly drops serves 3.2 ml n - BuLi (5 mmol, 1.6 M in hexane) and stirred for 2 hours. When this occurs a spontaneous red/brown colour of the solution. Then 1,90 g (5 mmol) of bis(pentafluorophenyl)bacillaria dissolved in 40 ml of tetrahydrofuran and added in drops to the above solution. The resulting suspension is slowly heated to room temperature, thus there is a white precipitate, which is separated by filtration and the resulting filtrate is vacuum concentrated until dry. The output obtained as an orange oil [(diphenylphosphino) ethinyl]-deintercalation is 57%.

19F-NMR (C6D6): -134,4 ppm (m, 4F, o-(C6F5)2); -155,6 ppm (m, 2F, n-(C6F5)2); -161,1 ppm (m, 4F, m-(C6F5)2)

1H-NMR (C6D6): 7,0 - of 7.3 ppm (m, 10H, P(C6H5is oral

0,62 g bromopentafluorobenzene (2.5 mmol) is dissolved in 40 ml of n-hexane and at a temperature of -78oC add 1.6 ml of n-BuLi (2.5 mmol, of 1.6 M in hexane). The suspension is stirred for 1 hour at a temperature of -10oC. Then 2.1 g (2.5 mmol) of 1,4 - bis(departuresarrivals)-2,3,5,6-tetrafluorobenzene in 40 ml of n - hexane are slowly added in drops to the above solution. The resulting suspension is slowly heated to room temperature, thus there is a precipitate, which is separated by filtration and the resulting filtrate is vacuum concentrated until dry. Thus obtained lithium salt was dissolved in 40 ml of n-pentane and mixed at room temperature with 0.7 g (2.5 mmol) of triphenylmethylchloride. After 8 hours of stirring sucked orange solid. The filtrate is extracted in methylene chloride to separate the formed LiCl. The deposition of n - pentane allows you to select an orange solid (yield 56%).

19F-NMR (C6D6): -133,2 ppm (m, 4F, o-(C6F5)2); -134,8 ppm (m, 6F, o-(C6F5)2); -152,6 ppm (m, 2F, n-(C6F5)2); -155,2 ppm (m, 3F, n-B(C6F5)2); -160,8 ppm (m, 4F,6F4); -162,8 ppm(m, 4F, m-(C6F5)2); -165,9 ppm(m, 6F, m - B(Cthe 6:

10 g of SiO2(MS 3030, Fa, PQ, dried at 600oC in a stream of argon) are suspended in 50 ml of toluene and added dropwise with constant stirring, slowly add a solution of 100 mg (0,229 mmol) dimethylsilane(2-methylindenyl)zeronicotine and 128 mg (0,153 mmol) of 1,4-bis(debentureholders)-2,3,5,6-tetrafluorobenzene in 3 ml of toluene. After stirring for 1 hour then remove the solvent in vacuo to achieve constant weight. For introduction into the polymerization system 1 g of the catalyst carrier resuspending 30 cm3Zola EHH (EHH sol).

Polymerization:

In parallel, a dry reactor volume 16 DM3purge with nitrogen and then with propylene and with 10 DM3liquid propylene. Then diluted with 0.5 cm3a 20% solution of triisobutylaluminum in Warzone (Varsol) with 30 cm3Zola EHH (EHH sol) is added to the reactor and stirred the mixture for 30 minutes at a temperature of 30oC. Then, the reactor serves a suspension of the catalyst. The reaction mixture is heated to the polymerization temperature of 60oC (4oC/min) and the polymerization system was incubated for 1 hour at a temperature of 60oC upon cooling. The polymerization is stopped by venting the gaseous stattera there are no deposits on the inner surface and on the stirrer. The catalyst activity is 144 kg of polypropylene/g of metallocene per hour.

EXAMPLE 7:

In a solution of 100 mg (0,229 mmol) dimethylsilane (2 - methylindenyl)zeronicotine and 143 mg (0,114 mmol) triphenylcarbenium [(debentureholders) -2,3,5,6-tetrafluorophenyl] -carpentercarpenter.ca in 50 ml of toluene portions serves 10 g of SiO2(MS 3030, Fa, PQ, dried at 600oC in a stream of argon). After stirring for 1 hour to remove the solvent in vacuo to achieve constant weight. For introduction into the polymerization system 1 g of the catalyst carrier resuspendable 30 cm3Zola EHH (EHH sol).

Polymerization:

In parallel, a dry reactor volume 16 DM3purge with nitrogen and then with propylene and with 10 DM3liquid propylene. Then diluted with 0.5 cm3a 20% solution of triisobutylaluminum in Warzone (Varsol) with 30 cm3Zola EHH (EHH sol), is added to the reactor and stirred the mixture for 30 minutes at a temperature of 30oC. Then, the reactor serves a suspension of the catalyst. The reaction mixture is heated to the polymerization temperature of 60oC (4oC/min) and the polymerization system was incubated for 1 hour at a temperature of 600oC upon cooling. The floor is drying Cabinet. Received 1.8 kg of polypropylene powder. In the reactor there are no deposits on the inner surface and on the stirrer. The catalyst activity is 186 kg of polypropylene/g of metallocene per hour.

EXAMPLE 8

OBTAINING CATALYTIC SYSTEM

To a solution of 56 mg (90 ╬╝mol) dimethylsilane(2-methyl-4-phenyl-indenyl)-zirconiabased 9.9 ml of toluene, add 0.1 ml of trimethylaluminum (2 M in toluene, 200 mmol) and the solution stirred for 30 minutes at room temperature. Then portioned add 225 mg (180 mmol) of the compound obtained according to example 5. Then carry out stirring for one hour at room temperature. The color of the solution changes from yellow to red.

EXAMPLE 9

POLYMERIZATION

Autoclave for polymerization of 300 ml fill in argon atmosphere 150 ml of heptane. Then metered in 1.1 ml of triisobutylaluminum (20%) and stirred for 20 minutes at 20oC. thereafter, the reactor is heated to 50oC and inject 0.25 ml of the catalyst obtained according to example 8. Then add the ethylene pressure 10 bar, and conducting polymerization for one hour at a constant pressure of ethylene.

As a result of polymerization floor is C.

1. Organoboron compound of the formula I

[RjM-Xd-MRj]a-c;

d equals 1;

j is an integer from 1 to 3;

A is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl-cation or compound Quaternary ammonium.

2. Organoboron compound of the formula I on p. 1, where R are, independently of one another, identical or different and signify a group of C1- C40-alkyl, C6- C40-aryl, C6- C40-halogenared; X are, independently of one another, identical or different and signify a group of C6- C40-halogenation, C2- C40-akinyan.

3. Organoboron compound of formula I under item 1 or 2, where R is a halogenated C6- C40-allgraph, C7- C40-arylalkyl; M is an element of IIIa group of the Periodic system of elements, a, b and c is equal to 0, 1 or 2; j is 3 and A is an ion of carbene or a Quaternary ammonium ion.

4. The method of obtaining the organoboron compounds of the formula I according to one or more paragraphs.1 to 3, characterized in that the compound of formula YXY in the presence of a base is subjected to interaction with compounds which my group and X, M, R, j and A have the meanings specified in paragraph 1.

5. Catalytic system for producing olefin polymer containing at least one boron compound and at least one metallocene-zirconocene, characterized in that the quality of organoboron compounds it contains a compound of the formula I on PP.1 - 3.

6. The catalytic system under item 5, characterized in that it further comprises a carrier.

7. Organoboron compound of the formula I according to one or more paragraphs.1 to 3, is used to obtain a catalytic system under item 5 or 6.

8. The method of obtaining the olefin polymer by polymerization of at least one olefin in the presence of a catalytic system containing at least one boron compound and at least one metallocene-zirconocene, wherein the method is carried out in the presence of a catalytic system under item 5 or 6.

9. Organoboron compound of the formula I according to one or more paragraphs.1 to 3 used in the preparation of olefin polymer.

10. The polyolefin, characterized in that it is obtained by the method according to p. 8.

 

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