KR20010021604A - Metallocenes, ligands and olefin polymerization - Google Patents

Abstract

A metallocene compound of formula 1 is disclosed:

[Formula 1]

R _n (Cp) (A) ML _p

[Wherein R _n is a structural bridge;

Cp is a heterocyclic cyclopentadienyl group of the formula:

[Formula 2]

(Wherein R ¹ and R ² are hydrogen or a hydrocarbon group,

X and Y are selected from (CR ⁴ ₂ ) _n , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ , wherein substituent R ⁴ is a hydrogen atom or a hydrocarbon radical, provided that both X and Y are both At the same time cannot be a carbon atom);

M is a transition metal of Group 3, 4, 5 or 6 or lanthanum or actinium in the Periodic Table of the Elements (new IUPAC version);

L is a monoanionic ligand;

Z is NR ³ or O;

A is a substituted or unsubstituted cyclopentadienyl, = NR ⁵ , -O-, -S- = PR ⁵ group which may contain one or more condensed rings, wherein R ⁵ is defined as substituents R ¹ and R ² And the groups correspond to Formula 2);

p is an integer from 0 to 3;

The metallocene compound is useful as a catalyst component for olefin polymerization.

Description

Metallocene, Ligand, and Olefin Polymerization Methods {METALLOCENES, LIGANDS AND OLEFIN POLYMERIZATION}

The present invention relates to a novel metallocene compound, a catalyst for olefin polymerization containing the same, and a polymerization method carried out in the presence of the catalyst. The present invention also relates to corresponding ligands useful as intermediates in the synthesis of the metallocene compounds, as well as methods of preparing the ligands and the metallocene compounds.

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

EP 0 129 368 describes, for example, a catalyst system for the polymerization of olefins containing a bis-cyclopentadienyl coordination complex (a) and aluminoxane (b) having a transition metal. Two cyclopentadienyl groups can be linked with a bridging group, which is usually a divalent radical containing one or more carbon atoms or heteroatoms. Crosslinked metallocene compounds are also known which condense cyclopentadienyl moieties into one aromatic or non-aromatic ring.

For example, European patent application EP 0 815 918 describes the use of suitable promoters for the preparation of ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and isotactic polyolefins. It is.

Metallocene compounds having a heteroatom in which a cyclopentadienyl group contains a substituent and a catalyst containing the same are also known.

Metallocene compounds having cyclopentadienyl groups containing heteroatoms as part of a substituted or condensed ring system are known from European patent application EP-A2-0 743 317. Demonstration is an indenyl moiety substituted with a chinoline or pyridine radical. The catalyst containing the metallocene is useful for olefin polymerization.

U.S. Patent 5 489 659 is a kind of silicon-containing metallocene compound for the polymerization of alpha-olefins in which silicon atoms are part of a non-aromatic ring condensed with a cyclopentadienyl ring, for example ethylenebis (4,4-dimethyl-4 , 5,6,7-tetrahydro-4-siladeninyl) zirconium dichloride.

European patent application EP 0 590 486 describes metallocene compounds containing cyclopentadienyl groups having heteroatoms in the ring system for use in the preparation of polyolefins. The only demonstrations are bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride and tetrakis (2,5-dimethylpyrrole) zirconium. International patent application PCT / EP97 / 6297 discloses a kind of crosslinked and uncrosslinked heterocyclic metallocene compound containing a cyclopentadienyl group which fuses a heteroatom containing ring under the name of the same applicant. Catalyst systems containing such metallocenes are useful for olefin polymerization.

When used in catalysts for olefin polymerization, it is desirable to provide new types of metallocenes suitable for the production of polyolefins.

A novel metallocene compound having a specific cyclopentadienyl ligand system was unexpectedly found, which can be advantageously used as a catalyst component for olefin polymerization.

In a first aspect, the present invention provides a metallocene compound of formula 1:

R _n (Cp) (A) ML _p

[Wherein R _n is a structural bridge;

Cp is a heterocyclic cyclopentadienyl group of the formula:

Wherein the substituents R ¹ and R ² are the same or different and represent 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 -A C ₂₀ alkylaryl, or C ₇ -C ₂₀ arylalkyl radical, two adjacent substituents R ¹ and R ² may optionally form a ring of 5 to 8 carbon atoms, furthermore, substituents R ¹ and R ² are silicon or May contain germanium atoms;

Z is NR ³ (wherein R ³ is defined as substituents R ¹ and R ² ) or O;

X and Y are the same or different and (CR ⁴ ₂ ) _n , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ (wherein substituent R ⁴ is the same or different and 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 alkylaryl, or C ₇ -C ₂₀ arylalkyl radical; further, substituent R ⁴ May contain hetero atoms such as nitrogen, phosphorus, oxygen, silicon or germanium atoms, provided that X and Y cannot both be carbon atoms at the same time;

A is a substituted or unsubstituted cyclopentadienyl, = NR ⁵ , -O-, -S- and = PR ⁵ group which may contain one or more condensed rings, wherein R ⁵ is substituted R ¹ and R ² And groups are selected from Formula 2);

M is a transition metal selected from the group 3, 4, 5 or 6 in the periodic table of the elements (new IUPAC version) or lanthanide or actinium series;

Substituents L are the same or different and are hydrogen, halogen, -SR ⁶ , -R ⁶ , -OR ⁶ , -NR ⁶ ₂ , -OCOR ⁶ , -OSO ₂ CF ₃ and -PR ⁶ ₂ , wherein substituent R ⁶ Are the same or different and 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 alkyl Aryl, or a C ₇ -C ₂₀ arylalkyl radical, optionally containing silicon or germanium atoms);

p is an integer from 0 to 3, where p is the oxidation state of the metal M ^2- ;

n is an integer from 0 to 4;

r is an integer from 1 to 4;

In another aspect of the present invention, there is provided a novel ligand of Formula 3, which is particularly useful as an intermediate in the preparation of metallocene compounds of Formula 1:

R _n (Cp) (A) _q

Wherein R, n, Cp, A are the meanings reported above and q is 0 if n is 0 and 1 if n is 1-4.

Another aspect of the invention is a process for the preparation of ligand R _n (Cp) (A) _q of formula 3 wherein R _n , Cp, A and q are the meanings reported above.

Another aspect of the present invention is the ligand R _n (Cp) (A) _q of formula 3 and formula ML _{p + 2} , wherein M, in the presence of a compound capable of forming a corresponding dianionic compound of ligand of formula 3 L and p are the processes for the preparation of metallocene compounds of formula (I) which can be obtained by contacting a compound of formula (I).

Another aspect of the invention is a catalyst for the polymerization of olefins containing said heterocyclic metallocenes and their use in olefin polymerization.

Reference to the present invention, the number of substituents on the cyclopentadienyl group of the formula (2) is as follows:

[Formula 2]

In the metallocene compound of the above form, the cyclopentadienyl group represented by the formula (2) linking the cyclopentadienyl group to the same cyclopentadienyl group, cyclopentadienyl derivative or heteroatom-containing group at the 4 position of the ring system Can be linked by pentadienyl groups, cyclopentadienyl derivatives or heteroatom-containing groups, such as amino groups, by divalent radicals containing one or more carbon atoms, such as CH ₂ groups, or by atoms other than carbon atoms such as dimethylsilanediyl groups have.

Advantageous species of heterocyclic metallocenes according to the invention may contain formula 1 (where A is one or more aromatic or nonaromatic condensed rings such as indenyl, fluorenyl, benzoindenyl, hydrogenated or partially hydrogenated rings). N is not 0, i.e., two cyclopentadienyl groups are linked to each other by a bridging divalent group). Preferably, the divalent group (QR ⁷ _m ) _n is selected from the group consisting of CR ⁷ ₂ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ and the R ⁷ groups are the same or different And 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 alkylaryl, or C _{When a 7} -C ₂₀ arylalkyl radical and optionally Q is C, Si or Ge, all substituents R ⁷ may form a ring of 3 to 8 atoms. More preferably, the divalent bridge 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, and 2 when Q is C, Si or Ge; n ranges from 0 to 6; When n> 1, the atoms Q can be the same or different, for example in the bridges -CH ₂ -Si (CH ₃ ) _2- , -CH ₂ -NR ² -and CH ₂ -PR ^2- .

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

Substituents R ¹ and R ² are preferably hydrogen atoms.

The substituent L is preferably a halogen atom or a R ⁶ group and R ⁶ is defined above. More preferably, it is a chlorine atom or a methyl group.

More advantageous species of the heterocyclic metallocenes according to the invention correspond to formula (1) in which A is represented by formula (2), ie two cyclopentadienyl moieties of the metallocene compound of the invention are identical.

Non-limiting examples of such metallocenes are as follows:

Isopropylidenebis [2- (methyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium di Chloride or dimethyl;

Isopropylidenebis [2- (ethyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium di Chloride or dimethyl;

Isopropylidenebis [2- (isopropyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium Dichloride or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadi Silol] zirconium dichloride or dimethyl;

Isopropylidenebis [2- (ethyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] Zirconium dichloride or dimethyl;

Isopropylidenebis [2- (isopropyl) -l, 1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol ] Zirconium dichloride or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] zirconium dichloride Or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopentaa [c] [1,2,5] azaphosphacyrrole] zirconium Dichloride or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole] zirconium dichloride or dimethyl ;

Isopropylidenebis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride or dimethyl ;

Isopropylidenebis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] Zirconium dichloride or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacylol ] Zirconium dichloride or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole] zirconium dichloride Or dimethyl;

Isopropylidenebis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride Or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] zirconium di Chloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacyrrole] zirconium Dichloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [l, 2,5] azadiborole] zirconium dichloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,3,5-trimethyl-l, 2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborol] zirconium di Chloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,3.5-trimethyl-l, 2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride or dimethyl;

Isopropylidene [2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin] zirconium dichloride or dimethyl;

Dimethylsilanediylbis [2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin] zirconium dichloride or dimethyl.

Another species of interest of the heterocyclic metallocenes according to the invention correspond to formula 1 in which A corresponds to formula 2 and n = 0, ie two identical cyclopentadienyl groups are not linked to each other by a crosslinked bivalent group do.

Non-limiting examples of such species are:

[2- (tert-butyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [l, 2,5] azadisilol] zirconium di Chloride or dimethyl;

[2- (methyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride or dimethyl;

[2- (methyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride or dimethyl;

[2- (ethyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride or dimethyl;

[2- (ethyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride or dimethyl;

[2- (isopropyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [l, 2,5] azadisilol] zirconium dichloride or dimethyl ;

[2- (isopropyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] zirconium dichloride Or dimethyl;

[2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -I, 1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacyrol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3.3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] zirconium dichloride or dimethyl ;

[2- (tert-butyl) -1,1,3,5-tetramethyl-1,2.3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacyrrole] zirconium dichloride or dimethyl ;

[2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin] zirconium dichloride or dimethyl;

[2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin] zirconium dichloride or dimethyl;

In another aspect of the invention, a ligand species of Formula 3 is provided:

[Formula 3]

R _n (Cp) (A) _q

[Wherein R _n is a structural bridge;

Cp is a heterocyclic cyclopentadienyl group of the formula (4):

(Wherein R, R ¹ , R ² , X, Y and Z, n and q are the meanings reported above),

A is a substituted or unsubstituted cyclopentadienyl, = NR ⁵ , -0-, -S- and = PR ⁵ group, which may contain one or more condensed rings, wherein R ⁵ is substituted R ¹ and R ² Wherein the groups correspond to formula 4).

Two double bonds of the cyclopentadienyl ring of the ligand of formula 4 may be present at any permitted position.

The compound of formula 4 is particularly useful as an intermediate ligand for the preparation of the heterocyclic metallocene compound of formula 1.

Advantageous species of heterocyclic ligands according to the invention are substituted or unsubstituted cyclopentas in which A may contain one or more aromatic or non-aromatic condensed rings, such as indenyl, fluorenyl, benzoindenyl, hydrogenated or partially hydrogenated rings. Group is selected from dienyl, n is not zero, ie two cyclopentadienyl moieties are linked to each other by a bridging divalent radical. See above for the divalent group R _n .

More advantageous species of the heterocyclic ligands according to the invention correspond to formula 3 in which n is not 0 and A corresponds to formula 4.

Non-limiting examples of such ligand species according to the present invention are:

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

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

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

Isopropylidenebis [2- (isopropyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol;

Isopropylidene [2- (tert-butyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol ];

Isopropylidene [2- (ethyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Isopropylidene [2- (isopropyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol] ;

Isopropylidenebis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol];

Isopropylidenebis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacylol];

Isopropylidenebis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole];

Isopropylidenebis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol];

Isopropylidenebis [2- (tert-butyl) -1, l, 3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol] ;

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

Isopropylidenebis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole];

Isopropylidenebis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol];

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol];

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [l, 2,5] azaphosphacylol];

Dimethylsilanediylbis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole];

Dimethylsilanediylbis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol];

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol ];

Dimethylsilanediylbis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacyl role];

Dimethylsilanediylbis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborole];

Dimethylsilanediylbis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol];

Isopropylidenebis [2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin];

Dimethylsilanediylbis [2- (tert-butyl) -1,1-dimethyl-2,3,4,7a-tetrahydro-1H-cyclopenta [c] [1,2] azacillin].

Further species of interest according to the invention correspond to formula 3 wherein A corresponds to formula 4 and n = 0, ie two identical cyclopentadienyl groups are linked to each other by a bridging divalent moiety.

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] azadisilol];

Bis [2- (tert-butyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (methyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (methyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (ethyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (ethyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (isopropyl) -1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (isopropyl) -1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol];

Bis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol];

Bis [2- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacylol];

Bis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborol];

Bis [2- (tert-butyl) -1,3-dimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol];

Bis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol];

Bis [2- (tert-butyl) -1,1,3,5-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacylol];

Bis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiborol];

Bis [2- (tert-butyl) -1,3,5-trimethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadiphosphol].

In another aspect of the invention, a compound of formula 5 and a double bond isomer thereof in the presence of a base is contacted with a compound of formula YZ ' ₂ wherein Y is defined above and Z' is a halogen atom A ligand R _n (Cp) (A) _q of Formula 3, wherein R is the above meaning, Cp corresponds to Formula 4, and A is defined above, comprising the steps of forming a compound of 6 and a double bond isomer thereof And n and q are both 0).

[Wherein X, R ¹ and R ² are defined above and Z is nitrogen],

Cyclopentadienyl derivatives of the formula (5) can be prepared using known methods such as those described in international patent application PCT / US92 / 08730.

In another aspect of the invention, the ligand R _n (Cp) (A ′) _q of formula 3a, wherein R is as defined above, wherein n is 1 to 4, consisting of the following steps (a) and (b): Integer and q is 1, ie two groups Cp and A 'are linked by a bivalent bridge, and A' is a substituted or unsubstituted cyclopentadienyl, which may contain one or more condensed rings, = NR ⁵ ,- Process for the preparation of groups 0-, -S- and = PR ⁵ , wherein R ⁵ is defined as substituents R ¹ and R ² , Cp corresponds to formula 4 and Z ′ is a halogen atom Provides:

(a) contacting a compound of formula (5) and a double bond isomer thereof with a compound of formula YZ ' ₂ (wherein Y and Z' are defined above) in the presence of a base to give a compound of formula (6) and a double bond isomer thereof Forming:

[Formula 5]

Wherein X, R ¹ and R ² are defined above and Z is nitrogen;

[Formula 6]

(b) contacting the compound of Formula 5 and a double bond isomer thereof with a compound capable of forming an anion of Formula 7, and then contacting a compound of Formula 8 (the molar ratio of Formula 7 / Formula 8 is 2 or more). Or contact with a compound of formula 9 wherein the molar ratio of Formula 7 / Formula 9 is one or more:

R _n Z ' ₂

Z'R _n A'HR ⁵

With regard to the structural bridges R _n in the ligand, see above.

Non-limiting examples of bases used to form the compound of Formula 6 are hydroxides or hydrides of alkali metals or alkaline earth metals, metallic sodium and potassium, and organometallic lithium compounds. Preferably methyllithium or n-butyllithium is used.

Non-limiting examples of compounds capable of forming anionic compounds of formula 7 are hydroxides and hydrides of alkali or alkaline earth metals, metallic sodium or potassium and organometallic lithium compounds. Preferably methyllithium or n-butyllithium is used.

Non-limiting examples of compounds of formula 8 R _n Z ′ ₂ are dimethyldichlorosilane, diphenyldichlorosilane, dimethyldichlorogernium, 2,2-dichloropropane and 1,2-dibromoethane.

The synthesis of the crosslinked ligand is preferably carried out by adding a solution of the organolithium compound in a nonpolar solvent to a solution of compound 6 in an aprotic polar solvent. The obtained solution containing compound 7 in anionic form is then added to a solution of the compound of formula R _n Z ′ ₂ in an aprotic polar solvent. The crosslinked ligand can finally be separated by conventionally known processes.

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

A still further aspect of the invention is contacting ligand R _n (Cp) (A) _q of Formula 3 with a compound capable of forming a corresponding dianionic compound thereof, followed by formula ML _{p + 2} (wherein M, L and p are the processes for the preparation of metallocene compounds of formula (I) which can be obtained by contacting a compound of formula (I).

The compound capable of forming the dianion is selected from the group consisting of hydroxides and hydrides of alkali metals and alkaline earth metals, metallic sodium and potassium, and organometallic lithium salts, preferably the anion is n-butyllithium.

Non-limiting examples of compounds of formula ML _{p + 2} are titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.

When n is not 0 and A is a cyclopentadienyl derivative, the metallocene compound of formula (1) may be prepared by using the crosslinked ligand of formula (3) prepared above with a compound capable of forming an unlocalized anion on the cyclopentadienyl ring. And then reacted first with a compound of formula ML _{p + 2} , wherein M and substituent L are defined above. Non-limiting examples of compounds of formula ML _{p + 2} are titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.

More specifically, the crosslinked ligand is dissolved in an aprotic polar solvent and a solution of the organolithium compound in the nonpolar solvent is added to the resulting solution. The anionic form obtained is separated and dissolved in an aprotic polar solvent and then added to the suspension of compound ML _{p + 2 in} an aprotic polar solvent. At the end of the reaction, the solid product obtained is separated from the reaction mixture by conventionally used techniques. Non-limiting examples of suitable aprotic polar solvents for the above reported methods are tetrahydrofuran, dimethoxyethane, diethyl ether, toluene and dichloromethane. Non-limiting examples of suitable nonpolar solvents for the process are pentane, hexane and benzene.

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

The non-crosslinked metallocene compound of formula 1 wherein n = 0 and A corresponds to formula 2 reacts the anion of formula 7 with a tetrahalide of transition metal M (ie ML ₄ ) where M and L are the above meanings Can be prepared, and the reaction is carried out in a suitable solvent.

If at least one L substituent in the metallocene compound of formula 1 is not halogen, it is necessary to substitute at least one substituent L in the obtained metallocene with at least one other substituent which is not halogen. The substitution reaction is carried out by a method 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 a lithiumalkyl compound.

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

The heterocyclic metallocene compound of the present invention can be conveniently used as a catalyst component for olefin polymerization.

Thus, in another aspect of the present invention, there is provided a catalyst for olefin polymerization, which can be obtained by contacting the following (A) and (B):

(A) a metallocene compound of formula 1, and

(B) A compound capable of forming aluminoxanes and / or alkyl metallocene cations.

Aluminoxanes used as component (B) can be obtained by reacting water with an organoaluminum compound of the formula AlR ⁸ ₃ or Al ₂ R ⁸ ₆ , wherein R ⁸ is not halogen. The molar ratio of Al / water in the reaction consists of 1: 1 to 100: 1.

The metal to metal molar ratio of aluminum to metallocene consists of about 10: 1 to about 20000: 1, and preferably about 100: 1 to about 5000: 1.

Aluminoxanes used in the catalysts according to the invention are believed to be linear, branched or cyclic compounds containing one or more groups of the form:

Wherein the R ⁹ substituents are the same or different and represent a hydrogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl, or C ₇ -C ₂₀ arylalkyl, optionally containing silicon or germanium atoms, or —O—Al (R ⁹ ) ₂ groups, where appropriate, some R ⁹ substituents may be halogen atoms.

In particular, aluminoxanes of the general formula can be used in the case of linear compounds:

[Wherein n is 0 or an integer from 1 to 40 and R ⁹ substituents are defined above],

Aluminoxanes of the general formula can be used in the case of cyclic compounds:

[Wherein n is an integer from 2 to 40 and R ⁹ substituents are defined above].

Examples of aluminoxanes suitable for use according to the invention are methylaluminoxanes (MAO), isobutylaluminoxanes (TIBAO) and 2,4,4-trimethyl-pentylaluminoacids (TIOAO).

In the catalysts used in the process according to the invention for the production of polyolefins, the heterocyclic metallocene compound of formula 1 and aluminoxane are of the formula AlR ⁸ ₃ or Al ₂ R ⁸ ₆ , wherein the R ⁸ substituents are the same or different , Hydrogen atom, halogen atom, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl, optionally silicon or germanium Containing atoms) as a reaction product with the organometallic aluminum compound.

Non-limiting examples of aluminum compounds of formula AlR ⁸ ₃ or Al ₂ R ⁸ ₆ 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) ₂ 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 , wherein Me = methyl, Et = ethyl, iBu = isobutyl, iHex = isohexyl, iOct = 2,4,4-trimethyl-pentyl.

Among the aluminum compounds, trimethylaluminum (TMA), triisobutylaluminum (TIBAL) and tris (2,4,4-trimethyl-pentyl) aluminum (TIOA) are preferred. Non-limiting examples of compounds capable of forming a metallocene alkyl cation to metal is not coordinated to, two to stabilize the active catalytic species originating in the reaction of the compound, and easy enough to be removed from an olefinic material, formula T ⁺ D ^- Wherein T ⁺ is a compound of Bronsted acid capable of providing protons and irreversibly reacting with substituent L of metallocene of formula 1, and D ⁻ is a miscible anion. . Preferably, the anion D ⁻ contains one or more boron atoms. More preferably, the anion D ⁻ is an anion of the formula BAr ⁽⁻⁾ ₄ wherein the substituents Ar are the same or different from each other and are aryl radicals such as phenyl, pentafluorophenyl, bis (trifluoromethyl) phenyl . Especially preferred are tetrakis-pentafluorophenyl borate. Moreover, the compound of the formula BAr ₃ may be suitably used.

The catalyst used in the process of the invention can also be used on an inert support. This may comprise metallocene (A), or the reaction product of this with component (B), or component (B) and subsequently metallocene (A), a support such as silica, alumina, styrene-divinylbenzene copolymer, polyethylene or Obtained by deposition on polypropylene.

With the addition of the alkyl aluminum compound itself or the alkyl aluminum compound pre-reacted with water, the obtained solid compound is usefully used in gas phase polymerization.

Therefore, another further object of the present invention is an olefin polymerization process consisting of a polymerization reaction of one or more olefinic monomers in the presence of the catalyst.

The catalyst of the invention can be used in the homopolymerization of olefins, preferably ethylene for the production of HDPE, or a-olefins such as propylene and 1-butene. In the ethylene polymerization reaction, the heterocyclic metallocene of the present invention exhibits good activity even when used at an Al / Zr ultra low rate.

Another use of the catalyst according to the invention is in the copolymerization of ethylene and higher olefins. In particular, the catalyst of the invention can be used for the production of LLDPE.

Suitable olefins to be used as comonomers include α-olefins of the formula CH ₂ = CHR ¹⁰ , wherein R ¹⁰ is an alkyl radical having 1 to 10 carbon atoms, and a cycloolefin. Examples of the 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, cyclohexene, norbornene and 4,6-dimethyl-1-heptene.

The copolymers are also derived from polyenes, in particular linear or cyclic, conjugated or nonconjugated dienes such as 1,4-hexadiene, isoprene, 1,3-butadiene, 1,5-hexadiene and 1,6-heptadiene It may contain a small fraction of the monomers to be.

Units derived from α-olefins, cycloolefins and / or polyenes of the formula CH ₂ = CHR ¹⁰ are preferably present in the copolymer in amounts ranging from 1 to 20% by weight.

Saturated elastomeric copolymers may contain ethylene units and α-olefins and / or nonconjugated diolefins that can be cyclopolymerized. Unsaturated elastomeric copolymers, together with units derived from the polymerization of ethylene and α-olefins, may also contain small fractions of unsaturated units derived from the copolymerization of one or more polyenes.

Non-limiting examples of suitable α-olefins include propylene, 1-butene and 4-methyl-1-pentene. Suitable nonconjugated diolefins that can be cyclopolymerized include 1,5-hexadiene, 1,6-heptadiene and 2-methyl-1,5-hexadiene.

Non-limiting examples of suitable polyenes are as follows:

(i) polyenes capable of providing unsaturated units, such as:

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

Dicyclic diolefins such as 4,5,8,9-tetrahydroindene and 6 and 7-methyl-4,5,8,9-tetrahydroindene;

Alkenyl or alkylidene norbornene, such as 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene and exo-5-isopropenyl-2-norbornene;

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

(ii) nonconjugated diolefins which can be cyclopolymerized 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 propylene polymerization process carried out in the presence of the catalyst.

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

The polymerization process according to the invention can optionally be carried out in the gas phase or in the liquid phase in the presence of an inert hydrocarbon solvent, aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane and cyclohexane).

The polymerization temperature is preferably in the range of about 0 ° C to about 250 ° C. In particular, in the method for producing HDPE and LLDPE, the temperature is preferably 20 ° C. to 150 ° C., more preferably 40 ° C. to 90 ° C., and the production of the elastomeric copolymer is preferably 0 ° C. to 200 ° C., And more preferably 20 ° C to 100 ° C.

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

The molecular weight of the polymer can simply be varied by changing the polymerization temperature, the form or concentration of the catalyst component, or by using a molecular weight modifier such as hydrogen.

The molecular weight distribution can be varied by using a mixture of different metallocenes or by running the polymerization at different stages of different polymerization temperatures and / or different molecular weight regulator concentrations.

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

The catalyst component can be contacted prior to the polymerization. Pre-contact concentrations are 1 to 10 ^-8 mol / ℓ for the metallocene component (A) to a normal metal, it is usually from 10 to 10 ^-8 mol / ℓ for the component (B). Precontacting is usually effected in the presence of a hydrocarbon solvent and, if appropriate, a small amount of monomer. The precontact time is usually 1 minute to 24 hours.

The following examples demonstrate the present invention but do not limit it.

General manufacturing features

All operations are performed using conventional Schlenk-line techniques under nitrogen. The solvent is distilled from blue Na-benzophenone ketil (Et ₂ O), CaH ₂ (CH ₂ Cl ₂ ) or AliBu ₃ (hydrocarbon) and stored under nitrogen. Use as you receive BuLi (Aldrich).

¹ H-NMR analysis of the metallocene is performed on an AC200 Bruker spectrometer (CD ₂ Cl ₂ , reference to the middle peak of the triplet of residual CHDCl ₂ at 5.35 ppm). All NMR solvents are dried over P ₂ O ₅ and distilled before use. The preparation of the samples is carried out using standard inert atmosphere techniques under nitrogen.

¹ H-NMR and ¹³ C-NMR analysis of the polymer is performed on a Bruker 400 MHz instrument. The sample is analyzed as a solution in tetrachlorodideuterethane at 130 ° C.

The intrinsic viscosity [η] (dl / g) is evaluated in tetralin at 135 ° C.

The melting point Tm (° C.) and ΔH (J / g) of the polymer are evaluated by differential scanning calorimetry (DSC) on a Mettler apparatus according to the following procedure: about 10 mg of the sample obtained from the polymerization is injected at a rate of 20 ° C. Heated to 180 ° C./min; The sample is held at 180 ° C. for 5 minutes and then cooled at a scanning rate of 20 ° C./min. The second scan is then performed according to the same aspect as the first scan. Reported values were obtained from the second injection.

Density (g / ml) is measured by depositing a sample of the extruded copolymer in a column filled with density particles according to ASTM D-1505 method.

In the copolymer according to the invention, the reaction rate of the product is r ₁ r ₂ (wherein r ₁ is the relative reactivity of the alpha-olefin to ethylene and r ₂ is the reactivity of ethylene to the alpha-olefin).

Preparation of Ligands

(Nt-butylamino) (dimethyl) (cyclopentadienyl) silane and (Nt-butylamino) (dimethyl) (methylcyclopentadienyl) silane in International Patent Application PTC / US92 / 08730, 1992, Nickias, PN Manufactured as described under the name Devore, DD.

Bis (1,3-bistrimethylsilylcyclopentadienyl) zirconium dichloride is purchased from Boulder Scientific Co., Mead Co, USA. Bis (cyclopentadienyl) zirconium dichloride is purchased from Strem Chemicals, Inc., Newburyport, MA.

Example 1

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

(Nt-butylamino) (dimethyl) (cyclopentadienyl) silane (0.071 mol, 13.9 g) is dissolved in THF (100 mL) and treated with BuLi (144 mmol of 2.5 M solution in hexane) at 0 ° C. After stirring for 16 hours at room temperature, a bi-anion solution and a THF solution (75 mL) of dichlorodimethylsilane (0.071 mol) are added dropwise to a flask containing 25 mL of THF with stirring at −10 ° C. The mixture is allowed to warm to room temperature and stirred overnight. The solvent is removed in vacuo and the residue is extracted with pentane. After filtration and evaporation of pentane, the extract was distilled to 1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol and isomers. Provide 1.2 g of a colorless liquid that is proven. ¹ H-NMR δ (CDCl ₃ ) (major isomers): 6.7 (m, 3H), 5.7 (wide s, 2H), 1.3 (s, 9H), 0.2 (s, 12H), ms (m / e) ( Relative strength): 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] azadisilol

(Nt-butylamino) (dimethyl) (methylcyclopentadienyl) silane (0.070 mol, 14.7 g) was dissolved in THF (199 mL) and butyllithium (0.14 mol of 2.5 M solution in hexane) at -78 ° C. Process it. After stirring for 16 hours at room temperature, the dianionic solution is added dropwise to a solution of dichlorodimethylsilane (0.070 mol, 9.03 g) in THF (100 mL) at -78 ° C. The mixture is slowly warmed to room temperature with stirring overnight. After evaporation of the solvent, the residue is extracted with pentane, filtered and evaporated to an oil. Distillate oil to prove 1,1,3,3,5-pentamethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azadisilol and colorless liquid 5.0 as isomers gives g ¹ H-NMR δ (CDCl ₃ ) (major isomers): 6.3 (m, 1H), 5.8 (wide s, 1H), 4.9 (wide s, 1H), 2.1 (s, 3H), 1.3 (s, 9H) , 0.3 (wide s, 6H), 0.15 (wide s, 6H), ms (m / e) (relative intensity): 265 ([PM], 14), 250 (100), 193 (4), 135 (4 ), 73 (16).

Example 3

Preparation of 1,1,5-trimethyl-3-phenyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaborasilol

(Nt-butylamino) (dimethyl) (methylcyclopentadienyl) silane (95.7 mmol, 20 g) was dissolved in THF (120 mL) cooled at -78 ° C and 2.1 equivalents of butyllithium (2.5 M solution in hexane) 201 mmol). The solution is stirred for 4 hours at room temperature. 95.1 mmol (15.7 g) of PhBCl ₂ is added dropwise in 20 mL of pentane at -78 ° C. The mixture is slowly cooled to room temperature and stirred overnight. After filtration and evaporation of the solvent an orange oil is obtained. The oil is distilled off to give 7.0 g of a colorless liquid which is proven as the title compound. ms (m / e) (relative intensity): 295 ([PM], 80), 280 (70), 239 (30), 224 (70), 160 (100).

Example 4

Preparation of 1,1,5-trimethyl-3-phenyl-1,2,3,3a-tetrahydrocyclopenta [c] [1,2,5] azaphosphacylol

(Nt-butylamino) (dimethyl) (methylcyclopentadienyl) silane (20 mmol, 4.17 g) was dissolved in THF (25 mL) cooled at -78 ° C and butyllithium (40 mmol of 2.5 M solution in hexane) , 16 ml). After completion of the reaction the solution is stirred for 1.5 h at room temperature. To the separated 250 ml flask is added 2.7 ml (20 mmol) dichlorophenylphosphine and 25 ml THF. The dianion is added dropwise at −78 ° C., warmed to room temperature and stirred for 2 hours. 6.61 g of orange oil is obtained after filtration and evaporation of the solvent. After washing with hexane, 3.68 g of pentane soluble oil is obtained which proved to be the title compound. ms (m / e) (relative intensity): 315 ([PM], 100), 300 (40), 244 (50), 135 (30), 57 (60).

Preparation of Metallocenes

Example 5

Preparation of bis (1,1,3,3-tetramethyl-1,2,3-trihydrocyclopentadienyl [c] [1,2,5] azadisilol) ZrCl ₂

Butyl lithium (4.0 mmol of a 2.5 M solution in hexane) was added 1,1,3,3-tetramethyl-1,2,3,3a-tetrahydrocyclopenta [c] [1 in ether (30 mL) at -78 ° C. , 2,5] added slowly to a solution of azadisilol (3.8 mmol, 0.95 g). The reaction mixture is allowed to warm up to room temperature and stirred for an additional 3 hours. The solvent is removed in vacuo and the residue is mixed with ZrCl ₂ (1.9 mmol, 0.443 g) in a glove box. The mixture is suspended in pentane (40 mL) / ether (1 mL) and stirred for 16 h. After evaporation of the solvent, the residue is extracted with dichloromethane and filtered. The filtrate was evaporated to give 1.0 g of bis (1,1,3,3-tetramethyl-1,2,3, trihydrocyclopentadienyl [c] [1,2,5] azadisilol) ZrCl ₂ , (1,2 (tBuN = (SiMe ₂ ) ₂ ) Cp) ₂ ZrCl ₂ is provided as tannin powder. ¹ H-NMR δ (CD ₂ Cl ₂ ): 6.85 (s, 2H), 6.5 (t, 1H), 1.4 (s, 9H), 0.6 (s, 6H), 0.3 (s, 6H).

Ethylene polymerization

Methyl Aluminoxane (MAO)

The product sold by Schering is used as a 10% by weight solution in toluene.

Examples 6-9

A 200 mL dry glass autoclave with a magnetic stirrer, a temperature probe, and a supply line for ethylene is sparged with ethylene at 35 ° C. Introduce 90 mL hexane at room temperature. The catalyst system was mixed with methylaluminoxane, or triisooctyl aluminum / water (Al / H ₂ O = 2.1) mixture in 10 mL hexane, and a metallocene compound (1,2 (tBuN) dissolved in a minimum amount of toluene after stirring for 5 minutes. = (SiMe ₂ ) ₂ ) Cp) ₂ Prepared separately by successive introduction of ZrCl ₂ . After stirring for 5 minutes, the solution is introduced into the autoclave under ethylene flow, the reaction is sealed, the temperature is raised to 80 ° C. and pressurized with ethylene to 4.6 barg. The total pressure is kept constant by feeding ethylene if necessary. The polymerization is stopped by cooling, reactant degassing, and introducing 1 mL methanol. The resulting polymer is washed with acidic methanol, methanol and dried under vacuum in a 60 ° C. oven. The results are listed in Table 1. The polymerization conditions are reported in Table 1.

Examples 10 and 11 (comparative)

Bis [1,3-bis (trimethylsilyl) cyclopentadienyl] zirconium dichloride was converted to bis (1,1,3,3-tetramethyl-1,2,3, trihydrocyclopentadienyl [c] [1 , 2,5] azadisilol) Except for using in place of ZrCl ₂ , the examples are repeated according to the processes described in Examples 6-9. The polymerization conditions are reported in Table 1.

Examples 12 and 13 (comparative)

Bis (cyclopentadienyl) zirconium dichloride to bis (1,1,3,3-tetramethyl-1,2,3, trihydrocyclopentadienyl [c] [1,2,5] azadisilol) Except for using instead of ZrCl ₂ , the examples are repeated following the process described in Examples 6-9. The polymerization conditions are reported in Table 1.

Ethylene Polymerization Results Example Metallocene mg (μmol) Promoter (mmol) Al / Zr molar ratio Minutes Polymer g Active Kg / gZr / h [μ] dL / g 6 1.00 (1.51) MAO (1.51) 1000 10 2.43 105.83 Not measured 7 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 1.26 9 0.50 (0.76) TIOA-H ₂ O (0.765) 1013 8 0.42 45.73 3.58 10 Comparison 0.13 (0.22) MAO (0.23) 1028 15 1.34 262.68 2.05 11 Comparison 0.13 (0.22) TIOA-H ₂ O (0.24) 1073 20 0.20 29.40 Not measured 12 Comparison 0.10 (0.34) MAO (0.35) 1023 10 1.07 205.76 2.99 Compare 13 0.30 (1.03) TIOA-H ₂ O (1.02) 997 20 a very small amount

Copolymerization of Ethylene and 1-hexene

Example 14

A 200 mL dry glass autoclave with a magnetic stirrer, a temperature probe, and a supply line for ethylene is sparged with ethylene at 35 ° C. Heptane (80 mL) and 1-hexene (10 mL) are introduced at room temperature. The catalyst system is prepared separately in 10 mL heptanes by continuously introducing methylaluminoxane (0.33 mmol) and metallocene (0.2 mg) dissolved in 3 mL of toluene. After stirring for 5 minutes, the solution is introduced into the autoclave under ethylene flow, the reaction is sealed, the temperature is raised to 70 ° C. and pressurized with ethylene to 4.5 barg. The total pressure is kept constant by feeding ethylene if necessary. After 10 minutes, the polymerization is stopped by cooling, reactant degassing, and introducing 1 mL methanol. The resulting polymer is washed with acidic methanol, methanol and dried under vacuum in a 60 ° C. oven. 1.2 g of the polymer is recovered (active 261 Kg / g-Zr / h) and [μ] value = 1.0 dL / g is obtained and 7.7% by weight 1-hexene is incorporated.

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

¹³C NMR analysis showed 2.72 mol% 1-hexene content, n_E(Mean ethylene sequence length) 37 and r_One = 62.1, r₂= 0.034, and r_Onexr₂= 2.11 indicates the presence of a value.

Claims (34)

A metallocene compound of Formula 1 [Formula 1] R _n (Cp) (A) ML _p [Meal, R _n is a structural bridge; Cp is a heterocyclic cyclopentadienyl group of the formula: [Formula 2] Wherein the substituents R ¹ and R ² are the same or different and represent 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 -A C ₂₀ alkylaryl, or C ₇ -C ₂₀ arylalkyl radical, two adjacent substituents R ¹ and R ² may optionally form a ring of 5 to 8 carbon atoms, furthermore, substituents R ¹ and R ² are silicon or May contain germanium atoms; Z is NR ³ or O and R ³ is defined as substituents R ¹ and R ² ; X and Y are the same or different and are selected from (CR ⁴ ₂ ) _n , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ ; Substituents R ⁴ are the same or different and represent 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 alkylaryl, Or a C ₇ -C ₂₀ arylalkyl radical; Moreover, substituent R ⁴ may contain heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atoms, provided that neither X nor Y can be a carbon atom at the same time; A is a substituted or unsubstituted cyclopentadienyl, = NR ⁵ , -O-, -S- and = PR ⁵ group which may contain one or more condensed rings, wherein R ⁵ is substituted R ¹ and R ² And groups are selected from Formula 2); M is a transition metal selected from the group 3, 4, 5 or 6 in the periodic table of the elements (new IUPAC version) or lanthanide or actinium series; Substituents L are the same or different and are hydrogen, halogen, -SR ⁶ , -R ⁶ , -OR ⁶ , -NR ⁶ ₂ , -OCOR ⁶ , -OSO ₂ CF ₃ and -PR ⁶ ₂ , wherein substituent R ⁶ Are the same or different and 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 alkyl Aryl, or a C ₇ -C ₂₀ arylalkyl radical, optionally containing silicon or germanium atoms); p is an integer from 0 to 3, where p is the oxidation state of the metal M ^2- ; n is an integer from 0 to 4; r is an integer from 1 to 4; The compound of claim 1, wherein R is QR ⁷ _m (wherein Q is C, Si, Ge, N or P, and R ⁷ groups are the same or different and 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 _{When it is a 20} alkylaryl, or a C ₇ -C ₂₀ arylalkyl radical, and optionally Q is C, Si or Ge, the substituents R ⁷ can form a ring containing from 3 to 8 atoms, and m is 1 or 2 Metallocene compound, which is 1 when Q is N or P and 2 when Q is C, Si or Ge. The compound of claim 2, wherein (QR ⁷ _m ) _n is CR ⁷ ₂ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ , wherein R ⁷ is defined in claim ₂ Metallocene compound, characterized in that it is selected from the group consisting of). 4. The metallo of claim 3, wherein (QR ⁷ _m ) _n is selected from the group consisting of Si (CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ and C (CH ₃ ) ₂ . Sen compound. 2. The metallocene compound of claim 1, wherein the transition metal is selected from titanium, zirconium and hafnium. The metallocene compound according to claim 1, wherein the substituent L is halogen or substituent R ⁶ . The metallocene compound according to claim 1, wherein the substituents R ¹ and R ² are hydrogen atoms. The metallocene compound according to claim 1, wherein A corresponds to formula (2) as defined in claim 1. Ligands of Formula 3: [Formula 3] R _n (Cp) (A) _q [Wherein R _n is a structural bridge; Cp is a heterocyclic cyclopentadienyl group of Formula 4 and its double bond isomers: [Formula 4] Wherein the substituents R ¹ and R ² are the same or different and represent 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 -A C ₂₀ alkylaryl, or C ₇ -C ₂₀ arylalkyl radical, two adjacent substituents R ¹ and R ² may optionally form a ring of 5 to 8 carbon atoms, furthermore, substituents R ¹ and R ² are silicon or May contain germanium atoms; Z is NR ³ or O, wherein R ³ is as defined as substituents R ¹ and R ² ; X and Y are the same or different and are selected from (CR ⁴ ₂ ) _n , BR ⁴ ₂ , PR ⁴ , SiR ⁴ ₂ or GeR ⁴ ₂ ; A is a substituted or unsubstituted cyclopentadienyl, which may contain one or more condensed rings, = NR ⁵ , -O-, -S- and = PR ⁵ , wherein R ⁵ is defined as substituents R ¹ and R ² Groups correspond to formula 2); n is an integer from 0 to 4; q is an integer of 0 or 1; r is an integer from 1 to 4; The compound of claim 9, wherein R is QR ⁷ _m (wherein Q is C, Si, Ge, N or P, and R ⁷ groups are the same or different and 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 _{When it is a 20} alkylaryl, or a C ₇ -C ₂₀ arylalkyl radical, and optionally Q is C, Si, or Ge, both substituents R ⁷ can form a ring containing 3 to 8 atoms, and m is 1 or 2 Ligand (1 when Q is N or P, and 2 when Q is C, Si, or Ge). The compound of claim 10, wherein (QR ⁷ _m ) _n is CR ⁷ ₂ , SiR ⁷ ₂ , GeR ⁷ ₂ , NR ⁷ , PR ⁷ and (CR ⁷ ₂ ) ₂ , wherein R ⁷ is defined in claim 1 Ligand is selected from the group consisting of). The ligand of claim 11, wherein (QR ⁷ _m ) _n is selected from the group consisting of Si (CH ₃ ) ₂ , SiPh ₂ , CH ₂ , (CH ₂ ) ₂ and C (CH ₃ ) ₂ . 10. The ligand of claim 9 wherein the substituents R ¹ and R ² are hydrogen atoms. 10. The ligand of claim 9, wherein A corresponds to formula 4 as defined in claim 9. To the presence of a base formula to compounds and their double bond isomers of the formula 5 YZ _'2 (wherein, Y is as defined in claim 9, wherein Z' is a halogen atom is a) contacting the compound to compound and derivatives of formula (VI) the double of A process for preparing the ligand R _n (Cp) (A) _q of Formula 3 wherein Cp and A are defined in claim 9 and n and q are all 0, comprising the step of forming a binding isomer: [Formula 5] Wherein X, R ¹ and R ² are defined in claim 9 and Z is nitrogen; [Formula 6] The ligand R _n (Cp) (A ′) _q of formula 3a, wherein R is QR ⁷ _m as defined in any one of claims 10 to 12, consisting of the following steps (a) and (b): Is an integer from 1 to 4 and q is 1 and A 'is from substituted or unsubstituted cyclopentadienyl, = NR ⁵ , -0-, -S- and = PR ⁵ groups which may contain one or more condensed rings A selected group, R ⁵ is defined as substituents R ¹ and R ² , Cp corresponds to formula 4 and Z ′ is a halogen atom) (a) a compound of formula 6 by contacting a compound of formula 5 and a double bond isomer thereof in the presence of a base with a compound of formula YZ ' ₂ wherein Y is defined in claim 9 and Z' is a halogen atom And forming double bond isomers thereof, [Formula 5] Wherein X, R ¹ and R ² are defined in claim 9 and Z is nitrogen; [Formula 6] (b) contacting the compound of Formula 5 and a double bond isomer thereof with an anion forming compound of Formula 7 and then contacting the compound of Formula 8 (the molar ratio of Formula 7 / Formula 8 is 2 or more), or Contact with a compound of formula 9 (formula 7 / formula 9 molar ratio is at least 1): [Formula 7] ; [Formula 8] R _n Z '₂; [Formula 9] Z'R _n A'HR ⁵ . 17. The compound according to claim 15 or 16, wherein the base for forming the compound of formula 6 and the compound capable of forming the anion of formula 7 are both hydroxides and hydrides of alkali and alkaline earth metals, metallic sodium and potassium, and organic Method selected from the group consisting of metallic lithium salts. 18. The method of claim 17, wherein both the base for forming the compound of formula 6 and the compound capable of forming the anion of formula 7 are n-butyllithium. 17. The method of claim 16, wherein the halogen atoms Z 'of formulas 8 and 9 are chlorine atoms. The ligand R _n (Cp) (A) _q of formula 3 according to claim 9 is contacted with a compound capable of forming a corresponding dianionic compound thereof, followed by the formula ML _{p + 2} (wherein M, L and p A process for producing the metallocene compound according to claim 1, which is obtainable by contact with a compound of claim 1. The method for producing a metallocene compound according to claim 20, wherein A corresponds to formula (2). 21. The method of claim 20, wherein the compound capable of forming a corresponding dianionic compound is selected from the group consisting of hydroxides and hydrides of alkali metals and alkaline earth metals, metallic sodium and potassium, and organometallic lithium salts. . 23. The method of claim 22, wherein the compound capable of forming a dianionic compound is n-butyllithium. 21. The method of claim 20, wherein the compound of formula ML _{p + 2} is selected from titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride. Catalyst for olefin polymerization obtainable by contacting. Metallocene compound of formula (I) according to any one of claims 1 to 8 (Q). Compound (R) capable of forming aluminoxanes and / or alkyl metallocene cations. The catalyst of claim 25 wherein the aluminoxane is obtained by contacting water with an organoaluminum compound of formula AlR ⁸ ₃ or Al ₂ R ⁸ ₃ , wherein at least one R ⁸ is not halogen. 27. The catalyst of claim 26 wherein the molar ratio of aluminum to water is in the range of 1: 1 to 100: 1. 26. The catalyst of claim 25, wherein the aluminoxane is selected from MAO, TIBAO and TIOAO and the organoaluminum compound is TIOA, TMA and / or TIBA. The compound of claim 25, wherein the compound capable of forming a metallocene alkyl cation is capable of stabilizing the active catalytic species originating in the reaction of the two compounds without coordination, and is easy to be removed from the olefinic material. T ⁺ D ^- (wherein, T ⁺ is a Bronsted acid (Bronsted acid), that it is possible to irreversibly react with a substituent L of the metallocene of formula (I) to provide protons, D ^- is a compatible anion A compound of claim 1). 30. The catalyst of claim 29 wherein the anion D ⁻ contains at least one boron atom. 31. A process for the polymerization of olefins which consists of a polymerization reaction of at least one olefin monomer in the presence of a catalyst according to any one of claims 25-30. 32. The process of claim 31 wherein the olefin monomer is ethylene and / or propylene.