HK1090935B - Catalyst combination, isotactic polymers, method for producing linear isotactic polymers, and the use of said polymers - Google Patents

Description

Catalyst composition, isotactic polymer, process for producing linear isotactic polymer and use of said polymer

The present invention relates to novel catalyst compositions as well as thermoplastic polymers and a process for producing linear isotactic polymers having thermoplastic properties and the use thereof.

One of the main requirements in olefin polymerization catalysis is to control the microstructure of the polymer, whereby the properties of the material can be influenced. It is known, for example, from DE 19816154 that, when highly reactive zirconocenes dichloride are used, individual stereo dislocations can be introduced along the isotactic chain depending on the monomer concentration. These asymmetric catalysts have alkyl or alkoxy substituents at the 5, 6-positions of the indenyl groups, resulting in increased activity and thus extremely high molecular weights. These 5, 6-substituted metallocene catalysts thus produce a high concentration of isolated stereo dislocations, which results in a soft polypropylene with low crystallinity and high elasticity.

Starting from this, it is an object of the present invention to provide novel polymers having thermoplastic properties and catalysts which make it possible to polymerize isotactic polymers having thermoplastic properties.

This object is achieved by a catalyst composition having the features of claim 1 and a process for producing linear isotactic polymers using the catalyst composition having the features of claim 12. The features of claim 16 indicate the novel polymers and the features of claim 26 indicate their use. The other dependent claims describe advantageous embodiments.

According to the present invention, there is provided a catalyst composition for producing a linear isotactic polymer, comprising an activator and a metal complex of the general formula 1.

Wherein the substituents have the following meanings:

R¹-R⁴linear or branched C₁-to C₁₀-alkyl, 5-7 membered cycloalkyl, part of which may carry one or more C₁-to C₁₀Alkyl as a substituent, C₆-to C₁₈Aryl or aralkyl or alkaryl radicals R¹/R²、R³/R⁴May be partially or simultaneously bonded to a 5-7 membered anellated cycloalkyl or aromatic ring, which in turn may contain heteroatom units (e.g., O, S, NR);

R⁶-R⁹hydrogen, linear or branched C₁-to C₁₀Alkyl or hydrogen, linear or branched C₁-to C₁₀-alkyl, 5-7 membered cycloalkyl, part of which may carry one or more C₁-to C₆Alkyl as a substituent, C₆-to C₁₈Aryl or aralkyl or alkaryl radicals, provided that the radical R⁶/R⁷Or R⁸/R⁹Bonded to a 5-7 membered anellated cycloalkyl or aromatic ring, which may be substituted, interrupted with heteroatoms and/or in combination with other cycloalkyl and/or aromatic rings;

R¹⁰-R¹¹hydrogen, C₁-to C₈-alkyl, 4-7 membered cycloalkyl, aryl, R¹⁰、R¹¹Together with E, may form a 4-7 membered cycloalkyl or aryl group;

R¹²C₁-to C₈Alkyl, aryl, C₁-to C₈-alkoxy, C₁-to C₈-a trialkylsiloxy group;

m is titanium, zirconium, hafnium, vanadium, niobium, tantalum;

x is hydrogen, halogen or C₁-to C₈-alkyl, aryl, benzyl;

e carbon, silicon, germanium or 1, 2-ethyl, 1, 3-propyl, 1, 4-butyl.

The metal complex according to the invention is thus characterized in that it is asymmetric and has a structure with respect to the group R⁶-R⁹Specific substitution of (2). Thus, having a substituent R¹-R⁴The ring(s) of (a) is preferably a fluorene ring system which may also be substituted.

Preferably, the metal complex of formula 1 is a compound of formula II.

Here the radical R¹-R⁴And R¹⁰-R¹²And E and MX₂Has the meaning of the formula I, and E₂＝CH₂O or S and n is 1 or 2. Thus, E²May be the same or different.

A similar preferred catalyst composition is based on compounds of formula III.

The radicals here have the meanings indicated in the general formula I.

Preferably, the catalyst composition contains a compound of formula IV as metal complex.

Wherein the radical R¹-R⁴And R¹⁰-R¹²And E and MX₂Has the meaning indicated in the formula I, and E²＝CH₂O or S and n is 1 or 2. Thus, E²May be the same or different.

In another advantageous embodiment, the catalyst composition has a compound of the formula V as metal complex.

Here too, the radicals have the meanings indicated in the formula I.

Another advantageous variant is a metal complex having the general formula XII.

Here the radical R¹-R⁴And R¹⁰-R¹²And E and MX₂Has the meaning shown in the general formula I.

A similar preferred catalyst composition is based on a compound of formula XIII.

Here the radical R¹-R⁴And R¹⁰-R¹²And E and MX₂Has the meaning in the general formula I.

Preferably, the activator is an open-chain or cyclic aluminoxane compound having the general formula VI or VII.

Here, R¹³Finger C₁-to C₄-alkyl and n is a number between 5 and 30.

Cationic activators of formulas VIII-XI can similarly be included in the catalyst composition.

(VIII)B(C₆F₅)₃、Al(C₆F₅)₃

(IX)R¹⁴ ₃C[B(C₆F₅)₄]、R¹⁴ ₃C[Al(C₆F₅)₄]

(X)[R¹⁴ ₃NH][B(C₆F₅)₄]、[R¹⁴ ₃NH][Al(C₆F₅)₄]

(XI)R¹⁴ ₃C[C₅R¹⁵ ₅]、[R¹⁴ ₃NH][C₅R¹⁵ ₅]

Where R is¹⁴Finger C₁-to C₄-alkyl or aryl and R¹⁵Is a perfluorinated alkyl or aryl group.

Other suitable alternatives are described in WO 03/082879A 1 (e.g. claim 40) and WO 03/082466A 1 (e.g. claim 11). Therefore, the detailed content refers to the disclosure.

The foregoing activators may thus be present alone or in combination.

The metal complexes according to the formulae VI to XI and the activators are preferably used in such amounts that the atomic ratio between the aluminium from the aluminoxane and/or the boron (or aluminium) from the cationic activator and the transition metal from the metal complex is 1: 1-10⁶∶1。

Using the catalyst composition according to the invention, it is possible to provide pentadienes concentrations higher than 60% [ mmmm [ ]]Of up to 5.0 x 10⁶A novel class of flexible polypropylene thermoplastics of very high molecular weight in g/mol. Thus, such polymers are clearly between soft thermoplastic elastomers and rigid polypropylene materials with isotactic microstructure.

According to the present invention, there is similarly provided a process for producing a linear isotactic polymer (claims 12 to 16). For the process according to the invention for producing linear isotactic polymers, the polymer is formed from a polymer selected from C₂-to C₂₀At least one monomer constituent of an olefin, C₂-to C₂₀-olefins are converted in the presence of the aforesaid catalyst composition. The tacticity of the obtained polymer is more than 60% [ mmmm%]The concentration of pentadiene (g). Preference is therefore given to carrying out the polymerization in the gas phase, in suspension or in supercritical monomer, in particular in a solvent which is inert under the polymerization conditions. As the inert solvent, a solvent containing no reactive molecule should be used. Examples of such solvents are benzene, toluene, xylene, ethylbenzene or alkanes, such as propane, n-butane, isobutane, pentane, hexane, heptane or mixtures thereof. The polymerization reaction can be carried out under known conditions. It is therefore advantageous to operate at a pressure of from 1 to 100 bar, preferably from 3 to 20 bar, particularly preferably from 5 to 15 bar. As regards suitable temperatures, it is considered that these should be from-50 to 200 ℃, preferably from 10 to 150 ℃ and particularly preferably from 20 to 40 ℃.

As previously mentioned, the method comprises C₂-to C₂₀-reaction of the olefin and, if desired, further monomers and a catalyst composition comprising at least one activator of the formulae VI to XI in the presence of at least one metal complex of the formulae I to V.

The activator is preferably an open-chain or cyclic aluminoxane compound of the general formula VI or VII.

Here, R¹³Finger C₁-to C₄-alkyl and n is a number between 5 and 30.

Cationic activators of formulas VIII-XI can likewise be included in the catalyst composition.

(VIII)B(C₆F₅)₃、Al(C₆F₅)₃

(IX)R¹⁴ ₃C[B(C₆F₅)₄]、R¹⁴ ₃C[Al(C₆F₅)₄]

(X)[R¹⁴ ₃NH][B(C₆F₅)₄]、[R¹⁴ ₃NH][Al(C₆F₅)₄]

(XI)R¹⁴ ₃C[C₅R¹⁵ ₅]、[R¹⁴ ₃NH][C₅R¹⁵ ₅]

Where R is¹⁴Finger C₁-to C₄-alkyl or aryl, R¹⁵Is a perfluorinated alkyl or aryl group.

Other suitable alternatives are described in WO 03/082879A 1 (e.g. claim 40) and WO 03/082466A 1 (e.g. claim 11). Therefore, the detailed content refers to the disclosure.

The foregoing activators may thus be present alone or in combination.

The metal complexes according to the formulae VI to XI and the activators are preferably used in such amounts that the atomic ratio between the aluminium from the aluminoxane and/or the boron or aluminium from the cationic activator and the transition metal from the metal complex is from 1: 1 to 10⁶∶1。

The invention also relates to novel isotactic polymers having thermoplastic properties (patent claims 17-24).

The main factor of the novel isotactic polymer according to the invention is that it has a content of greater than 60% [ mmmm [ ]]Tacticity of pentadiene concentration. At the same time, the polymers according to the invention have a molecular weight of at most 5,000,000g/mol and a Tg of from-50 ℃ to 30 ℃. The polymers according to the invention therefore relate to first ultrahigh molecular weight polyolefins having a molecular weight of at most 5,000,000 g/mol. Therefore, it is preferable that the tacticity is in the range of more than 60% to 98%. Therefore, the molecular weight is preferably 1,000,000-3,000,000g/mol, particularly preferably 1.3 to 2000000 g/mol. As previously mentioned, the novel thermoplastic polymers can preferably be produced using the aforementioned catalyst compositions. From a material point of view, the polymers according to the invention may consist of all C₂-to C₂₀-an olefin composition. As olefins, preference is given to using C₃-to C₂₀-1-alkenes. Examples thereof are propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicosene. As regards the olefin, this may also be C₅-to C₂₀-a cyclic olefin. For cycloolefins, cyclopentene, cyclohexene, norbornene and derivatives thereof are exemplified. It is particularly preferred to use polypropylene as olefin.

The isotactic polymers according to the invention can obviously also be constructed from polypropylene and C₄-to C₂₀Copolymers of olefins and/or cycloolefins. The isotactic polymers according to the invention can also be prepared from propylene, C₂-to C₂₀-terpolymers of olefins and cycloolefins. Furthermore, all additives known from the prior art may be included. Examples of additives are fillers, plasticizers and nucleating agents.

The linear isotactic polymers according to the invention can of course also be granulated by themselves, as is known from polymer chemistry, so that they can be processed further conveniently.

Possible fields of application for the isotactic polymers described here are films, filaments, moulded articles, etc.

The invention will be illustrated in more detail with reference to several production examples of catalysts and with reference to polymerization examples.

The results are shown in FIGS. 1 to 7 (tables 1 to 7).

In the following examples, reference is made to the following compounds.

Example 1

Preparation of the compound

The compounds according to the invention were synthesized according to the following reaction scheme.

A. Preparation of 2-methyl-1H-benzo [ b ] indeno {4, 5-d } thiophene

20g (108.7mmol) of dibenzothiophene (1) are added at-78 ℃ to 10.6ml of methacryloyl chloride (108.7mmol) and 15.3g of AlCl₃(114.8mmol) in 250ml of dichloromethane and at room temperature overnight. The solution is carefully hydrolyzed at 0 ℃ and the organic phase is separated off and treated with K₂CO₃Is washed with an aqueous solution of (1) and passed over Na₂SO₄And (5) drying. After removal of the solvent and crystallization in toluene/pentane. apprxeq.10: 1, 2-methyl-1, 2-dihydrobenzo [ b ] is obtained as a crystalline solid material]Indeno [4, 5-d ]]Thiophen-3-one (2) (21.6g, 85.9mmol, 79%).

16.8g (66.7mmol) of 2-methyl-1, 2-dihydrobenzo [ b ] diluted with 50ml of THF]Indeno [4, 5-d ]]Thiophene-3-one (2) was added at 0 ℃ to 0.9g LiAlH dissolved in 100ml THF₄In suspension. The reaction mixture was stirred overnight and carefully hydrolyzed with ice and aqueous HCl. After the separation of the organic phase,applying the solution to a support₂CO₃Neutralizing with Na solution₂SO₄And (5) drying. After evaporation of the solvent and with Et₂After O wash, diastereomeric alcohol (16.6g, 65.4mmol, 98%) was obtained as crystalline solid material.

The diastereomeric alcohol (16.6g, 65.4mmol) was dissolved in 100ml toluene and 1.0g p-toluenesulfonic acid was added. The solution was heated under reflux and water separation means was used until no more water was formed. The reaction mixture was neutralized by washing with aqueous KOH and passed over Na₂SO₄And (5) drying. After evaporation of the solvent, 2-methyl-1H-benzo [ b ] is obtained as a crystalline solid material]Indeno [4, 5-d ]]Thiophene (3) (14.9g, 63.1mmol, 97%).

-a ketone:¹H NMR(400MHz，CDCl₃)：δ1.37(d，3H，CH₃)，2.84，3.22(2m，2H，CH₂indanone ring), 3.94(m, 1H, CH, indanone system), 7.45, 7.80, 8.22(3m, 6H, aromatic). MS (GC-MS) M/z 252(M +, 100%).

Analyzing and calculating results: c, 76.19; h, 4.76.

Actually measuring: c, 76.05; h, 4.72.

-an alcohol:¹H NMR(400MHz，CDCl₃)：δ1.28(d，3H，CH₃) 1.75 (broad, 1H, OH-group), 2.43, 2.88(2m, 2H, CH)₂Indenole ring), 3.72(m, 1H, CH, indenole ring), 4.85(d, 1H, CH, indenole ring), 7.67(d, 1H, aromatic), 7.40, 7.80, 8.13(3m, 5H, aromatic). MS (GC-MS) M/z254 (M)⁺，100％)。

Analyzing and calculating results: c, 75.59; h, 5.51.

Actually measuring: c, 75.45; h, 5.56.

-(3)：¹H NMR(400MHz，CDCl₃)：δ2.29(s，3H，CH₃)，3.74(s，2H，CH₂Indenyl), 6.66(s, 1H, CH, ene), 7.74(d, 1H, aromatic), 7.48, 7.85,8.27(3m, 5H, aromatic). MS (GC-MS) M/z236 (M)⁺，100％)。

Analyzing and calculating results: c, 81.36; h, 5.08.

Actually measuring: c, 81.49; h, 5.23.

B. Preparation of 1- (9-fluorenyl) -2- (2-methyl-1H-benzo [ b ] indeno [4, 5-d ] thiophen-1-yl) ethane (5a) and 1- (9-fluorenyl) -2- (2-methyl-1H-benzo [ b ] indeno [4, 5-d ] thiophen-3-yl) ethane (5b)

2.67g (12.72mmol) of 2- (9-fluorenyl) ethanol in 100ml of CH₂Cl₂Diluted and 1.8ml triethylamine was added. The solution was cooled to 0 ℃ and slowly added to 30ml CH₂Cl₂Of (CF)₃SO₂)₂O (2.1ml, 13.99 mmol). The reaction mixture was stirred at 0 ℃ for 1 hour, washed twice with ice water and over Na₂SO₄And (5) drying. The solvent was removed in vacuo and the resulting triflate (4) was diluted in 50ml THF. The lithium salt of (3) was separated from 3.00g (3) (12.72mmol) at-78 deg.c to yield p-methoxyphenyllithium (12.72mmol) dissolved in toluene: dioxane 10: 1 and after stirring for 2 hours at room temperature, a yellow solid material was isolated. Subsequently, diluted trifluoromethanesulfonic acid (4) was added to a solution of the lithium salt of (3) in 50ml THF at-78 deg.C and overnight at room temperature. By NH₄The crude product was treated with a saturated aqueous solution of Cl and washed several times with water. Separating the organic phase over Na₂SO₄Dried and the solvent evaporated. By CH₂Cl₂Removal of the silicic acid by chromatography yields a 1: 1 mixture of the two structural isomers 5a, 5b as crystalline material (3.81g, 8.90mmol, 70%).

(5a)：¹H NMR(400MHz，CDCl₃)：δ1.85(s，3H，CH₃)，1.01-1.27(m，1H，CH₂Bridge), 1.42-1.68(m, 2H, CH)₂Bridge), 1.80-1.85(m, 1H, CH)₂Bridge), 3.53(t, 1H, CH, indene), 3.64(t, 1H, CH, 9-H-fluorene), 6.45(s, 1H, indene), 6.42, 6.56, 6.89-7.73(m, 14H, indene system proton, aromatic fluorene).

(5b)：¹H NMR(400MHz，CDCl₃)：δ1.81(s，3H，CH₃)，2.07-2.13(m，2H，CH₂Bridge), 2.26-2.30(m, 2H, CH)₂Bridge), 3.44(s, 2H, CH)₂Indene), 4.00(t, 1H, CH 9-H-fluorene), 7.06-7.97(m, 14H, indene system aromatic proton, aromatic fluorene). MS (Cl) M/z428 (M)⁺，100％)。

Analyzing and calculating results: c, 86.92; h, 5.61.

Actually measuring: c, 86.86; h, 5.73.

C. Preparation of rac- [1- (9-. eta.)⁵-fluorenyl) -2- (2-methyl-benzo [ b ]]Indeno (4, 5-d) thiophen-1-eta⁵-radical) ethane]Zirconium dichloride (7a) and rac- [1- (9-. eta.) ]⁵-fluorenyl) -2- (2-methyl-benzo [ b ]]Indeno (4, 5-d) thiophen-3-eta⁵-radical) ethane]Zirconium dichloride (8)

0.96g (2.24mmol) of the isomeric mixture of 5a and 5b was diluted in 100ml of toluene/dioxane 10: 1 and cooled to-78 ℃. After addition of a 1.6M solution of n-butyllithium in n-hexane (2.80ml, 4.48mmol), the reaction mixture was stirred at room temperature for 4 hours. Subsequently, the resulting lithium salt was separated and diluted with 100ml of toluene. Cooling to-78 deg.C and adding solid ZrCl₄(0.52g, 2.24mmol) to form an orange suspension. The mixture was stirred overnight, filtered and the residual solid was extracted several times with toluene. Fractional crystallization from toluene gave 7a (0.34g, 0.58mmol, 52%) and 8(0.12g, 0.20mmol, 18%) as orange solid materials in pure form. (7a) The method comprises the following steps¹H NMR(400MHz，CDCl₃)：δ2.35(s，3H，CH₃)，3.88-3.94(m，1H，CH₂Bridge), 4.16-4.23(m, 1H, CH)₂Bridge), 4.55-4.71(m, 2H, CH)₂Bridge), 6.47(s, 1H, indene), 5.94(d, 1H, aromatic), 6.56(t, 1H, aromatic), 7.13-7.92(m, 10H, aromatic), 8.08(d, 1H, aromatic), 8.82(d, 1H, aromatic). MS (El) m/z 588, according to the isotopic range distribution claimed.

Analyzing and calculating results: c, 63.27; h, 3.74.

Actually measuring: c, 63.39; h, 3.80.

(8)：¹H NMR(400MHz，CDCl₃)：δ2.32(s，3H，CH₃)，3.85-3.96(m，1H，CH₂Bridge), 4.04-4.12(m, 1H, CH)₂Bridge), 4.13-4.26(m, 1H, CH)₂Bridge), 4.56-4.68(m, 1H, CH)₂Bridge), 6.82(s, 1H, indene), 7.05-8.10(m, 14H, aromatic). MS (El) m/z 588, according to the isotopic range distribution claimed.

Analyzing and calculating results: c, 63.27; h, 3.74.

Actually measuring: c, 63.41; h, 3.85.

D. Preparation of rac- [1- (9-. eta.)⁵-fluorenyl) -2- (2-methyl-benzo [ b ]]Indeno (4, 5-d) thiophen-1-eta⁵-radical) ethane]Hafnium dichloride (7b)

Corresponding to the preparation of said 7a, 0.83g (1.93mmol) of the isomeric mixture of 5a and 5b, 2.41ml of a 1.6M solution of n-butyllithium in n-hexane (3.86mmol) and 0.62g of HfCl₄(1.93mmol) was converted to yellow solid 7b (0.22g, 0.33mmol, 34%).

(7b)：¹H NMR(400MHz，CDCl₃)：δ2.44(s，3H，CH₃)，4.05-4.13(m，1H，CH₂Bridge), 4.27-4.36(m, 1H, CH)₂Bridge), 4.47-4.62(m, 2H, CH)₂Bridge), 6.38(s, 1H, indene), 5.90(d, 1H, aromatic), 6.53(t, 1H, aromatic), 7.09-8.89(m, 10H, aromatic), 8.08(d, 1H, aromatic), 8.82(d, 1H, aromatic). MS (El) m/z 676, according to the isotopic range distribution claimed.

Analyzing and calculating results: c, 55.07; h, 3.26.

Actually measuring: c, 55.21; h, 3.29.

E. Preparation of rac- [1- (9-. eta.)⁵-fluorenyl) -2- (2-methyl-benzo [ b ]]Indeno (4, 5-d) thiophen-1-eta⁵-radical) ethane]Hafnium dimethyl (7c)

Will be 0.15g(0.22mmol)rac-[1-(9-η⁵-fluorenyl) -2- (2-methyl-benzo [ b ]]Indeno (4, 5-d) thiophen-1-eta⁵-radical) ethane]Dilution of hafnium dichloride 7b in 50ml Et₂O and cooled to 0 ℃. Et with excess 1.6M MeLi₂O (5.55ml, 8.88mmol) solution and the resulting yellow suspension was stirred at room temperature for 1 hour. The remaining mixture was cooled again to 0 ℃ and 0.8ml dibromoethane was added to destroy any unconverted MeLi. After stirring at room temperature for a further 1 hour, the solvent was removed in vacuo and the residual solid fraction was extracted with toluene. Toluene was then removed to give yellow solid 7c (0.11g, 0.17mmol, 78%).

(7c)：¹H NMR(400MHz，CDCl₃)：δ-2.47，-1.50(2s，6H，CH₃)，2.20(s，3H，CH₃)，3.65-3.77(m，1H，CH₂Bridge), 3.94-4.06(m, 1H, CH)₂Bridge), 4.08-4.19(m, 2H, CH)₂Bridge), 6.39(s, 1H, indene), 5.81(d, 1H, aromatic), 6.42(t, 1H, aromatic), 6.99-8.07(m, 11H, aromatic), 8.78(d, 1H, aromatic).

Analyzing and calculating results: c, 62.40; h, 4.41.

Actually measuring: c, 62.49; h, 4.43.

Example 2

X-ray image of Complex (7a)

Crystals of the complex (7a) are in the triclinic space group P_-1. Suitable crystals were obtained by diffusion of pentane in toluene solution of (7 a). Fig. 1 shows a front view (fig. 1a) and a side view (fig. 1 b). Thus, the front view shows the position of the ethylene bridge at MBIT unit C3, and the bonds of the benzothiophene segments at C8 and C15 of the central indene ring result in the rear orientation of the group, with the sulfur atom pointing forward. Because of the remote location of the sulfur atom, adverse intramolecular interactions with the zirconium center can be excluded.

The side view of complex (7a) (fig. 1b) shows certain features of the complex structure. Cp^Flu-Zr-Cp^MBITThe angles are δ 128.0 ° and Φ 62.9 °. The corresponding angle can be derived from fig. 2. Angle gamma^FluAt 189.5 deg. and unlike the results of the bridged indenyl and fluorenyl complexes of the prior art, values of less than 180 deg. are generally observed for the latter. The resulting improvement in the accessibility of the zirconium centre is apparently responsible for the higher activity of the complex (7 a). Furthermore, it was observed that the post-orientation of the angled MBIT segment leads to the intramolecular repulsive interaction of the phenyl hydrogen atom at the position behind the fluorenyl unit with the post-oriented MBIT system. To avoid this unfavorable steric strain, the benzothiophene moiety of the ligand is bent away from these hydrogen atoms, which results in the aromatic rings being out of plane alignment.

(7a) Average distance between Zr (IV) and fluorenyl carbon atomIs obviously larger than the distance between Zr (IV) and fluorenyl carbon atom in MBIT unitThis results in an asymmetric arrangement of zr (iv) centers between the two Cp planes. Beta is a^FluThe value is 80.74 deg., corresponding to a distance between Zr and carbon atoms ofThis results in a relative η⁵The keys have less tooth contact. In contrast, β^MBITA value of 88.33 ℃ showing the almost ideal η of aromatic 5-membered Cp ring pairs Zr (IV) in MBIT units⁵And (4) arranging.

The structural data of the X-ray images are summarized in tables 1 and 2.

Example 3

Experiments involving Compounds relating to polymerization

After activation with MAO, zirconocene (7a), (8)/MAO proved to be suitable catalysts for the polymerization of polypropylene. In Table 3, the dependence of the novel metallocenes (heterocene) on the monomer and on the temperature is illustrated. Compounds of the types (7a), (7c) and (8) are thus used as monomers.

The activity during the polymerization of the two catalysts increases with increasing polymerization temperature and monomer concentration. The highest activity for MAO activation was achieved by (7a)/MAO (Table 3: No.3, T)_p＝60℃，13.5×10³kg PP(molZr[C₃]h)^-1) (8)/MAO can result in polypropylene with significantly reduced activity. (in Table 3: No.11, T)_p＝60℃，4.9×10³kg PP(mol Zr[C₃]h)^-1). The influence of heteroatom electrons on the activity can be excluded due to the almost no difference in electronegativity of carbon (2.55) and sulfur (2.58) and due to the separation position of the sulfur atom. The overall construction of the complex (7a) which gives better accessibility to the zr (iv) centres may lead to a higher (7a) activity.

In the polymerization test with (7a)/MAO, [ mmmm ] was obtained]Pentadiene concentration 65-85% and molecular weight up to 2X 10⁵g/mol isotactic polypropylene. Although changes in monomer concentration do not significantly affect stereoregularity, a linear decrease in stereoselectivity with increasing polymerization temperature can be observed, contrary to the expected chain inversion mechanism for other asymmetric zirconocenes based on indenyl and fluorenyl units. In contrast, the use of complex (8)/MAO produced a polypropylene of low tacticity with a lower molecular weight (see Table 3: No.15, T)_p＝30℃，[mmmm]＝17％，Mw＝5.9×10⁴g/mol)。

Was carried out with respect to (7C)/[ (C) dimethyl hafnium complex₆H₅)₃C⁺][(C₆F₅)4B^-]To obtain a further increase in the molecular weight of the thermoplastic material, this was achieved with the complex (7a)/MAO of the same structure. Polymerization tests in liquid polypropylene show that the molecular weight can be increased up to 1.5X 10 at 0 ℃⁶g/mol, with the effect of a slight decrease in stereoselectivity observed. Furthermore, at 30 ℃ borate activation leads to an increase in activity up to 15.9kg PP (mol Zr [ C ]₃]H)^-1As a result, it is clear that the maximum concentration of the cocatalyst can be obtainedActive Zr (IV) centers of (2). These results are consistent with the known knowledge that significantly higher molecular weights and activities can be obtained by borate activated dimethyl complexes, which can be caused by the absence of chain transfer to aluminum and higher concentrations of active catalyst upon borate activation.

In Table 4, the pentadiene distribution of complexes 1-7 (see Table 3) is shown. MAO was used as an activator.

Example 4

Preparation of the Compounds

Compounds according to the invention were synthesized according to the following reaction scheme:

to synthesize the compounds according to the invention, the operation starts with 2-methylinden-1-one, the resulting yield of the desired 2-methylindene being more than 60% in a three-step process. As shown, m-xylene (1) is converted with methacryloyl chloride in a first step. After washing, the yield of pure indanone (2) obtained by distillation and Friedel-Crafts alkylation was 66%. With NaBH₄Reducing indanone (2). Indene (3) is obtained in the form of a viscous fluid. Using the reaction of the compound (4) produced by adding 1, 2-dibromoethane and fluorenyllithium, two isomers (5) and (6) were obtained in the subsequent reaction in a yield of 45%. The desired isomer (5) is subsequently isolated by crystallization from a mixed solution of toluene/hexane in a ratio of 1: 2.

The ligand (5) can be converted to the desired hafnium complex by deprotonation at-78 ℃ using n-BuLi in a toluene/dioxane mixture and stirring at room temperature for 2 hours. It is also necessary to add HfCl into the solution₄. The reaction was completed by stirring at room temperature for 20 hours. The hafnium complex (7) was then isolated in 45% yield. The precipitated yellow complex was separated from the toluene solution and extracted with cold toluene. Followed by removing the toluene as quickly as possible and drying the mixture in vacuoYellow powder.

Example 5

Polymerization examples

Propylene polymerization in various solvents was carried out using the hafnium complex (7) prepared according to the foregoing example 1.

A.) polymerization in toluene

The polymerization in toluene was carried out in a 500ml autoclave at constant temperature and pressure. The autoclave was charged with 250ml of toluene and the catalyst according to example 1. Next, the polymerization temperature and the desired pressure were adjusted and propylene and the co-catalyst solution (pentafluorotetraphenylborate) were fed into the reactor. Monomer consumption was measured using a calibrated gas flow meter (Bronkhorst F-111C-HA-33P) and the pressure was kept constant during the polymerization. The pressure/temperature and the propylene consumption were measured without interruption. The polymerization was terminated with methanol and the polymer product was isolated.

A.) polymerization in liquid propylene

Alternatively, the polymerization reaction may be carried out in liquid propylene. For this purpose, the temperature of a 500ml autoclave was set to-10 ℃ and propylene was charged into the reactor. The desired polymerization temperatures for the catalyst and cocatalyst are then provided as described above. The polymerization is likewise terminated with methanol and the product obtained is isolated.

In fig. 5-7 (tables 5-7), the corresponding measurements are summarized. From table 5 in fig. 5, the effect of temperature on the polymerization conditions can be examined. Fig. 5 shows in a durable manner that the polymers obtainable with the catalyst composition according to the invention not only have very high molecular weights of up to 800,000, but at the same time also have very high tacticities associated with mmmm-pentadiene.

The effect of the monomer concentration can be inferred from FIG. 6.

Subsequently, fig. 7 also reproduces the measurements obtained during the polymerization in liquid propylene.

In conclusion, it should be emphasized that, in particular, hafnium complex (7) has excellent properties with respect to polymerization.

Claims (18)

1. A catalyst composition for the production of linear isotactic polymers comprising an asymmetric metal complex of the general formula III and an activator,

wherein the substituents have the following meanings:

R¹-R⁴linear or branched C₁-to C₁₀-alkyl, -orOptionally carrying one or more C₁-to C₆5-7 membered cycloalkyl with alkyl as a substituent, or C₆-to C₁₈Aryl or aralkyl or alkaryl radicals R¹And R²Optionally bonded to a 5-7 membered cycloalkyl or aryl ring, R³And R⁴Optionally bonded to a 5-7 membered cycloalkyl or aromatic ring;

R¹⁰-R¹¹hydrogen, C₁-to C₈-alkyl, 4-7 membered cycloalkyl, or aryl, R¹⁰、R¹¹Optionally forming a 4-7 membered cycloalkyl or aryl group with E;

R¹² C₁-to C₈Alkyl, aryl, C₁-to C₈-alkoxy, or C₁-to C₈-a trialkylsiloxy group;

m titanium, zirconium, hafnium, vanadium, niobium, or tantalum;

x is hydrogen, halogen or C₁-to C₈-alkyl, aryl, or benzyl;

e carbon, silicon, germanium or 1, 2-ethyl, 1, 3-propyl, or 1, 4-butyl.

2. A catalyst composition for the production of linear isotactic polymers comprising an asymmetric metal complex of the general formula V and an activator,

wherein the radical R¹-R⁴And R¹⁰-R¹²And E and M, X have the meanings indicated for the formula III in claim 1.

3. A catalyst composition for the production of linear isotactic polymers comprising an asymmetric metal complex of the general formula I and an activator,

wherein the radical R¹-R⁴And R¹⁰-R¹²And E and M, X have the meanings indicated for the formula III in claim 1, and R⁶And R⁸Is C₁-to C₁₀-alkyl, R⁷And R⁹Is hydrogen.

4. Catalyst composition according to claim 3, characterized in that the metal complex according to formula I is a compound of formula XII,

wherein the radical R¹-R⁴And R¹⁰-R¹²And E and M, X have the meanings indicated for the formula III in claim 1.

5. A catalyst composition for the production of linear isotactic polymers comprising an asymmetric metal complex of the general formula I and an activator,

wherein the radical R¹-R⁴And R¹⁰-R¹²And E and M, X have the meanings indicated for the formula III in claim 1, and R⁷And R⁹Is C₁-to C₁₀-alkyl, R⁶And R⁸Is hydrogen.

6. Catalyst composition according to claim 5, characterized in that the metal complex according to formula I is a compound of formula XIII,

wherein the radical R¹-R⁴、R¹⁰-R¹²And E and M, X have the meanings indicated for the formula III in claim 1.

7. Catalyst composition according to at least one of claims 1 to 6, characterized in that the activator is an open-chain or cyclic aluminoxane compound of the general formula VI or VII,

R¹³represents C₁-to C₄-alkyl, n represents a number between 5 and 30, and/or a cationic activator of formulae VIII to XI,

(VIII)B(C₆F₅)₃、Al(C₆F₅)₃

(IX)R¹⁴ ₃C[B(C₆F₅)₄]、R¹⁴ ₃C[Al(C₆F₅)₄]

(X)[R¹⁴ ₃NH][B(C₆F₅)₄]、[R¹⁴ ₃NH][Al(C₆F₅)₄]

(XI)R¹⁴ ₃C[C₅R¹⁵ ₅]、[R¹⁴ ₃NH][C⁵R¹⁵ ₅]

R¹⁴finger C₁-to C₄-alkyl or aryl, R¹⁵Refers to a perfluorinated alkyl or aryl group.

8. Catalyst composition according to claim 7, characterized in that the amounts of metal complex and activator are chosen such that the atomic ratio of aluminium of the aluminoxane and/or boron or aluminium of the cationic activator to the transition metal of the metal complex is from 1: 1 to 10⁶∶1。

9. A process for the production of linear isotactic polymers consisting of at least one C₂-to C₂₀-olefin monomers and having a tacticity of more than 60% [ mmmm]Pentadiene concentration wherein C₂-to C₂₀-the conversion of olefins into polymers in the presence of the catalyst composition according to at least one of claims 1 to 8.

10. The process according to claim 9, characterized in that the polymerization is carried out in the gas phase, in suspension or in supercritical monomer.

11. The process according to claim 10, characterized in that the polymerization is carried out in a solvent inert to the polymerization conditions.

12. Process according to claim 11, characterized in that the inert solvent is selected from benzene, toluene, xylene, ethylbenzene or alkanes.

13. Process according to claim 12, characterized in that the alkane is selected from propane, n-butane, isobutane, pentane, hexane, heptane or mixtures thereof.

14. Process according to any one of claims 10 to 13, characterized in that the polymerization is carried out at a pressure of from 1 to 100 bar and a temperature of from-50 to 200 ℃.

15. The process according to claim 14, characterized in that the polymerization is carried out at a pressure of 3 to 20 bar.

16. The process according to claim 14, characterized in that the polymerization is carried out at a pressure of 5 to 15 bar.

17. The process according to claim 14, characterized in that the polymerization is carried out at a temperature of 10 to 150 ℃.

18. The process according to claim 14, characterized in that the polymerization is carried out at a temperature of 20-70 ℃.