WO2002038637A1

WO2002038637A1 - Method for copolymerizing propene and/or ethene with 1-olefins on metallocene carrier catalysts

Info

Publication number: WO2002038637A1
Application number: PCT/EP2001/012264
Authority: WO
Inventors: Jürgen Suhm; Hans-Herbert Brintzinger; Sarah Reybuck
Original assignee: Basell Polypropylen Gmbh
Priority date: 2000-11-09
Filing date: 2001-10-24
Publication date: 2002-05-16
Also published as: AU2002219055A1

Abstract

The invention relates to a method for copolymerizing propene and/or ethene with 1-olefins on metallocene carrier catalysts. Said monomers are polymerized in the presence of a catalyst system that contains as the active components those components that are obtained by polymerizing A) a transition metal compound with B) a cation-forming compound of the general formula (II), wherein M3 is an element of the third main group of the periodic system, X?1, X2 and X3¿ represent hydrogen, C1 to C10 alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl with 1 to 10 carbon atoms each in the alkyl group and 6 to 20 carbon atoms in the aryl group or fluorine, chlorine, bromine or iodine, and/or of the general formula (III) wherein Y is an element of the first to sixth main group or the first to eighth subgroup of the periodic system, Q¿1? to Qz represents groups with a single negative charge such as C1 to C28 alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl with 6 to 20 carbon atoms each in the aryl and 1 to 28 carbon atoms in the alkyl group, C3 to C10 cycloalkyl, which can be optionally substituted with C1 to C10 alkyl groups, halogen, C1 to C28 alkoxy, C6 to C15 aryloxy, silyl or mercaptyl groups, a represents integers of from 1 to 6, and z represents integers of from 0 to 5, and d corresponds to the difference a-z, with d being greater or equal 1.

Description

Process for the copolymerization of propene and / or ethene with 1-olefins on supported metallocene catalysts

description

The present invention relates to a process for the copolymerization of propene and / or ethene with 1-olefins on supported metallocene catalysts, these monomers in the presence of a catalyst system containing, as active constituents, those which are obtainable by the reaction of

A) a transition metal compound

With

B) a cation-forming compound of the general formula II

M ³ χ ^! χ ² X ³ II

in the

M ^{3 is} an element of III. Main group of the periodic table means

X ¹ , X ² and X ³ for hydrogen, Cl to CIO alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the Aryl radical or fluorine, chlorine, bromine or iodine,

and / or the general formula III

^[( Y ^{a +) Q} ιQ ₂ ... Qz- ^{ä +} III

in which

Y is an element of I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means

Qi to Q _z for simply negatively charged residues such as Ci to

C ₂₈ alkyl, C ₆ to C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C atoms in the alkyl radical, C ₃ to Cio. Cycloalkyl , which if necessary with Ci to Cio alkyl groups can be substituted, halogen, Ci to C ₂₈ alkoxy, C ₆ to C ₅ aryloxy, silyl or mercaptyl groups

a for integers from 1 to 6 and

z represents integers from 0 to 5,

d corresponds to the difference a-z, but d is greater than or equal to 1, are polymerized.

Metallocene catalysts with high activity are used for the production of poly (1-olefins) with a defined molar mass distribution, uniform stereo and regional regularity and controlled co-monomer incorporation. A frequently occurring disadvantage of the heterogeneous, supported metallocene / cation activator systems [MAO, Tris (pentafluorophenyDboran, Trityltetra (pentafluorophenyl.borat and N, N-Dimethylaniliniumtetr (pentafluorophenyDborat]) is the loss of stereo- and regio-regularity however, the activity due to interactions of the metallocene / cation activator system with the surface of the carrier material. Up to now, no studies of the influence of the cation activator on the comonomer incorporation are known, but the influence of the metallocene structure was examined in detail by Kaminsky, who examined the influence of Symmetry of the metallocene used on the copolymerization showed that he found that the isospecific metallocenes, such as rac-Et (Ind) ZrCl / MA0, have higher comonomer incorporation than the stereospecific CpZrCl ₂ / MAO, as a consequence of these studies that bridged metallocenes are basically a better co onomer have efficiency as unbridged metallocenes. Studies by Soga, Zambelli, Fink and other working groups on the C ₃ symmetric, syndiospecific Me ₂ Si (Cp) Flu) -ZrCl ₂ / MAO and i-Pr (Cp) (Flu) -ZrCl ₂ / MAO demonstrated the superiority of the syndiospecific Metallocenes versus isospecific metallocenes such as Me ₂ Si (Ind) ZrCl ₂ / MAO.

It is known that polymerization-for manufacturing metal compounds such as metallocenium catalysts can make for example the following reactions: ^'

a) Metallocendialkyl + strong cation-forming compound

(Lewis acid), X. Yang, CL. Star. TF Marks, J. Am. former Soc. 1991, 113, 3623-5 b) Metallocendialkyl + Brönsted acid with non-nucleophilic anion EP 0 591 756 c) Metallocene compound + aluminoxane EP 0 035 242

The reaction c) requires large amounts of expensive aluminoxane, which has a disruptive effect in the polymer formed.

The. molar ratios of transition metal compound described in part of the prior art, e.g. Metallocendialkyl, for the cation-forming compound e.g. An organic boron compound is 1: 1 or the transition metal compound is even used in excess (see e.g. EP-A 0 468 537, page 12, lines 24 ff) in order to achieve acceptable catalyst activities.

In EP-A 0 700 934, EP-A 0 700 935 a range from 10: 1 to 1: 100 is described in WO-A 97/31038, WO-A 97/31029 and WO-A 97/31039 10: 1 to 1:10 with respect to the molar ratio of transition metal: cation-forming compound. WO-A 98/01481 states "The mixture of metallocenium ion-forming compound and transition metal complex preferably contains these two components in a weight ratio of 40: 1 to 3: 1, particularly preferably from 20: 1 to 5: 1".

The object of the present invention was therefore to provide an improved process for the copolymerization of propene and / or ethene with 1-olefins which avoids the above disadvantages of the prior art and in particular enables high comonomer incorporation rates.

Accordingly, the process defined at the outset for the copolymerization of propene and / or ethene with 1-olefins using the catalyst system defined at the outset was found.

Suitable transition metal compounds A) are in principle all those which chemically react with components B), if appropriate in combination with a further component C), an active catalyst being formed.

Examples of suitable transition metal compounds A) are Transition metal complexes with ^'a ligand of the general formulas FI to F-IV

F-I F-III

wherein the transition metal is selected from the elements Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt or an element of the rare earth metals. Compounds with nickel and palladium as the central metal are preferred.

E is an element of group 15 of the Periodic Table of the Elements (5th main group), preferably N or P, with N being particularly preferred. The two atoms E in a molecule can be the same or different.

The radicals R ^1A to R ^18A , which can be the same or different, represent the following groups:

R ^1A and R ^4A : independently of one another for hydrocarbon or substituted hydrocarbon radicals, preference is given here to hydrocarbon radicals in which the carbon atom adjacent to element E is linked to at least two carbon atoms. R2A _unc j 3A. independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, R ^2A and R ^3A can also together form a ring system in which one or more heteroatoms can also be present.

R ^6A : for hydrocarbon or substituted hydrocarbon residues,

R ^5A : for hydrogen, hydrocarbon or substituted hydrocarbon radicals, R ^6A and R ^5A can also together form a ring system.

R ^8A : for hydrocarbon or substituted hydrocarbon radicals,

R ^9A : for hydrogen, hydrocarbon or substituted hydrocarbon radicals, R ^8A and R ^9A together can also form a ring system.

R ^7A : independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals, two R ^7A can also form a ring system together, n is an integer between 1 and 4, preferably 2 or 3.

_R I ^O A _{un (} j 14A. Independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals

_R ιiA _fR i2A _{un (} j i3A. Independently of one another for hydrogen, carbon-hydrogen or substituted hydrocarbon radicals, here two or more radicals R ^11A , R ^12A and R ^13A together can form a ring system. 15A _{and R} i8A. Independently of one another for hydrogen , Carbon, hydrogen or substituted hydrocarbon radicals

_R 16A _{and <} R17A _: independently of one another for hydrogen, hydrocarbon or substituted hydrocarbon radicals

Particularly suitable compounds F-I to F-IV include:

Di (2,6-di-i-propylphenyl) -2,3-dimethyldiazabutadiene palladium dichloride

Di (di - i -propylphenyl) -2, 3 -dimethyldiazabutadiene-nickel-dichloride

D (2,6-di-i-propyl-phenyl) -dimethyl-diazabutadiene-palladium-dimethyl

Di (2 _r 6 -di-i-propyl-phenyl) -2, 3-dimethyl-diazabutadiene-nickel-dimethyl Di (2,6-dimethyl-phenyl) -2,3-dimethyl-diazabutadiene-palladium dichloride Di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene-nickel dichloride

Di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene-palladium-dimethyl Di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene-nickel-dimethyl

Di (2-methyl-phenyl) -2, 3 -dimethyl-diazabutadiene-palladium-dichloride di (2-methyl-phenyl) -2, 3 -dimethyl-diazabutadiene-nickel-dichloride di (2-methyl-phenyl) -2, 3 -dimethyl-diazabutadiene-palladium-dimethyldi (2 -methyl-phenyl) -2, 3 -dimethyl-diazabutadiene-nickel -dimethyl diphenyl-2, 3 -dimethyl-diazabutadiene-palladium-dichloride diphenyl -2, 3-dimethyl-diazabutadiene-nickel dichloride diphenyl-2,3-dimethyl-diazabutadiene-palladium-dimethyl diphenyl -2,3-dimethyl-diazabutadiene-nickel-dimethyl di (2,6-dimethyl-phenyl) -azanaphten-palladium- dichloride di (2, 6-dimethyl-phenyl) -azanaphten-nickel-dichloride di (2, 6 -dimethyl-phenyl) -azanaphten-palladium-dimethyl di (2, 6 -dimethyl-phenyl) -azanaphten-nickel-dimethyl 1 , 1 'dipyridyl palladium dichloride 1,1' dipyridyl nickel dichloride 1,1 'dipyridyl palladium dimethyl 1, 1' dipyridyl nickel dimethyl

Other highly suitable transition metal compounds are those with a ligand of the general formula F-V

in which the substituents and indices have the following meaning:

, ^_] R ^1B, R ^2B, C ₄ - to Ciε-heteroaryl, or C ₆ - to Cι ₆ aryl by halogen nitro, cyano, sulfonato or Trihalogenmethylsubsti- tuenten in the two positions ortho to the N ^a - and N ^b aryl or heteroaryl bond, R ^3B , R ^{4B are} hydrogen, Ci to C ₁₀ alkyl, C ₃ to C ₁₀ cycloalkyl, Cg to Ci ₆ aryl, alkylaryl with 1 to 10 C atoms in the alkyl and 6 to 14 C atoms in the aryl part or Si (R ^8B ) ₃ with

R ^8B C _x - to Cio-alkyl, C ₃ - to C ₁₀ -cycloalkyl, C ₆ - bis

Ci _ß- aryl, alkylaryl with 1 to 10 C atoms in the alkyl and 6 to 14 C atoms in the aryl part,

R ^5B , R ^6B , R ^{7B are} hydrogen, C ₁ to C ₀ alkyl, C ₃ to C ₁₀ cycloalkyl, C ₆ to C ₆ aryl, alkylaryl having 1 to 10 C atoms in the alkyl and 6 up to 14 carbon atoms in the aryl part or Si (R ^8B ) ₃ or functional groups based on the elements of groups IVA to VIIA of the periodic table of the elements or R ^5B and R ^6B and / or R ^6B and R ^7B each form a fused together five-, six- or seven-membered aliphatic or aromatic, substituted or unsubstituted carbo- or heterocycle.

Suitable transition metals are those mentioned for the formulas F-I to F-IV, preferably iron. Other ligands of the transition metals are not critical; They are usually neutral or preferably monoanionic, monodentate ligands, such as halogen, for example chlorine or bromine, or pseudohalogen, for example cyanide or chalcogen ligands, such as hydroxide, alkoxide, aryl oxide or the corresponding sulfur compounds.

For example, the following complexes with the ligands F-V may be mentioned:

2,6-bis [1- (2,6-dichlorophenylimino) ethyl] pyridine-iron

(II) chloride,

2,6-bis [1- (2,6-dichloro-4-methylphenylimino) ethyl] pyridine-iron

(II) chloride, 2,6-bis [1- (2,6-dibromophenylimino) ethyl] pyridine-iron (II) chloride,

2,6-bis [1- (2,6-dibromo-4-methylphenylimino) ethyl] pyridine-iron

(II) chloride and the corresponding iron (II) bromide complexes,

2,6-diacetylpyridinebis (2,6-diisopropylanil) FeCl _/

2, 6-diacetylpyridine (2, 6-diisopropylanil) MnCl _2/2 , 6-diacetylpyridine (2, 6-diisopropylanil) CoCl ₂

2, 6 -diacetylpyridinbis (2-tert-butylanil) FeCl _{2 /}

2, 6 -diacetylpyridinbis (2, 3 -dimethylanil) FeCl _2f

2,6-Diacetylpyridinbis (2 -methylanil) FeCl

2, 6 -diacetylpyridinbis (2, -dimethylanil) FeCl, 2, 6 -diacetylpyridinbis (2, 6 -dimethylanil) FeCl _{2 /}

2,6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl,

2,6-dialdiminepyridinebis (2,6-dimethylanil) FeCl _{2 (} 2, 6-Dialdiminpyridinbis (2, 6-diethylanil) FeCl _/ ^' ^• 2, 6-Dialdiminpyridinbis (2, 6 -diisopropylanil) FeCl ₂ , 2, 6 -Dialdiminpyridinbis (1-naphthil) FeCl _{2 n} ■ 2, 6 -Bis (1, l-diphenylhydrazone) pyridine FeCl ₂ .

Particularly suitable transition metal compounds A) are furthermore those with at least one cyclopentadienyl-type ligand, which are commonly referred to as metallocene complexes (two or more cyclopentadienyl-type ligands) or half-sandwich complexes (a cyclopentadienyl yp ligand).

As component A), the catalyst system according to the invention contains at least one or more metallocene complexes. Particularly suitable metallocene complexes are those of the general formula

in which the substituent ^'th following meanings:

M ^■ 'titanium, zirconium, hafnium, vanadium, niobium or

Tantalum, as well as elements of the III. Subgroup of the periodic table and the lanthanoids,

X fluorine, chlorine, bromine, iodine, hydrogen, Cι ~ bis

Cio-alkyl, C ₆ - to C ₅ -aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical ,. -OR ⁶ or -NR ⁶ R ⁷ ,

n is an integer between 1 and 3, where n is the

Valence of M minus the number 2 corresponds,

in which

R ⁶ and R ⁷ Ci to Cι ₀ alkyl, C ₆ to Cι ₅ aryl, alkylaryl,

Arylalkyl, fluoroalkyl or fluoroaryl with each

1 to 10 carbon atoms in the alkyl radical and

6 to 20 carbon atoms in the aryl radical, R ¹ to R ^{5 are} hydrogen, Ci- to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C - to Cio-alkyl as a substituent, C ₆ - to C ₅ -aryl or arylalkyl, where appropriate also two neighboring radicals together can represent 4 to 15 carbon atoms, saturated or unsaturated cyclic groups or Si (R ⁸ ) ₃ with

R ⁸ C - to Cio-alkyl, C ₃ - to Cio-cycloalkyl or C ₆ - to Cis-aryl,

Ri3

represents X or

being the leftovers

R ⁹ to R ¹³ are hydrogen, ~ to Cio-alkyl, 5- to 7-membered can carry as substituent cycloalkyl ^'in turn is a Ci to Cio-alkyl, C ₆ - to C ₅ aryl or arylalkyl and wherein gegebenenf lls two adjacent radicals together can also represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R ¹⁴ ) with

_R 14 -C ~ to Cio-alkyl, C ₆ - to cis-aryl or C ₃ - to Cio-cycloalkyl,

or wherein the radicals R ⁴ and Z together form a group -R ¹⁵ -A- in which

_R 16 _R 16 _R 16 _R 16

R15 M ² • M ² M ² M ² CR ₂ 18-

R ¹⁷ Rl ⁷ R ¹⁷ R "

_R 16 _R 16 _R 16 ^■ _R 16

OM ² ,

R ¹⁷ R "R ¹⁷ R ¹⁷ = BR ¹⁶ , = AIR ¹⁶ , -Ge-, -Sn-, -0-, -S-, = SO, = S0 ₂ , = NR ¹⁶ , = CO, = PR ¹⁶ or = P (0) R ¹⁶ .

in which

R ¹⁶ , R ¹⁷ and R ^{18 are the} same or different and a water

Stoffato, a halogen atom, a Ci -Cio-alkyl group, a -C-Cιo-fluoroalkyl group, a C _ö -Cio-fluoroaryl group, a C _Ö -C _IO aryl group, a Cι-Cι ₀ alkoxy group, a C -Cιo -Alkenyl group, a C -C ₄ o-arylalkyl group, a C ₈ -C ₄ o-arylalkenyl group or a C -C ₄₀ -alkyl aryl group or where two adjacent radicals each form a ring with the atoms connecting them, and

M ^{2 is} silicon, germanium or tin,

A - 0—, - S -, ..NR ¹⁹ or _^ PR ¹⁹ mean with

R ¹⁹ Ci to Cio alkyl, C ₆ to C ₅ aryl,

C ₃ to C ₁₀ cycloalkyl, alkylaryl or Si (R ²⁰ ) ₃ ,

R ^{20 is} hydrogen, -C ~ to Cio-alkyl, C ₆ - to cis-aryl, which in turn can be substituted with Ci- to C ₄ alkyl groups or C ₃ - to C ₁₀ cycloalkyl

or wherein the radicals R ⁴ and R ¹² together form a group -R ¹⁵ -.

Of the metallocene complexes of the general formula I are

MXn + l

prefers.

The radicals X can be the same or different, they are preferably the same.

Of the compounds of the formula Ia, those are particularly preferred in which

M titanium, zirconium or hafnium,

X is chlorine, C 1 -C ₄ -alkyl or phenyl, n is the number 2 and

R ¹ to R ^{5 are} hydrogen or -C ~ to C ₄ alkyl.

Of the compounds of the formula Ib, those are to be mentioned as preferred in which

M stands for titanium, zirconium or hafnium,

X is chlorine, C 1 -C ₄ -alkyl or phenyl,

n is the number 2,

R ¹ to R ^{5 are} hydrogen, C ¹ -C ₄ -alkyl or Si (R ⁸ ) ₃ ,

R ⁹ to R ^{13 are} hydrogen, Ci to C ₄ alkyl or Si (R ¹⁴ ) ₃ .

The compounds of the formula Ib in which the cyclopentadienyl radicals are identical are particularly suitable.

Examples of particularly suitable compounds include: bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-butylethyldiryl) zirconium dichloridyldiryldiumchloride as well as the corresponding dimethyl zirconium compounds.

Of the compounds of the formula Ic, those in which

R ¹ and R ^{9 'are the} same and represent hydrogen or Ci to Cio alkyl groups,

R ⁵ and R ^{13 are the} same and for hydrogen, a methyl,

Ethyl, iso-propyl or tert. -Butyl group,

R ² , R ³ , R ¹⁰ and R ^{11 have} the meaning

R ³ and R ¹¹ Ci to C ₄ alkyl

R ² and R ^{10 have} hydrogen or two adjacent radicals R ² and R ³ and R ¹⁰ and R ¹¹ together represent cyclic groups containing 4 to 12 carbon atoms, R ¹⁶ R16 _R 16

R ^{15 stands} for - M ² - or - _c - _c -,

R ¹⁷ 17 _R 17

M for titanium, zirconium or hafnium and

M ² for silicon

X represents chlorine, Ci to C4 alkyl or phenyl.

Of particular importance are those compounds of formula Ic which carry a C ₆ -C o-aryl group in the 4 position and a C ₁ -C ₄ alkyl group in the 2 position. An example of such compounds of the formula Ic is dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride.

The following nomenclature applies to the place of substitution:

Examples of particularly suitable complex compounds Ic are dimethylsilanediylbis (indenyl) zirconium dichloride

Dimethylsilanediylbis (-naphthyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-benzo-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-dichloride)

Dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4-t-butyl-indenylzirconium dichloride Dimethylsilanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4-ethyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dichloride Dimethylsilanediylbis (2, -dimethyl-indenyl) zirconium dichloride in dimethylsilidyldiumdiblorodimethyl (silyldiyldiryldiblorodis) -ethyl-4-ethyl-indenyl) zirconium dichloride i

Dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4, 5-benzo-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4, 6-diisopropyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4,5-diisopropyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2,4,6-trimethyl-indenyl) zirconium dichloride. Dimethylsilanediylbis (2,5, 6-trimethyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2, 4, 7-trimethyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-5-t-butyl-indenyl) zirconium dichloride dimethylsilanediylbis (2-methyl-4-phenanthrylinden) zirconium ^'dichloride

Dimethylsilanediylbis (2-ethyl-4-phenanthylindenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride

(Methyl (phenyl) silanediylbis (2-methyl-4, 6-diisopropyl-indenyl) -

'zirconium

Methyl (phenyl) silanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-4, 5-benzo-indenyl) zirconium dichloride

MethyKphenyl) silanediylbis (2-methyl-4, 5- (methylbenzo) -indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-4, 5- (tetramethylbenzo) indenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-methyl-4-phenanthrylindenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-ethyl-4-phenanthrylindenyl) zirconium dichloride 1,2-ethanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride-1,4-butanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride 1, 2-Ξthanediylbis (2-methyl-4, 6-diisopropyl-indenyl) zirconium dichloride 1, 4-butanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride 1, 4-butanediylbis (2-methyl-4, 5 -benzo-indenyl) zirconium dichloride 1,2-ethanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride 1,2-ethanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride J

1, 2-Ethanediylbis (2-methyl-indenyl) zirconium dichloride 1, 4-butanediylbis (2-methyl-indenyl) zirconium dichloride Dirnethylsilandiyl (tert-butylamino) (tetramethylcyclopentadienyl) - zirconium dichloride (trisophenyl) (borate (penthenyl)) (tris (pentadyl)) (tris (penthenyl)) (tris (penthenyl)) (tris (penthenyl)) (tris (penthenyl)) (tris) ) -1,2,3,4-tetraphenylbuta-1,3-dienyl-zirconium dimethylsilanediyl- [tris (pentafluorophenyl) (2-methyl-4-phenylindenylidene) borato] (2-methyl-4-phenylindenyl) -1,2 , 3, 4-tetraphenylbuta-1, 3-dienylzirconium dimethylsilanediyl- [tris (trifluoromethyl) (2-methylbenzindenylidene) borato] (2-methylbenzindenyl) -1, 2, 3, 4-tetraphenylbuta-l, 3- dienylZirkonium

Dimethylsilanediyl- [tris (pentafluorophethyl) (2-methyl-indenylidene) borato] (2-methyl-indenyl) -1, 2,3, -tetraphenylbuta-l, 3-dienylzirconium

Dimethylsilanediylbis indenyl) zirconium dimethyl

Dimethylsilanediylbis -naphthyl-indenyl) zirconiumdimethyl

Dimethylsilanediylbis 2-methyl-benzo-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4- (1-naphthyl) -indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4- (2-naphthyl) -indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-phenyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-t-butyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4-isopropyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4-ethyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4-a-acenaphth-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2, 4-dimethyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-ethyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-ethyl-4-ethyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-ethyl-phenyl-indenyl) zirconium dimethyl Dimethylsilanediylbis 2-methyl-4,5-benzo-indenyl) zirconiumdimethyl Dimethylsilanediylbis 2-methyl-4, 6-diisopropyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-4,5-diisopropyl-indenyl) zirconium dimethyl Dimethylsilanediylbis 2,4,6-trimethyl-indenyl) zirconiumdimethyl Dimethylsilanediylbis 2,5,6-trimethyl-indenyl) zirconiumdimethyl Dimethylsilanediylbis 2,4,7-trim ) zirconium dimethyl dimethylsilanediylbis 2-methyl-5-isobutyl-indenyl) zirconium dimethyl

Dimethylsilanediylbis 2-methyl-5-t-butyl-indenyl) zirconium dimethyl Dimethylsilanediylbis 2-methyl-phenanthrylindenyl) zirconium dimethyl Dimethylsilanediylbis (2-ethyl-4-phenanthrylindenyl) zirconium dimethyl

Methyl (phenyl) silanediylbis (2-methyl-4-phenyl-indenyl) zirconium dimethyl Methyl (phenyl) silanediylbis (2-methyl-4, 6-diisopropyl-indenyl) zirconium dimethyl

Methyl (phenyl) silanediylbis (2-methyl-4-isopropyl-inde- nyl) zirconium dimethyl Methyl (phenyl) silanediylbis (2-methyl-4, 5-benzo-indenyl) zirconium dimethyl

Methyl (phenyl) silanediylbis (2-methyl-4, 5- (methyl-benzo) -indenyl) zirconium dimethyl

Methyl (phenyl) silanediylbis (2-methyl-4, 5- (tetramethyl-benzo) -indenyl) zirconium dimethyl Methyl (phenyl) silanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dimethyl

Methyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dimethyl Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenyl) zirconiumdimethyl Methyl (phenyl) silanediylbis (2-methyl-4-phenanthrylindenyl) - zirconiumdimethyl

Methyl (phenyl) silanediylbis (2-ethyl-4-phenanthrylindenyl) zirconium dimethyl 1,2-ethanediylbis (2-methyl-4-phenyl-indenyl) zirconium dimethyl 1,2-butanediylbis (2-methyl-4-phenyl-indenyl) zirconium dimethyl 1,2-ethanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium dimethyl

1,4-butanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dimethyl 1,4-butanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dimethyl 1,2-ethanediylbis (2-methyl-4,5- benzo-indenyl) zirconiumdimethyl 1,2-ethanediylbis (2,4,7-trimethyl-indenyl) zirconiumdimethyl 1,4-butanediylbis (2-methyl-indenyl) zirconiumdimethyl

The following are very particularly preferred:

Dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) -indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4- (para-t-butylphenyl) -indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4-a-acenaphth-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-ethyl-phenyl-indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4, 6-diisopropyl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-methyl-4-phenanthryl-indenyl) zirconium dichloride

Dimethylsilanediylbis (2-ethyl-4-phenanthryl-indenyl) zirconium dichloride

Methyl (phenyl) silanediylbis (2-methyl-4-phenanthryl-indenyl) - zirconium dichloride Methyl (phenyl) silanediylbis (2-ethyl-4-phenanthryl-indenyl) - zirconium dichloride, dimethylsilanediylbis- (-2-methyl- 4- (para- 4-butyl) -penylindenyl) zirconium dichloride, as well as the corresponding Dirnethylzirkoniumverbindungen.

In the case of the compounds of the general formula Id, those in which

M for titanium or zirconium,

X represents chlorine, C 1 -C ₄ -alkyl or phenyl.

R ¹⁶ Rl «Rio ■

^{Rl5 stands for} - M - or - _c - _c -, III

R ¹⁷ _R 17 _R 17

A for 0 -, S, NR ¹⁹

and

R ¹ to R ³ and R ⁵ for hydrogen, Cι ~ to Cio-alkyl, C ₃ - to Cio-cycloalkyl, C _e - to cis-aryl or

Si (R ⁸ ) ₃ , or where two adjacent radicals stand for cyclic groups having 4 to 12 carbon atoms.

Examples include:

(Benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride,

(2-Hethoxyphenylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride, ((2,6 -Di (1-methylethyl) phenyl) amido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride, (4-methoxyphenylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride,

(4-methylphenylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride, (phenylamido) dimethyl- (tetramethyl-η ⁵ "cyclopentadienyl) silantitanium dichloride,

(tert-butylamido) dimethyl- (η ⁵ -cyclopentadienyl) silantitanium dichloride,

(Anilido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride,

(Methylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silantitanium dichloride,

(tert-Butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium (III) chloride.

Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred. Examples of corresponding manufacturing processes include in the Journal of Organometallic Chemistry, 369 (1989), 359-370. Mixtures of different metallocene complexes can also be used.

According to the invention, for example, a cation-forming compound B) of the general formula II.

M ³ X ¹ X ² X ³ II,

in the

M ^{3 is} an element of III. Main group of the periodic table means, in particular B, Al or Ga, preferably B,

X ¹ , X ² and X ³ for hydrogen, Ci- to Cι ₀ alkyl, C ₆ - to Cι ₅ aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C. Atoms in the aryl radical or fluorine, chlorine, bromine or iodine are used, in particular for haloaryls, preferably for pentafluorophenyl.

Compounds of the general formula II in which X ¹ , X ² and X ^{3 are} identical are particularly preferred, such as trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (4fluoromethylphenyDboran , Tris (pentafluorophenyl) borane, Tris (tolyl) borane, tris (3, 5-dimethylphenyl) borane, tris (3, 5-dimethylfluorophenyl) borane and / or tris (3, 4, 5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.

Compounds of the general formula III are preferred as component B)

[(γa ⁺ ) QιQ ₂ ... Q ₂ ] a ⁺ III

in which

an element of the I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means.

Qi to Q _z for single negatively charged radicals such as Ci to C ₂₈ alkyl, C ₆ to Cis aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, each having 6 to 20 C atoms in the aryl and 1 to 28 C Atoms in the alkyl radical, C ₃ - to Cio-cycloalkyl, which can optionally be substituted with Ci- to Cio-alkyl groups, halogen, Ci- to C ₈ -alkoxy, Cξ - to Cis-aryloxy, silyl or mercaptyl groups

for integers from 1 to 6 and

represents integers from 0 to 5,

d corresponds to the difference a-z, but d is greater than or equal to 1.

Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable. The triphenylmethyl cation, the silver cation and the 1, 1 '-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate. Examples include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis (phenyl) aluminate, ferrocenium tetrakis (pentafluorophenyl) borate and / or ferrocenium aluminum tetrakis (pentafluorophenyl). Ionic compounds as component B) with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 91/09882, the preferred cation is N, N-dimethylanilinium. The N, N-dimethylcyclohexylammonium cation is very particularly preferred. Examples include triethylammonium tetra (phenyl) borate, tributylammonium tetra (phenyl) borate, trimethylammonium tetra (tolyl) borate, tributylammonium tetra (tolyl) borate, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (pentafluorophenyl), pentafluoromethyl

• tributylammonium tetra (trifluoromethylphenyl) borate, tributylammonium tetra (4-fluorophenyl) borate, N, N-dimethylanilinium tetra- (phenyl) borate, N, N-diethylanilinium tetra (phenyl) borate, N, N-dimethylanilentium boron tetraishen, p N-dimethylaniline tetrakis (pentafluorophenyl) aluminate, di (propyl) ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (phenyl) boronate (triethylphosphate), triethylphosphate

Diphenylphosphonium tetrakis (phenyl) borate, tri (methylpheny1) phosphonium tetrakis (phenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate.

Mixtures of the compounds described above or a part of these compounds are also suitable as component B), the mixing ratio not being critical.

The molar ratio of transition metal compound A): cation-forming compound B) is preferably 1: 3 to 1: 9, particularly preferably 1: 4 to 1: 8, in particular 1: 5 to 1: 7, very particularly preferably 1: 6.

The catalyst system according to the invention can, as a further component C), optionally also an organometallic compound, preferably a metal compound of the general formula IV

M ¹ (R ² ) _r (R ² ) _s (R ²³ ) _t iv

in the

M ^{1 is} an alkali metal, an alkaline earth metal or a metal of III. Main group of the periodic table, i. H . Means boron, aluminum, gallium, indium or thallium, R ^{21 is} hydrogen, Ci to C ₁₀ alkyl, C ₆ to C ₅ aryl,

Alkylaryl or arylalkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,

R ²² and R ^{23 are} hydrogen, halogen, Ci to -Cι ₀ alkyl,

C ₆ - to cis-aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,

an integer from 1 to 3

and

s and t are integers from 0 to 2, the

Sum r + s + t corresponds to the valence of M ¹ ,

and / or an aluminoxane of the general formula V or VI

wherein R ^{24 is} a -C ~ to C ₄ ~ alkyl group, preferably a methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25, contain.

These oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 284 708 and US A 4,794,096.

As a rule, the oligomeric alumoxane compounds obtained in this way are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean. The alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls. Can continue as component C) aryloxyaluminoxanes as described in US-A 5,391,793 describes Aminoaluminoxane, as described in the ^■ US-A 5,371,260, Aminoaluminoxanhydrochloride, as described in EP-A described 633,264, Siloxyaluminoxane, as described in EP-A 621 279 described, or mixtures thereof are used.

It has proven advantageous to use the transition metal compound A) and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the transition metal compound A is in the range from 1: 1 to 10 ⁶ : 1, preferably 1: 1 to 10 ⁴ : 1, in particular in the range from 1: 1 to 10: 1.

If component C) is present together with A) and / or B), in this case it is not identical to components A) and in particular B).

Of the metal compounds of the general formula IV, those are preferred in which

M ^{1 means} lithium, magnesium or aluminum and

R ²¹ to R ^{23 represent} Ci to Cio alkyl.

Particularly preferred metal compounds of the formula IV are n-butyl lithium, n-butyl-n-octyl magnesium, n-butyl-n-heptyl magnesium, tri-n-hexyl aluminum, tri-iso-butyl aluminum, triethyl aluminum and trimethyl aluminum.

If the compounds IV are used, they are preferably present in the catalyst system in an amount of 800: 1 to 1: 1, in particular 500: 1 to 50: 1 (molar ratio of M ¹ from IV to transition metal M from I).

The catalyst system used in the process according to the invention comprises, in addition to the components A), B), C) and, where appropriate, the compounds IV to VI, a carrier substance.

Suitable carrier substances are, for example, organic polymers, but preferably porous inorganic materials.

The carrier materials used are preferably finely divided carriers which have a particle diameter in the range from

Have 0.1 to 1000 μm, preferably from 10 to 300 μm, in particular from 30 to 70 μm. Suitable organic carriers are such as fine-particle polymers, for example fine-particle polyethylene or fine-particle polypropylene. Examples of suitable inorganic carriers are aluminum trioxide, silicon dioxide, titanium dioxide or their mixed oxides, aluminum phosphate or magnesium chloride. Preferably silica gels come the formula Si0 ₂ ^■ a A1 ₂ 0 ₃ is used, wherein a is a number ranging from 0 to 2, preferably 0 to 0.5, is. The carrier particles can be used in granular form and spray-dried in microscopic form. Products of this type are commercially available, for example silica gel 332 from Grace or ES 70 X from Crosfield.

Preferred inorganic carrier materials are acidic, inorganic metal or semimetal oxides with very high porosity, which are described, for example, in WO-A-97/47662.

The carrier materials can be pretreated thermally or chemically (e.g. with metal alkyl compounds) in order to achieve a specific property profile of the carrier (e.g. water and / or OH group content).

The catalyst system used in the process according to the invention is generally obtained by reacting a transition metal compound A) with a cation former B). This reaction can be carried out in a homogeneous, liquid phase or in the presence of a carrier material, organic solvents being generally used as suspending agents. The compound thus obtained can be used directly in suspension as a catalyst. ^'But it is also possible to isolate the compound and use it as such as a catalyst e.g. B. in gas phase processes, it can also be brought back into suspension after isolation and then used as a catalyst.

A preferred method of production of a supported catalyst of transition metal compound A), preferably those ^'of the general formula I, in particular those of formula Ic with cation-forming compound B) is as follows. The carrier substance, preferably inorganic, porous oxides, in particular silica gel, is optionally deactivated with organometallic compounds of the formula IV, preferably organoaluminum compounds, and this precursor is isolated and with the cation-forming compound B), preferably that of the formulas II- and III or Bronsted acids with non- nucleophilic anion, in an organic solvent, preferably aliphatic or aromatic C ₆ - to C ₃ o-hydrocarbon, in particular toluene. Then the

Transition metal component A), preferably metallocenes of the formula I, in particular those of the formula Ic, and added to the mixture 4 the solvent is removed immediately or after an exposure time of up to 48 h, preferably up to 10 h, in particular up to 90 minutes.

In the process according to the invention, propene and / or ethene are polymerized with 1-olefins. The polymerization process according to the invention is preferably used for the copolymerization of propene and / or ethene with C ₄ -C 1 -alk-1-enes. As C ₄ to C 1 -alk-1-enes are but-1-enes, pent-1-enes, 4-methyl-pent-1-enes, hex-1-enes, hept-1-enes or oct-1 -en or mixtures of these C ₄ - to -C -alk-1-enes preferred. Copolymers of ethene or propene are particularly preferred, the proportion of ethene or propene in the copolymers being at least 50 mol%. In the copolymers of ethene, preference is given to those which contain propene, but-1-ene, hex-1-ene or oct-1-ene or mixtures thereof as further monomers. The copolymers of propene are, in particular, those copolymers which contain ethene or but-1-ene or mixtures thereof as further monomers.

The polymerization process according to the invention is preferably used to prepare those polymers which

50 to 98 mol% of ethylene and ^' ' - '2 to 50 mol%, in particular 2 to 30 mol% of C ₃ - to -C ₂ alk-l-ene

contain.

Also preferred are those polymers that

50 to 98 mol% of propylene, 0 to 50 mol%, in particular 0 to 30 mol% of ethylene and 2 to 20 mol%, in particular 0 to 10 mol% of C 1 -C ₁ -alk-1-ene

exhibit.

The sum of the mol% always results in 100.

The polymerization according to the invention can be carried out continuously or batchwise in the processes customary for the polymerization of olefins, such as solution processes, suspension processes, stirred gas phase processes or gas phase fluidized bed processes. Inert hydrocarbons such as isobutane or the monomers themselves can be used as solvents or suspending agents. These are particularly suitable processes for the preparation of the polymers Suspension process and the gas phase process (stirred gas phase, gas phase fluidized bed).

Suitable reactors include continuously operated stirred tanks, loop reactors or fluidized bed reactors, it also being possible to use a number of several reactors connected in series (reactor cascade).

The copolymerization with the aid of the process according to the invention is generally carried out at temperatures in the range from -50 to 300 ° C., preferably in the range from 0 to 150 ° C., and at pressures generally in the range from 0.5 to 3000 bar, preferably in Range from 1 to 80 bar. In the polymerization processes according to the invention, it is advantageous to set the residence times of the respective reaction mixtures to 0.5 to 5 hours, in particular to 0.7 to 3.5 hours. During the polymerization, i.a. antistatic agents and molecular weight regulators, for example hydrogen, can also be used.

Examples

Examples 1 to 4, Comparative Example 1

Manufacture of activated supported metallocene catalyst solids

Various activated metallocene supported catalysts with a loading of 20 μmol / g Si0 rac-dimethylsilanediyl bis (2-methyl -4-phenylindenyl) zirconium dichloride and 90 μmol / g Si0 _{2 of} a cation-forming compound B) were produced.

example 1

4000 g of finely divided, spherical silica gel, which had previously been dried for 8 hours at 130 ° C. and under a pressure of less than 10 mbar, was suspended in 20 l of heptane and mixed with 8 l of a 2 M solution of triisobutylaluminum in heptane. The addition was so slow that the temperature of the suspension always remained below 40 ° C. The mixture was then stirred for 2 hours, the suspension was allowed to settle and the supernatant solution was removed. The solid was suspended with 20 L toluene and stirred briefly. Then the suspension was allowed to settle again and the supernatant solution was lifted off. This process was repeated two more times. The deactivated carrier was finally suspended with 20 L of toluene, 290.6 g (90 μmol / g SiO ₂ ) N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate were added and the mixture was heated to 85 ° C. At this temperature the suspension was stirred for 30 minutes. Thereafter, 50.3 g of rac-dimethylsilanediyl bis (2-methyl-phenylindenyl) zirconium dichloride (20 μmol / g Si0 ₂ ). The mixture was then stirred at 85 ° C. for a further 90 minutes. The color of the suspension changed from white to turquoise and then to black-violet. The catalyst was then dried in vacuo at 85 ° C.

Example 2

The procedure was as in Example 1, but using N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate as the cation-forming compound.

Example 3

The procedure was as in Example 1, but using trityltetra (pentafluorophenyl) borate as the cation-forming compound.

Example 4

The procedure was as in Example 1, but using tris (pentafluorophenyl) borane as the cation-forming compound.

Comparative Example 1

The procedure was as in Example 1, but using methylaluminoxane as the cation-forming compound.

Example 5

Ethene propene copolymerization

The copolymerization was carried out in a 1 L autoclave. The reactor temperature was 65 ° C, the pressure 29 bar, the polymerization time 60 minutes. The propene (350 g) was placed in the reactor with 4 mmol of triisobutylaluminum (2 mol / L in heptane). Then 3.5 g of ethene were added. The catalyst from Example 1 was metered into the 1-olefin / ethene mixture at 25 ° C. using argon overpressure.

The ethene-propene copolymer obtained had an ethene content of 2.5% by weight.

Examples 6 to 9, Comparative Example 2 Ethene-hexene-1 copolymerizations The copolymerizations were carried out in a 1L autoclave. Toluene and 1-hexene were added to the reactor and the system was saturated with ethene after constant thermal equilibrium and evacuation (constant ethylene pressure: 2 bar). Ethene was supplied during the reaction and the pressure was kept constant using a mass flow control instrument. In all cases the final toluene volume was 400 ml. Typically, the ethene concentration was 0.2 mol / 1, the 1-hexene concentration 0.6 mol / 1 and the catalyst concentration 2 (mol / 1.

For the MAO-activated copolymerizations, a toluene solution of the catalyst was placed in a vessel containing MAO and injected into the polymerization reactor after an equilibration time of 15 minutes. For the cationically activated copolymerizations, a standard catalyst solution was added to a toluene solution of borane or borate in the presence of an Al (i-Bu) 3 scavenger and equilibrated for 3 minutes before injection into the polymerization reactor. The polymerization times varied in order to keep the polymerization conversion low in all cases. The polymerization was terminated by adding an acidic methanol solution. The polymers were filtered, washed with acidic methanol and dried at 40 ° C for at least 3 days. The comonomer incorporation was determined by means of 13C NMR spectroscopy.

The procedure was as described in Example 5. The ethene / hexene ratios were kept constant. In Examples 6 to 9 and Comparative Example 2, the catalyst solids from Examples 1 to 4 and Comparative Example 1 were used. The respective rates of incorporation of 1-hexene based on the total monomer content were determined on the copolymers obtained.

Example 6 ^l , •

Catalyst solid from example 1. The copolymer obtained had a proportion of incorporated 1-hexene of 56.2 mol%.

Example 7

Catalyst solid from Example 2. The copolymer obtained has a 56.5 mol% proportion of incorporated 1-hexene.

Example 8

Catalyst solid of Example 3. The copolymer obtained had a proportion ^'of incorporated 1-hexene 50.8 mol%. Example 9

Catalyst solid from Example 4. The copolymer obtained had a proportion of 44.8 mol% of incorporated 1-hexene. 5th

Comparative Example 2

Catalyst solid from comparative example 1. The copolymer obtained had a proportion of 1-hexene incorporated of 10 44.5 mol%.

The examples illustrate that significantly higher incorporation rates for the comonomer are found with the cation-forming compounds according to the invention than when using methyl-15 aluminoxane.

20

25

30

35

40

45

Claims

claims

1. A process for the copolymerization of propene and / or ethene with 1-olefins on supported metallocene catalysts, characterized in that these monomers in the presence of a catalyst system containing as active ingredients those which are obtainable by the reaction of

A) a transition metal compound

With

B) a cation-forming compound of the general formula II

M ³ χiχX ³ II

in the

M ^{3 is} an element of III. Main group of the periodic table means

X ¹ , X ² and X ³ for hydrogen, Cl to CIO alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the Aryl radical or fluorine, chlorine, bromine or iodine,

and / or the general formula III

_[( γa + _{) Q1Q2} ... _Qz] d + _{ι τ τ} in which

Y is an element of I. to VI. Main group or the

I. to VIII. Subgroup of the periodic table means,

Qi to Q _z for simply negatively charged radicals such as Ci- to C ₂₈ alkyl, C ₆ - to C ₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl with each

6 to 20 C atoms in the aryl and 1 to 28 C atoms in the alkyl radical, C ₃ - to Cio-cycloalkyl, which optionally substituted with Ci to C ₀ alkyl groups, halogen, Ci to Cs alkoxy, C ₆ to Cis aryloxy, silyl or mercaptyl groups

a for integers from 1 to 6 and

z represents integers from 0 to 5,

2. The method according to claim 1, characterized in that the molar ratio of the transition metal compound A) to the cation-forming compound B) is in the range from 1: 3 to 1: 9.

3. The method according to claim 1 or 2, characterized in that the cation-forming component B) is selected from

N, N-dimethylcyclohexylammonium tetrakis (pentafluoropheny) borate, |

Trifluoroborane, 'triphenylborane, tris (4-fluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (4-fluoromethylphenyDborane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3, 5-dimethylphen ) borane, tris (3, 5 -dimethylfluorophenyl) borane and / or tris (3, 4, 5-trifluorophenyl) borane, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbeniumtetrakat (phenylrobenium) tetrahis (pentafluorophenyl) borate, , ferrocenium tetrakis (pentafluorophenyl) aluminate, triethylammonium tetra (phenyl) borate, tributylammoniumtetra (phenyl) borate, trimethylammoniumtetra (tolyl) borate, tributylammoniumtetra (tolyl) borate, tributylammonium tetra (pentafluorophenyl) borate, tributylammoniumtetra (pentafluorophenyl) aluminate, tripropylammoniumtetra (dimethylphenyl) borate, tributylammoniumtetra (trifluoromethylphenyl) borate, tributylammonium tetra (4-fluorophenyl) borate, N, N-dimethylanilinium tetra (phenyl) borate, N, N-diethylani linium tetra (phenyl) borate, N, -dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, di (propyl) ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) pentafluorophenyl (boron) boron Triphenylphosphonium tetrakis (phenyl) borate,

Triethylphosphonium tetrakis (phenyl) borate,

Diphenylphosphonium tetrakis (phenyl) borate,

Tri (methylphenyl) phosphonium tetrakis (phenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate,

7, 8-dicarbaundecaboran (13),

Undecahydrid-7, 8-dimethyl-7, 8-dicarbaundecaboran,

Dodecahydrid-l-phenyl-1,3-dicarbaundecaboran,

Tri (butyl) ammonium decahydride-8-ethyl-7, 9-dicarbaundecaborate, 4-carbanonaborane (14) bis (tri (butyl) ammonium) nonaborate,

Bis (tri (butyl) ammonium) undecaborate,

Bis (tri (butyl) ammonium) dodecaborate,

Bis (tri (butyl) ammonium) decachlorodecaborate,

Tri (butyl) ammonium-1-carbadodecaborate, tri (butyl) ammonium-1-carbadodecaborate,

Tri (butyl) ammonium-1-trimethylsilyl-l-carbadecaborate,

Tri (butyl) ammonium bis (nonahydrid-1,3-dicarbonnonaborate) - cobaltate (III).

4. The method according to any one of claims 1 to 3, characterized in that component B) is N, N-dimethylcyclohexylammonium umtetrakis (pentafluorophenyl) borate.

Summary

Process for the copolymerization of propene and / or ethene with 1-olefins on metallocene catalysts, these monomers in the presence of a catalyst system containing, as active constituents, those which are obtainable by the reaction of

A) a transition metal compound

With

B) a cation-forming compound of the general formula

II

M ³ X ^X XX ³ II

in the

M ^{3 is} an element of III. Main group of the periodic table means

X ¹ , X ² and X ³ for hydrogen, Cl to CIO alkyl, C6 to C15 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to

20 carbon atoms in the aryl radical or _fluorine. Chlorine, bromine or iodine,

and / or the general formula III

[(Y ^{a +} ) Q _l Q ₂ ... Q _z ] ^{d +} III in which

Y is an element of I. to VI. Main group or the

I. to VIII. Subgroup of the periodic table means

Qi to Q _z for single negatively charged radicals such as Ci to C ₂₈ alkyl, C ₆ to C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C. -atoms in the alkyl radical, C ₃ - to -C ₀ cycloalkyl, which can optionally be substituted with Ci- to Cio-alkyl groups, halogen, Ci- to C β-alkoxy, C ₆ - to Cis-aryloxy, silyl or mercaptyl groups

a for integers from 1 to 6 and

z represents integers from 0 to 5,