CN1268951A - Metallocene, ligands and olefin polymerization - Google Patents

Abstract

A class of metallocene compounds is disclosed having the following general formula (I): Rn(Cp)(A)MLp wherein Rn is a structural bridge; Cp is a heterocyclic cyclopentadienyl group of formula (II) wherein R<1> and R<2> are hydrogen or hydrocarbon groups; M is a transition metal of group 3, 4, 5 or 6 or to the lanthanides or the actinides in the Periodic Table or the Elements (new IUPAC version); L is a monoanionic ligand; Z is NR<3> or O; X and Y are selected from (CR<4>2)n, BR<4>2, PR<4>, SiR<4>2 or GeR<4>2; and substituents R<4> are hydrogen atoms or hydrocarbon radicals, with the proviso that both X and Y cannot be carbon atoms at the same time; A is a group selected from substituted or unsubstituted cyclopentadienyls, which may carry one or more condensed cycles, =NR<5>, -O-, -S- and =PR<5> groups, R<5> being defined as substituents R<1> and R<2>, and groups corresponding to formula (II); p is an integer from 0 to 3. These metallocene compounds are useful as catalyst components for the polymerization of olefins.

Description

Metallocene, Ligand and Olefin Polymerization Methods

field of invention

The present invention relates to a new class of metallocene compounds, as well as olefin polymerization catalysts containing them and processes for polymerization in the presence of said catalysts. The invention also relates to the corresponding ligands used as intermediates in the synthesis of said metallocene compounds, and to processes for the preparation of said ligands and said metallocene compounds.

Description of prior art

Metallocene compounds having two cyclopentadienyl groups are known as catalyst components for olefin polymerization.

European Patent 0129368, for example, describes a catalyst system for the polymerization of olefins comprising (a) a biscyclopentadienyl coordination complex with a transition metal and (b) an aluminoxane. Two cyclopentadienyl groups can be linked by a bridging group, which is usually a divalent group containing one or more carbon atoms or heteroatoms. Bridged metallocene compounds in which cyclopentadiene groups are fused into an aromatic or non-aromatic ring are also known.

For example, European patent application EP 0185918 describes the preparation of isotactic polyolefins using ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride together with a suitable cocatalyst.

Metallocene compounds in which the cyclopentadienyl group contains substituent-containing heteroatoms, and catalysts containing them are also known.

Metallocene compounds having heteroatom-containing cyclopentadienyl groups as part of a substituted or fused ring system are known from European patent application EP-A2-0743317. Illustrative examples are indenyl substituted with quinoline or pyridyl. These catalysts containing said metallocenes can be used for the polymerization of olefins.

U.S. Patent 5,489,659 relates to a class of silicon-containing metallocene compounds for α-olefin polymerization, wherein the silicon atom is part of a non-aromatic ring fused to a cyclopentadienyl ring, such as ethylene dichloride bis (4,4-Dimethyl-4,5,6,7-tetrahydro-4-silaindenyl)zirconium.

European patent application EP 0590486 describes metallocene compounds containing cyclopentadienyl groups containing heteroatoms in different systems for the preparation of polyolefins. The only illustrative examples are bis(1-phospha-2,3,4,5-tetramethylcyclopentadienyl)zirconium dichloride and tetrakis(2,5-dimethylpyrrole)zirconium. International Patent Application PCT/EP97/6297, by the same applicant, discloses a class of bridged and non-bridged heterocyclic metallocene compounds containing cyclopentadiene fused to a heteroatom-containing ring Alkenyl. Catalyst systems containing said metallocenes are used for the polymerization of olefins.

It would be desirable to provide a new class of metallocenes which, when used as catalysts for the polymerization of olefins, are suitable for the preparation of polyolefins.

Brief description of the invention

The present inventors have unexpectedly discovered a new class of metallocene compounds containing a specific cyclopentadienyl ligand system which can be advantageously used as catalyst components for the polymerization of olefins.

According to a first aspect, the present invention provides metallocene compounds of formula (I):

R _n (Cp)(A)ML _p

where _Rn is a structural bridge;

Cp is heterocyclopentadienyl of formula (II):

Wherein the substituents R ¹ and R ² , the same or different, are hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aromatic Group, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optional two adjacent substituents R ¹ and R ² can form a ring containing 5-8 carbon atoms, in addition, the substituent ^R1 and ^R2 may contain silicon or germanium atoms;

Z is NR ³ or O, the definition of R ³ is the same as that of substituents R ¹ and R ² ;

X and Y, the same or different, are selected from (CR ⁴ ₂ ) _r , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ ; the substituent R ⁴ , the same or different, is a hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl; In addition, the substituent ^R4 may also contain heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atoms, provided that both X and Y cannot be carbon atoms at the same time;

A is selected from substituted or unsubstituted cyclopentadienyl which may bear one or more fused rings, =NR ⁵ , -O-, -S-, and =PR ⁵ The group, R ⁵ has the same definition as the substituents R ¹ and R ² , and corresponds to the group of formula (II);

M is those transition metals selected from Groups 3, 4, 5 or 6 of the Periodic Table of the Elements (new IUPAC edition) or the lanthanides or actinides;

Substituents L, identical or different, are monovalent anionic ligands selected from hydrogen, halogen, -SR ⁶ , R ⁶ , -OR ⁶ , -NR ⁶ ₂ , OCOR ⁶ , OSO ₂ CF ₃ and PR ⁶ ₂ , wherein the substituents R ⁶ , the same or different, are linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optionally containing silicon or germanium atoms;

p is an integer from 0 to 3, and p is equal to the oxidation state of metal M minus 2;

n is an integer from 0-4; and

r is an integer of 1-4.

According to another aspect of the present invention, a new class of ligands such as formula (III) is provided

R _n (Cp)(A) _q

Wherein R, n, Cp, A have the same meaning as above, when n is 0, q is 0, and when n is 1-4, q is 1, and this ligand is especially used as the alkene in the preparation formula (I) Intermediate products of metal compounds.

Another aspect of the invention is a process for the preparation of ligands _Rn (Cp)(A) _q of formula (III), wherein _Rn , Cp, A and q have the same meanings as above.

Yet another aspect of the present invention is a process for the preparation of metallocene compounds of formula (I), which comprises combining a ligand of formula (III) R _n (Cp) (A) _q with molecular formula ML _p+2 , wherein M , L and p are as defined above, contacted in the presence of a compound capable of forming the corresponding dianionic compound of the ligand of formula (III).

Another aspect of the present invention is a catalyst for olefin polymerization containing said heterocyclic metallocene and its use in olefin polymerization.

Detailed description of the invention

The labeling of the substituent on the cyclopentadienyl of formula (II) in the present invention is as follows:

In the above-mentioned types of metallocene compounds, the cyclopentadienyl group of formula (II) can be passed through a divalent group containing one or more carbon atoms, such as CH ₂ group, or a divalent group containing atoms other than carbon atoms group, such as dimethylsilyldiyl, connected to an identical cyclopentadienyl group, connected to a cyclopentadienyl derivative, or connected to a heteroatom-containing group, such as an amino group, the divalent The group attaches the cyclopentadienyl group to the same cyclopentadienyl group, cyclopentadienyl derivative or heteroatom-containing group at the 4-position of the above ring system.

A class of advantageous heterocyclic metallocenes corresponding to the formula (I) according to the invention, wherein A is a group selected from substituted or unsubstituted cyclopentadienyl, which may carry one or more aromatic Aromatic or non-aromatic fused rings, such as indenyl, fluorenyl, benzindenyl, hydrogenated or partially hydrogenated rings, n is not 0, that is, two cyclopentadienyl groups pass through a divalent The abutments are connected to each other. Preferably, the divalent group (QR ⁷ _m ) _n is selected from CR ⁷ ₂ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ , the R ⁷ group is the same or Different, optionally linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl , C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, when Q is C, Si or Ge, two substituents R ⁷ can form a ring containing 3-8 atoms. More preferably, the divalent group is Si(CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ or C(CH ₃ ) ₂ .

m is 1 or 2, 1 when Q is N or P, 2 when Q is C, Si or Ge; the range of n is 0-6 and, when n>1, the atom Q can be the same or different, Such as, for example, the bridging groups _-CH2 -Si( _CH3 ) _2- , _-CH2 - ^NR2- , and _CH2 - ^PR2- .

The transition metals are preferably titanium, zirconium and hafnium, more preferably zirconium.

The substituents ^R1 and ^R2 are preferably hydrogen atoms.

The substituent L is preferably a halogen atom or an R ⁶ group, and R ⁶ is as defined above. More preferably they are chlorine atoms or methyl groups.

A more advantageous class of heterocyclic metallocenes according to the invention corresponds to the formula (I), wherein A is represented by the above formula (II), that is, the two cyclopentadiene groups of the metallocene compounds of the invention Are the same.

Non-limiting examples of such metallocenes are:

Dichloride or dimethyl isopropylidenebis{2-(methyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c ] [1,2,5] azadisilole (azadisilole) zirconium;

Dichloride or dimethyl isopropylidenebis{2-(ethyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c ][1,2,5]azadisilacyclopentene}zirconium;

Dichloride or dimethylisopropylidenebis{2-(isopropyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[ c] [1,2,5] azadisilacyclopentene} zirconium;

Dichloride or dimethylisopropylidenebis{2-(tert-butyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene And[c][1,2,5]azadisilacyclopentene}zirconium;

Dichloride or dimethylisopropylidenebis{2-(ethyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene [c][1,2,5]azadisilacyclopentene}zirconium;

Dichloride or dimethylisopropylidenebis{2-(isopropyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene And[c][1,2,5]azadisilacyclopentene}zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c] [1,2,5]azaborasilole (azaborasilole) zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c] [1,2,5]azaphosphasilole} zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1 , 2,5] azadiborole} zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1 , 2,5] Azadiphosphole (azadiphosphole)} zirconium;

Dichloride or dimethyl isopropylidenebis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[ c] [1,2,5]azaborosasilole} zirconium;

Dichloride or dimethyl isopropylidenebis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[ c] [1,2,5] azaphosphasilacyclopentene} zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c] [1,2,5]aza-diborole}zirconium;

Dichloride or dimethyl·isopropylidenebis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c] [1, 2, 5] aza meta-diphosphole} zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,1,3,-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene And[c][1,2,5]azaborosasilole}zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene Alkeno[c][1,2,5]azaphosphorasilyl}zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c ][1,2,5]aza-diborole}zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c ][1,2,5]aza-diphosphorole}zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene [c][1,2,5]aza-diborole}zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene [c][1,2,5]aza-2-phosphorole}zirconium;

Dichloride or dimethyl isopropylidene {2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopentadiene[c] [1,2]azasiline} zirconium;

Dichloride or dimethyl dimethylsilyl diylbis{2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopentadiene And [c] [1,2] azasiloline} zirconium;

Another interesting class of heterocyclic metallocenes according to the invention corresponds to formula (I), where A corresponds to formula (II) and n=0, ie two identical cyclopentadienyl groups have no Connected to each other through a divalent bridging base.

Said non-limiting examples of such are:

Dichloro or dimethyl{2-(tert-butyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2 , 5] aza-disilacyclopentene} zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1 , 2,5] aza-disilacyclopentene} zirconium;

Dichloro or dimethyl{2-(methyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2, 5] Aza-disilacyclopentene} zirconium;

Dichloro or dimethyl{2-(methyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1, 2,5] Azadisilacyclopentene} zirconium;

Dichloro or dimethyl{2-(ethyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2, 5] Aza-disilacyclopentene} zirconium;

Dichloro or dimethyl{2-(ethyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1, 2,5] Azadisilacyclopentene} zirconium;

Dichloro or dimethyl{2-(isopropyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2 , 5] aza-disilacyclopentene} zirconium;

Dichloro or dimethyl{2-(isopropyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1 , 2,5] aza-disilacyclopentene} zirconium;

Dichloride or dimethyl{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5 ]azaborosasilole}zirconium;

Dichloride or dimethyl{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5 ] azaphosphasilole} zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen intercalated diborole (azadiborol) zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen Heterodiphosphorole}zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2 , 5] azaborasilazine} zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2 , 5] azaphosphasilole} zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2,5 ]aza-diborole}zirconium;

Dichloro or dimethyl{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2,5 ]aza-diphosphorole}zirconium;

Dichloride or dimethyl{2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta[c][1,2] Azasiloline} zirconium;

Dichloride or dimethyl{2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta[c][1,2] Zirconium azasiloline;

According to another aspect of the present invention, there is provided a class of ligands of formula (III):

R _n (Cp)(A) _q (II])

where _Rn is a structural bridge;

Cp is heterocyclopentadienyl of formula (IV):

Wherein R, R ¹ , R ² , X, Y and Z, n and q have the same meanings as above, and A is a group selected from substituted or unsubstituted cyclopentadienyl, which may carry one or more fused rings, =NR ⁵ , -O-, -S- and =PR ⁵ groups, R ⁵ as defined for substituents R ¹ and R ² , and groups corresponding to formula (IV).

The two double bonds of the cyclopentadienyl ring of the ligand of formula (IV) can be in any permissible position.

Compounds of formula (IV) above are particularly useful as intermediate ligands for the preparation of heterocyclic metallocene compounds of formula (I).

An advantageous class of heterocyclic ligands corresponding to the formula (III) according to the invention, wherein A is a group selected from substituted or unsubstituted cyclopentadienyl groups, which may carry one or more Aromatic or non-aromatic fused rings, such as indenyl, fluorenyl, benzindenyl, hydrogenated or partially hydrogenated rings, n is not 0, that is, two cyclopentadienyl groups through a divalent bridge bases are connected to each other. As for the divalent group _Rn, reference can be made to the above description.

A more advantageous class of heterocyclic ligands according to the invention corresponds to formula (III) in which n is not 0 and A corresponds to formula (IV).

According to the invention, non-limiting examples of such ligands are:

Isopropylidenebis{2-(tert-butyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5 ]azadisilacyclopentene};

Isopropylidenebis{2-(methyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5] Azadisilacyclopentene};

Isopropylidenebis{2-(ethyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5] Azadisilacyclopentene};

Isopropylidenebis{2-(isopropyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2,5 ]azadisilacyclopentene};

Isopropylidenebis{2-(tert-butyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2 , 5] aza-disilacyclopentene};

Isopropylidenebis{2-(ethyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2, 5] Aza-disilacyclopentene};

Isopropylidenebis{2-(isopropyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2 , 5] aza-disilacyclopentene};

Isopropylidenebis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen Borasilacyclopentene};

Isopropylidenebis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen heterophosphasilacyclopentene};

Isopropylidenebis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azepine Diborole};

Isopropylidenebis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azepine diphosphole};

Isopropylidenebis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2,5 ]azaborosasilole};

Isopropylidenebis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene[c][1,2,5 ]azaphosphasilacyclopentene};

Isopropylidenebis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen heterodiborole};

Isopropylidenebis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen heterodiphospholene};

Dimethylsilyldiylbis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2, 5] azaborasilacyclopentene};

Dimethylsilyldiylbis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2, 5] Azaphosphasilacyclopentene};

Dimethylsilyldiylbis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5] Aza-diborole};

Dimethylsilyldiylbis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5] Aza-diphosphorole};

Dimethylsilyldiylbis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1, 2,5] azaborasilole};

Dimethylsilyldiylbis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1, 2,5] azaphosphasilacyclopentene};

Dimethylsilyldiylbis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2, 5] aza-diborole};

Dimethylsilyldiylbis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2, 5] aza-diphosphole};

Isopropylidenebis{2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta[c][1,2]azepine Silicone (azasiline)};

Dimethylsilyldiylbis{2-(tert-butyl)-1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopentadien[c][1,2 ]azasiloline};

Another interesting class of ligands according to the invention corresponds to formula (III), where A corresponds to formula (IV) and n=0, ie two identical cyclopentadienyl groups do not pass through each other The bivalent bridging bases are interconnected.

Non-limiting examples of such ligands are:

Bis{2-(tert-butyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]aza disilacyclopentene};

Bis{2-(tert-butyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen Inter-disilacyclopentene};

Bis{2-(methyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]aza Silole};

Bis{2-(methyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]azepine m-disilacyclopentene};

Bis{2-(ethyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]aza Silole};

Bis{2-(ethyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azepine m-disilacyclopentene};

Bis{2-(isopropyl)-1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]aza disilacyclopentene};

Bis{2-(isopropyl)-1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen Inter-disilacyclopentene};

Bis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]azaborasila heterocyclopentene};

Bis{2-(tert-butyl)-1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azaphosphasilicate heterocyclopentene};

Bis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azaborine pentene};

Bis{2-(tert-butyl)-1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]aza-diphosphorane pentene};

Bis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]azaborin heterosilacyclopentene};

Bis{2-(tert-butyl)-1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azaphosphorus heterosilacyclopentene};

Bis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopentadieno[c][1,2,5]azainter-diboron heterocyclopentene};

Bis{2-(tert-butyl)-1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]aza-diphosphorus heterocyclopentene};

和其双键异构体，其中X、R¹和R²的定义同上：Z是氮，与通式YZ’₂的化合物接触，其中Y的定义同上，Z’是卤素原子，形成式(VI)化合物和其双键异构体的步骤。According to another aspect of the present invention, there is provided a method for preparing a ligand of formula (III) R _n (Cp) (A) _q , wherein R is as described above, Cp corresponds to formula (IV), A has the same meaning as above and n and q are all 0, the method comprises in the presence of a base, making the compound of formula (V):

And its double-bond isomer, wherein X, R ¹ and R ² are as defined above: Z is nitrogen, contacted with a compound of general formula YZ' ₂ , wherein Y is as defined above, and Z' is a halogen atom, forming formula (VI ) compound and the steps of its double bond isomers.

The above cyclopentadienyl derivatives of formula (V) can be prepared by known methods, such as those described in International Patent Application PCT/US92/08730.

According to another aspect of the present invention, there is provided a method for preparing the R _n (Cp) (A') _q ligand of formula (IIIa), wherein R is as defined above, n is an integer of 1-4 and q is 1, That is to say, the two groups of Cp and A' are connected by a divalent bridging group, and A' is a group selected from substituted or unsubstituted cyclopentadienyl groups, which can carry one or more Condensed rings, groups of =NR ⁵ , -O-, -S- and =PR ⁵ , R ⁵ is defined as substituents R ¹ and R ² , Cp corresponds to formula (IV) and Z' is a halogen atom, The method includes the following steps:

和其双键异构体，其中X、R¹和R²的定义同上，Z是氮，与通式YZ’₂的化合物接触，其中Y和Z’的定义同上，形成式(VI)化合物和其双键异构体，和(a) in the presence of a base, make the compound of formula (V)

and its double bond isomer, wherein X, ^R and ^R are as defined above, and Z is nitrogen, contact with a compound of general formula YZ _' , wherein Y and Z' are as defined above, to form a compound of formula (VI) and its double bond isomers, and

(b) contacting with a compound capable of forming an anion of formula (VII), and thereafter contacted with a compound of general formula (VIII),

R _n Z' ₂ (VIII) molar ratio (VII)/(VIII) is equal to or greater than 2, or is contacted with the compound of general formula (IX),

The Z'R _n A'HR ⁵ (IX) molar ratio (VII)/(IX) is equal to or greater than 1.

As for the structural bridge R _n in the above ligands, reference can be made to the above description.

Non-limiting examples of all bases which form the compounds of formula (VI) above are alkali metal or alkaline earth metal hydroxides and hydrides, metal sodium or potassium and organometallic lithium compounds. Preference is given to using methyllithium or n-butyllithium.

Non-limiting examples of compounds capable of forming anions of formula (VII) are alkali metal or alkaline earth metal hydroxides and hydrides, metal sodium or potassium and organometallic lithium compounds. Preference is given to using methyllithium or n-butyllithium.

Non-limiting examples of compounds of general formula R _n Z' ₂ (VIII) are dimethyldichlorosilane, diphenyldichlorosilane, dimethyldichlorogermanium, 2,2-dichloropropane and 1,2 - dibromoethane.

The synthesis of the above bridged ligands is preferably carried out by adding a solution of an organolithium compound in a non-polar solvent to a solution of compound (VI) in an aprotic polar solvent. The solution thus obtained containing compound (VII) in anionic form is then added to a solution of formula R _n Z' ₂ in an aprotic polar solvent. The bridging ligands are then finally isolated using generally known methods.

Non-limiting examples of aprotic polar solvents used in the above process are tetrahydrofuran, dimethoxyethane, diethyl ether, toluene and dichloromethane. Non-limiting examples of non-polar solvents suitable for the above process are pentane, hexane and benzene. Throughout the process, the temperature is preferably maintained at -180°C to 80°C, more preferably -20°C to 40°C.

Another aspect of the present invention is the preparation method of the metallocene compound of formula (I), the method for obtaining the metallocene compound is by making the ligand R _n (Cp) (A) _q of the above formula (III) and capable of forming its The compound of the corresponding dianionic compound is then contacted with a compound of formula ML _p+2 , wherein M, L and p are as defined above.

Compounds capable of forming said dianions are alkali metal or alkaline earth metal hydroxides and hydrides, metal sodium or potassium and organometallic lithium salts, preferably said anion is n-butyllithium.

Non-limiting examples of compounds of formula ML ¹ _p+2 are titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.

The metallocene compound of formula (I), when n is not 0 and A is a cyclopentadienyl derivative, the preparation method can be by at first making the bridging ligand of formula (III) prepared as above, and can be in Compounds forming delocalized anions on the cyclopentadienyl ring are reacted with compounds of formula ML _p+2 wherein M and substituents L are as defined above. Non-limiting examples of compounds of formula ML _p+2 are titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.

More specifically, the bridged ligand is dissolved in an aprotic polar solvent, and the resulting solution is added to a solution of the organolithium compound in a nonpolar solvent. The anion thus obtained is isolated, redissolved in an aprotic polar solvent, and thereafter added to a suspension of compound ML _p+2 in an aprotic polar solvent. At the end of the reaction, the obtained solid product is separated from the reaction mixture by methods commonly used in the art. Non-limiting examples of aprotic polar solvents suitable for the above process are tetrahydrofuran, dimethoxyethane, diethyl ether, toluene and dichloromethane. Non-limiting examples of non-polar solvents suitable for the above process are pentane, hexane and benzene.

Throughout the process, the temperature is preferably maintained at -180°C to 80°C, more preferably -20°C to 40°C.

An unbridged metallocene compound of formula (I), wherein n=0 and A corresponds to formula (II), can be obtained by reacting an anion of formula (VII) with a tetrahalide of a transition metal M (ie ML ₄ ) Prepared by reaction, M and L have the same meaning as above, and the reaction is carried out in a suitable solvent.

When at least one L substituent in the metallocene compound of formula (I) is not a halogen, it is necessary to substitute at least one substituent L in the resulting metallocene with at least one other substituent which is not a halogen. Such substitution reactions can be carried out by methods known in the art. For example, when the substituent L is an alkyl group, the metallocene can be reacted with an alkylmagnesium halide (Grignard reagent) or an alkyllithium compound.

Throughout the process, the temperature is preferably maintained at -180°C to 80°C, more preferably -20°C to 40°C.

The heterocyclic metallocene compounds of the present invention can be conveniently used as catalyst components for olefin polymerization.

Therefore, according to still another aspect of the present invention, a catalyst for olefin polymerization is provided, which can be obtained by contacting the following two components:

(A) a metallocene compound of formula (I), and

(B) Aluminoxanes and/or compounds capable of forming alkyl metallocene cations.

_The aluminoxanes ^used as _component (B ⁾ can be obtained by reacting water with an organoaluminum compound of the formula _Al2R83 or _Al2R86 , where at least one ^R8 is not a halogen. in this response. The molar ratio of Al/water is 1:1-100:1.

The molar ratio of aluminum to metal of the metallocene is from about 10:1 to about 20000:1, preferably from about 100:1 to about 5000:1.

The aluminoxanes used in the catalysts of the present invention are considered linear, branched or cyclic compounds containing at least one of the following types of groups:

Wherein R ⁹ substituents, same or different, are hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optionally containing silicon or germanium atoms, or an -O-(AlR ⁹ ) ₂ group and, if appropriate, some of the R ⁸ substituents may be halogen atoms.

的铝氧烷，其中n是2-40的整数和R⁹取代基的定义同上。In particular, for linear compounds, the formula can be used: Aluminoxane, wherein n is 0 or an integer of 1-40 and the substituents of ^R are as defined above, if it is a cyclic compound, the formula can be used:

An aluminoxane, wherein n is an integer of 2-40 and R ⁹ substituents are as defined above.

Examples of alumoxanes suitable for use in the present invention are methylalumoxane (MAO), isobutylalumoxane (TIBAO) and 2,4,4-trimethyl-pentylalumoxane (TIOAO).

In the catalyst used for the preparation of polyolefins in the method of the present invention, both the heterocyclic metallocene compound of formula (I) and aluminoxane can be used as an organometallic aluminum compound with formula Al ₂ R ³ ₃ or Al ₂ R ⁸ ₆ The form of the reaction product exists, wherein R ⁸ substituents, the same or different, are C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkane Aryl or C ₇ -C ₂₀ aralkyl, optionally containing silicon or germanium atoms.

Non ^- limiting examples of aluminum compounds of formula _Al2R86 or ^Al2R86 are Al(Me) ₃ , _Al (Et) ₃ , _AlH (Et) ₂ , Al(iBu _{) 3} , Al(iHex) ₃ , Al(iOct) ₃ , Al(C ₆ H ₅ ) ₃ , Al(CH ₂ C ₆ H ₅ ) ₃ , Al(CH ₂ CMe ₃ ) ₃ , Al(CH ₂ SiMe ₃ ) ₃ , Al(Me) ₂ iBu, Al(Me) ₃ Et, AlMe(Et) ₂ , AlMe(iBu) ₂ , Al(Me) ₂ iBu, Al(Me) ₂ Cl, Al(Et) ₂ Cl, AlEtCl ₂ , Al ₂ (Et) ₃ Cl ₃ , where M = methyl, Et = ethyl, iBu = isobutyl, iHex = isohexyl, iOct = 2,4,4-trimethylpentyl.

Among the aforementioned aluminum compounds, trimethylaluminum (TMA), triisobutylaluminum (TIBAL) and tris(2,4,4-trimethyl-pentyl)aluminum are preferred.

A non-limiting example of a compound capable of forming a metallocene alkyl cation is a compound of the formula T ^{+ D-} , where T ⁺ is a protic acid capable of donating a proton and undergoing an irreversible reaction with the substituent L of the metallocene of formula (I) , and D ^- are compatible anions that are noncoordinating, capable of stabilizing the active catalyst species from the reaction of the two compounds, and are easily removed from the olefinic substrate. Preferably the anion D ^- contains one or more boron ions. More preferably, the anion D ⁻ is an anion of the formula BAr ⁽⁻⁾ ₄ , wherein the substituents Ar, the same or different from each other, are aryl groups such as phenyl, pentafluorophenyl, bis(trifluoromethyl)phenyl. Especially preferred is tetrakis-pentafluorophenyl borate. Furthermore, compounds of the formula BAr ₃ are also suitable.

The catalysts used in the process of the invention can also be used on inert supports. This can be done by depositing metallocene (A), or its reaction product with component (B), or component (B) and subsequently metallocene (A), on a support such as, for example, silicon oxide, aluminum oxide, Styrene-divinylbenzene copolymer, polyethylene or polypropylene.

The solid compound thus obtained, in combination with an alkylaluminum compound added as such or prereacted with water, is usually used for gas phase polymerization.

The catalyst of the present invention can be used for homopolymerization and copolymerization of olefins.

Therefore, still another object of the present invention is a process for the polymerization of olefins comprising the polymerization of at least one olefin monomer in the presence of a catalyst as described above.

The catalyst of the present invention can be used for the homopolymerization of olefins, preferably ethylene, to produce HDPE, or alpha-olefins, such as propylene and 1-butene. In the polymerization of ethylene, the heterocyclic metallocenes of the present invention show good activity even when using very low Al/Zr ratios.

Another interesting application of the catalysts of the invention is the copolymerization of ethylene with higher olefins. In particular, the catalysts of the invention can be used in the preparation of LLDPE.

Suitable olefins that may be used as comonomers include alpha-olefins of the formula _CH2 = ^CHR10 , where ^R10 is an alkyl group of 1-10 carbon atoms, and cycloolefins. Examples of these olefins are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene, 1-esadecene, 1-octadecene, 1-eicosene, allylcyclohexene, cyclopentene, norbornene, and 4,6-dimethyl-1-heptene.

Copolymers may also contain a small proportion of units derived from polyenes, especially linear or cyclic, conjugated or non-conjugated dienes, such as 1,4-hexadiene, isoprene, 1,3- Butadiene, 1,5-hexadiene and 1,6-heptadiene.

The amount of units from alpha-olefins of the formula CH ₂ =CHR ¹⁰ , from cyclic olefins and/or from polyenes in the copolymer is preferably 1-20 mol %.

Saturated elastomeric copolymers may contain ethylene units and units of alpha-olefins and/or non-conjugated dienes capable of ring-opening polymerisation. The unsaturated elastomeric copolymers may contain, together with units derived from the polymerization of ethylene and alpha-olefins, also a minor fraction of unsaturated units derived from the copolymerization of one or more polyolefins. The content of unsaturated units is preferably 0-5% by weight.

Non-limiting examples of suitable alpha-olefins include propylene, 1-butene, and 4-methyl-1-pentene. Suitable copolymerizable non-conjugated dienes include 1,5-hexadiene, 1,6-heptadiene and 2-methyl-1,5-hexadiene.

Non-limiting examples of suitable polyenes are:

(i) Polyenes capable of giving unsaturated units, such as:

- Linear, non-conjugated dienes such as trans-1,4-hexadiene, cis-1,4-hexadiene, 6-methyl-1,5-heptadiene, 3,7-dimethyl -1,6-octadiene and 11-methyl-1,10-dodecadiene;

- bicyclic dienes, such as 4,5,8,9-tetrahydroindene and 6 and 7-methyl-4,5,8,9-tetrahydroindene;

- alkenyl or alkylene norbornene, such as 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene and exo-5-isopropenyl-2-norbornene alkene;

- polycyclic diolefins, such as dicyclopentadiene, tricyclo-[6.2.1.0 ^2.7 ]4,9-undecadiene and its 4-methyl derivatives;

(ii) non-conjugated dienes capable of ring-opening polymerization, such as 1,5-hexadiene, 1,6-heptadiene and 2-methyl-1,5-hexadiene;

(iii) Conjugated dienes such as butadiene and isoprene.

Another object of the present invention is a process for the polymerization of propylene in the presence of the above mentioned catalyst.

A further interesting application of the catalysts of the invention is the preparation of cycloolefin polymers. Monocyclic and polycyclic olefin monomers can be either homopolymerized or copolymerized with linear olefin monomers.

The polymerization process of the present invention can be carried out in the gas phase or in the liquid phase, optionally with an inert hydrocarbon solvent, whether aromatic (such as toluene), or aliphatic (propane, hexane, heptane, isobutane and cyclo hexane), exists.

The polymerization temperature is preferably from about 0°C to about 250°C. In particular, in the process of preparing HDPE and LLDPE, it is preferably 20-150°C, more preferably 40-90°C, and when preparing elastomeric copolymers, it is preferably 0-200°C and, more preferably 20-100°C .

The polymerization pressure is preferably 0.5-100 bar, preferably 2-50 bar, and more preferably 4-30 bar.

Changes in the molecular weight of the polymers can also be achieved simply by varying the polymerization temperature, the type and concentration of catalyst components, or the use of molecular weight regulators such as, for example, hydrogen.

Variation of the molecular weight distribution can be achieved by using mixtures of different metallocenes, or by performing multi-stage polymerizations at different polymerization temperatures and/or different concentrations of molecular weight regulators.

The polymerization yield depends on the purity of the metallocene component of the catalyst. Therefore, in order to increase the polymerization yield, metallocenes are usually used after purification treatment.

The catalyst components may be contacted prior to polymerization. For the metallocene component (A), the precontacted concentration is generally 1-10 ⁻⁸ mol/l, and for component (B) 10-10 ⁻⁸ mol/l. Precontacting is generally carried out in the presence of a hydrocarbon solvent and, if appropriate, small amounts of monomers. Precontact times typically range from 1 minute to 24 hours.

The following examples illustrate rather than limit the invention.

Characteristics of the general method

All manipulations were performed under nitrogen by using conventional Schlenk line techniques. Solvents were distilled in the presence of blue Na-benzophenone ketyl (Et ₂ O), CaH ₂ (CH ₂ Cl ₂ ) or 6AliBu ₃ (hydrocarbon) and stored under nitrogen. BuLi (Aldrich company) was used directly.

¹ H-NMR analysis of the metallocenes was carried out on an AC200 Bruker spectrometer (CD ₂ Cl ₂ , middle peak of the triplet at 5.35 ppm with reference to residual CHDCl ₂ ). All NMR solvents were dried over _P2O5 and distilled before _use . Sample preparation was performed under nitrogen using standard inert atmosphere techniques.

¹ H-NMR and ¹³ C-NMR analyzes of the polymers were carried out on a Bruker 400 MHZ instrument. The samples were analyzed as a solution of tetrachlorodideuterioethane at 130°C. The intrinsic viscosity [η] (dl/g) was measured in tetralin at 135°C.

The melting point Tm (°C) and AH (J/g) of the polymer are determined by differential scanning calorimetry (DSC) on a Mettler apparatus as follows: about 10 mg of a sample obtained from the polymerization The scan rate is heated to 180°C; the sample is kept at 180°C for 5 minutes and thereafter cooled with a scan rate equal to 20°C/min. Then perform a second scan in the same manner as the first scan. The reported value is the data obtained in the second scan.

Density (g/ml) was determined by immersing extruded copolymer samples in a column with a density gradient according to the method of ASTM D-1505.

In the copolymers of the present invention, the product of the activity ratio r ₁ r ₂ , where r ₁ is the relative reactivity of α-comonomer to ethylene and r ₂ is the relative reactivity of ethylene to α-comonomer.

Ligand preparation

(N-tert-butylamino)(dimethyl)(cyclopentadienyl)silane and (N-tert-butyl Amino)(dimethyl)(methylcyclopentadienyl)silane.

Bis(1,3-trimethylsilylcyclopentadienyl)zirconium dichloride was purchased from Boulder Scientific Corporation, Mead Corporation, USA. Bis(cyclopentadienyl)zirconium dichloride was purchased from Strem Chemical Company, Newburyport, MA, USA.

Example 1

Preparation of 1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azadisilacyclopentene

(N-tert-butylamino)(dimethyl)(cyclopentadienyl)silane (0.071mol, 13.9g) was dissolved in THF (100ml) and dissolved in BuLi (144mmol in 2.5M hexane) at 0°C deal with. After stirring at room temperature for 16 hours, the dianion solution and a THF solution (75 ml) of dichlorodimethylsilane (0.071 mol) were simultaneously added dropwise to a flask containing 25 ml of THF at -10°C under stirring. The mixture was warmed to room temperature and stirred overnight. The solvent was removed under vacuum and the residue was extracted with pentane. After filtration and evaporation of pentane, the extract was distilled to give 1.2 g of a colorless liquid identified as 1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c] [1,2,5]Azadisilazoles and isomers. ¹ H-NMRδ(CDCl ₃ ) (main isomer): 6.7 (m, 3H), 5.7 (broad peak s, 2H), 1.3 (s, 9H), 0.2 (s, 12H). Mass spectrum (m/e) (relative density): 251 ([PM], 12), 236 (100), 179 (4), 114 (4), 73 (7).

Example 2

Preparation of 1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azadisilacyclopentene

Dissolve (N-tert-butylamino)(dimethyl)(methylcyclopentadienyl)silane (0.070mol, 14.7g) in THF (199ml) and add butyllithium (0.14mol 2.5M hexane solution). After stirring at room temperature for 16 hours, the dianion solution was added dropwise to a THF solution (100 ml) of dichlorodimethylsilane (0.070 mol, 9.03 g) at -78°C. The mixture was slowly warmed to room temperature and stirred overnight. After evaporation of the solvent, the residue was extracted with pentane, an oil was obtained after filtration and evaporation. Distillation of the oil gave 5.0 g of a colorless liquid identified as 1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5 ] Azadisilazoles and isomers. ¹ H-NMRδ(CDCl ₃ ) (main isomer): (6.3 (m, 1H), 5.8 (broad peak s, 1H), 4.9 (broad peak s, 1H), 2.1 (s, 3H), 1.3 ( s, 9H), 0.3 (broad peak s, 6H), 0.15 (broad peak s, 6H). Mass spectrum (m/e) (relative density): 265 ([PM], 14), 250 (100), 193 ( 3), 135(4), 73(16).

Example 3

1,1,5-Trimethyl-3-phenyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azaborosilacyclopentene preparation

Dissolve (N-tert-butylamino)(dimethyl)(methylcyclopentadienyl)silane (95.7mmol, 20g) in THF (120ml) and cool at -78°C and wash with butyllithium (2.1eq , 201mmol of 2.5M hexane solution) treatment. After the solution was stirred at room temperature for 4 hours, a solution of 95.1 mmol (15.7 g) of PhBCl ₂ in 20 ml of pentane was added dropwise at -78°C. The mixture was slowly warmed to room temperature and stirred overnight. An orange oil was obtained after filtration and evaporation of the solvent. Distillation of the oil gave 7.0 g of a colorless liquid, identified as the title compound. Mass spectrum (m/e) (relative density): 295 ([PM], 80), 280 (70), 239 (30), 224 (70), 160 (100).

Example 4

1,1,5-Trimethyl-3-phenyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azaphosphasilacyclopentene preparation

Dissolve (N-tert-butylamino)(dimethyl)(methylcyclopentadienyl)silane (20mmol, 4.17g) in THF (25ml) and cool at -78°C and wash with butyllithium (40mmol, 16ml of 2.5M hexane solution). After the reaction was complete, it was stirred at room temperature for 1.5 hours. 2.7 ml (20 mmol) of dichlorophenylphosphine and 25 ml of THF were added to a separate 250 ml flask. At -78°C, the above dianion was added dropwise, warmed to room temperature and stirred for 2 hours. 6.61 g of an orange oil were obtained after filtration and evaporation of the solvent. After washing with hexane, 3.68 g of a pentane-soluble oil were obtained, which was identified as the title compound. Mass spectrum (m/e) (relative density): 315 ([PM], 100), 300 (40), 244 (50), 135 (30), 57 (60).

Preparation of metallocenes

Example 5

Bis(1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]azadisilacyclopentene)ZrCl ₂ preparation

Add butyllithium (4.0 mmol in 2.5 M hexane) slowly to 1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopentadiene at -78°C And [c][1,2,5]azadisilacyclopentene (3.8mmol, 0.95g) in ether (30ml) solution. The reaction mixture was warmed to room temperature and stirred for an additional 3 hours. The solvent was removed under vacuum and the residue was mixed with _ZrCl4 (1.9 mmol, 0.443 g) in a glovebox. The mixture was slurried in pentane (40ml)/ether (1ml) and stirred for 16 hours. After evaporating off the solvent, the residue was extracted with dichloromethane and filtered. Evaporation of the filtrate gave 1.0 g of bis(1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta[c][1,2,5]nitrogen in the form of a tan powder heterodisilacyclopentene)ZrCl ₂ , (1,2(tBuN=(SiMe ₂ ) ₂ Cp) ₂ ZrCl ₂ . ¹ H-NMRδ(CD ₂ Cl ₂ ): 6.85(s, 2H), 6.5( t, 1H), 1.4(s, 9H), 0.6(s, 6H), 0.3(s, 6H).

Polymerization of ethylene

Methylaluminoxane (MAO)

A commercial product commercially available from Schering was used as a 10% by weight solution in toluene.

Example 6-9

A dry 200ml glass autoclave equipped with a magnetic stirrer, temperature probe and ethylene feed line was purged with ethylene at 35°C. 90 ml of hexane were introduced at room temperature. The catalyst system was independently prepared in 10 ml of hexane by sequentially introducing methylaluminoxane, or a mixture of triisooctylaluminum/water (Al/H ₂ O = 2.1), and after stirring for 5 minutes, introducing a solution in a small amount of toluene The metallocene compound (1,2(tBuN=(SiMe ₂ ) ₂ Cp) ₂ ZrCl ₂ in . After stirring for 5 minutes, the solution was introduced into the autoclave in ethylene flow, the reactor was closed, the temperature was raised to 80°C, and the Ethylene was pressurized to 4.6 bar (gauge pressure). The total pressure was kept constant as required by feeding ethylene. Polymerization was terminated by cooling, venting the reactor and adding 1 ml methanol. The polymer obtained was washed with acidic methanol, methanol, and Dry in a vacuum oven at 60 ° C. The results are listed in Table 1. The polymerization conditions are shown in Table 1.

Embodiment 10-11 (comparative example)

These examples repeat the procedure described in Examples 6-9, but replace the bis(1,1,3, 3-Tetramethyl-1,2,3-trihydrocyclopentadieno[c][1,2,5]azadisilacyclopentene)ZrCl ₂ . Polymerization conditions are shown in Table 1.

Embodiment 12-13 (comparative example)

These examples repeat the procedure described in Examples 6-9, but substituting bis(cyclopentadienyl)zirconium dichloride for bis(1,1,3,3-tetramethyl-1,2,3-tri Hydrocyclopenta[c][1,2,5]azadisilacyclopentene)ZrCl ₂ . Polymerization conditions are shown in Table 1.

Table 1. Results of ethylene polymerization Example Metallocene Cocatalyst Al/Zr Time Polymer Activity [η], mg (μmol) (mmol) mol.ratio min g Kg/gZr/h dL/g 6 1.00 (1.51) MAO (1.51) 1000 10 2.43 105.83 ND7 0.50 (0.76) MAO (0.76) 1000 10 2.65 230.83 1.48 ^* 8 0.16 (0.24) MAO (0.25) 1026 10 0.84 228.65 1.269 0.50 (0.50) TIOA-H2O 1013 8 0.42 45.73 3.58 (0.765) 10 0.13 (0.22) MAO (0.23) 1028 15 1.34 262.68 2.05 Comparative Example 11 0.13 (0.22) TIOA-H ₂ O 1073 20 0.20 29.40 nd Comparative Example 1 (0.20 nd Comparative Example (0.35) 1023 10 1.07 205.76 2.99 Comparative Example 13 0.30(1.03) TIOA-H ₂ O 997 20 Weight Comparative Example (1.02) nd = not detected

Copolymerization of Ethylene and 1-Hexene

Example 14

A dry 200ml glass autoclave equipped with a magnetic stirrer, temperature probe and ethylene feed line was purged with ethylene at 35°C. Heptane (80ml) and 1-hexene (10ml) were introduced at room temperature. The catalyst system was prepared separately in 10 ml of heptane by sequentially introducing methylaluminoxane (0.33 mmol) and metallocene (0.2 mg) dissolved in 3 ml of toluene. After stirring for 5 minutes, the solution was introduced into the autoclave in a stream of ethylene, the reactor was closed, the temperature was raised to 70°C and the pressure was increased to 4.5 barg (gauge) with ethylene. The total pressure was kept constant as required by feeding ethylene. After 10 minutes, the polymerization was terminated by cooling, venting the reactor and adding 1 ml of methanol. The obtained polymer was washed with acidic methanol, methanol, and dried in a vacuum oven at 60°C. 1.2 g of polymer was recovered (activity 261 Kg/g-Zr/h), and the obtained [?] value was 1.0 dL/g, 7.7% by weight of 1-hexene was incorporated.

DSC analysis (2° melt) (2° melt) Tm = 114°C; ΔH = 142 J/g.

¹³ C-NMR analysis showed the presence of 1-hexene in an amount of 2.72 mol%, n _E (average ethylene sequence length) of 37 and r ₁ =62.1, r ₂ =0.034, and r ₁ ×r ₂ =2.11.

Claims (34)

1. A metallocene compound of formula (I): _Rn (Cp)(A) _MLp wherein _Rn is a structural bridge; Cp is a heterocyclopentadienyl group of formula (II):

Wherein the substituents R ¹ and R ² , the same or different, are hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aromatic Group, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optional two adjacent substituents R ¹ and R ² can form a ring containing 5-8 carbon atoms, in addition, the substituent ^R1 and ^R2 may contain silicon or germanium atoms; Z is NR ³ or O, the definition of R ³ is the same as that of substituents R ¹ and R ² ; X and Y, the same or different, are selected from (CR ⁴ ₂ ) _r , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ ; the substituent R ⁴ , the same or different, is a hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl; The substituent ^R4 may also contain heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atoms, provided that both X and Y cannot be carbon atoms at the same time; A is selected from substituted or unsubstituted cyclopentadienyl which may bear one or more fused rings, =NR ⁵ , -O-, -S-, and =PR ⁵ The group, R ⁵ has the same definition as the substituents R ¹ and R ² , and corresponds to the group of formula (II); M is selected from those transition metals belonging to Groups 3, 4, 5 or 6 or the Lanthanides or Actinides of the Periodic Table of the Elements (new IUPAC edition); Substituents L, identical or different, are monovalent anionic ligands selected from hydrogen, halogen, -SR ⁶ , R ⁶ , -OR ⁶ , -NR ⁶ ₂ , OCOR ⁶ , OSO ₂ CF ₃ and PR ⁶ ₂ , wherein the substituents R ⁶ , the same or different, are linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optionally containing silicon or germanium atoms; p is an integer from 0 to 3, and p is equal to the oxidation state of metal M minus 2; n is an integer from 0-4; and r is an integer of 1-4. 2. Metallocene compounds according to claim 1, characterized in that R is QR ⁷ _m , Q is C, Si, Ge, N and P, and R ⁷ groups, identical or different, are optionally linear or branched saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, when Q is C, Si or Ge, two substituents R ⁷ can form a ring containing 3-8 atoms; m is 1 or 2, when Q is N or P is 1, and is 2 when Q is C, Si or Ge. 3. The metallocene compound according to claim 2, characterized in that (QR ⁷ _m ) _n is selected from CR ⁷ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ ; R ⁷ The definition of group is as claim 2. 4. The metallocene compound according to claim 3, characterized in that (QR ⁷ _m ) _n is selected from Si(CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ and C(CH ₃ ) ₂ . 5. The metallocene compound according to claim 1, wherein the transition metal is selected from titanium, zirconium and hafnium. 6. The metallocene compound according to claim 1, wherein the substituent L is halogen or the substituent ^R6 . 7. The metallocene compound according to claim 1, wherein the substituents ^R1 and ^R2 are hydrogen atoms. 8. The metallocene compound according to claim 1, wherein A corresponds to formula (II), as defined in claim 1. 9. A ligand of formula (III) R _n (Cp)(A) _q (III) where _Rn is a structural bridge; Cp is heterocyclopentadienyl of formula (IV): and its double bond isomers, wherein the substituents R ¹ and R ² , the same or different, are hydrogen atoms, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenes radical, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl, optional two adjacent substituents R ¹ and R ² can form a 5-8 carbon atom ring, in addition, the substituents ^R1 and ^R2 may contain silicon or germanium atoms; Z is NR ³ or O, the definition of R ³ is the same as that of substituents R ¹ and R ² ; X and Y, the same or different, are selected from (CR ⁴ ₂ ) _r , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ ; the substituent R ⁴ , the same or different, is a hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl; The substituent ^R4 may also contain heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atoms, provided that both X and Y cannot be carbon atoms at the same time; A is selected from substituted or unsubstituted cyclopentadienyl which may bear one or more fused rings, =NR ⁵ , -O-, -S-, and =PR ⁵ The group, R ⁵ has the same definition as the substituents R ¹ and R ² , and corresponds to the group of formula (IV); n is an integer of 0-4; q is an integer from 0-1; and r is an integer of 1-4. 10. The ligand according to claim 9, wherein R is QR ⁷ _m , Q is C, Si, Ge, N or P, R ⁷ groups are the same or different, linear or branched, saturated or not Saturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ Aralkyl, when Q is C, Si or Ge, two substituents R ⁷ can form a ring containing 3-8 atoms; m is 1 or 2, 1 when Q is N or P, when Q 2 when it is C, Si or Ge. 11. The ligand according to claim 10, characterized in that (QR ⁷ _m ) _n is selected from CR ⁷ ₂ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ , R The definition of ⁷ groups is as claim 1. 12. Ligand according to claim 11, characterized in that (QR ⁷ _m ) _n is selected from Si(CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ and C(CH ₃ ) ₂ . 13. The ligand according to claim 9, wherein the substituents ^R1 and ^R2 are hydrogen atoms. 14. Ligands according to claim 9, wherein A corresponds to formula (IV), as defined in claim 9. 15. A method for preparing the ligand of formula (III) R _n (Cp) (A) _q , the definition of Cp and A is as claimed in claim 9, n and q are all 0, the method comprises in the presence of alkali, Make the compound of formula (V):

And its double bond isomer, wherein X, R ¹ and R ² are as defined in claim 9, and Z is nitrogen, contacted with a compound of general formula YZ' ₂ , wherein Y is as defined in claim 9, and Z' is a halogen atom, forming a compound of formula (VI) and the steps of its double bond isomers. 16. A method for preparing the R _n (Cp) (A') _q ligand of formula (IIIa), wherein R is QR ⁷ _m , and its meaning is as in any one of claims 10-12, and n is 1- 4 is an integer and q is 1, A' is a group selected from substituted or unsubstituted cyclopentadienyl, which may carry one or more fused rings, =NR ⁵ , -O-, -S- and =PR ⁵ groups, R ⁵ is defined as substituent R ¹ and R ² , Cp corresponds to formula (IV), Z' is a halogen atom, and the method comprises the following steps: (a) in the presence of a base, make the compound of formula (V)

And its double bond isomer, wherein X, R ¹ and R ² are as defined in claim 9, and Z is nitrogen, contacted with a compound of general formula YZ' ₂ , wherein Y is as defined in claim 9, and Z' is Halogen atom, forming formula (VI) compound and its double bond isomers, and (b) contact with a compound capable of forming an anion of formula (VII) Thereafter contacted with compound R _n Z' ₂ of general formula (VIII), its molar ratio (VII)/(VIII) is equal to or greater than 2, or contacted with compound Z'R _n A'HR ⁵ of general formula (IX) , the molar ratio (VII)/(IX) is equal to or greater than 1. 17. The method according to claim 15 or 16, wherein both the base forming the compound of formula (VI) and the compound capable of forming the anion of the formula (VII) are selected from the group consisting of hydroxides of alkali metals and alkaline earth metals and Hydrides, metallic sodium and potassium, and organometallic lithium salts. 18. A process according to claim 17, wherein both the base forming the compound of formula (VI) and the compound capable of forming the anion of formula (VII) are n-butyllithium. 19. The method according to claim 16, wherein the halogen atom Z' of the general formulas (VIII) and (IX) is a chlorine atom. 20. A process for the preparation of a metallocene compound according to claim 1, which can be obtained by making the ligand _Rn (Cp)(A) _q of formula (III) of claim 9 be capable of forming its corresponding The compound of the dianionic compound is then contacted with a compound of formula ML _p+2 , wherein M, L and p are as defined in claim 1. 21. A process for preparing a metallocene compound according to claim 20, wherein A corresponds to formula (II). 22. The method according to claim 20, wherein the compound capable of forming said corresponding dianionic compound is selected from the group consisting of hydroxides and hydrides of alkali metals and alkaline earth metals, metal sodium and potassium, and organometallic lithium salts. 23. The method according to claim 22, wherein the compound capable of forming the dianionic compound is n-butyllithium. 24. The method according to claim 20, wherein the compound of formula ML _p+2 is selected from titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride. 25. A catalyst for olefin polymerization can be obtained by contacting: 26. (Q) a metallocene compound of formula (I) according to any one of claims 1-8, and 27. (R) Aluminoxanes and/or compounds capable of forming alkyl metallocene cations. 28. Catalyst according to claim 25, characterized in that the aluminoxane is obtained ^by reacting water with an organoaluminum compound of formula ^AlR83 or _Al2R83 , where _at least one _R8 is not a ^halogen . 29. The catalyst according to claim 26, wherein the molar ratio of aluminum to water is from 1:1 to 100:1. 30. Catalyst according to claim 25, characterized in that the aluminoxane is selected from MAO, TIBAO and TIOAO and the organoaluminum compound is TIOA, TMA and/or TIBA. 31. The catalyst according to claim 25, characterized in that the compound capable of forming a metallocene alkyl cation is a compound of formula T ^{+ D-} , wherein T ⁺ is a protonic acid capable of donating a proton and reacting with the metallocene of formula (I) The metal substituent L undergoes an irreversible reaction and D ^- is a compatible anion that is non-coordinating, capable of stabilizing the active catalyst species from the reaction of the two compounds, and is very easy to remove from the olefinic substrate. 32. Catalyst according to claim 29, characterized in that the anion D contains one or more boron atoms. 33. A process for the polymerisation of olefins comprising the polymerisation of one or more olefinic monomers in the presence of a catalyst as claimed in any one of claims 25-30. 34. The method according to claim 31, wherein the olefin monomer is ethylene and/or propylene.