KR100472591B1 - Method for Producing High Melting-Point Polyolefins - Google Patents

Abstract

The high melting point polyolefins of the present invention can be prepared in bulk, solution, suspension or gas phase using the metallocene compound of formula I or formula XIII or? Complex as a catalyst.

<Formula I>

<Formula XIII>

(In the above formula,

CpI and CpII are carbanions having a cyclopentadienyl containing structure,

πI and πII are charged or electrically neutral π-based,

D is a donor atom,

A is a receptor atom,

Where D and A are connected by reversible coordination bonds such that the donor has a (partially) positive charge and the receptor has a (partially) negative charge,

M is a transition metal of the III, IV, V or VI subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actinides,

X is a monovalent anion equivalent,

n is 0, 1, 2, 3 or 4 depending on the charge of M).

Description

Method for Producing High Melting Polyolefins {Method for Producing High Melting-Point Polyolefins}

All reactions were performed under strictly anaerobic conditions using Schlenk technique or high vacuum technique. The solvents used were free of moisture and saturated with argon. Chemical shift δ is determined for specific standards ¹ H (tetramethylsilane), ¹³ C (tetramethylsilane), ³¹ P (85% H ₃ PO ₄ ), ¹¹ B (boron trifluoride-etherate-18.1 ppm) It is expressed in ppm. Minus signs indicate a shift to a higher field.

<Example 1>

(Bis- (trimethylsilyl) -cyclopentadiene, compound 1 )

14.7 g (0.106 mol) of trimethylsilyl-cyclopentadiene (manufactured by Fluka) and 150 ml of tetrahydrofuran (THF) were introduced into the reaction flask and cooled to 0 ° C. 47.4 ml (2.3 moles; total amount 0.109 moles) of butyl-lithium solution in n-hexane were added dropwise over 20 minutes. When the addition was complete, the yellow solution was further stirred for 1 hour, after which the cooling bath was removed. The solution was further stirred at rt for 1 h and then cooled to -20 ° C. Then 14.8 ml (0.117 mol) of trimethylsilyl chloride were added dropwise over 10 minutes, and the reaction mixture was stirred at -10 ° C for 2 hours. After that, the cooling bath was removed and the reaction solution was allowed to warm to room temperature and then further stirred for 1 hour. The reaction mixture was filtered through celite, and this filter was washed with hexane and hexane was removed from the collected filtrate under vacuum. Distillation at 26 ° C. under 0.4 mbar gave 19 g (85% of theoretical yield) of the pure product of compound 1 from the crude product. Melting point and NMR data are described in literature data [J. Organometallic Chem. 29 (1971), 227; ibid. 30 (1971), C 57; J. Am. Chem. Soc. 102 , (1980), 4429; J. Gen. Chem. USSR, English Translation 43 (1973), 1970; J. Chem. Soc., Dalton Trans. 1980 , 1156.

¹ H-NMR (400 MHz, C ₆ D ₆ ); delta = 6.74 (m, 2H), 6.43 (m, 2H), -0.04 (s, 18H).

<Example 2>

(Trimethylsilyl-cyclopentadienyl-dichloroborane, compound 2 )

16 g (0.076 mol) of compound 1 were introduced into a round bottom flask equipped with a dry ice cooling bath. 8.9 g (0.076 mol) of BCl ₃ were condensed into a -78 ° C Schlenk tube and then added dropwise to a round bottom flask over 5 minutes. The reaction mixture was slowly warmed to room temperature over 1 hour and then held at 55-60 ° C. for 2 hours. All volatile compounds were removed in vacuo (3 mmHg = 4 mbar). Thereafter, distillation at 39 ° C. under 0.012 mbar gave 14.1 g (85% of theoretical yield) of compound 2 . ¹ H-NMR is consistent with literature data and showed that many isomers were prepared [J. Organometallic Chem. 169 (1979), 327]. ¹¹ B-NMR (64.2 MHz, C ₆ D ₆ ): δ = +31.5.

<Example 3>

(Dichloroboranyl-cyclopentadienyl-titanium trichloride, compound 3 )

3

11.4 g (0.052 mol) of compound 2 and 100 ml of methylene chloride (CH ₂ Cl ₂ ) were introduced into a 250 ml Schlenk tube. The solution was cooled to -78 ° C and 9.8 g (5.6 ml, 0.052 ml) of titanium tetrachloride were added dropwise over 10 minutes. The resulting red solution was slowly warmed up to room temperature and stirred for 3 more hours. This solvent was removed in vacuo to give a pale yellow product. 200 ml of hexane was added to this crude solid and the resulting yellow solution was filtered, cooled overnight in a refrigerator and 12.3 g (79% of theoretical yield) of yellow crystals of compound 3 were obtained. J. Organometallic Chem. 169 (1979), 373, it should be noted that 62% of the theoretical yield was obtained by carrying out the reaction in a hydrocarbon solvent such as petroleum ether or methylcyclohexane.

¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 7.53 (t, J = 2.6 Hz, 2H), 7.22 (t, J = 2.6 Hz, 2H). ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = + 33.

<Example 4>

(Dimethylboranyl-cyclopentadienyl-titanium trichloride, compound 4 )

4

2.37 g (0.0079 mol) of compound 3 were dissolved in 100 ml of hexane in a round bottom flask. The solution was cooled to 0 ° C. and 4 ml (0.008 mol) of a 2 molar solution of aluminum-trimethyl in toluene were added dropwise. When the addition was complete, the cooling bath was removed and all volatile compounds were removed under vacuum. The remaining yellow solid was dissolved in pentane, the solid contents were filtered off, the clear filtrate was cooled to -78 ° C and 1.5 g of compound 4 (74% of theoretical yield) were obtained. J. Organometallic Chem. 169 (1979), 373, mentioning that the yield is 87% of the theoretical yield using tetramethyl tin as the alkylating agent, it should be noted that it was not possible to obtain compound 4 in the form without trimethyltin chloride formation.

¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 7.48 (t, J = 2.5 Hz, 2H), 7.23 (t, J = 2.5 Hz, 2H), 1.17 (s, 6H). ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = + 56.

Example 5

((Diphenylphosphine-cyclopentadiethyl) -lithium, compound 6 )

  5 6

50 g (0.186 mole) of cyclopentadienyl- thallium (Fluka) were introduced into a 500 ml flask with 300 ml of diethyl ether. The suspension was cooled to 0 ° C and 34.2 ml (0.186 mol) of diphenylchlorophosphine were added dropwise over 10 minutes. The suspension was allowed to warm to rt, stirred for 1 h and finally filtered through frit. The solvent was then removed in vacuo to give 39.5 g (85% of theoretical yield) of the intermediate product diphenylphosphinocyclopentadiene, compound 5 . Then 18.6 g (0.074 mol) of compound 5 were diluted with toluene and cooled to 0 ° C. 33.2 ml (0.074 mol) of a 2.24 molar solution of butyl-lithium in hexane was added to this solution over 10 minutes. After warming to room temperature and stirring for 2 hours, a precipitate was obtained from a yellow solution which was filtered off, washed with toluene and then with hexane. After drying in vacuo, 13.2 g of compound 6 (70% of theoretical yield) were obtained as a brown powder [J. Am. Chem. Soc. 105 (1983), 3882; Organometallics 1 (1982), 1591].

¹ H-NMR (400 MHz, d ₈ THF): δ = 7.3 (m, 4H), 7.15 (m, 6H), 5.96 (m, 2H), 5.92 (m, 2H), ³¹ P-NMR (161.9 MHz , d ₈ THF): δ = -20.

<Example 6)

((C ₆ H ₅ ) ₂ P → B (CH ₃ ) ₂ -bridged bis- (cyclopentadienyl) -titanium dichloride, compound 7 )

7

0.36 g (0.00139 mol) of compound 6 and 20 ml of toluene were introduced into a round bottom flask. The resulting solution was cooled to −20 ° C. and a solution of 0.36 g (0.00139 mol) of compound 4 in 20 ml of toluene was added dropwise over 20 minutes. At the end of the dropping, the solution was heated to room temperature over 2 hours and stirred at this temperature for an additional hour. Undissolved material was removed with frit and the solvent was distilled under vacuum. The red oily solid was then washed with hexane, which was decanted and the solid was dried again under vacuum. In this way 0.28 g (42% of theoretical yield) of compound 7 were obtained as a red powder.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 7.6-7.3 (br, m, 10H), 6.92 (m, 2H), 6.77 (m, 4H), 6.60 (m, 2H), 0.29 ( d, J _PH = 19 Hz, 6H); ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ = 17.1 (br); ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ); delta = -29 (br).

<Example 7>

(Tributylstannyl-diphenylphosphino-indene, compound 8 )

10 g (0.086 mol) of indene were introduced into a round bottom flask, diluted with 200 ml of diethyl ether and cooled to -20 ° C. 36 ml (0.085 mol) of a 2.36 mol solution of butyl-lithium in n-hexane were added to this solution and the solution immediately turned yellow. The cold bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for 1 h more. Thereafter, the reaction mixture was cooled back to 0 ° C. and 19 g (15.9 ml, 0.086 mol) of diphenylchlorophosphine were added to form a precipitate. The cooling bath was removed again and the solution was then warmed to room temperature with stirring for an additional hour. The solution was then cooled back to -20 ° C and 36 ml (0.085 mol) of butyl-lithium in n-hexane were added dropwise. At the end of the addition, the cooling bath was removed again and the temperature was raised to room temperature, after which the solution was further stirred for 1.5 hours. The suspension was then cooled back to 0 ° C. and 28 g (0.086 mol) of tributyltin chloride were added dropwise. The resulting suspension was allowed to warm to rt, stirred for 1.5 h more, then filtered through frit and the solvent removed in vacuo. 46.9 g (92% of theoretical yield) of compound 8 were obtained as a dark yellow oil.

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.5-7.3 (m, 6H), 7.28 (br, s, 6H), 7.14 (quasi-dt, 7.3 Hz / 1.0 Hz, 1H), 7.08 (t , J = 7.3 Hz, 1H), 6.5 (br m, 1H), 4.24 (br s, 1H), 1.4-1.25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J = 7.2 Hz, 9H), 0.53 (t, J = 8 Hz, 6H), ³¹ P-NMR (161.9 MHz, CDCl ₃ ): δ = -20.6.

<Example 8>

(Diphenylphosphino-indenyl-zirconium trichloride, compound 9 )

9

A solution of 37 g (0.0628 mol) of compound 8 in 300 ml of toluene was added to a suspension of 14.6 g of ZrCl ₄ (99.9% purity, 0.0628 mol, manufactured by Aldrich) in 100 ml of toluene over 3 hours at room temperature. The solution immediately turned red, slowly turning orange and eventually turning yellow. After stirring for 4 hours, the yellow precipitate was filtered off and washed with toluene and then with hexane. The solid was dried under vacuum and 15.3 g (50% of theoretical yield) of compound 9 were obtained as a free flowing yellow powder. The yield can easily be increased to at least 70% by running the reaction at low temperature, for example for 30 minutes at −30 ° C., for 5 hours at 0 ° C. The product can be further purified by washing the residual tin compound (extraction time: 8 hours) using pentane in a Soxhlet extractor.

Example 9

((C ₆ H ₅ ) ₂ P-BCl ₂ -bridged indenyl-cyclopentadienyl-zirconium dichloride, compound 10 )

10

4.43 g (0.0089 mol) of purified compound 9 and 100 ml of toluene were introduced into a Schlenk tube. 1.95 g (0.0089 mol) of compound 2 were added to this suspension. The yellow suspension was stirred for 6 hours at room temperature, during which time a pale white precipitate formed. This precipitate (4.1 g, 75% of theoretical yield) was isolated by filtration and found to be essentially pure material.

¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 7.86 (similar ddd, J = 8.5 / 2.5 / 1 Hz, 1H), 7.75-7.55 (m, 10H), 7.35 (similar ddd, J = 8.5 /6.9/0.9 Hz, 1H), 7.32 (br t, J = 3.1 Hz, 1H), 7.22 (similar ddd, J = 8.8 / 6.8 / 1.1 Hz, 1H), 7.06 (similar ddd, J = 3.4 / 3.4 / 0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H), 6.61 (similar q, J = 2.3 Hz, 1H), 6.53 (br d, 8.7 Hz, 1H ); ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ = 6.2 (br, m); ¹¹ B (64.2 MHz, CD ₂ Cl ₂ ): δ = -18 (br).

<Example 10>

((C ₆ H ₅ ) ₂ PB (CH ₃ ) ₂ -bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 11 )

11

50 ml of toluene was added to 1.5 g (0.00247 mol) of compound 10 of Example 9. The suspension was cooled to 0 ° C. and 1.2 ml (0.0024 mol) of a 2 molar solution of trimethylaluminum in hexanes were added dropwise over 5 minutes. When the addition was complete, the cooling bath was removed and the solution was allowed to warm to room temperature and stirred for a further 2 hours. The residual precipitate was filtered off, the solvent was removed from the filtrate under vacuum and 0.37 g (26% of theoretical yield) of compound 11 were obtained as a brown solid.

³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ = 14.6; ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = -28

<Example 11>

(Trimethylsilyl-indene, compound 12 )

12

25 ml of indene (0.213 moles distilled in CaH ₂ under vacuum) were introduced into a round bottom flask containing 100 ml of THF and cooled to 0 ° C. 94 ml (0.216 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added over 20 minutes. When the addition was complete, the mixture was stirred for 20 minutes, then warmed to room temperature and further stirred for 30 minutes. After cooling to −20 ° C., 27.5 ml (0.216 mol) of trimethylchlorosilane were added dropwise to form a slightly cloudy orange solution. After stirring at −10 ° C. for 1 hour and at 0 ° C. for 1.5 hours, the solution is warmed to room temperature and the solvent is removed in vacuo. After dissolving again in hexane, LiCl was filtered off and hexane was removed in vacuo. The product (0.045 mbar, 58-60 ° C.) was distilled to give 26.6 g of compound 12 (66% of theoretical yield).

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.49 (t, J = 7.6 Hz, 1H), 7.28 (ddd, J = 7.3 / 7.2 / 1 Hz, 1H), 7.21 (ddd, J = 7.3 / 7.3 / 1.1 Hz, 1H), 6.96 (dd, J = 5.6 / 1.2 Hz, 1H), 6.69 (dd, J = 5.3 / 1.8 Hz, 1H), 3.56 (s, 1H), 0.0 (s, 9H).

<Example 12>

(Bis- (trimethylsilyl) -indene, compound 13 )

25.4 g (0.135 mol) of compound 12 were introduced into a round bottom flask containing 100 ml of THF and cooled to 0 ° C. 59 ml (0.136 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added over 20 minutes. When the addition was complete, the mixture was stirred for 20 minutes and then warmed to room temperature. After stirring for 30 minutes, it was cooled to -20 ° C and 17.3 ml (0.136 mol) of trimethylchlorosilane was added dropwise to form a slightly cloudy orange solution. The solution was stirred at 0 ° C. for 1 hour and at room temperature for 1 hour and then the solvent was removed under vacuum. After redissolution in hexane, LiCl was filtered off and hexane was removed in vacuo. 32 g (90% of theoretical yield) of compound 13 were obtained as an oil. J. Organometal. Chem. 23 (1970), 407; Use hexane instead of THF].

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.62 (d, J = 7.6 Hz, 1H), 7.52 (d, J = 7.5 Hz, 1H), 7.23 (ddd, J = 7.35 / 7.3 / 0.9 Hz , 1H), 6.9 (d, J = 1.7 Hz, 1H), 3.67 (d, J = 1.6 Hz, 1H), 0.38 (s, 9H), 0.0 (s, 9H).

Example 13

(Trimethylsilyl-dichloroboranyl-indene, compound 14 )

In a similar manner to the preparation of Compound 2 , 12.3 g (0.047 mol) of Compound 13 were introduced into a round bottom flask having a reflux condenser cooled to −30 ° C. and cooled with dry ice. 5.6 g (0.046 mol) BCl ₃ was added to this flask. When the addition was complete, the cooling bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for 3 hours. The temperature was then raised to 55 ° C. for 6 hours. After cooling and removal of the volatile components under vacuum, the crude product is obtained. Distillation under high vacuum gave the major isomers identified as the purified product as follows.

¹ H-NMR (200 MHz, CDCl ₃ ): δ = 8.3 (d, J = 7 Hz, 1H), 8.1 (d, J = 1.8 Hz, 1H), 7.5 (dd, J = 7.0 / 1.2 Hz, 1H ), 7.4 (m, 3H), 4.0 (d, J = 1.8 Hz, 1H), 0.1 (s, 9H); ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = 38 (br).

<Example 14>

((C ₆ H ₅ ) ₂ P-BCl ₂ -bridged bis- (indenyl) -zirconium dichloride, compound 15 )

4.5 g (0.017 mol) of compound 14 were added to a suspension of 8.3 g (0.017 mol) of compound 9 in 200 ml of toluene, and the mixture was heated to 50 ° C. and stirred for 5 hours. After cooling and filtration, 200 ml of hexanes were added, after which the precipitate precipitated out of a clear yellow solution, which was filtered and dried under vacuum. The product was identified by its X-ray analysis to be the meso-isomer of compound 15 . The PB bond length of the bridge was measured to be 2.01 mm 3. A second precipitate, determined to be the racemate isomer of Compound 15 , was obtained by concentrating the toluene / hexane solution to about 10 ml and further adding 200 ml of hexane.

<Example 15>

(N, N-dimethyl-O- (methylsulfonyl) -hydroxylamine, compound 16 )

(CH ₃ ) ₂ NOSO ₂ CH ₃ 16

9.0 g (0.092 mol) of N, N-dimethyl-O-hydroxylamine hydrochloride were suspended in 70 ml of CH ₂ Cl ₂ containing 20 g (0.2 mol) of triethylamine and the suspension was cooled to −10 ° C. . 9.5 g (0.083 mol) of methylsulfonyl chloride dissolved in 70 ml of CH ₂ Cl ₂ were slowly added dropwise to the cooled suspension. When the addition was complete, the mixture was then stirred for 1 hour. After that, ice water was added to the reaction mixture, and the organic layer was separated. The remaining water was washed with ether. The wash liquor ether and CH ₂ Cl ₂ fractions were combined, dried over Na ₂ SO ₄ , and the solvent was removed under vacuum at −10 ° C. 5.9 g (46% of theoretical yield) of compound 16 were obtained as an oil, which was stored at -20 ° C. Angew. Chem. Int. Ed. Engl. 17 (1978), 687.

¹ H-NMR (400 MHz, CDCl ₃ ): δ = 3.03 (s, 3H), 2.84 (s, 6H).

<Example 16>

(N, N-dimethylamino-cyclopentadienyl-lithium, compound 17 )

17

A solution of 3 g (0.042 mol) of cyclopentadienyl-lithium in 30 ml of THF was slowly added to a solution of 5.9 g (0.042 mol) of compound 16 in 20 ml of THF at −30 ° C. The mixture was then warmed to -20 ° C and stirred for 30 minutes. Hexane was then added and the solution was filtered. Thereafter, 1.8 ml (0.042 mol) of a 2.3 mol solution of butyl-lithium in hexane were added at -20 ° C, after which a precipitate formed. The precipitate was filtered off and washed twice with 20 ml of hexane each time. After drying in vacuo, 2.0 g of compound 17 (40% of theoretical yield) were obtained as a white powder. Angew. Chem. Int. Ed. Engl. 19 (1980), 1010.

¹ H-NMR (400 MHz, THF): δ = 5.34 (br d, J = 2.2 Hz, 2H), 5.15 (br d, J = 2.2 Hz, 2H), 2.56 (s, 6H).

<Example 17>

((CH ₃ ) ₂ NB (CH ₃ ) ₂ -bridged bis- (cyclopentadienyl) -titanium dichloride, compound 18 )

18

A solution of 0.18 g (0.7 mmol) of compound 4 in 10 ml of toluene was added to a suspension of 0.081 g (0.7 mmol) of compound 17 in 10 ml of toluene over 10 minutes at −20 ° C. to form a dark red solution. After warming at room temperature for 2 hours, the solution is filtered and the solvent is removed in vacuo. The red powder formed was redissolved in 10 ml of warm toluene, the insoluble material was filtered off, and the solution was stored overnight in the refrigerator to form 0.1 g (43% of theoretical yield) of the red needle-shaped product.

¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 6.85 (t, J = 2.3 Hz, 2H), 6.15 (t, J = 2.3 Hz, 2H), 6.1 (t, J = 2.8 Hz, 2H ), 5.57 (t, J = 2.8 Hz, 2H), 1.98 (s, 6H), 0.35 (s, 6H); ¹¹ B-NMR (64.2 MHz, CD ₂ Cl ₂ ): δ = 2.8 (br).

Example 18

(Tributylstannyl-diisopropylphosphine-indene, compound 19 )

19

100 ml of ether was introduced into a round bottom flask containing 3.8 g (0.033 mol) of indene and the mixture was cooled to -20 ° C. 14.4 ml (0.033 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added to this solution over 5 minutes to form a yellow solution. After the cooling bath was removed, the solution was warmed to room temperature and then stirred for 1.5 hours. Thereafter, the reaction mixture was cooled to 0 ° C., and 5.0 g (0.033 mol) of chlorodiisopropylphosphine were added, after which a precipitate formed. After removing the cooling bath, the solution was warmed to room temperature and stirred for 1 hour. Thereafter, the solution was cooled to −20 ° C. and 14.4 ml (0.033 mol) of a 2.3 mol solution of butyl-lithium in hexane were added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 10.1 g (0.031 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered and the filtrate was dried under vacuum to give 16.6 g (yield: 97%) of compound 19 as a dark yellow oil. Two isomers were obtained in a ratio of 1.5: 1. The main isomers were distinguished as follows: ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ 7.71 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 7.3 Hz, 1H), 7.13 ( m, 2H), 6.96 (m, 1H), 4.28 (Sn adjacent s, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 (m, 39H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ-11.3 ppm. The second isomer was identified as follows: ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.6 (d, J = 7.4 Hz, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.1 (m, 1H), 6.71 (m, 1H), 3.48 (m, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 ( m, 39H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): d-11.5 ppm.

Example 19

(Diisopropylphosphino-indenyl-zirconium trichloride, compound 20 )

20

A solution of 15.0 g (0.029 mol) of compound 19 in 50 ml of toluene was added dropwise to a suspension of 6.7 g (0.029 mol) of 99.9% purity ZrCl ₄ in 300 ml of toluene at −78 ° C. When the addition was complete, the reaction mixture was stirred at −30 ° C. for 0.5 h and then at 0 ° C. for 4 h. The yellow precipitate formed was filtered off and washed with toluene and hexane. The solid was dried under vacuum and 8.8 g of compound 20 (yield: 71%) was obtained as a free flowing yellow powder. The powder was further purified by extraction in a Soxhlet extractor with toluene fed at reflux over 30 h under 30 mmHg, followed by pentane over 2 h to remove the remaining tin compound. Because of the insolubility of the formed compound, no ¹ H-NMR was obtained.

Example 20

(Diisopropylphosphino-dichloroboranyl-bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 21 )

21

0.52 g (0.0012 mol) of compound 20 and 30 ml of toluene were introduced into a Schlenk tube. 0.27 g (0.0012 mol) of compound 2 were added to this suspension over 5 minutes. The yellow suspension was stirred for 3 hours at room temperature to give a slightly cloudy solution. The precipitate was removed by filtration to give a pale yellow toluene solution. After removing toluene under vacuum, the product was obtained as a white solid in an amount of 0.47 g (yield: 87%). ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.84 (similar dd, J = 8.5, 0.8 Hz, 1H), 7.73 (d, J = 8.8 Hz, 1H), 7.5 (similar dt, J = 7.8, 0.8 Hz, 1H), 7.38 (m, 2H), 6.98 (m, 1H), 6.67 (m, 1H), 6.64 (m, 1H), 6.54 (m, 1H), 6.29 (m, 1H), 3.39 ( septet, J = 7.1 Hz, 1H), 2.94 (m, 1H), 1.68 (dd, J _HP = 18.1 Hz, J = 7.2 Hz, 3H), 1.64 (dd, J _HP = 17.4, J = 7.2 Hz, 3H ), 1.45 (dd, J _HP = 15 Hz, J = 7.2 Hz, 3H), 1.33 (dd, J _HP = 14.6 Hz, J = 7.3 Hz, 3H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ 23.1 (br, m); ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ): δ-14.8 (br d, J = 110 Hz).

Example 21

(Tributylstannyl-dimethylphosphino-indene, compound 22 )

22

150 ml of ether was introduced into a round bottom flask containing 5.5 g (0.047 mol) of indene and the mixture was cooled to -20 ° C. 20.8 ml (0.048 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added to this solution over 5 minutes to form a yellow solution. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. After cooling the reaction mixture to −30 ° C., 4.6 g (0.048 mol) of chlorodimethylphosphine in 30 ml of ether were added over 20 minutes, and a precipitate formed. After stirring at −20 ° C. for 2 hours, 20.8 ml (0.048 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 15.6 g (0.048 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered, the filtrate was dried under vacuum and compound 22 17.4 g (yield: 78%) was obtained as a dark yellow oil. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.67 (d, J = 7.5 Hz, 1H), 7.47 (d, J = 7.4 Hz, 1H), 7.18 (m, 2H), 6.83 (m, 1H ), 4.28 (Sn adjacent s, 1 H), 1.43-0.78 (m, 33 H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): δ-61.6 ppm.

<Example 22>

(Dimethylphosphino-indenyl-zirconium trichloride, compound 23 )

23

A solution of 17.0 g (0.037 mol) of compound 22 in 50 ml of toluene was added to a suspension of 8.5 g (0.036 mol) of 99.9% purity ZrCl ₄ in 200 ml of toluene at −78 ° C. When the addition was complete, the reaction mixture was stirred at −30 ° C. for 0.5 h and then at 0 ° C. for 4 h. The yellow precipitate formed was filtered off and washed with toluene and hexane. The solid was dried under vacuum and 8.3 g (yield: 61%) of compound 23 were obtained as a free flowing yellow powder. The powder was further purified by removal of the remaining tin compound by extraction in a Soxhlet extractor with toluene supplied under reflux over 3 hours under 30 mmHg and pentane over 2 hours, product 7.2 g (yield: 53%) Obtained. Because of the insolubility of this compound, no ¹ H-NMR was obtained.

<Example 23>

(Dimethylphosphino-dichloroboranyl-bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 24 )

24

30 ml of toluene and 0.55 g (0.0015 mol) of compound 23 were introduced into a Schlenk tube. 0.31 g (0.0014 mol) of compound 2 were added to this suspension over 5 minutes. The yellow suspension was stirred for 6.5 hours at room temperature and a slightly cloudy solution was obtained. The precipitate was removed by filtration to give a pale yellow toluene solution. After removal of toluene under vacuum, the product was obtained as a white solid. The product was washed with hexane and dried in vacuo to give compound 24 as a pale white solid (0.54 g; yield: 76%). ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.84 (similar dd, J = 7.4 Hz, 1.0 Hz, 1H), 7.60 (m, 2H), 7.51 (m, 1H), 7.38 (m, 1H) , 6.93 (m, 1H), 6.71 (m, 1H), 6.66 (m, 1H), 6.49 (m, 1H), 6.30 (br s, 1H), 2.11 (d J _HP = 11.9 Hz, 3H), 1.94 (d, J _HP = 11.9 Hz, 3H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) -5.9 (br, m); ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ-14.6 (br d, J _BP = 126 Hz).

<Example 24>

(2-methylindene, compound 26 )

    25 26

38.7 g (0.29 mol) of 2-indanonone and 300 ml of ether were introduced into a round bottom flask. Diluted with 150 ml of ether, 96.7 ml (0.29 mol) of a 3.0 molar solution of CH ₃ MgI in ether was introduced into a second flask. Thereafter, the 2-indanonone solution was added to the CH ₃ MgI solution via a cannula in an amount such that reflux was maintained, and a precipitate formed. When the addition was complete, the suspension was kept under reflux for an additional 4 hours, cooled to 0 ° C., after which slowly 100 ml of saturated solution of NH ₄ Cl were added. The product was extracted with ether and dried over MgSO ₄ . After removal of the solvent in vacuo, 30.1 g (yield: 70%) of 2-methyl-2-indanol ( compound 25 ) were obtained as an oily solid. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.15 (br m, 4H), 3.01 (s, 2H), 2.99 (s, 2H), 1.5 (s, 3H); OH variability.

25.5 g (0.17 mole) of compound 25 , 3.2 g (0.017 mole) of p-toluenesulfonic acid and 500 ml of hexane were introduced into a round bottom flask with Dean-Stark collector. This suspension was kept under reflux for 3 hours. After cooling, the hexane fraction was removed from the insoluble product, the solvent was removed under vacuum to leave an oil, followed by distillation in a short distillation column at 45 ° C. under 0.03 mbar, after which compound 26 15 g (yield: 68%) were obtained. Obtained. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.33 (d, J = 7.6 Hz, 1H), 7.21 (m, 2H), 7.06 (similar dt, J = 7.2, 1.4 Hz, 1H), 6.45 (br s , 1H), 3.25 (s, 2H), 2.12 (s, 3H).

1. Morrison, H; Giacherio, D., J. Org. Chem. 1982 , 47, 1058.

2. Ready, TE; Chien, JCW; Rausch, MD, J. Organom. Chem. 591, 1996 , 21.

3. Wilt, Pawlikowki, Wieczorek, J. Org. Chem. 37, 1972 , 824.

See also.

<Example 25>

(Tributylstannyl-diisopropylphosphino-2-methylindene, compound 27 )

27

150 ml of ether was introduced into a round bottom flask containing 5.08 g (0.039 mol) of 2-methylindene compound 26 , the mixture was cooled to -20 ° C and 17.0 ml (0.039 mol of butyl-lithium 2.3 mol solution in hexane ) Was added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. Thereafter, the reaction mixture was cooled to -20 ° C, 5.8 g (0.039 mol) of chlorodiisopropylphosphine was added over 5 minutes, and a precipitate formed. After that, the cooling bath was removed and the reaction mixture was stirred for 1 hour at room temperature. After cooling to −20 ° C., 17.0 ml (0.039 mol) of a 2.3 mol solution of butyl-lithium in hexanes were added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 12.4 g (0.038 mol) of chlorodibutyltin were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered, the filtrate was dried under vacuum and 20.4 g (yield: 98%) of compound 27 were obtained as a dark yellow oil. Two isomers were identified by ³¹ P-NMR. ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ-5.9 and −6.6 (ratio of 2: 1).

Example 26

(Diisopropylphosphino-2-methylindenyl-zirconium trichloride, compound 28 )

28

A solution of 17.7 g (0.033 mol) of compound 27 in 100 ml of methylene chloride was added to a suspension of 7.7 g (0.033 mol) of 99.9% purity ZrCl ₄ in 200 ml of methylene chloride over 10 minutes at −25 ° C. When the addition was complete, the reaction mixture was slowly warmed to 10 ° C. over 3 hours, after which a clear orange solution formed. After 1 hour at room temperature, the solvent was removed in vacuo and the oil formed was washed twice with 50 ml of hexane, after which an oily crude product ( compound 28 ) was obtained, which was used directly for the preparation of compound 29 . Because of the insolubility of the compound, no ¹ H-NMR was obtained.

Example 27

(Diisopropylphosphino-dichloroboranyl-bridge 2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 29 )

29

5.5 g (0.025 mol) of compound 2 were introduced into a round bottom flask containing 0.025 mol of impure compound 28 in 200 ml of toluene at 0 ° C. over 5 minutes. After 1 hour at 0 ° C., stirring was terminated and the soluble toluene fraction was removed from the oil formed. After toluene was removed in vacuo, 100 ml of hexane was added to the oily solid and 7.4 g (yield: 54%) of yellow powder was formed with a purity of about 90%. The product was further purified in a Soxhlet extractor with pentane fed under reflux. The final product contained a pale yellow powder. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.67 (br d, J = 7.6 Hz, 1H), 7.71 (m, 1H), 7.35 (m, 2H), 6.62 (br s, 1H), 6.54 (br s, 1H), 6.47 (m, 1H), 6.33 (m, 1H), 6.06 (br s, 1H), 3.3 (br m, 1H), 3.2 (br m, 1H), 2.6 (s, 3H ), 1.78 (dd, J = 7.1 Hz, J _HP = 15.3 Hz, 3H), 1.70 (dd, J = 7.2 Hz, J _HP = 15.7 Hz, 3H). 1.57 (dd, J = 7.1 Hz, H _HP = 15.3 Hz, 3H), 1.12 (dd, J = 7.1 Hz, J _HP = 14.0 Hz, 3H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) 28.4 (br m); ¹¹ B (80 MHz, CD ₂ Cl ₂ ) δ-14.3 (br d, J _PB = 106 Hz).

<Example 28>

(Bis (trimethylsilyl) -diphenylphosphino) -cyclopentadiene, compound 30 )

30

76.6 ml (0.19 mol) of a 2.5 mol solution of butyl-lithium in hexane was added to a solution of Compound 1 (40.2 g; 0.19 mol) in 500 ml of ether at 0 ° C. over 10 minutes. When the addition was complete, the bath was removed and the solution was stirred for 1 hour at room temperature. After cooling to 0 ° C., 42.2 g (0.19 mol) of chlorodiphenylphosphine were added over 10 minutes, after which the bath was removed and the suspension was allowed to warm to room temperature. After stirring for 1 hour at room temperature, the ether was removed in vacuo and the product dissolved again in hexane. After the salts were filtered off, the hexanes were removed in vacuo and 69.1 g (yield: 91%) of compound 30 were obtained as an oil. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.45 (m, 4H), 7.35 (m, 6H), 6.8 (m, 1H), 6.65 (m, 1H), 6.6 (m, 1H), 0 (s , 18H). ³¹ P-NMR (161.9 MHz, CDCl ₃ ): δ-19.5 ppm.

<Example 29>

(Trimethylsilyl-diphenylphosphino-cyclopentadienyl-zirconium trichloride, compound 31 )

31

A solution of Compound 30 (69.1 g, 0.175 mol) in 200 ml of methylene chloride was added via cannula to a suspension of 41.5 g (0.178 mol) of 99.9% purity ZrCl ₄ in 200 ml of methylene chloride and the mixture was allowed to stand at room temperature for 8 hours. Stirred. During this time, the solution became cloudy. The solid was filtered off, washed twice with 20 ml of toluene and then twice with 20 ml of hexanes and dried under vacuum. The product contained 35 g pale yellow powder (yield: 39%). Because of the insolubility of the product, no ¹ H-NMR was obtained.

<Example 30>

(Diphenylphosphino-dichloroboranyl-bridge trimethylsilylcyclopentadienyl-cyclopentadienyl-zirconium dichloride, compound 32 )

32

A solution of compound 2 (2.6 g, 0.012 mole) was added to a suspension of compound 31 (5.6 g, 0.011 mole) in 100 ml of toluene at 0 ° C. After the mixture was stirred for 5 hours at 0 ° C., the tan solid was removed by filtration and a white solution was obtained. After toluene was removed under vacuum and the solid remaining with pentane was washed, compound 32 was obtained as an air-high sensitivity white powder (5.5 g; yield: 81%). ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ: 7.8-7.5 (m, 10H), 7.06 (m, 1H), 6.92 (m, 1H), 6.83 (m, 1H), 6.75 (m, 2H ), 6.68 (m, 1 H), 6.63 (m, 1 H), 0.26 (s, 9 H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ 0 (br, m); ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ-16.3 (br d, J _BP = 82 Hz).

<Example 31>

(Diisopropylphosphino-cyclopentadienyl-lithium, compound 33 )

33

50 ml of ether was introduced into a round bottom flask containing 1.68 g (0.023 mol) of cyclopentadienyl-lithium. After cooling the reaction flask to -20 ° C, 3.6 g (0.023 mol) of chlorodiisopropylphosphine was added dropwise. When the addition was complete, the cooling bath was warmed to 0 ° C. and the reaction mixture was stirred for 1 hour. Thereafter, the ether was removed in vacuo, the product was dissolved in toluene and the solution was filtered. After frit was washed twice with 10 ml of toluene, the reaction mixture was cooled to -20 ° C, 9.3 ml (0.023 mol) of a 2.5 molar solution of butyllithium in hexanes were added and an orange solution formed. The small fractions were subjected to NMR analysis to give a pale yellow solid ( Compound 33 ) after removal of toluene under vacuum and washing of the oil formed with hexane. ¹ H-NMR (400 MHz, THF) δ: 5.89 (m, 2H), 5.83 (br s, 2H), 1.86 (m, 2H), 1.0-0.8 (m, 12H). Most of the amount was used directly in the preparation of compound 34 .

<Example 32>

(Diisopropylphosphino-dimethylboranyl-bridge bis-cyclopentadienyl-titanium dichloride, compound 34 )

34

A solution of 6.1 g (0.023 mol) of compound 4 in 50 ml of toluene was added to the toluene solution of compound 33 (0.023 mol) from the reaction described above at -78 ° C. The mixture was stirred for 30 minutes at -78 ° C, then the cooling bath was removed, after which the solution was stirred for 2 hours at room temperature. Thereafter, the solids were removed by filtration and toluene was removed under vacuum. Hexane was then added to the red oily product, which formed a red powder, which was filtered off, washed twice with 20 ml of hexane, dried under vacuum, and then compound 34 was red powder (5.95 g, yield: CpLi). 61%). ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ: 6.96 (m, 2H), 6.94 (similar t, J = 2.4 Hz, 2H), 6.59 (m, 2H), 6.42 (m, 2H), 2.58 (m, 2H), 1.44 (dd, J = 7.3 Hz, J _HP = 14.7 Hz, 6H), 1.27 (dd, J = 7.2 Hz, J _HP = 13.1 Hz, 6H), 0.31 (d, J _HP = 16.4 Hz, 6H). ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ 28.7 (br m); ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ-29.7 (br m).

<Example 33>

(Dimethylphosphino-tributylstannyl-2-methylindene, compound 35 )

35

100 ml of ether was introduced into a round bottom flask containing 6.76 g (0.052 mol) of 2-methylindene ( compound 26 ) and the mixture was cooled to -20 ° C. 21 ml (0.052 mol) of a 2.5 molar solution of butyl-lithium in hexanes were added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. After cooling the reaction mixture to −20 ° C., 5.0 g (0.052 mol) of chlorodimethylphosphine were added over 5 minutes and a precipitate formed. The cooling bath was then removed and the reaction mixture was stirred for 1 hour at room temperature. After cooling to −20 ° C. 21.0 ml (0.052 mol) of a 2.5 mol solution of butyl-lithium in hexanes were added dropwise. When the addition was complete, the cooling bath was removed, after which the solution was slowly warmed to room temperature and stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 16.9 g (0.052 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. After the ether was removed in vacuo, the crude product was again dissolved in hexane, the solution was filtered off, the filtrate was dried under vacuum and 24.3 g (yield: 98%) of compound 35 was obtained as a dark yellow oil. ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ-68.5 (s).

<Example 34>

(Dimethylphosphino-2-methylindenyl-zirconium trichloride, compound 36 )

36

A solution of 17.4 g (0.036 mol) of compound 35 in 100 ml of toluene was added to a suspension of 8.5 g (0.036 mol) of purity 99.9% ZrCl ₄ in 100 ml of toluene over 10 minutes at 0 ° C. When the addition was complete, the reaction mixture was slowly warmed to 10 ° C. over 1 hour and then stirred at room temperature for 6 hours. The yellow precipitate was then filtered off, washed twice with 20 ml of toluene, twice with 20 ml of hexanes and dried under vacuum. The powder is further purified by removal of the remaining tin compound by toluene fed under reflux over 30 hours at 30 mmHg, followed by extraction in a Soxhlet extractor with pentane over 2 hours, compound 5.8 g (yield: 41 %) Was obtained as a luminescent yellow powder. Because of the insolubility of this compound, no ¹ H-NMR was obtained.

<Example 35>

(Dimethylphosphino-dichloroboranyl-bridge 2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 37 )

37

2.7 g (0.012 mol) of compound 2 were introduced into a round bottom flask containing 4.8 g (0.012 mol) of compound 36 in 125 ml of toluene over 5 minutes at room temperature. After the mixture was stirred for 7 hours, the dark yellow solid was filtered, washed twice with 20 ml of hexane, dried under vacuum and 5.5 g (yield: 89%) of compound 37 were obtained as a pale yellow solid. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.39 (d, J = 8.5 Hz, 1H), 7.71 (m, 1H), 7.4 (m, 2H), 6.64 (m, 2H), 6.46 (similar to q, J = 5.3, 2.9 Hz, 1H), 6.37 (m, 1H), 6.08 (m, 1H), 2.51 (s, 3H), 2.1 (d, J _HP = 12 Hz, 3H), 2.0 (d, J _HP = 12 Hz, 3H); ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) 5.3 (br, m); ¹¹ B (80 MHz, CD ₂ Cl ₂ ) δ-16.5 (br d, J _BP = 116 Hz).

<Example 36>

(Dicyclohexylboranylcyclopentadienyl-lithium, Compound 39 )

 38 39

See Herberich, G. E; Fischer, A. Organometallics 1996, 15, 58.

40 ml (0.04 mol) of a 1 molar solution of chlorodicyclohexylborane in hexane were added to 20 ml of cyclopentadienyl-sodium (2M in THF; 0.04 mol) in 100 ml of hexane at −78 ° C. After removal of the cooling bath, the reaction mixture was warmed to room temperature and stirred for 1 hour. After filtration and solvent removal under vacuum, 9.1 g (yield: 94%) of compound 38 remained as a yellow oil, which was used directly for the synthesis of compound 39 .

5.3 g (0.038 mol) of 2,2,6,6-tetramethylpiperidine were introduced into a round bottom flask containing 40 ml of THF. After cooling to −20 ° C. and 15 ml (0.038 mol) of a 2.5 molar solution of butyl-lithium in hexanes, the mixture was stirred at −20 ° C. for 1 hour and cooled at −78 ° C. 9.1 g (0.038 mol) of compound 38 in 20 ml of hexanes were added to this solution over 10 minutes. The cooling bath was removed and the solution was stirred for 1 hour at room temperature. The solvent was removed in vacuo and hexane was added, after which the mixture was stirred for 2 h, a white suspension formed, which was filtered off and the product was dried in vacuo. 4.6 g (yield 50%) of compound 39 were formed as a white powder. ¹¹ B-NMR (80 MHz, THF) δ 43.9.

<Example 37>

(Diphenylphosphino-dicyclohexylboranyl-bridge trimethylsilyl-cyclopentadienyl-cyclopentadienyl-zirconium dichloride, compound 40 )

40

The Schlenk flask containing 1.4 g (0.0056 mol) of compound 39 and 2.9 g (0.0056 mol) of compound 31 was cooled to −20 ° C., and then 100 ml of toluene was added. After the bath was removed, the suspension was stirred for 6 hours at room temperature and then filtered. The solvent was removed in vacuo and the remaining oily solid was washed with hexane and filtered. After drying the solid under vacuum, 1.9 g of compound 40 (yield: 48%) were obtained as a pink solid. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.6-7.2 (br m, 10H), 7.04 (br s, 1H), 6.95 (m, 1H), 6.82 (m, 1H), 6.76 (br s , 1H), 6.66 (m, 1H), 6.63 (m, 1H), 6.52 (m, 1H), 1.6-1.1 (br m, 22H), 0.26 (s, 9H); ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ 16.3; ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ-13.8.

<Example 38>

(4,7-dimethylindene, compound 41 )

41

See Erker G. et al., Tetrahedron 1995 , 51, 4347.

A 30% solution of 153 g (2.8 mol) of sodium methoxide in methanol was diluted with 60 ml of methanol and cooled to 0 ° C. 34 g (0.52 mol) of cyclopentadiene were added to this solution. After 15 minutes, 39 g (0.34 mol) of 2,5-hexanedione were added dropwise, after which the cooling bath was removed and the reaction mixture was stirred for 2 hours at room temperature. Then 200 ml of water and 200 ml of ether were added. The ether layer was removed, washed with water and sodium chloride solution and then dried over Na ₂ SO ₄ . After removal of the solvent in vacuo and distillation at 0.1 mbar, 65 ° C., compound 41 was obtained as an orange oil (40 g, yield: 81%). ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.35-7.27 (m, 2H), 7.23 (d, J = 7.6 Hz, 1H), 6.82 (m, 1H), 3.51 (s, 2H), 2.75 (s , 3H), 2.63 (s, 3H).

<Example 39>

(Diisopropylphosphino-tributylstannyl-4,7-dimethylindene, compound 42 )

42

100 ml of ether was introduced into a round bottom flask containing 5.0 g (0.035 ml) of 4,7-dimethylindene ( compound 41 ) and the mixture was cooled to -20 ° C. 14 ml (0.035 mol) of a 2.5 mol solution of butyl-lithium in hexanes were added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. The reaction mixture was cooled to -20 ° C, 5.3 g (0.035 mol) of chlorodiisopropylphosphine was added over 5 minutes, and a precipitate formed. After that, the cooling bath was removed and the reaction mixture was stirred at room temperature for 1 hour. After cooling to −20 ° C., 14.0 ml (0.035 mol) of a 2.5 mol solution of butyl-lithium in hexanes were added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 11.4 g of chlorotributyltin (0.035 mol) was added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was again dissolved in hexane, the solution was filtered, the filtrate was concentrated in vacuo and 16 g (yield: 83%) of compound 42 were obtained as a dark yellow oil. ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ-9 ppm.

<Example 40>

(Diisopropylphosphino-4,7-dimethylindenyl-zirconium trichloride, compound 43 )

43

A solution of 16.0 g (0.029 mol) of Compound 42 in CH ₂ Cl ₂ (100 ml) was added to a suspension of 6.4 g (0.029 mol) of purity 99.9% ZrCl ₄ in 100 ml of CH ₂ Cl ₂ over 10 minutes at −20 ° C. . When the addition was complete, the reaction mixture was slowly warmed to room temperature over 2 hours and then stirred for a further 2 hours at room temperature. Thereafter, the solid was removed by filtration, the solvent was removed in vacuo, and crude compound 43 remaining as an oil was used directly for the preparation of compound 44 .

<Example 41>

(Diisopropylphosphino-dichloroboranyl-bridge 4,7-dimethylindenyl cyclopentadienyl-zirconium dichloride, compound 44 )

44

5.0 g (0.023 mol) of compound 2 were introduced into a round bottom flask containing 10.6 g (0.023 mol) of compound 43 in 125 ml of toluene at 0 ° C. over 5 minutes. The mixture was stirred for 1.5 h at 0 ° C., then the cooling bath was removed and the suspension was stirred for another 3 h at room temperature. Thereafter, the toluene-soluble fractions were removed from the large amount of oil formed during the reaction, dried in vacuo to give a thick oil. 100 ml of hexane was added to this oil, after which the mixture was stirred and the dark yellow powder was filtered off and dried under vacuum. After this treatment, 6.3 g (yield 48%) of compound 44 were obtained as a dark yellow powder. The product can be further purified by precipitation of a CH ₂ Cl ₂ solution of compound 44 in a hydrocarbon solvent. ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.03 (similar, t, J = 8.5 Hz, 1H), 7.22 (d, J = 7 Hz, 1H), 7.08 (d, J = 7.1 Hz, 1H ), 7.02 (m, 1H), 6.77 (m, 1H), 6.70 (m, 1H), 6.58 (m, 1H), 6.44 (br s, 1H), 3.51 (m, 1H), 2.82 (m, 1H ), 2.64 (s, 3H), 2.50 (s, 3H), 1.77 (dd, J = 7.2 Hz, J _HP = 16.3 Hz, 3H), 1.69 (dd, J = 7.1 Hz, J _HP = 15.2 Hz, 3H ), 1.58 (dd, J = 7.1 Hz, J _HP = 15.5 Hz, 3H), 1.28 (dd, J = 7.2 Hz, J _HP = 14.5 Hz, 3H); ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ) δ 28.4 (br m); ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ-15.3 (d, J _PB = 107 Hz).

<Example 42>

(Pyrrole-Lithium, Compound 45 )

45

59 ml of a butyl-lithium (2.5 mol in hexane, 0.148 mol) solution was slowly added to a solution of 9.9 g (0.148 mol) of pyrrole in 200 ml of hexane at −20 ° C., and a white solid formed. The mixture was then stirred at rt for 2 h, the solids were separated by filtration, washed twice with 20 ml of hexane each time and dried under vacuum. This method yielded 6 g of compound 45 (56% of theoretical yield).

¹ H-NMR (400 MHz, THF): δ = 6.71 (s, 2H), 5.95 (s, 2H).

<Example 43>

(Dimethylboranyl-bridged cyclopentadienyl-pyrrole-titanium dichloride, compound 46 )

46

A solution of 1.34 g (0.005 mol) of compound 4 in 20 ml of toluene was added to 0.38 g (0.005 mol) of compound 45 over 5 minutes at −78 ° C. The cooling bath was then removed and stirred for 2 hours at room temperature. Thereafter, the formed red solid was filtered off and the yellow filtrate was discarded. The red solid was washed with toluene and dried under vacuum. 1.14 g were obtained with a small amount of LiCl.

¹ H-NMR (400 MHz, THF): δ = 6.89 (Like-t, J = 2.3 Hz, 2H), 6.64 (m, 2H), 6.59 (Like-t, J = 2.35 Hz, 2H), 5.73 ( Pseudo-t, J = 1.7 Hz, 2H), 0.06 (s, 6H). ¹¹ B-NMR (80 MHz, THF) δ = -26 ppm.

<Example 44>

(1-phenyl-2,3,4,5-tetramethyl-phosphol, compound 47 )

47

Document [Organometallics 7 (1988), 921 ], CH 2 Cl 2 150 ml solution of 2-butyne 11.7 g (0.216 mol) was slowly added to the AlCl ₃ 15.3 g (0.115 mol) in CH ₂ Cl ₂ (0 according to C; 30 minutes). The mixture was then stirred at 0 ° C. for 45 minutes, then the cooling bath was removed, after which the mixture was further stirred for 1 hour. Thereafter, the solution was cooled to −50 ° C., and a solution of 21.4 g (0.12 mol) of phenyl-dichlorophosphine in CH ₂ Cl ₂ was added over 20 minutes. The cooling bath was then removed and the dark red solution was then stirred for 1 hour and then added to a solution of 27 g (0.13 mol) of tributylphosphine in 100 ml of CH ₂ Cl ₂ at −30 ° C. Immediately the red disappeared and a yellow solution was obtained. At the end of the addition, the solvent was removed in vacuo to give a dark yellow oil. The oil was taken up in hexanes and washed with saturated aqueous NaHCO ₃ and H ₂ O under Ar atmosphere. After drying with MgSO ₄ , hexanes were removed in vacuo. 18.2 g was obtained as a clear oil (yield: 78%).

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.3 (m, 5H), 2.0 (m, 12H), ³¹ P-NMR (161.9 MHz, CDCl ₃ ) δ: 16.8 ppm.

<Example 45>

(Lithium-2,3,4,5-tetramethyl-phosphol, compound 48 )

48

According to Organicmetallics 7 (1988), 921, 0.52 g (0.074 mol) of lithium was added to a solution of 7 g (0.032 mol) of compound 47 in 150 ml of tetrahydrofuran (THF) and the mixture was stirred overnight. . The resulting red solution was filtered through frit to remove residual solids and the filtrate was cooled to 0 ° C. Thereafter, a solution of 1.45 g (0.01 mol) of AlCl ₃ in 20 ml of THF was added dropwise, and the solution was brought to room temperature. Aliquots were separated for analysis and the remaining solution was used directly for the preparation of compound 49 . ³¹ P-NMR (161.9 MHz, THF) δ: 63.7 ppm.

<Example 46>

(Dimethylboranyl-cyclopentadienyl-tetramethylphosphol-titanium dichloride, compound 49 )

49

The THF solution of Example 45 with 1.46 g (0.01 mol) of Compound 48 was introduced into a round bottom flask and the THF was removed under vacuum. Toluene was added and cooled to −78 ° C., then a solution of 2.6 g (0.01 mol) of compound 44 in 20 ml of toluene was added slowly with stirring to form a red suspension. At the end of the addition, the suspension was brought to room temperature and then stirred for 1 hour. After filtration of the solid remaining insoluble, toluene was removed under vacuum and hexane was added to the remaining oily solid. In addition, the solid that remained undissolved was filtered from the hexane solution and the solution was stored overnight at -20 ° C. After removal of the hexanes, 0.5 g (14% yield) of green solid identified as compound 49 was obtained. ¹ H-NMR (200 MHz, CD ₂ Cl ₂ ) δ: 6.64 (m, 2H), 6.57 (m, 2H), 2.11 (d, J _HP = 10 Hz, 6H), 2.09 (s, 6H), 0.87 (d, J _HP = 5.3 Hz, 6H). ³¹ P-NMR (161.9 MHz, THF) δ: 95.6 ppm, ¹¹ B-NMR (80 MHz, CD ₂ Cl ₂ ) δ: 39 (br, m) ppm.

<Example 47>

(Ethylene polymerization)

50 ml of dry, oxygen-free toluene was sucked into a dry, oxygen-free, magnetically stirred V4A steel autoclave which was heated strictly in vacuo. A D / A metallocene catalyst ( Compound 10 ) with MAO (methylaluminoxane, 10% in toluene, molecular weight 900 g / mol) in Al / Zr = 66,666: 1 over 15 minutes in toluene at room temperature ( Molar) ratio. An aliquot containing 1.5 × 10 ⁻⁷ moles of Zr and 1.0 × 10 ⁻² moles of Al in 6.8 ml was injected into an airless autoclave, after which the autoclave was charged with additional 50 ml of toluene. Subsequently, the polymerization was carried out under constant ethylene pressure of 10 bar at room temperature for 1 hour, and the internal temperature was raised to 42 ° C. After lowering the autoclave, the reaction mixture is introduced into 500 ml of ethanol and 50 ml of concentrated hydrochloric acid solution, stirred overnight, the polymer is filtered off, washed thoroughly with ethanol and dried to constant weight in a rotary air drying cabinet at 100 ° C. I was. The PE yield was 2.9 g, which corresponds to 19.3 tonnes of catalytic activity per mole of Zr and per hour. The limit viscosity measured in o-dichlorobenzene at 140 ° C. was 4.36 dl / g. DSC measurements yielded a melting point of 139 ° C. and a heat of fusion of 164 J / g.

<Examples 48 to 51>

(Ethylene polymerization)

In another ethylene polymerization experiment, the method of Example 47 was identical except that D / A-metallocene 7 was used as catalyst and another amount of MAO was used. The amount of Ti was 1 × 10 ⁻⁶ mol and the autoclave was heated to about 100 ° C. Al / Zr ratios varied among 1250, 2500, 5000 and 10,000. In all four experiments, the catalytic activity was about 3-4 tons of PE per mole of Ti and per hour.

<Example 52>

(Ethylene polymerization)

The method of Example 47 was followed except that 100 ml of toluene was initially introduced directly into the autoclave. The autoclave was heated to 80 ° C., the catalyst was injected and the ethylene pressure was adjusted to 10 bar. 1 x 10 ^-6 moles of compound 18 in 2.4 ml of toluene, carried out with 5 x 10 ^-3 moles of MAO in 3.3 moles of toluene, was used as catalyst. The internal temperature was raised from 80 ° C to 94 ° C. After 30 minutes, the polymerization was stopped. The PE yield was 3.5 g, which corresponds to about 7 tons of catalyst activity per mole of catalyst and per hour. The limit viscosity η was measured in ortho-dichlorobenzene at 140 ° C. and was 2.95 dl / g. DSC measurements gave a melting point of 139 ° C. and a heat of fusion of 165 J / g.

<Examples 53 to 56>

(Ethylene polymerization)

The method was the same as in Example 51. The amount of Ti ( Compound 7 ) was 1 × 10 ⁻⁶ mole and the Al / Zr ratio was 10,000. The autoclave was heated to different temperatures and the polymer properties of the limit viscosity and melting point T _m were measured.

T at 60 ° C. = 7.2 dl / g at RT, T _m = 143 ° C.

T: 80 ° C = 4.6 dl / g at RT, T _m = 142 ° C

T: 100 ° C. = 3.2 dl / g at RT, T _m = 144 ° C.

T: 120 ° C. = 2.2 dl / g at RT, T _m = 140 ° C.

(RT-room temperature)

<Example 57>

(Ethylene polymerization)

The method of Example 52 was followed except that the internal pressure was adjusted to 100 ° C. 5 x 10 ^-7 moles of compound 24 in 0.4 moles of chlorobenzene performed with 5 x 10 ^-3 moles in 3.3 moles of toluene were used as catalyst. The internal temperature was raised from 100 ° C to 120 ° C. After polymerization for 30 minutes, 6.2 g of PE were formed, which corresponds to about 2.5 tons of catalytic activity per mole of catalyst and per hour. The limit viscosity η measured in ortho-dichlorobenzene at 140 ° C. was 1.85 dl / g.

<Example 58>

(Ethylene polymerization)

The method of Example 57 was followed except that Compound 21 was used as a catalyst. In this case, internal temperature was raised from 100 degreeC to 128 degreeC. After 30 minutes the PE yield was 7.9 g, which corresponds to about 31.6 tonnes of catalytic activity per hour per mole of catalyst. The limit viscosity η in ortho-dichlorobenzene at 140 ° C. was 1.01 dl / g.

<Example 59>

(Ethylene polymerization)

The method of Example 52 was followed except that the polymerization was started at 20 ° C. In this method, metallocene 32 was used as a catalyst. To this end, 2.5 × 10 ⁻⁷ moles of catalyst were carried out with 2.5 × 10 ⁻³ moles of MAO in toluene. The internal temperature was raised to 20 ° C to 34 ° C. After polymerization for 30 minutes, 1.3 g of PE were formed, corresponding to 10.4 tonnes of catalyst activity per mole of catalyst and per hour. The limit viscosity η (ortho-dichlorobenzene, 140 ° C.) was 5.3 dl / g.

DSC measurements showed a melting point of 153 ° C. on the first heating at a rate of 20 K / min. After the sample was terminated at 320 K / min, the maximum melting point at the second heating was measured at 146 ° C.

<Example 60>

(Ethylene polymerization)

The experiment of Example 47 was carried out except that D / A metallocene used as catalyst was compound meso- 15 . The amount of Zr was 5 x 10 ^-7 mol, and the amount of Al was 1 x 10 ^-2 mol. After the catalyst and ethylene were added, the autoclave was quickly heated to about 120 ° C. After polymerization for 30 minutes, 4.3 g of polyethylene was isolated, corresponding to an activity of about 17 t of PE per mole of Zr and per hour. At 140 ° C., the limit viscosity η measured in o-dichlorobenzene was 1.9 dl / g.

<Example 61>

(Diphenylphosphino-dichloroboranyl-crosslinked bis (indenyl) -zirconium dichloride, compound 50 )

0.011 mol of trimethylsilyl-dichloroboranyl-indene was added to a suspension of 0.012 mol of diphenylphosphino-indenyl-zirconium trichloride in 150 ml of toluene at room temperature. The reaction mixture was then stirred at 75 ° C. for 1 hour. After cooling and filtration, 150 ml of hexane was added to a clear orange solution, which then formed a dark red oil and a pale yellow precipitate. The precipitate was filtered off, washed with hexanes and dried in vacuo. Pale yellow solid was identified as pure meso compound by ¹ H-NMR spectroscopy. The red oil and the filtrate were concentrated to 30 ml, 200 ml of hexane was added dropwise, after which a second pale yellow precipitate formed, which was filtered and dried in vacuo. This product was identified as pure rac isomer with the aid of X-ray structural analysis. Crystals suitable for this purpose were incubated with slow diffusion of hexane with saturated CH ₂ Cl ₂ solution at room temperature. Donor-receptor bonds P → B have a length of 2.02 mm 3. Yield 40% and meso / rac ratio 1: 1. The reaction mixture was stirred at 75 ° C. (instead of 1 hour) for 5 hours when the amount of desired rac isomer was increased and the meso / rac ratio was 1: 4. At the same time, the total yield increased slightly from 40% to 45%.

Elemental analysis: 56.05% C (55.90% of theoretical yield), 4.35% H (4.38%)

Spectral meso isomer: ¹ H-NMR (400 MHz, CD ₂ Cl ₂ , room temperature RT): 8.01 ppm (1H, d, 8.8 Hz); 7.8-7.0 ppm (some overlapping multiple peaks, 28H); 6.94 ppm (1H, t, 3.3 Hz); 6.77 ppm (1 H, d, 3.44 Hz); 6.31 ppm (1H, d, 8.7 Hz), ³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): 5.6 ppm. ¹¹ B-NMR (80.2 MHz, CD ₂ Cl ₂ ): -17.0 ppm (72 Hz).

Spectral rac isomer: ¹ H-NMR (400 MHz, CD ₂ Cl ₂ , RT): 8.39 ppm (1H, d, 8.5 Hz); 7.68-7.05 ppm (27H, multiple overlapping multiple peaks); 6.65 ppm (1H, d, 2.9 Hz), 6.59 ppm (1H, t, 3.5 Hz); 6.51 ppm (1H, t, 2.8 Hz); 6.40 ppm (1H, d, 3.5 Hz).

³¹ P-NMR (161.9 MHz, CD ₂ Cl ₂ ): 8.1 ppm. ¹¹ B-NMR (80.2 MHz, CD ₂ Cl ₂ ) =-14.0 ppm (J _PB = 74 Hz).

<Example 62-64>

(Dialkylphosphino-dichloroboranyl-crosslinked bis (indenyl) -zirconium dichloride; alkyl = i-propyl = compound 51 ; ethyl = compound 52 ; methyl = compound 53 )

0.016 mol of trimethylsilyl-dichloroboranyl-indene in 50 ml of toluene was added to a suspension of 0.0157 mol of dialkylphosphinoinyl-zirconium trichloride in 250 ml of toluene at room temperature. The reaction mixture was then heated for several hours with stirring. After cooling and filtration, 300 ml of hexane was added to a clear orange solution, which then formed a dark red oil and a clear yellow solution. The meso and rac isomers were separated from the toluene / hexane solution by fractional distillation.

Characterization of the compound (NMR spectra in CD ₂ Cl ₂ at room temperature; ¹ H-NMR: 400 MHz, ³¹ P-NMR: 61.9 MHz, ¹¹ B-NMR: 80.2 MHz):

rac compound 51 (i-Pr):

¹ H-NMR: 8.41 ppm (1H, d, 9.0 Hz); 8.31 ppm (1H, d, 8.4 Hz); 7.84 ppm (1 H, d, 8.5 Hz); 7.64-7.24 ppm (6H, several overlapping multiple peaks); 6.70 ppm (2H, m); 6.60 ppm (1H, m): 3.78 ppm (1H, m, P (C H (CH ₃ ) ₂ ) ₂ ; 3.21 ppm (1H, m, P (C H (CH ₃ ) ₂ ) ₂ ; 1.81 ppm (6H , m, P (CH (C H ₃ ) ₂ ) ₂ ; 1.72 ppm (3H, dd, P (CH (C H ₃ ) ₂ ) ₂ , 14.9 Hz, 7.3 Hz); 1.32 ppm (3H, dd, P ( _{CH (C H 3) 2)} 2, 14.1Hz, 7.4 Hz) 31 P-NMR:.. 22.7 ppm 11 B-NMR: -14.1 ppm (100 Hz).

Elemental analysis: 49.4% C (48.9% of theoretical yield), 4.6% H (4.4%).

meso compound 52 (Et):

¹ H-NMR: 7.83 ppm (1 H, d, 9.0 Hz); 7.76 ppm (1 H, m); 7.63 ppm (1 H, d, 7.2 Hz); 7.47 ppm (1H, d, 8.5 Hz); 7.33 ppm (2H, m); 7.20-7.03 ppm (4H, multiple overlapping multiple peaks); 6.76 ppm (2H, m); 2.68 ppm (2H, m, P (C H ₂ (CH ₃ ) ₂ ); 2.44 ppm (2H, m, P (C H ₂ CH ₃ ) ₂ ); 1.62 ppm (3H, m, P (CH ₂ (C H ₃ ) ₂ ; 1.27 ppm (3H, m, P (CH ₂ (C H ₃ ) ₂ ) ^.31 P-NMR: 7.1 ppm. ¹¹ B-NMR: -15.8 ppm (100 Hz).

rac compound 52 (Et):

¹ H-NMR: 8.28 ppm (1 H, d, 8.6 Hz); 8.10 ppm (1 H, d, 8.6 Hz); 7.62 ppm (1 H, d, 8.4 Hz); 7.46 ppm (1 H, d, 8.5 Hz); 7.41-7.10 ppm (4H, several overlapping multiple peaks); 6.81 ppm (1 H, m); 6.47 ppm (2H, m): 6.38 ppm (1H, d, 3.4 Hz), 2.68 ppm (2H, m, P (C H ₂ (CH ₃ ) ₂ ); 2.35 ppm (2H, m, P (C H ₂ (CH ₃ ) ₂ ); 1.30 ppm (6H, m, P (CH ₂ (C H ₃ ) ₂ ) ^.31 P-NMR: 12.3 ppm. ¹¹ B-NMR: -15.7 ppm.

Elemental analysis: 47.6% C (47.1% of theoretical yield), 4.3% H (4.0%).

meso compound 53 (Me):

¹ H-NMR: 7.84 ppm (1 H, d); 7.75 ppm (1 H, d, 8.2 Hz); 7.68 ppm (1 H, d, 7.7 Hz); 7.51 ppm (1H, d, 8.5 Hz); 7.40-7.10 ppm (4H, several overlapping multiple peaks); 6.77 ppm (2H, br); 2.13 ppm (3H, P (C H ₃ ) ₂ , d, 11.8 Hz); 1.92 ppm (3H, P (C H ₃ ) ₂ , d, 11.8 Hz). ³¹ P-NMR: -8.4 ppm. ¹¹ B-NMR: −16.1 ppm (103 Hz).

rac compound 53 (Me):

¹ H-NMR: 8.21 ppm (1H, d, 8.7 Hz); 8.15 ppm (1H, d, 8.6 Hz); 7.63 ppm (1 H, d, 8.5 Hz); 7.44-7.07 ppm (6H, several overlapping multiple peaks); 6.40 ppm (3H, br); 2.03 ppm (3H, d, P (C H ₃ ) ₂ , 11.9 Hz); 1.98 ppm (3H, d, P (C H ₃ ) ₂ , 11.6 Hz). ³¹ P-NMR: -1.5 ppm. ¹¹ B-NMR: −16.0 ppm (119 Hz).

<Example 65>

(1,3-bis (trimethylsilyl) -2-methylindene, compound 54 )

500 ml of hexane and 70 ml of butyllithium (2.5 molar solution in hexane) were introduced into a 1000 ml flask. 0.175 mol of 2-methylindene was added dropwise at external temperature, and the mixture was further stirred for 10 hours. Subsequently, 0.18 mol of trimethylsilyl chloride was added dropwise at room temperature, and the mixture was further stirred for 10 hours. LiCl was filtered off and 70 ml of butyllithium (2.5 molar solution in hexane) was added to the clear filtrate. After further stirring for 10 hours, 0.18 mole of trimethylsilyl chloride was added again and the mixture was further stirred for 10 hours. LiCl was filtered off and the solvent was removed in vacuo. Compound 54 was obtained as a colorless oil. Yield: 85% of theoretical yield.

¹ H-NMR (CD ₂ Cl ₂ ): 7.51 ppm (1H, d, 7.7 Hz); 7.38 ppm (1 H, d, 7.5 Hz); 7.19 ppm (1H, t, 7.4 Hz); 7.08 ppm (1H, t, 7.3 Hz); 3.54 ppm (1 H, s); 2.32 ppm (3H, s); 0.41 ppm (9H, s, Si (C H ₃ ) ₃ ); 0.0 ppm (9H, s, Si (C H ₃ ) ₃ ).

Example 66

(Trimethylsilyl-dichloroboranyl-2-methylindene, compound 55 )

0.096 moles of compound 54 were introduced into a 250 ml flask equipped with a dry ice condenser (-30 ° C.). Then 0.096 moles of BCl ₃ were added and the mixture was stirred at external temperature for 3 hours and 55 ° C. for 6 hours. Byproduct (CH ₃ ) ₃ SiCl was removed and a brown oil was obtained as crude product. Distillation from the cold trap to the cold trap gave 75% yield of compound 55 as a tacky solid.

¹ H-NMR (CD ₂ Cl ₂ ): 8.09 ppm (1H, d, 7.9 Hz); 7.37 ppm (1H, d, 7.6 Hz); 7.26 ppm (1H, t, 7.5 Hz); 7.16 ppm (1H, t, 7.5 Hz); 3.89 ppm (1 H, s); 2.61 ppm (3H, s); 0.0 ppm (9H, s, Si (C H ₃ ) ₃ ). ¹¹ B-NMR (CD ₂ Cl ₂ ): 31.9 ppm.

<Example 67>

(Tributylstannyl-diethylphosphino-2-methylindene; compound 56 )

The method was the same as in Example 7.

<Example 68>

(Dienylphosphino-2-methylindenyl-zirconium trichloride, compound 57 )

The procedure of Example 8 was identical except that CH ₂ Cl ₂ was used instead of toluene as the solvent. The reaction temperature was 25 ° C. Purification was performed by Soxhlet extraction with CH ₂ Cl ₂ . Compound 57 was obtained in 78% of an insoluble yellow solid in theoretical yield.

<Example 69>

((C ₂ H ₅ ) ₂ P-BCl ₂ -crosslinked bis (2-methylindenyl) -zirconium dichloride, compound 58 )

0.019 moles of compound 55 in 50 ml of toluene were added to a suspension of 0.019 moles of compound 57 in 350 ml of toluene at room temperature.

The reaction mixture was then heated to 80 ° C. and stirred for 24 hours. After cooling and filtration, 300 ml of hexane was added to a clear, orange solution, which then formed a dark orange oil and a clear yellow solution. Condensation and cooling to -25 ° C afforded compound rac-58 as pale yellow powder.

¹ H-NMR: 8.14 ppm (1H, d, 8.6 Hz); 7.96 ppm (1H, d, 8.9 Hz); 7.47-7.05 ppm (6H, several overlapping multiple peaks) 6.53 ppm (1H, d, 1.9 Hz); 6.47 ppm (1 H, s); 3.0-2.55 ppm (4H, several overlapping multiple peaks), P (C H ₂ (CH ₃ ) ₂ ); 2.21 ppm (3H, s, C H ₃ ); 2.08 ppm (3H, s, C H ₃ ); 1.44 ppm (3H, m, P (CH ₂ (C H ₃ ) ₂ ), 1.07 ppm (3H, m, P (CH ₂ (C H ₃ ) ₂ ). ³¹ P-NMR: 21.4 ppm. ¹¹ B-NMR : -14.7 ppm.

<Example 70>

(Propene polymerization)

A thoroughly heated 300 ml V4A steel autoclave was charged to 100 ml of dry, oxygen-free toluene and 0.5 ml of 1 mol triisobutylaluminum / toluene solution. Then about 1 mole of propene was transferred to the autoclave. 1 ml of a chlorobenzene solution containing 4 × 10 ⁻⁶ moles of dimethylanilinium tetrakis (pentafluorophenyl) borate was carried out for 30 minutes at room temperature and rac [(2-Me-ind) Et ₂ PBCl ₂ (2- Me-ind) ZrCl ₂ ] 3.1 ml of a catalyst solution in toluene containing 1 × 10 ⁻⁶ mol and 0.1 mmol of triisobutylaluminum (TiBA) was added via pressure passage and the mixture was charged with toluene to 5 ml. After moving the catalyst solution to the autoclave under pressure, the internal temperature was raised from 20 ° C. to 48 ° C., despite external cooling with dry ice / acetone.

20 minutes after the addition of the catalyst, the polymerization was stopped and the contents of the autoclave were extracted with stirring for 2 hours in 500 ml of ethanol and 50 ml of concentrated aqueous hydrochloric acid solution. The polypropylene white powder was then separated by filtration, washed with ethanol and dried at 115 ° C.

Polymer yield: 11.6 g

Catalyst activity: 34.8 tons of i-PP per mole of catalyst and per hour

DSC measurements at the second heating gave a melting point of T _m = 155 ° C.

NMR measurements yielded isotactility index I.I. = 88%.

The limit viscosity [η] measured in ortho-dichlorobenzene (ODCB) at 140 ° C. was determined by molecular weight M _visc. = 3.60 dl / g, corresponding to 798 kg / mol (calculated by the method of Atkinson et al., Makromol. Chem. (1976), 177 , 213).

Under the experimental conditions comparable at a polymerization temperature of 10 ℃ to 20 ℃ as rac -52, II = 92%, and [η] i-PP having a = 1.20 dl / g was obtained, which is the theoretical average molecular weight M _visc. Equivalent to = 169 kg / mol.

<Example 71>

(Ethylene polymerization)

100 ml of dry, oxygen-free toluene was charged to a thoroughly heated 300 ml V4A steel autoclave and heated to 100 ° C. The pressure was kept constant at 10 bar with ethylene and the catalyst was added to the pressure passage.

5 × 10 ⁻⁷ moles of meso-[(ind) Et ₂ PBCl ₂ (ind) ZrCl ₂ ] carried out for 15 minutes at room temperature with 5 × 10 ⁻³ moles of MAO in 5 ml of toluene were used as catalyst.

The internal temperature was raised to 111 ° C during the polymerization.

Polyethylene yield after 30 minutes: 12.1 g

Catalytic activity: 48.4 tons of polymer per mole of catalyst and per hour

Limit viscosity in ortho-dichlorobenzene at 140 ° C .: [η] = 0.91 dl / g

DSC analysis: T _m = 136 ° C

<Example 72>

Same as the method of Example 70 except for the difference that it was performed under propene pressure of only 2 bar. The internal temperature was raised from 20 ° C to 23 ° C. In this case, the melting point T _m of the formed polypropylene was 158 占 폚.

The present invention relates to a process for producing a high melting point polyolefin by homopolymerization or copolymerization of one or more monomers selected from the group consisting of an optionally substituted α-olefin having two or more carbon atoms. Two π systems, in particular aromatic π systems, for example anionic cyclopentadienyl ligands (cabanions) are complexed, which are reversibly linked to each other by one or more bridges of donor and acceptor , π-based or metallocene compound. Coordination bonds formed between donor and acceptor atoms generate (partially) positive charges on the donor and (partially) negative charges on the acceptor.

Δ ⁺ Δ ^-

[Donor → receptor]

Its use as catalyst in metallocene and olefin polymerizations has long been known (European Patent Publication 129 368 and references cited therein). European Patent Publication No. 129 368 also discloses that metallocenes together with aluminum-alkyl / water as promoters are effective systems for the polymerization of ethylene (for example, methylaluminoxane (MAO) is 1 mole of trimethylaluminum). And from 1 mole of water, and other stoichiometric ratios have also been used successfully (WO 94/20506). Metallocenes in which the cyclopentadienyl skeleton is covalently bonded to each other via a bridge are already known. An example of a number of patents and applications in this field is European Patent Publication No. 704 461, wherein the linking groups mentioned here are (substituted) methylene groups or ethylene groups, silylene groups, substituted silylene groups, substituted germanyls Group or substituted phosphine group. EP 704 461 also shows that bridged metallocenes as polymerization catalysts for olefins. Despite numerous patents and applications in this field, there is a continuing need for improved catalysts that are highly active and have a small amount of catalyst residual in the polymer, which is suitable for the polymerization and copolymerization of olefins.

Particularly advantageous catalysts are coordination bonds or so-called datives, in which two π-based bridges are produced by one, two or three reversible donor-receptor bonds, in each case at least formally overlapped by ionic bonds. It has been found that a bond is formed between a donor atom and a receptor atom, wherein one of the donor or acceptor atoms can be prepared from a bridged π complex, in particular a metallocene compound, which can be part of a particular π system. In addition to the bridging state indicated by the arrows between D and A, the reversibility of the donor-receptor bonds, as a result of their inherent rotational energy while preserving the integrity of the metal complexes, result in the two π systems being 360 ° It also allows an unbridged state to be rotated. When the rotation is complete, the donor-receptor binding is "quickly coupled". If there are multiple donors and / or receptors, the “quick binding” may occur after rotation at an angle of less than 360 °. Thus, the π-based, for example metallocenes used in accordance with the present invention can be represented only by double arrows to include both states of sub-formulas Ia and Ib or formulas XIIIa and XIIIb.

Accordingly, the present invention provides the presence of organometallic catalysts that can be activated by a promoter, including the use of a metallocene compound of formula (I) or a π complex of formula (XIII), in particular a metallocene compound, as organometallic catalyst The invention relates to a process for the preparation of high melting point polyolefins by homopolymerization or copolymerization of at least one monomer from the group consisting of optionally substituted α-olefins having two or more carbon atoms.

(In the above formula,

CpI and CpII are two identical or different carbanions having a cyclopentadienyl containing structure, wherein one to all H atoms are monosubstituted to all substituted by halogen, or monosubstituted to trisubstituted by phenyl, Or linear or branched C ₁ -C ₂₀ -alkyl which may be monosubstituted or trisubstituted by vinyl; C ₆ -C ₁₂ -aryl; halogenoaryl having 6 to 12 carbon atoms; silyl, trimethylsilyl or ferro May be substituted by the same or different radicals from the group consisting of organometallic substituents such as cenyl, one or two may be substituted by D and A),

D is a donor atom that may have additional substituents and has at least one free electron pair in a particular bond state,

A is a receptor atom which may have additional substituents and lacks an electron pair in certain binding states,

Where D and A are connected by reversible coordination bonds such that the donor has a (partially) positive charge and the receptor has a (partially) negative charge,

M is a transition metal of the III, IV, V or VI subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actinides,

X is a monovalent anion equivalent,

n is 0, 1, 2, 3 or 4 depending on the charge of M)

(In the above formula,

πI and πII are differently charged or electrically neutral π systems, which can be fused with one or two unsaturated or saturated five or six membered rings,

D is a substituent of πI or a donor atom that is part of a π system of πI and has at least one free electron pair in a particular bonding state,

A is a substituent of πII or a part of π system of πII and a receptor atom lacking an electron pair in a specific bonding state

Wherein D and A are linked by reversible coordination bonds such that the donor is (partially) positively charged and the receptor is (partially) negatively charged, and at least one of D and A is of Part and D and A may have substituents,

Each π system and each fused ring system may contain one or more D or A, or D and A,

In unfused or fused form of π I and π II, one to all H atoms of the π system may be monosubstituted to fully substituted by halogen, or monosubstituted to trisubstituted by phenyl, or vinyl Linear or branched C ₁ -C ₂₀ -alkyl which may be substituted with 1 to 3 substituents; C ₆ -C ₁₂ -aryl; Halogenoaryl having 6 to 12 carbon atoms; Reversible D → A, since one or two may be substituted independently by one another or by the same or different radicals from the group consisting of organometallic substituents such as silyl, trimethylsilyl or ferrocenyl, or by one or two The coordination bond is (i) both D and A are part of a particular π or fused ring system, or (ii) D or A is part of the π system, or is part of a fused ring system, and in each case the other May be formed between D and A, which is a substituent of an unfused π or fused ring system,

M and X are as defined above,

n is 0, 1, 2, 3 or 4 depending on the charge of M and the charges of π-I and π-II).

The π systems according to the invention are species produced by substituting substituted or unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, cyclopentadienyl anions and one or more C atoms by heteroatoms.

Among the species, cyclic species are preferred. The coordination binding property of the ligand (π-based) to the metal may be σ type or π type.

The metallocene compound of formula (I) used according to the invention is a compound of formula (II) and (III), or a compound of formula (IV) and (V), or formula (VI) Compounds of formula (VIII) and (III), reacting compounds of VII with each other or removing E (R ¹ R ² R ³ ) X and F (R ⁴ R ⁵ R ⁶ ) X in the presence or absence of an aprotic solvent Or by reacting a compound of Formula (IV) with Formula (IX), or a compound of Formula (X) with Formula (VII).

MX _{n + 2}

In the above formula,

CpI, CpII, D, A, M, X and n are as defined above,

CpIII, CpIV are two identical or different uncharged molecules having a cyclopentadiene containing structure or are the same as CpI and CpII,

M 'is a monovalent cation equivalent of an alkali or alkaline earth metal or Tl,

E and F are independently of each other one of the elements Si, Ge or Sn,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another are linear or branched C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₂ -aryl, C ₁ -C ₆ -alkyl-C _6- C ₁₂ -aryl, C ₆ -C ₁₂ -aryl-C ₁ -C ₆ -alkyl, vinyl, allyl or halogen,

Wherein in formulas VIII, IX and X, hydrogen may be present in place of E (R ¹ R ² R ³ ) and F (R ⁴ R ⁵ R ⁶ ), in which case X is also of R ₂ N ⁻ type Amide anion or a carbanion of R ₃ C ^- type or an alcoholate anion of RO ^- type, wherein the compound of Formula II or Formula VIII is also directly converted in the presence of the compound of Formula V or Formula IX React with the compound.

In the reaction of formula (VIII) and (III), or (IV) and (IX), or (X) and (VII), in the last mentioned variant method, the structure of formula (I) is represented by the amine R ₂ NH or R ₂ NE (R ¹ R ² R ³ ) or R ₂ NF (R ⁴ R ⁵ R ⁶ ), or a hydrocarbon compound of the formula R ₃ CH or R ₃ CE (R ¹ R ² R ³ ) or R ₃ CF (R ⁴ R ⁵ R ⁶ ) Or is formed while removing the ether ROE (R ¹ R ² R ³ ) or ROF (R ⁴ R ⁵ R ⁶ ), wherein the organic radicals R are the same or different and independently C ₁ -C ₂₀ -alkyl, C _6- C ₁₂ -aryl, substituted or unsubstituted allyl, benzyl or hydrogen. Examples of amines or hydrocarbons, ethers, silanes, alkyltins or germanes that have been removed include dimethylamine, diethylamine, di- (n-propyl) -amine, di- (isopropyl) -amine, di- (tert-butyl) -Amine, tertiary butylamine, cyclohexylamine, aniline, methyl-phenyl-amine, di- (allyl) -amine or methane, toluene, trimethylsilylamine, trimethylsilyl ether, tetramethylsilane and the like.

It is also possible to directly react the compound of formula II or formula VIII with the transition metal compound of formula VII in the presence of a compound of formula V or IX.

[pi] Complexes of the formula (XIII) in which the [pi] system is cyclic and aromatic (metallocene) can be prepared using the following compounds in a similar manner.

Chain cleaved π complexes are prepared by donor and acceptor insertion methods known to the expert.

Furthermore, according to the invention for the homopolymerization or copolymerization of at least one optionally substituted α-olefin with monomers, the reaction is from 0.5 to 5000, preferably from -60 to + 250 ° C, preferably from 0 to 200 ° C. Metallocene compound, at 1 to 3000 bar, in the presence of a gas, solution, high pressure or slurry, in the presence or absence of saturated or aromatic hydrocarbons, or saturated or aromatic halogeno-hydrocarbons, and in the presence or absence of hydrogen π complex is used as a catalyst so that all monomers per mole of metallocene or π complex are in an amount of 10 ¹ to 10 ¹² and the reaction is also in the presence of Lewis acid, Brønsted acid or Pearson acid or additionally Lewis base It can also be done.

The Lewis acid includes, for example, boranes or alans, and includes both aluminum-alkyl, aluminum halides, aluminum alcoholates, organoborane compounds, boron halides, boric acid esters, or halide substituents and alkyl or aryl or alcoholate substituents. Containing boron or aluminum compounds, and mixtures or triphenylmethyl cations above. Especially preferably, there is a mixture of aluminoxane or aluminum containing Lewis acid and water. In the present knowledge, all acids act as ionizers to form metallocene cations, where charges are compensated by poorly coordinated bulky anions.

In addition, according to the present invention, a reaction product of the ionizing agent with the metallocene compound of formula I may be provided. These can be represented by the formulas (XIa) to (XId).

In the above formula,

Anions represent total bulky anions that are not easily coordinated, and the base is a Lewis base.

Catalysts of formulas (I) and (XIII) that can be used according to the invention may exist in the form of monomers and dimers or oligomers.

It is also possible to use several D / A catalysts simultaneously in order to obtain a specific property profile of the material. Thus, it is also possible to use one or more D / A catalysts in combination with other metallocenes that do not have a D / A bridge.

Examples of non-coordinating anion is easy _{B (C 6 H 5) 4} -, B (C 6 F 5) 4 -, B (CH 3) (C 6 F 5) 3 -, Or bulky aggregate molecular anions of type sulfonates, for example tosylate or triflate, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate, perchlorate, and carborane, for example C ₂ a ^- B ₉ H ₁₂ ^-, or CB ₁₁ H _12. When the anion is present, the metallocene compound can act as a high activity polymerization catalyst even in the absence of aluminoxane. This is especially true when one X ligand is an alkyl group, allyl or benzyl. However, aluminum-alkyl such as (CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ Al, (n- / i-propyl) ₃ Al, (n- / t-butyl) ₃ Al, (i- Butyl) ₃ Al, pentyl-, hexyl- or octyl aluminum-alkyl isomers, or lithiumalkyl, for example methyllithium, benzyllithium or butyllithium, or the corresponding organomagnesium compound, for example Grignard compound, or It may be advantageous to use such metallocene complexes having bulky anions mixed with the organoazin compound. The metal alkylate, on the one hand, moves the alkyl group to the central metal, while on the other hand removes water or catalyst poisons from the reaction medium or monomer in the polymerization reaction. Metal-alkyls of this type can advantageously be used with, for example, aluminoxane cocatalysts to reduce the amount of aluminoxane required. When used, examples of the boron compound from which the anion can be derived include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate , N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (penta Fluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetra Kis (pentafluorophenyl) borate, N, N-dimethyl (2,4,5-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluoro Rophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n -Butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N -Dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and N , N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate, dialkylammonium salts such as di (i-propyl) ammonium tetra Keith (Pentafluoro) Phenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate, trisubstituted phosphonium salts such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) force Phonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tritolylmethyl tetrakis (pentafluorophenyl) borate, triphenylmethyl tetra Phenylborate (trityl tetraphenylborate), trityl tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, tris (pentafluorophenyl) borane, and tris (trifluoromethyl) borane.

The metallocene compounds and π complexes used according to the invention can be isolated as pure materials for use in (co) polymerization. However, they can also be produced and used “in the same reaction system” in a (co) polymerization reactor by methods known to those skilled in the art.

The first and second carbanion CpI and CpII containing the cyclopentadienyl backbone may be the same or different. The cyclopentadienyl backbone can be selected from the group consisting of, for example, cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene. There may be 1 to 4 substituents per cyclopentadiene or fused benzene ring. These substituents may be C ₁ -C ₂₀ -alkyl, for example methyl, ethyl, propyl, isopropyl, butyl or isobutyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl or eicosyl, C ₁ -C ₂₀ -alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, hexoxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, Eicosyloxy, halogen, for example fluorine, chlorine or bromine, C ₆ -C ₁₂ -aryl, for example phenyl, C ₁ -C ₄ -alkylphenyl, for example tolyl, ethylphenyl, (i-) propyl Phenyl, (i-, tert-) butylphenyl or xylyl, halogenophenyl, for example fluorophenyl, chlorophenyl or bromophenyl, naphthyl or biphenylyl, triorganyl-silyl, for example trimethyl Silyl (TMS), ferrocenyl, and D or A as defined above. In addition, the fused aromatic ring can be partially or fully hydrogenated such that only double bonds are shared by both the fused ring and the cyclopentadiene ring. Benzene rings such as indene or fluorene may additionally contain one or two fused benzene rings. In addition, the cyclopentadiene or cyclopentadienyl ring and the fused benzene ring may together contain further fused benzene rings.

The cyclopentadiene skeleton of the anionic form is an excellent ligand of the transition metal, wherein the optionally substituted form of cyclopentadienyl carbanion is to compensate for the positive charge of the central metal in the complex. Individual examples of the carbanion include cyclopentadienyl, methylcyclopentadienyl, 1,2, -dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, indenyl, phenylindenyl, 1,2- Diethylcyclopentadienyl, tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl, β-phenylpropyl-cyclopentadienyl, Tetrahydroindenyl, propyl-cyclopentadienyl, t-butyl-cyclopentadienyl, benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl, trimethylgeryl-cyclopentadienyl, trimethylstannyl- Cyclopentadienyl, trifluoromethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl, 6-membered ring Fluorenyl and indenyl benzo fused to a phase, N, N-dimethylamino-cyclopentadienyl, dimethylphosphino-cyclopentadienyl, methoxy-cyclopentadienyl, dimethylboranyl-cyclopentadienyl, and (N, N-dimethylaminomethyl) -cyclo Pentadienyl.

In addition to the first donor-receptor bond between D and A, which is necessarily present, additional donor-receptor bonds may occur when additional D and / or A is present as a substituent of a specific cyclopentadiene system or as a substituent or moiety of π system Can be formed. All donor-receptor bonds have the reversibility described above. In the case of many D and A, they may be located at various positions among those described above. Thus, the present invention encompasses both the bridged molecular state (Formula Ia and Formula XIIIa) and the unbridged state (Formula Ib and Formula XIIIb). The number of group D may be the same as or different from the number of group A. Preferably CpI and CpII are linked only through one donor-receptor bridge.

In addition to the D / A bridge according to the present invention, there may also be a shared bridge. In this case, the D / A bridge enhances the steric fixation and thermal stability of the catalyst. By changing closed D / A bonds and cleaved D / A bonds, sequence polymers are copolymers of different chemical compositions.

As such, the π complex is characterized by the presence of one or more coordination bonds between donor atom D and acceptor atom A. While both D and A may be substituents of certain π-based πI and πII, or part of the π-based, at least one of D and A is always part of the π-based. Here, the π system is understood to mean the entire π system, optionally fused once or twice. In the following embodiments, D is a part of π-based, A is a substituent of π-based; D is a π-based substituent, and A is part of a π-based; D and A result from the fact that they are part of a particular π system.

The following heterocyclic ring systems in which D or A are part of the ring system can be illustrated as follows.

Important heterocyclic ring systems are labeled (a), (b), (c), (d), (g), (m), (n) and (o), labeled (a), (b) ), (c) and (m) are particularly important.

When one of D and A is a substituent of a bonded ring system, the ring system is a three-, four-, five-, six-, seven- or eight-membered ring system with or without an electric charge and the method described above May be further substituted and / or fused. 5- and 6-membered ring systems are preferred. Particular preference is given to negatively charged cyclopentadienyl systems.

The first and second π systems πI and πII may each correspond to CpI and CpII when one of D and A is a substituent of the ring system, if formed as a ring system.

Possible donor groups include the donor atom D which is an element of group 5, 6 or 7, preferably of group 5 or 6 of the Periodic Table of the Elements (Mendelib), having one or more free electron pairs and a group 5 element The atoms are in a bonded state with substituents, and in the case of a Group 6 element, the donor atoms can be in this state, and the Group 7 donor atoms have no substituents. This may, for example, describe phosphorus P, oxygen O and chlorine Cl as examples of donor atoms, where "substituent" is the aforementioned substituent and "-Cp" is a bond to the cyclopentadienyl containing carbanion. In the formula (I), the arrow represents a coordination bond and the other lines represent electron pairs present.

Suitable receptors are, in particular, the acceptor atom A being an element of group 3 of the periodic table (mendelib), for example boron, aluminum, gallium, indium and thallium, in combination with substituents and lacking electrons.

D and A are joined by coordination bonds, where D is (partially) positively charged and A is (partially) negatively charged.

Thus, donor atom D and donor group are also distinguished from acceptor atom A and acceptor group. Coordination bonds D → A are formed between donor atom D and acceptor atom A. The donor group is a unit consisting of donor atom D, any substituent present and an electron pair present, and thus the acceptor is a unit lacking acceptor atom A, any substituent and electron pair.

The bond between the donor atom or the acceptor atom and the cyclopentadienyl containing carbanion can be interrupted by a spacer group at D-Spacer-Cp or A-Spacer-Cp. In the example of the third formula, = C (R)-is a spacer between O and Cp. Examples of the spacer group include dimethylsilyl, diethylsilyl, di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, di-t-butylsilyl, di-n-hexylsilyl, methylphenylsilyl, ethylmethyl Silyl, diphenylsilyl, di (pt-butylphenylsilyl), n-hexylmethylsilyl, cyclopentamethylenesilyl, cyclotetramethylsilyl, cyclotrimethylenesilyl, dimethylgermanyl, diethylgermanyl, phenylamino, t- Butylamino, methylamino, t-butylphosphino, ethylphosphino, phenylphosphino, methylene, dimethylmethylene (i-propylidene), diethylmethylene, ethylene, dimethylethylene, diethylethylene, dipropylethylene, propylene, Dimethylpropylene, diethylpropylene, 1,1-dimethyl-3,3-dimethylpropylene, tetramethyldisiloxane, 1,1,4,4-tetramethylsilylethylene, diphenylmethylene.

Preferably, D and A are bonded to the cyclopentadienyl containing carbanion without a spacer.

D and A, independently of one another, may be located on the cyclopentadiene (dienyl) ring or on the fused benzene ring or other substituents of CpI and CpII, or on other substituents of πI and πII, respectively. If D or A are plural, they may occupy various positions among those mentioned above.

Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te or substituents on the acceptor atoms B, Al, Ga, In or Tl are for example C ₁ -C _12- (cyclo) alkyl For example methyl, ethyl, propyl, i-propyl, cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, phenyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, and isomers as heptyl, octyl, Nonyl, decyl, undecyl, and dodecyl; Corresponding C ₁ -C ₁₂ -alkoxy groups; Vinyl, butenyl, and allyl; C ₆ -C ₁₂ -aryl, for example phenyl, naphthyl or biphenylyl, and benzyl (they are each halogen, 1 or 2 C ₁ -C ₄ -alkyl groups, C ₁ -C ₄ -alkoxy groups, nitro or May be substituted with a halogenoalkyl group, C ₁ -C ₆ -alkyl-carboxyl, C ₁ -C ₆ -alkyl-carbonyl or cyano (eg perfluorophenyl, m, m'-bis (trifluoro) Methyl) -phenyl, and cognate substituents familiar to those skilled in the art)); Aryloxy group homologs; Indenyl; Halogen, for example F, Cl, Br and I, 1-thienyl, disubstituted amino, for example (C ₁ -C ₁₂ -alkyl) ₂ amino, and diphenylamino, tris- (C _1- C ₁₂ -alkyl) -silyl, NaSO ₃ -aryl, such as NaSO ₃ -phenyl and NaSO ₃ -tolyl, and C ₆ H ₅ -C≡C; Aliphatic and aromatic C ₁ -C ₂₀ -silyl, wherein the alkyl substituents may be octyl, decyl, dodecyl, stearyl or eicosyl, in addition to those mentioned above, and the aryl substituents may be phenyl, tolyl, xylyl, naphthyl or And may be biphenylyl, wherein the substituted silyl group is bonded to a donor atom or a receptor atom via -CH _2- , for example (CH ₃ ) ₃ SiCH _2- , and (C ₁ -C ₁₂₎ having the aryl group above -Alkyl) (phenyl) -amino, (C ₁ -C ₁₂ -alkylphenyl) ₂ amino, C ₆ -C ₁₂ -aryloxy, C ₁ -C ₈ -perfluoroalkyl, and perfluorophenyl. Preferred substituents include C ₁ -C ₆ -alkyl, C ₅ -C ₆ -cycloalkyl, phenyl, tolyl, C ₁ -C ₆ -alkoxy, C ₆ -C ₁₂ -aryloxy, vinyl, allyl, benzyl, perfluoro Phenyl, F, Cl, Br, di- (C ₁ -C ₆ -alkyl) -amino, diphenylamino.

The donor groups are free electron pairs which are localized on N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, and I, of which N, P, O, and S are preferred. Do. Examples of donor groups that may be mentioned include (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (C ₃ H ₇ ) ₂ N-, (C ₄ H ₉ ) ₂ N-, (C ₆ H ₅ ) ₂ N-, (CH ₃ ) ₂ P, (C ₂ H ₅ ) ₂ P-, (C ₃ H ₇ ) ₂ P-, (iC ₃ H ₇ ) ₂ P-, (C ₄ H ₉ ) ₂ P-, (tC ₄ H ₉ ) ₂ P-, (cyclohexyl) ₂ P-, (C ₆ H ₅ ) ₂ P-, CH ₃ O-, CH ₃ S-, C ₆ H ₅ S-,- C (C ₆ H ₅ ) = O, -C (CH ₃ ) = O, -OSi (CH ₃ ) ₃ and -OSi (CH ₃ ) ₂ -t-butyl, where N and P are each 1; Having two free electron pairs, O and S each having two free electron pairs, in the last two examples discussed here, the double bonded oxygen is bonded via a spacer group and a system such as a pyrrolidone ring is also bonded through a spacer, The ring members then act as spacers rather than N.

Receptors are those lacking an electron pair on B, Al, Ga, In or Tl, preferably B or Al, for example (CH ₃ ) ₂ B-, (C ₂ H ₅ ) ₂ B-, H ₂ B-, (C ₆ H ₅ ) B-, (CH ₃ ) (C ₆ H ₅ ) B-, (vinyl) ₂ B-, (benzyl) ₂ B-, Cl ₂ B-, (CH ₃ O) ₂ B-, Cl ₂ Al-, (CH ₃ ) Al-, (iC ₄ H ₉ ) ₂ Al-, (Cl) (C ₂ H ₅ ) ₂ Al-, (CH ₃ ) ₂ Ga-, (C ₃ H ₇ ) ₂ Ga-, ((CH ₃ ) ₃ Si-CH ₂ ) ₂ Ga-, (vinyl) ₂ Ga-, (C ₆ H ₅ ) ₂ Ga-, (CH ₃ ) ₂ In-, ((CH ₃ ) ₃ Si -CH ₂ ) ₂ In- and (cyclopentadienyl) ₂ In- are mentioned.

Donor and acceptor groups which contain chiral centers or in which two substituents together with the D or A atoms form a ring are also possible. Examples of these are There is this.

Preferred donor-receptor bridges between CpI and CpII are as follows, for example.

One or two π-based πI and / or πII may be present as a heterocyclic ring in the form of the ring systems (a) to (r). Here, D is preferably a Group 5 or 6 element of the Periodic Table of the Elements (Mendelib). Here, boron is preferable. Specific examples of such hetero-π-based, in particular heterocyclic, compounds are as follows.

Wherein R and R 'are H, alkyl, aryl or aralkyl such as methyl, ethyl, t-butyl, phenyl or o, o'-di- (i-propyl) -phenyl

Examples of heterocyclic radicals are pyrrolyl, methylpyrrolyl, dimethylpyrrolyl, trimethylpyrrolyl, tetramethylpyrrolyl, t-butylpyrrolyl, di-t-butylpyrrolyl, indolyl, methylindolyl, dimethyl Doryl, t-butylindolyl, di-t-butylindolyl, tetramethylphosphoryl, tetraphenylphosphoryl, triphenylphosphoryl, trimethylphosphoryl, phosphininyl, dibenzophosphoryl (phosphafluorenyl ) And dibenzopyrrolyl.

Preferred donor-receptor bridges between π I and / or π II are, for example, N → B, N → Al, P → B, P → Al, O → B, O → Al, Cl → B, Cl → Al, C ═O → B and C═O → Al, both of the donor-receptor bridges may be part of the hetero-π system, or one atom (donor or acceptor) is part of the π system and the other Or a second atom is a substituent of a particular ring, and one of the rings further contains a hetero atom.

As noted above, the two ligand systems πI and πII can be linked by one, two or three donor-receptor bridges. This is because the formula (Ia) according to the invention contains the D → A bridge described above, however, the additional D → A that is produced since the ligand systems πI and πII may have additional D and A as substituents or hetero-π centers. The number of bridges is zero, one or two. The number of D and A substituents on πI and πII may be the same or different, respectively. The two ligand systems pi and pi can be further covalently bridged (an example of a covalent bridge is described in the spacer group above). However, preference is given to compounds without a covalent bridge, in which [pi] I and [pi] II are bound only via a donor-receptor bridge.

M is a transition metal from the 3, 4, 5 or 6 subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actiniums, examples being Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf , Th, V, Nb, Ta, and Cr. Ti, Zr, and Hf are preferred.

In forming the metallocene structure or the π complex structure, in each case the positive charge of the transition metal M is compensated by the cyclopentadienyl containing carbanion in each case. The positive charge still remaining at the central atom M is typically a further monovalent anion X (two identical or different anions (dianions) ) May be linked to each other), for example offset by monovalent or divalent negative radicals from the same or different linear or branched, saturated or unsaturated hydrocarbons, amines, phosphines, thioalcohols, alcohols or phenols . Simple anions, _{^{e.g., CR 3 -, NR 2 -}} , PR 2 -, OR -, SR - , etc. can be connected by a saturated or unsaturated hydrocarbon or silane bridges, the dia trunnion is formed, the number of the bridge atoms are It may be 0, 1, 2, 3, 4, 5 or 6, with 0 to 4 bridge atoms being preferred, with 1 or 2 bridge atoms being particularly preferred. In addition, the bridge atom may further have a hydrocarbon substituent R in addition to the H atom. Examples of bridges between simple anions include, for example, -CH _2- , -CH ₂ -CH ₂ -,-(CH ₂ ) _3- , CH = CH,-(CH = CH) _2- , -CH = CH- CH ₂ —, CH ₂ —CH═CH—CH ₂ —, —Si (CH ₃ ) ₂ — and C (CH ₃ ) ₂ —. Examples of X include hydride, chloride, methyl, ethyl, phenyl, fluoride, bromide, iodide, n-propyl radical, i-propyl radical, n-butyl radical, amyl radical, i-amyl radical, hexyl radical, i-butyl radical, heptyl radical, octyl radical, nonyl radical, decyl radical, cetyl radical, methoxy, ethoxy, propoxy, butoxy, phenoxy, dimethylamino, diethylamino, methylethylamino, di-t- Butylamino, diphenylamino, diphenylphosphino, dicyclohexylphosphino, dimethylphosphino, methylidene, ethylidene, propylidene, and ethylene glycol dianione. Examples of dianions include 1,4-diphenyl-1,3-butadiendiyl, 3-methyl-1,3-pentadiendiyl, 1,4-dibenzyl-1,3-butadiendiyl, 2,4-hexa Dienediyl, 1,3-pentadienediyl, 1,4-ditolyl-1,3-butadienediyl, 1,4-bis (trimethylsilyl) -1,3-butadienediyl and 1,3-butadienediyl . 1,4-diphenyl-1,3, -butadienediyl, 1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 3-methyl-1 Particular preference is given to, 3-pentadiendiyl, 1,4-ditolyl-1,3-butadienediyl and 1,4-bis (trimethylsilyl) -1,3-butadienediyl. Further examples of dianions include those containing hetero atoms, for example Where the bridge has the meaning defined above. Weak or uncoordinated anions of the type described above are particularly preferred for charge compensation.

Such bulky anionic activators are for example D / A- [pi] complexes, especially D / A metallocenes, such as tris- (pentafluorophenyl) -borane, triphenylborane, triphenylaluminum, Phosphonium or sulfonium salts of trityl tetrakis- (pentafluorophenyl) -borate or N, N-dialkylphenylammonium tetrakis- (pentafluorophenyl) -borate or the corresponding borate, or borate, carborane Activated by reaction with an alkali metal or alkaline earth metal, thallium or silver salt of tosylate, triflate, perfluorocarboxylate (eg trifluoroacetate), or the corresponding acid. D / A metallocenes in which the anionic equivalent X represents alkyl, allyl, aryl or benzyl groups are preferably used. The derivatives may also be selected from D / A metallocenes having other anionic equivalents, such as X = F, Cl, Br, OR, aluminum alkyl, organolithium compounds or Grignard compounds, or zinc- or lead It can be prepared in a "same reaction system" by reacting with alkyl in advance. The reaction product obtained from above can be activated by the borane or borate described above without isolation.

The index n means 0, 1, 2, 3 or 4 depending on the charge of M, preferably 0, 1 or 2. The subgroup metals described above may in fact be from 2 to 6, preferably from 2 to 4 valences / charges, depending on the subgroup to which they belong, and in each case the valences / charges of 2 are compensated by the carbanion of the metallocene compound do. In the case of La ³⁺ , the index n is thus 1, in the case of Zr ⁴⁺ the value of n is 2 and in the case of Sm ²⁺ the value of n is zero.

In order to prepare the metallocene compound of formula (I), at a temperature of -78 ° C to + 120 ° C, preferably -40 ° C to + 70 ° C in an aprotic solvent, Formula II: Formula III, or Formula IV: Formula V, or Formula VI: Formula VII, or Formula VIII: Formula III, or Formula IV: Formula IX, or Formula X: Formula VII: 1: 0.5-2, preferably 1: 0.8-1.2, particularly preferably 1 A compound of Formula II and Formula III, or a compound of Formula IV and Formula V, or a compound of Formula VI and Formula VII, or a compound of Formula VIII and Formula III, or a compound of Formula IV and Formula IX Or reacting a compound of formula (X) with a compound of formula (VII), wherein the alkali metal-X, alkaline earth metal-X ₂ , silyl-X, germanyl-X, stanyl-X or HX compounds are removed or removed. When reacting Formula VIII with Formula III, or Formula IV with Formula IX, or Formula X with Formula VII, an aprotic solvent may not be used when Formula VIII, IX or X is a liquid under reaction conditions. Examples of compounds to be removed or eliminated include TlCl, LiCl, LiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl ₂ , MgBr ₂ , CaCl ₂ , CaF ₂ , trimethylchlorosilane, triethylchlorosilane, tri- (n-butyl) -chlorosilane, triphenylchlorosilane, trimethylchlorogerman, trimethylchlorostannan, dimethylamine, diethylamine, dibutylamine and other compounds that can be predicted by experts from such substitution types.

Thus, compounds of formulas (II) and (IV) are carbanions having a cyclopentadienyl skeleton or a heterocyclic skeleton, which are covalently linked or incorporated as heterocyclic ring members and used in the formation of D / A bridges. Donor groups and cations as relative ions to the negative charge of the cyclopentadienyl skeleton. Compounds of formula (VIII) are uncharged cyclic backbones having from 1 to 3 donor groups used to form D / A bridges, or leaving groups E (R ¹ R ² R ³ ) which can be easily released instead of ionic groups , For example, silyl, germanyl or stanyl groups or hydrogen.

The second component forming the metallocene compound to be used according to the invention, i.e. the compound of the formula III or V, is the same or different from the cyclopentadienyl skeleton of the formula II or IV but instead of 1 to 3 acceptors Carbanion having a cyclopentadienyl skeleton having In a corresponding manner, the compound of formula IX is an uncharged cyclopentadiene skeleton having 1 to 3 receptors and an easily leaving group F (R ¹ R ² R ³ ).

In a very similar manner, the compound of formula VI or X is a starting material with a D → A bond, which is a counter cationic compound or uncharged cyclopentadiene structure of carbanion with a total of one to three D → A bonds, Reaction with a compound of formula VII produces a metallocene compound of formula I.

When the two starting materials, i.e., formula II and formula III, or formula IV and formula V, or formula VI and formula VII, or formula VIII and formula III, or formula IV and IX, or formula X and VII are present together At the same time, a donor-receptor, -D → A-, or spontaneously reacts with complexes with metal cations M, wherein M'X or E (R ¹ R ² R ³ ) X or F (R ⁴ R ⁵ R ⁶ ) X or HX are removed. In the description of the donor-acceptor, the substituents on D and A have been omitted for the sake of brevity.

M 'is a monovalent cation equivalent of an alkali metal or alkaline earth metal, for example Li, Na, K, 1/2 Mg, 1 / 2Ca, 1 / 2Sr, 1 / 2Ba or thallium.

Compounds of formula (XIIIa + b) are prepared analogously to the process described above.

Suitable solvents for the preparation include aprotic, polar or nonpolar solvents such as aliphatic and aromatic hydrocarbons or aliphatic and aromatic halogenated hydrocarbons. Other aprotic solvents known to those skilled in the art are also possible in principle, but too high a boiling point is not preferred due to ease of operation. Representative examples are n-hexane, cyclohexane, pentane, heptane, petroleum ether, toluene, benzene, chlorobenzene, methylene chloride, diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether.

Starting materials of the formulas (II), (III), (IV) and (V) can be prepared by methods analogous to or known in the literature. Thus, for example, commercially available trimethylsilyl-cyclopentadiene is first reacted with butyl-lithium and then with trimethylsilyl chloride to produce bis (trimethylsilyl) -cyclopentadiene as described in J. of Organometallic Chem. (1971), 29 , 227]. This product then reacts with boron trichloride to form trimethylsilyl-cyclopentadienyl-dichloroborane (in a similar manner to J. of Organometallic Chem. (1979), 169 , 327), and finally J. of Organometallic Chem. (1979), 169 , 373, can be reacted with titanium tetrachloride to form dichloroboryl-cyclopentadienyl-titanium trichloride. The last mentioned compound is already a prototype of the compound of formula III, and the last mentioned compound can further react selectively with trimethylaluminum, and two chlorine atoms bonded with boron atoms are Substituted, it proves to be a further compound of formula III. Commercially available cyclopentadienyl thallium is described in J. Chem. Am. Chem. Soc. (1983) 105 , 3882 and Organometallics (1982) 1 , 1591, can be reacted with chlorodiphenylphosphine and further with butyl-lithium to obtain the original form of the compound of formula II. As further described, dimethylstannyl-diphenylphosphine-indene is formed by first reacting indene with butyl-lithium and then with chlorodiphenylphosphine, which may be mentioned as further examples. First reaction with butyl-lithium followed by chloro-butyltin to form the compound described above, followed by further reaction with zirconium tetrachloride to produce diphenylphosphino-indenyl-zirconium trichloride as a representative compound of formula IV. do. Such synthesis and preparation methods are familiar to those skilled in the organometallic and organo elemental chemistry and are published in numerous references, but few are provided by these exemplary methods.

The examples listed below show how to use such heterocyclic precursors and catalysts according to the present invention. Pyrrolyl-lithium (Formula II) is described, for example, in J. Amer. Chem. Soc. (1982), 104 , 2031, can be prepared by reacting pyrrole with butyl-lithium. Trimethylstannyl-phosphol (Formula VIII) is characterized in that 1-phenylphosphol reacts with lithium, followed by aluminum trichloride to form phospholyl-lithium (Formula II), and further with trimethylchlorostannan Trimethylstannyl-phosphole is formed. J. Chem. Soc. Chem. Comm. (1988), 770. This compound can react with titanium tetrachloride to form phospholyl-titanium trichloride (Formula IV).

Gas phase, solution phase, high pressure phase of at least one optionally substituted α-olefin at a pressure of from 0.5 to 5000 bar, preferably from 1 to 3000 bar, at -60 to +250 ° C, preferably 0 to 200 ° C, or In slurry phase homopolymerization and copolymerization processes, the metallocene compounds used according to the invention are particularly suitable as catalysts, and it is possible to carry out the reaction in the presence or absence of saturated or aromatic hydrocarbons, or saturated or aromatic halogeno-hydrocarbons. Do. This polymerization can be carried out discontinuously or preferably continuously. Furthermore, these can be performed by the semibatch method. It is also possible to carry out this method in one or more reactors or reaction zones. If there are a plurality of reaction zones, the polymerization can be carried out under different polymerization conditions. Thus, particularly suitable prepolymers can be formed in one reactor with heterogeneous catalysts for actual (co) polymerization in further reactors. Heterogeneous D / A catalysts on inorganic supports are particularly suitable for the formation of such prepolymers. ¹ to 10 to ¹² moles of (co) monomer per mole of? complex or metallocene compound are reacted. π complex compound or metallocene compound can be used together with a promoter. The quantitative ratio between the? complex or metallocene compound and the promoter is from 1 to 100,000 moles of promoter per mole of? complex or metallocene. For example, a promoter should be understood in the sense of an aluminoxane compound of the formula:

(In the above formula,

R is C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₂ -aryl or benzyl,

n is a number from 2 to 50, preferably 10 to 35)

Mixtures of various aluminoxanes or mixtures of their precursors (aluminum alkyls) mixed with water can be used (in gas, liquid, solid or combined form, for example in the form of crystalline water). In addition, water may be supplied to the (residual) moisture of the polymerization medium of the support, such as monomer or silica gel.

The bond protruding from the square brackets of formula (XII) contains an R group or an AlR ₂ group as an end group of the oligomeric aluminoxane. The aluminoxanes are generally present as a mixture of several of different chain lengths. Microanalysis also shows aluminoxanes of the same structure as cyclic or our form. Aluminoxane is a commercially available compound. In the case of R = CH ₃ , methylaluminoxane (MAO) is referred to.

Further promoters are aluminum-alkyl, lithium-alkyl or organo-Mg compounds such as Grignard compounds or partially hydrolyzed organoboron compounds. Preferred promoters are aluminoxanes.

Activation with a promoter or preparation of bulky uncoordinated or weakly coordinated anions can be carried out in an autoclave or in a separate reaction vessel. Activation can be carried out in the presence or absence of monomers to be polymerized. Activation can be carried out in the presence of an aliphatic or aromatic or halogenated solvent or suspending agent.

The π complex or metallocene compound and aluminoxane can be used either individually or together in homogeneous form and in heterogeneous form on a support. Here, the support material may be inorganic or organic in nature and may be, for example, silica gel, Al ₂ O ₃ , MgCl ₂ , NaCl, cellulose derivatives, starch and polymers such as polyethylene or polypropylene. It is possible to add the? complex compound or metallocene compound first, or first add aluminoxane to the support, and then add other specific components. However, it is equally possible to use aluminoxanes to activate π complexes or metallocene compounds in a homogeneous or heterogeneous form and to add the activated metallocene compounds to the support optionally filled with aluminoxane.

The support material is preferably treated by heating and / or compounding to control the moisture content or OH group concentration to a defined value or to keep it as low as possible. Chemical pretreatment includes, for example, reacting the support with aluminum-alkyl. The inorganic support is typically heated to 100 ° C. to 1000 ° C. for 1 to 100 hours before use. The surface area of the inorganic support, in particular silica (SiO ₂ ), is from 10 to 1000 m ² / g, preferably from 100 to 800 m ² / g. The particle size is 0.1 to 500 micrometers, preferably 10 to 200 micrometers.

The olefins to be reacted by homopolymerization or copolymerization are for example ethylene, propylene. But-1-ene, pent-1-ene, hex-1-ene, oct-1-ene, 3-methyl-but-1-ene, 4-methyl-pent-1-ene, 4-methyl-hex- 1-en and isooctene.

The olefin may further be substituted by, for example, phenyl, substituted phenyl, halogen, esterified carboxyl groups or acid anhydride groups, and compounds of this type are, for example, styrene, methylstyrene, chlorostyrene, fluorostyrene , 4-vinyl-biphenyl, vinyl-fluorene, vinyl-anthracene, methyl methacrylate, ethyl acrylate, vinylsilane, trimethyl-allylsilane, vinylchloride, vinylidene chloride, tetrafluoroethylene, vinylcarbazole, Vinylpyrrolidone, vinylether and vinyl esters. Also possible according to the invention are ring-opening polyaddition reactions, for example lactones (eg ε-caprolactone or δ-valenolactone), or lactams (eg ε-caprolactam) . Preferred monomers are ethylene, propylene, butene, hexene, octene and methyl methacrylate.

According to the present invention, homopolymerization or copolymerization using a π complex or metallocene compound, or polyaddition reaction is carried out adiabatic or isothermal. High pressure method in autoclave or tube reactor, solution method and also bulk polymerization, slurry phase method in stirred reactor or loop reactor, and gas phase method, and the slurry, solution and gas phase pressures do not exceed 65 bar. All these methods have been known for a long time and are familiar to professionals. As an advantage of the π complex or metallocene compound according to the present invention, by the choice of substituents, both of them can be prepared with soluble π complex or metallocene compound optionally used for the support, and insoluble π complex or metallocene compound. Is there. The soluble π complex and the metallocene compound use the high pressure method and the solution method, and the heterogeneous metallocene compound uses the slurry phase and the gas phase.

The (co) polymers that can be prepared according to the invention have the characteristics of high crystallinity and optimum melting range. This is achieved by low branching in the case of polyethylene and high stereoregularity (isotactic or syndiotactic) in the case of polymers of olefins having three or more C atoms. Copolymers are characterized by high regularity in the incorporation of comonomers. Examples of such polymers are high density linear polyethylene (HDPE), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), i- or s-polybutene or -polyhexene, polyoctene, linear low density copolymers, eg Ethylene with C ₃ -C ₈ -α-olefins (linear low density polyethylene LLDPE), ie ethylene / propylene, ethylene / butylene, ethylene / hexene and ethylene / octene, and also for example propylene / butylene , Propylene / hexene and others. Preferred are comonomers HDPE, LLDPE, iPP and sPP with butylene, hexene or octene.

Π complexes, in particular metallocene compounds, which can be used according to the invention, allow limited cleavage of two beta-shaped cyclopentadienyl backbones due to donor-receptor bridges, thereby allowing controlled selectivity, controlled molecular weight distribution in addition to high activity And uniform incorporation of the (co) monomer. Due to the limited beak-shaped cleavage, space is created for bulky (co) monomers. In addition, the high uniformity in molecular weight distribution is due to the constant polymerization by insertion and to occur at a defined site (single catalyst).

The molecular weight distribution can be modified (expanded) in a controlled manner using multiple D / A catalysts simultaneously to obtain a specific property profile of the material. Therefore, it is also possible to use one or more D / A catalysts in combination with other metallocenes having no D / A bridge at all.

The D / A structure can affect over-stabilization of the catalyst up to high temperature, so that the catalyst can be used even in the high temperature range. Possible thermal decomposition of the donor-receptor bonds is reversible and gives particularly high performance catalytic properties as a result of this self-organization and self-recovery mechanism. The D / A metallocene structure according to the invention allows, for example, the formation of some degree of defect-free polyethylene that cannot be achieved with conventional catalysts. Thus, the ethene polymer may exceptionally have a high melting point, for example, greater than 135 ° C. to 160 ° C. (maximum value of the DSC curve). The linear polyethylene obtained directly by the polymerization method is a compound having a melting point of 140 to 160 ° C. (maximum value of the DSC curve), preferably 142 to 160 ° C., particularly preferably 144 to 160 ° C., particularly preferably 146 to 160 ° C. It is preferable to include. This particularly corresponds to compounds which can be prepared with the claimed metallocene compounds. Compared with known polyethylenes, these new high melting point polyethylenes exhibit, for example, improved mechanical properties and thermal warping performance (sterilizing ability in medical applications) and as a result have been shown to be, for example, not so far seen as possible in polyethylene. This opens up the possibility of applications that have so far been met only in very regular polypropylene. Another property is high heat of fusion and high molecular weight of PE.

Within a wide temperature range, the PE molecular weight is reduced by increasing the polymerization temperature without significantly reducing activity and without leaving the total range of industrially beneficial PE high molecular weight and PE high melting point.

For the preparation of isotactic polyolefins, for example, at the 2 position or at the 4, 5, 6 or 7 position, for example, alkyl, aryl and / or silyl substituents or benzo-fusion structures can be further added to provide molecular weight and iso Particularly suitable are quasi- rac -bis (indenyl) metallocenes with D / A bridges which can increase isotacticity and melting point. However, D / A bis (cyclopentadienyl) -metallocenes with similar symmetrical (3,3 ') substitution patterns are also possible.

D / A-Bridge (cyclopentadienyl) (fluorenyl) -metallocene or (cyclopentadienyl) (3,4-disubstituted cyclopentadienyl) -metallocene is for example syndiotactic It is quite suitable for the production of polyolefins.

In addition, suitable symmetric metallocene compounds and π complexes which can be used according to the invention affect the stereospecific (isotactic, syndiotactic) polymerization of the α-olefins of three carbon atoms, but above the stated temperatures Has been found to induce significantly nonspecific (atactic) linkages of monomer units of the same monomer. This phenomenon is not yet fully understood, but it may be consistent with the observation that coordination bonds overlapped by ionic bonds, such as donor-receptor bonds in the metallocene compound according to the present invention, show an increase in reversibility at high temperatures. In addition, for example, in the case of ethylene propylene copolymerization, when the same amount of two comonomers are used, a copolymer containing a lot of propylene is formed at a low copolymerization temperature, whereas at high temperature, ethylene is finally predominant. The propylene content decreases with increasing polymerization temperature until a polymer containing LLDPE is formed. The reversible dissociation and coupling of the D / A structures and the rotation of the π skeletons relative to each other, which will be possible as a result, can be shown as follows.

And

Another useful property of the D / A- [pi] complexes according to the invention, for example D / A metallocene compounds, is the possibility of self activation, in particular dianion. In the case of derivatives, expensive catalysts may not be used.

In this case, in the cleaved form of the D / A- [pi] complex, for example the D / A metallocene compound, the receptor atom A binds the X ligand and, for example, binds to one side of the dianion to form an amphoteric metal. The Rosen structure forms a positive charge in the transition metal, while acceptor atom A takes a negative charge. Such self activation can be intramolecular or intermolecular. This can be explained by the two X ligands being preferably linked together to form a chelate ligand, ie, butadienediyl derivative.

And

The binding site between the transition metal M and H, or substituted or unsubstituted C, the substituted C of the butadienyl dianion shown in the illustrated formula is then the olefin insertion site for polymerization.

Claims (17)

In the presence of an organometallic catalyst that can be activated by a promoter, including using a metallocene compound of formula I or a π complex, or a π complex, in particular a metallocene compound, as an organometallic catalyst And a method for producing a high melting point polyolefin by homopolymerization or copolymerization of one or more monomers from the group consisting of α-olefins having two or more carbon atoms. <Formula I> (In the above formula, CpI and CpII are two identical or different carbanions having a cyclopentadienyl containing structure, wherein one to all H atoms are monosubstituted to all substituted by halogen, or monosubstituted to trisubstituted by phenyl, or Linear or branched C ₁ -C ₂₀ -alkyl which may be substituted or substituted by vinyl; C ₆ -C ₁₂ -aryl; halogenoaryl having 6 to 12 carbon atoms; silyl, trimethylsilyl or ferrocenyl May be substituted by the same or different radicals from the group consisting of organometallic substituents, such as one or two may be substituted with D and A, D is a donor atom which may have additional substituents and has at least one free electron pair in its bonded state, A is a receptor atom which may have additional substituents and lacks an electron pair in its bound state, Where D and A are connected by reversible coordination bonds such that the donor has a (partially) positive charge and the receptor has a (partially) negative charge, M is a transition metal of the III, IV, V or VI subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actinides, X is a monovalent anion equivalent, n is 0, 1, 2, 3 or 4 depending on the charge of M) <Formula XIII> (In the above formula, πI and πII are differently charged or electrically neutral π systems, which can be fused with one or two unsaturated or saturated five or six membered rings, D is a substituent of πI or a part of the π system of πI and a donor atom having at least one free electron pair in its bonded state, A is a substituent of πII or a part of π system of πII and a receptor atom lacking an electron pair in its bound state, Wherein D and A are linked by reversible coordination bonds such that the donor is (partially) positively charged and the receptor is (partially) negatively charged, and at least one of D and A is of Part and D and A may have substituents, Each π system and each fused ring system may contain one or more D or A, or D and A, In unfused or fused form of π I and π II, one to all H atoms of the π system may be monosubstituted to fully substituted by halogen, or monosubstituted to trisubstituted by phenyl, or vinyl Linear or branched C ₁ -C ₂₀ -alkyl which may be monosubstituted to trisubstituted by; C ₆ -C ₁₂ -aryl; Halogenoaryl having 6 to 12 carbon atoms; And independently from each other by the same or different radicals from the group consisting of organometallic substituents such as silyl, trimethylsilyl or ferrocenyl, or one or two may be substituted by D and A, The A coordination bond is (i) both D and A are part of a particular π- or fused ring system, or (ii) D or A is part of the π-system, in each case the remainder is an unfused π- or fused Or (iii) D and A are both substituents and one or more additional D or A or both can be formed between D and A, which are part of a π or fused ring system, M and X are as defined above, n is 0, 1, 2, 3 or 4 depending on the charge of M and the charges of pi and pi. The method of claim 1, wherein the metallocene compound or π complex is used as a catalyst in an amount of 10 ¹ to 10 ¹² moles of monomer per mole of metallocene compound or π complex. The process of claim 1 wherein the reaction is carried out in the presence or absence of a solvent from the group consisting of saturated or aromatic hydrocarbons, or saturated or aromatic halogeno-hydrocarbons. The method of claim 1, wherein the carbanion CpI and CpII in the metallocene compound or π complex, or πI in the π system are cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene Cyclopentadienyl skeleton from the group consisting of: C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, halogen, C ₆ -C ₁₂ -aryl, halogenophenyl, of the range defined in claim 1 Wherein 1 to 4 substituents from the group consisting of D and A are present per one cyclopentadiene or fused benzene ring and the fused aromatic ring can be partially or fully hydrogenated. The metallocene compound of claim 1, wherein in the metallocene compound an element from the group consisting of N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, and I is present as donor atom D. Way. The method of claim 1, wherein in the metallocene compound, an element from the group consisting of B, Al, Ga, In, and Tl is present as acceptor atom A. 7. The compound according to claim 1, wherein in the metallocene compound or π complex, N → B, N → Al, P → B, P → Al, O → B, O → Al, Cl → B, Cl → Al, C = O And there is a donor-receptor bridge from the group consisting of → B and C═O → Al. The method of claim 1, wherein in the metallocene compound, M represents Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf, Th, V, Nb, Ta, or Cr. The process according to claim 1, wherein the metallocene compound or [pi] complex is used as catalyst system with aluminoxane, borane or borate. The amphoteric metal of claim 1, wherein after cleavage of the D / A bond due to self activation, receptor atom A binds to X ligand, resulting in positive charge at transition metal M and negative charge at receptor atom A Claims 1 to claim 1, which form a rosene complex structure or a π complex structure, wherein the X ligand represents H, or substituted or unsubstituted C, and olefin insertion occurs at the bond with the transition metal M resulting in polymerization. Using a potential product due to self activation of a metallocene compound or a π complex. The method of claim 1, wherein the π complex as claimed in claim 1, wherein one of D or A atoms is part of a π-based ring to which it is bonded. The process according to claim 1, wherein the ionization agent is a reaction product of a metallocene compound according to formula (I) or formula (XIII) or [pi] complex. <Formula XIa> <Formula XIb> <Formula XIc> <Formula XId> (In the above formula, Anions represent total bulky anions that are not easily coordinated, and the base is a Lewis base) The process of claim 1, wherein HDPE, LLDPE, iPP and sPP with butylene, hexene or octene are prepared with comonomers. Linear polyethylene having a melting point of 140 to 160 ° C. (maximum value of the DSC curve), which may be prepared by the method as claimed in claim 1. The process of claim 1, wherein the metallocene compound or π complex is used as catalyst system in combination with aluminoxane, borane or borate, additional promoter and / or metal-alkyl. The amphoteric metal of claim 1, wherein after cleavage of the D / A bond due to self activation, receptor atom A binds to X ligand, resulting in positive charge at transition metal M and negative charge at receptor atom A Forms a rosene complex structure or a π complex structure, wherein the X ligand represents H, or substituted or unsubstituted C, olefin insertion takes place at the bond with the transition metal M to polymerize, and two X ligands are linked A method of using a translocation product due to self activation of a metallocene compound or a π complex as claimed in claim 1, which forms a chelate ligand. The process of claim 1 wherein the π complex as claimed in claim 1 wherein D is part of a π-based ring bonded.