RU2007213C1 - Catalyst for propylene polymerization - Google Patents

Abstract

FIELD: catalysts for polymerization. SUBSTANCE: catalyst has cyclopentadienyl-compound of the general formula 1 (R¹), where M - zirconium or germanium; Y - silicon or germanium; R¹-methyl or tert. -butyl. Position R² in cyclopentadienyl-ring and its type correspond configuration, in which any symmetry plane is absent involving M; R³ - methyl or cyclotetramethylene; n and q - are whole numbers 0-4. When n= q= O or n= q= 4, alumineoxane of the general formula 11 (

) or 111 (

) is excluded, where

Description

 The invention relates to catalysts for stereoregular polymerization of an olefin.

A known catalyst for the polymerization of olefins containing a cyclopentadienyl transition metal compound of the formula (cyclopentadienyl) 2 VeRHal, where R is cyclopentadienyl or C ₁ -C ₆ alkyl, or halogen, preferably chloride;
Me is a transition metal, preferably titanium or zirconium;
Hal is halogen, preferably chloride, and an aluminoxane of the formula Al ₂ OR ₄ (Al (R) -O) n or (Al (R) -O) n + 2, where n = 0-20, R is methyl or ethyl, preferably methyl.

 The disadvantages of the known catalyst include its insufficiently high activity and selectivity.

 The aim of the invention is to increase the activity and selectivity of the catalyst in relation to the formation of otactic polypropylene.

M

(I) где М - цирконий или гафний,
Y - кремний или германий.The specified goal, according to the invention, is achieved by the described catalyst for the polymerization of propylene to obtain stereoregular polypropylene containing a cyclopentadienyl transition metal compound of the formula: R $\genfrac{}{}{0ex}{}{\text{2}}{\text{2}}$ Y

M

(I) where M is zirconium or hafnium,
Y is silicon or germanium.

)_m-OAlR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ (II) или

где m= 13,3, R³ - метил, при молярном соотношении алюминий: переходный металл 5000-20000.R _n ¹ -C ₅ H _4-n and R _q ¹ -C ₅ H _4-q represents an unsubstituted or substituted cyclopentadienyl group; n and q represent an integer from 0 to 4, but cases where n = q = 0 and n = q = 4 are excluded; R ¹ is methyl or tert. butyl, and the position of the element R ¹ in the cyclopentadienyl ring and its type corresponds to a configuration in which there is no plane of symmetry, including M; R ² is methyl or cyclotetramethylene, and aluminoxane of the formula: R $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ Al- (O

) _m -OAlR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ (Ii) or

where m = 13.3, R ³ is methyl, with a molar ratio of aluminum: transition metal of 5000-20000.

 Compound (I) of the present invention is a new zirconium or hafnium compound containing a bidentate ligand with bisubstituted cyclopentadienyl rings, which has a bridging structure. This compound includes a racemic form and a meso form depending on the spatial configuration of the substituents in the two cyclopentadienyl rings and may have any of these structures. In addition, compounds obtained by mixing the two forms in arbitrary proportions also fall within the scope of this invention.

 In the zirconium or hafnium compound of the present invention, element Y in the formula (1) is silicon or germanium. The number of substituents in the corresponding cyclopentadienyl rings can be any number from zero to 4, but at least one of the cyclopentadienyl rings must have a substituent (s), and the case where both cyclopentadienyl rings have 4 substituents is excluded. The corresponding RI elements may have the same or different meanings and are methyl or tert-butyl.

The corresponding elements of R ² are methyl or cyclotetramethylene.

 As transition metal compounds, zirconium compounds are used: dimethylsilyl bis / methylcyclopentadienyl / zirconium chloride; diphenylsilyl bis (methylcyclopentadienyl) zirconium dichloride; cyclotrimethylene silyl bis (methylcyclopentadienyl) zirconium dichloride; cyclotetramethylene silyl bis (methylcyclopentadienyl) zirconium dichloride; cyclopentamethylene silyl bis (methylcyclopentadienyl) zirconium dichloride; dimethylsilyl bis (methylcyclopentadienyl) zirconium dibromide; methyl dimethylsilylbis (methylcyclopentadienyl) zirconium chloride; dimethyl dimethylsilylbis (methylcyclopentadienyl) zirconium; diphenyl-dimethylsilylbis (methylcyclopentadienyl) zirconium; dimethylsilyl bis (ethylcyclopentadienyl) zirconium dichloride; dimethylsilyl bis (isopropylcyclopentadienyl) zirconium dichloride; dimethylsilyl bis (tert-butylcyclopentadienyl) zirconium chloride; dimethylsilyl bis (phenylcyclopentadienyl) zirconium dichloride; dimethylsilibis dichloride (trimethylsilylcyclopentadienyl) zirconium; dimethylsilyl (cyclopentadienyl) methylcyclopentadienyl zirconium dichloride; diphenylsilyl (cyclopentadienyl)) methylcyclopentadienyl) zirconium dichloride; cyclotetramethylene silyl (cyclopentadienyl) methylcyclopentadienyl) zirconium dichloride; dimethyl-dimethylsilyl (cyclopentadienyl)) methylcyclopentadienyl) zirconium; diphenyl-dimethylsilyl (cyclopentadienyl)) methylcyclopentadienyl) zirconium; dimethylsilyl dichloride (cyclopentadienyl)) isopropylcyclopentadienyl) zirconium; dimethylsilyl (cyclopentadienyl) dichloride) tert-butylcyclopentadienyl) zirconium; dimethylsilyl dichloride (cyclopentadienyl)) phenylcyclopentadienyl) zirconium; dimethylsilyl (cyclopentadienyl) dichloride) trimethylsilyl cyclopentadienyl) zirconium; dimethylsilyl (methylcyclopentadienyl) phenylcyclopentadienyl) zirconium dichloride.

 Dimethylsilyl dichloride (methylcyclopentadienyl)) tert-butylcyclopentadienyl) zirconium; dimethylhermylbis dichloride (methylcyclopentadienyl) zirconium, dimethylgermylbis dichloride (tert-butylcyclopentadienyl) zirconium; dimethylhermylbis (phenylcyclopentadienyl) zirconium dichloride; dimethylgermyl (cyclopentadienyl) methylcyclopentadienyl) zirconium dichloride; dimethylgermyl dichloride (cyclopentadienyl)) phenylcyclopentadienyl) zirconium; dimethylgermyl dichloride (cyclopentadienyl)) tert-butylcyclopentadienyl) zirconium; dimethylsilyl dichloride (methylcyclopentadienyl)) dimethylcyclopentadienyl (zirconium; dimethylhermyl dichloride (methylcyclopentadienyl ((dimethylcyclopentadienyl (zirconium, etc.)

 Hafnium Compounds: Dimethylsilyl bis (methylcyclopentadienyl) hafnium dichloride; cyclotrimethylene silyl bis (methylcyclopentadienyl) hafnium dichloride; cyclotetramethylene silyl bis (methylcyclopentadienyl) hafnium dichloride; cyclopentamethylene silyl bis (methylcyclopentadienyl) hafnium dichloride; dimethylsilyl bis (methylcyclopentadienyl) hafnium dibromide; methyl dimethylsilyl bis) methylcyclopentadienyl) hafnium chloride; dimethyl dimethylsilylbis (methylcyclopentadienyl) hafnium; diphenyl-dimethylsilylbis (methylcyclopentadienyl) hafnium dimethylsilylbis (ethylcyclopentadienyl) hafnium dichloride; dimethylsilyl bis (isopropylcyclopentadienyl) hafnium dichloride; dimethylsilyl bis (tert-butylcyclopentadienyl) hafnium dichloride; dimethylsilyl bis (phenylcyclopentadienyl) hafnium dichloride; dimethylsilyl bis (trimethylsilycyclopentadienyl) hafnium dichloride; dimethylsilyl (cyclopentadienyl) dichloride) methylcyclopentadienyl (hafnium; diphenylsilyl (cyclopentadienyl) dichloride) methylcyclopentadienyl) hafnium; cyclotetramethylene silyl (cyclopentadienyl) methylcyclopentadienyl) hafnium dichloride; dimethyl-dimethylsilyl (cyclopentadienyl)) methylcyclopentadienyl (hafnium; diphenyl-dimethylsilyl (cyclopentadienyl)) methylcyclopentadienyl) hafnium; dimethylsilyl dichloride (cyclopentadienyl)) isopropylcyclopentadienyl) hafnium; dimethylsilyl (cyclopentadienyl) dichloride) tert-butylcyclopentadienyl (hafnium; dimethylsilyl (cyclopentadienyl) dichloride) phenylcyclopentadienyl) hafnium; dimethylsilyl dichloride (cyclopentadienyl)) trimethylsilyl cyclopentadienyl) hafnium; dimethylsilyl dichloride (methylcyclopentadienyl)) phenylcyclopentadienyl) hafnium; dimethylsilyl (methylcyclopentadienyl) dichloride) tert-butylcyclopentadienyl (hafnium; dimethylgermyl bis (methyl cyclopentadienyl) hafnium dichloride dimethylgermyl dichloride (cyclopentadienyl)) phenylcyclopentadienyl) hafnium; dimethylgermyl dichloride (cyclopentadienyl)) tert-butylcyclopentadienyl) hafnium; dimethylsilyl (methylcyclopentadienyl) dimethylcyclopentadienyl) hafnium dichloride; dimethylgermyl dichloride (methylcyclopentadienyl) dimethylcyclopentadienyl) hafnium, etc.

)_m-OAlR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ _(II)

в которых R³ - метил, m = 13,3. Эти соединения можно получить путем добавления триалкилалюминия к углеводородной суспензии соединения, содержащего адсорбированную воду, или соли, содержащей воду кристаллизации, такого как гидрат сульфата меди, гидрат сульфата алюминия и т. д. с последующим взаимодействием смеси.The zirconium or hafnium (I) compounds of the present invention are characterized by very high olefin polymerization activity in the presence of aluminoxane and are useful compounds as a component of the polymerization catalyst. Aluminoxane, which is one of the components of the catalyst used in the polymerization, is an organoaluminum compound expressed by formula (II) or formula (III) R $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ Al- (O

) _m -OAlR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ _(Ii)

in which R ³ is methyl, m = 13.3. These compounds can be prepared by adding trialkyl aluminum to a hydrocarbon suspension of a compound containing adsorbed water, or a salt containing crystallization water, such as copper sulfate hydrate, aluminum sulfate hydrate, etc., followed by reaction of the mixture.

 The olefins used for the polymerization using the catalyst of the present invention are a-olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc., as well as mixtures of two or more types of olefins. In addition, the a-olefins mentioned above may also be copolymerized with ethylene. Further, this catalyst is effective for copolymerization of a-olefins with dienes having conjugated double bonds, or with dienes having non-conjugated double bonds, such as butadiene, 1,4-hexadiene, 1-4-pentadiene, 1,7-octadiene and t e. styrene or cyclic olefins such as cyclopropene, cyclobutene, norbornene, dicyclopentadiene, etc.

 As for the polymerization method used in accordance with the present invention, it may be liquid phase polymerization or gas phase polymerization. As for the polymerization solvent for liquid-phase polymerization, hydrocarbons capable of dissolving both components of the zirconium or hafnium compound and aluminoxane, and more specifically aromatic hydrocarbons such as benzene, toluene, ortho-xylene, methaxylene, paraximol, can be used as such. , ethylenebenzene, butylbenzene, mesitylene, naphthalene, etc., with the use of toluene and xylene being preferred.

 In addition, even if solvents are used that are unable to dissolve the components of the zirconium compound or the hafnium and aluminoxane compounds, further polymerization is possible during the preliminary polymerization in aromatic hydrocarbons.

 Examples of such solvents are aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and. etc., alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, etc., petroleum fractions such as gasoline, kerosene, gas oil, etc. Among these compounds, aliphatic hydrocarbons are preferred. In addition, liquefied olefins themselves can be used, such as liquefied propylene, liquefied butene-1, etc.

As for the components of the catalyst, a mixture of components of a zirconium compound or a compound of hafnium and aluminoxane obtained by preliminary mixing of all components may be supplied to the reaction system, or the same components may be introduced separately into the reaction system. In any of these cases, the concentration and molar ratio of both components in the reaction system are not particularly limited, but the concentration of transition metals should preferably be in the range of 10 ^-3 to 10 ^-10 mol / L, and the molar ratio of AI and M should preferably be 100 or more, in particular 1000 or more.

The pressure of the olefin in the reaction system does not have a specific limitation, but it is preferable that it be in the range from atmospheric pressure to 50 kg / cm ² . The polymerization temperature also has no particular limitation, but it is usually in the range of ^about -50 to +230 ^C, preferably from ^-30 to 100 ° ^C. Regulation of the molecular weight during the polymerization time may, for example, by selecting the temperature or input hydrogen gas.

 Example 1. Dimethylsilyl bis (methylcyclopentadienyl) zirconium dichloride.

In this example, all reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent used is pre-dried. In a 200 ml glass reaction vessel, dimethylbis (methylcyclopentadienyl) silane) 3.5 g 16 mmol) is dissolved in tetrahydrofuran (50 ml), after which a solution of n-butyllithium (1.6 M) M is gradually added dropwise to the above solution. mol / l in hexane (23 ml) under ice cooling and the mixture was stirred at room temperature for 2 hours, to obtain a yellow transparent liquid [Li ₂ [Me ₂ Si / MeC ₅ h _3/2]).

In a glass reaction vessel of a capacity of 50.0 ml zirconium tetrachloride (3.5 g, 15 mmol) was cooled to ^-78 ° C, followed by adding tetrahydrofuran (200 ml), whereupon to this mixture at -78 ^{° C} was added dropwise the resulting above a yellow transparent liquid, stirred at room temperature for 15 h, the solvent was distilled off from a yellow-orange solution containing a white precipitate, methylene chloride (200 ml) was added, and then diluted hydrochloric acid (100 ml) under ice cooling, two layers were separated by drying a layer of methylene chloride over anhydrous sodium sulfate is removed, methylene chloride is distilled off, pentane is added, the resulting solid is filtered off to obtain a pale green solid (2.87 g) and the solid is recrystallized from hot heptane (400 ml), resulting in a yellowish off-white crystals (2.02 g). The physical properties of this compound are given below. In addition, infrared spectra were determined by the method using KBr, and ^I H-NMR spectra were determined using CDCl ₃ as a solvent.

The value of elemental analysis:
Calculated Value (%): C 44.66 H 4.82
The obtained value (%): C 45.02 N 4.91
PRI me R 2. Polymerization.

Purified toluene (500 ml), methylaluminoxane, manufactured by Toyo Staufer Chemical Company, LMT, are fed sequentially into a 1.5 L SUS autoclave, well purged with nitrogen gas. m. 770) (4.0 mmol) dichloride and dimethylsilylbis (methylcyclopentadienyl) zirconium, after which the temperature was raised ^to 30 ° C, continuously feeding propylene so as to keep the total pressure at 3 kg / cm ² G and polymerization was carried out for 2 hours, after which the decomposition of the catalyst components is carried out using methanol and the resulting polypropylene is dried to form isotactic polypropylene (130 g). The activity of the catalyst is 142 kg / g Zr h and its molecular weight is 9400.

 PRI me R 3. Polymerization.

Purified toluene (100 ml), methylaminoxane manufactured by Toyo Staufer Chemical Company, LMT (mol. M. 770) (4.0 mmol) and dichloride are fed sequentially into a 1.5 L SUS autoclave, well purged with nitrogen gas. dimethylsilylbis (methylcyclopentadienyl) zirconium (0.005 mmol), and then the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 1 kg / cm ² G, and polymerized for 10 minutes and then feeding of propylene was stopped remove the remaining propylene, add purified hex al (1000 ml), the temperature was raised to 30 ° ^C was continuously fed propylene to maintain the total pressure of 3 kg / cm ^2, and polymerized for 2 hours, whereupon the decomposition of the catalyst component with methanol, and the resultant polypropylene was dried , which allows to obtain isotactic polypropylene (125 g). The activity of the catalyst 137 kg / g Zr h

 Comparative example 1.

 Polymerization.

 The procedure described in Example 2 is repeated, except that dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride is replaced by dimethylsilylbis) cyclopentadienyl) zirconium dichloride to produce atactic polypropylene (29 g). The activity of the catalyst is 33 kg / g Zr h and its molecular weight is 5300.

 Comparative example 2. Polymerization.

 The procedure described in Example 2 is repeated except that dimethylsilyl bis (methylcyclopentadienyl) zirconium dichloride is replaced with bis (methyl tert-butylcyclopentadienyl (zirconium) dichloride to produce atactic polypropylene (2.6 g). Catalyst activity 2.9 kg / g Zr h

 Comparative example 3. Polymerization.

Purified toluene (500 ml), methylaluminoxane manufactured by the company (Toyo Staufer Chemical Company, lmt. (Mol. 909), (6.3 mmol) are successively fed into a 1.5 L SUS autoclave, well purged with nitrogen gas. ) dichloride and bis (methylcyclopentadienyl) zirconium (0.02 mmol), after which the temperature was raised ^to 50 ° C while continuously supplying propylene into the mixture so as to keep the total pressure of 8 kg / cm ² and the polymerization was carried out for 4 h, after which the decomposition of the catalyst components is carried out using methanol and dried Polypropylene would be formed, which enables to obtain atactic polypropylene (220 g)
The activity of the catalyst 30 kg / g Zr h

 Example 4. Dimethylsilyl (cyclopentadienyl)) methylcyclopentadienyl) zirconium chloride. All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process.

In a 200 ml glass reaction vessel, dimethyl (cyclopentadienyl) methylcyclopentadienyl) silane (3.4 g 17 mmol) is dissolved in pentane (50 ml), after which a solution (24 ml) of n-butyllithium is slowly added dropwise to this solution ( 1.6 M) under ice cooling, this mixture was stirred at room temperature for 2 hours, the solvent was distilled off to give a white solid [Li ₂ [Me ₂ Si / C ₅ H ₄ // Me-C ₅ H ₃ /], after whereupon tetrahydrofuran (50 ml) is added to it, which makes it possible to obtain a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (4.0 g 17 mmol) to ^-78 ° C after which was added tetrahydrofuran (200 mL), then slowly added dropwise at -78 ^{° C} a yellow transparent liquid obtained above, stir this mixture at room temperature for 1 h, heat it under reflux for one hour, leave it to cool, remove the solvent from a pale yellow solution containing a white precipitate, add methylene chloride (200 ml) and then dilute chlorine hydrochloric acid (100 ml), while cooling with ice, the liquid is separated off, the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added, the formed solids are filtered off, which allows to obtain a pale green solid (2.44 g) and recrystallized from hot heptane (400 ml) to form pale yellow crystals (1.18 g). The physical properties of this compound are given below. In addition, infrared spectra were determined in accordance with the KBr method, and 1H-NMR spectra were determined using CDCl ₃ as solvent.

The value of elemental analysis:
Calculated Value (%): C 43.08 H 4.45
The obtained value (%): C 42.86, H 4.49.

 PRI me R 5. Polymerization.

Purified toluene is successively added to a 1.5 L SUS autoclave, well purged with nitrogen gas. (500 ml), methylaluminoxane manufactured by (Toyo Steufer chemical company, lmt. "(Mol. 770) (4.0 mmol) and dimethylsilyl dichloride (cyclopentadienyl (methylcyclopentadienyl) zirconium (0.005 mmol), after which the temperature is raised to 30 ^° C and propylene is continuously fed in order to maintain a total pressure of 3 kg / cm ² G, and polymerization is carried out for 2 hours, then, after completion of the reaction, the catalyst components are decomposed with methanol and the resulting polypropylene is dried to obtain isotactic polyprop ilene (70 g). The activity of the catalyst is 77 kg / g Zr h. Its mol. m. 6600.

 PRI me R 6. Dimethylsilyl (cyclopentadienyl)) tert-butylcyclopentadienyl) zirconium chloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is pre-dried before being used in the process. In a 200 ml glass reaction vessel, dimethyl (cyclopentadienyl)) tert-butylcyclopentadienyl) silane (5.1 g 21 mmol) in pentane (50 ml) is dissolved, after which a solution (29 ml) of n-butyl lithium (1) is slowly added dropwise to this solution. , 6 M) in hexane under ice-cooling, the mixture is stirred at room temperature for 2 hours, the solvent is distilled off to obtain a white solid [Li ₂ / Me ₂ Si / C ₅ H ₄ // t-Bu-C ₅ H ₃ /// and add tetrahydrofuran (50 ml), which allows you to get a transparent yellow liquid.

In a glass vessel reatsionnom 500 ml cooled zirconium tetrachloride (5.0, 21 mmol) to ^-78 ° C after which was added tetrahydrofuran (200 ml) was slowly added dropwise the above obtained clear yellow liquid at the temperature of -78 ^C. This mixture is stirred at room temperature for 2 hours, heated under reflux for 2 hours, left to cool, the solvent is distilled off from the resulting pale yellow solution containing a white precipitate, methylene chloride (200 ml) is added and then diluted with chlorine hydrochloric acid (100 ml) while cooling with ice, the liquid is separated,
the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added, the resulting solid is filtered off to obtain a pale green solid and recrystallized from hot heptane (400 ml), which allows to obtain pale yellow crystals (0.8 g) . The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the KBr method and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

The value of elemental analysis:
Calculated Value (%): C 47.50 N 5.48
The obtained value (%): C 47.65, H 5.61.

 PRI me R 7. Polymerization.

Purified toluene (500 ml) methylaluminoxane manufactured by Toyo Staufer Chemical Company, lmt. (Mol. M. 770) (4.0 mmol) and dichloride are successively added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dimethylsilyl (cyclopentadienyl)), after which the temperature was raised ^to 30 ° C while continuously supplying propylene to maintain the total pressure of 3 kg / cm ² G, and polymerized for 2 hours t-butylcyclopentadienyl) zirconium (0.005 mmol) followed by after the reaction is complete, the components are decomposed to catalyst was with methanol and dried the resulting polypropylene, which allows to obtain isotactic polypropylene (75 g). The activity of the catalyst is 82 kg (g Zr h. Its mol. M. 4300.

 Example 8. Dimethylsilyl (methylcyclopentadienyl)) tert-butylcyclopentadienyl) zirconium chloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process. In a 200 ml glass reaction vessel, dimethyl (methylcyclopentadienyl) tert-butylcyclopentadienyl) silane (3.9 g 15 mmol) in pentane (50 ml) was dissolved, then a solution (20 ml) of n-butyl lithium (1.6) was slowly added dropwise. C) in hexane under ice-cooling, this mixture was stirred at room temperature for 2 hours, the solvent was distilled off to give a white solid / Li ₂ [Me ₂ Si / Me-C ₅ H ₃ // t-Bu-C ₅ H ₃ ] /, and then tetrahydrofuran (50 ml) is added to it, which makes it possible to obtain a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (3.5 g 15 mmol) to ^-78 ° C after which was added tetrahydrofuran (200 ml) was slowly added dropwise the above obtained clear yellow liquid kept at ^-78 ° C, this mixture is stirred at room temperature for 18 hours, heated under reflux for 4 hours, left to cool, the solvent is distilled off from a pale yellow solution containing a white precipitate, methylene chloride (200 ml) is added, and then diluted hydrochloric acid (100 ml), the liquid is separated, the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added and filtered, which allows to obtain pale yellow crystals (0.37 g) from a pale yellow filtrate. The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the KBr method and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

Elementary analysis values:
Calculated value (%): C 48.78, H 5.78
The obtained value (%): C 48.81, H 5.82
PRI me R 9. Polymerization.

Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer Chemical Company, lmt (mol. M. 770) (4.0 mmol) are successively added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride, dimethylsilyl (methylcyclopentadienyl)) t-butylcyclopentadienyl) zirconium dichloride (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² g and the polymerization was carried out for 2 h, then after the completion of the reaction, decomposition of the compo ENTOV catalyst with methanol, and dried the resulting polypropylene to obtain isotactic polypropylene (59 g). The activity of the catalyst is 65 kg Zr h. Its mol. M. 6400.

 PRI me R 10. Dichloride dimethylsilylbis (tert-butylcyclopentadienyl) - zirconium.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is pre-dried prior to use in this process. In a 200 ml glass reaction vessel, dimethylbis (tert-butylcyclopentadienyl) silane (4.6 g 15 mmol) in pentane (50 ml) is dissolved, then a solution (21 ml) of n-butyllithium (1.6 C) is slowly added dropwise. in hexane under ice-cooling and stirred the mixture at room temperature for 4 hours, distilling off the solvent to give a white solid Li ₂ [Me ₂ Si / t-Bu-C ₅ h _3/2] and added tetrahydrofuran (50 ml), which allows you to get a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (3.5 g, 15 mmol) to ^-78 ° C, then added THF (250 ml) was slowly added dropwise the above obtained clear yellow liquid at a temperature of ^-78, left this the mixture is allowed to stand, the temperature is brought to room temperature, the mixture is heated under reflux for 84 h, the resulting substance is left to cool, the solvent is removed from a clear yellow solution, methylene chloride (300 ml) is added, and then diluted with hydrochloride hydrochloric acid (100 ml) under ice cooling, the liquid is separated off, the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added and filtered, which allows to obtain yellowish-white crystals
(2.35 g) from the yellow filtrate. The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the KBr method and ^I H-NMR spectra are determined using CDCl ₃ as a solvent.

Elementary analysis values:
Calculated value (%): C 52.15, H 6.56
The resulting value (%): C 52.01, H 6.58
PRI me R 11. Polymerization.

Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer Chemical Company, LMT (mol. 770) (4.0 mmol) are sequentially added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride, dimethylsilylbis (t-butylcyclopentadienyl) zirconium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hr, then after the reaction, the decomposition of the catalyst components with using methanol and dried the resulting polypropylene, which allows to obtain isotactic polypropylene (3.1 g). The activity of the catalyst is 3.4 kg / g Zr h. Its mol. M. 9600.

 PRI me R 12. Dimethylhermsilbis (methylcyclopentadienyl) zirconium chloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process. In a 200 ml glass reaction vessel, dimethylbis / methyl cyclopentadienyl) germanium tetrahydride (1.2 g, 8 mmol) in pentane (50 ml) was dissolved, then a solution (11 ml) of n-butyllithium (1.6 M) was slowly added dropwise. ) in hexane under ice-cooling and stirred the mixture at room temperature for 2 h, the solvent was distilled off to give a white solid Li ₂ [Me ₂ Ge / Me-C ₅ h _3/2] is added thereto tetrahydrofuran (50 ml) with the formation of a transparent yellow liquid. In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (1.8 g, 9 mmol) to ^-78 ° C, followed by addition of tetrahydrofuran (150 ml) was slowly added dropwise the yellow transparent liquid obtained above and kept at a temperature of ^about -78 C, stir this mixture at room temperature for 14 hours, heat it under reflux for 2 hours, leave the resulting product under cooling, remove the solvent from a clear yellow solution, add methylene chloride (200 ml) and then dilute hydrochloride native acid (100 ml) under ice cooling, the liquid is separated, the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added, the resulting product is filtered and concentrated to give yellowish-white crystals
(0.31 g) from a pale yellow filtrate. The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the KBr method and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

Elementary analysis values:
Calculated value (%): C 39.94; H, 4.31.

 The obtained value (%): C 40.38; H, 4.38.

 PRI me R 13. Polymerization.

Purified toluene (500 ml) methylaluminoxane manufactured by Toyo Staufer Chemical Company, lmt. (Mol. M. 770) (4.0 mol) is sequentially added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride dimetilgermilbis (methylcyclopentadienyl) zirconium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hours, then after closure the reactions decompose the components of the catalyst with using methanol and dried the resulting polypropylene, which allows to obtain isotactic polypropylene (2.5 g). The activity of the catalyst is 27 kg / g Zr hour. Its molecular weight is 7600.

 PRI me R 14. Dichloride cyclotetramethylene silyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process. In a 200 ml glass reaction vessel, cyclotetramethylene (cyclopentadienyl) (methylcyclopentadienyl) silane (3.4 g 15 mmol, in pentane (50 ml) was dissolved, then a solution (22 ml) of 1.6 M n-butyllithium was slowly added dropwise) in hexane, this mixture is stirred at room temperature for 3 hours, the solvent is distilled off to form a white solid / Li ₂ [/ CH ₂ ) ₄ Si / C ₅ H ₄ // MeC ₅ H ₃ ] / and tetrahydrofuran is added to this substance , (50 ml), which allows to obtain a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (3.5 g 15 mmol) to ^-78 ° C, was added tetrahydrofuran (250 ml) was slowly added dropwise the above obtained clear yellow liquid at a temperature of ^-78 ° C, the mixture was stirred at room temperature for 48 hours, the solvent is distilled off from a yellow solution containing a white precipitate, methylene chloride (200 ml) is added, the resulting white solid is filtered off, the resulting yellow filtrate is concentrated, pentane is added and the mixture is cooled to -3 ⁰ ° C, which allows to obtain a yellowish white crystals (0.39 g). The physical properties of this compound are given below. In addition, infrared spectra are determined using the KBr method, and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

The values of elemental analysis; C ₁₅ H ₁₈ Cl ₂ SiZr
Calculated Value (%): C 46.37; H 4.67
The resulting value (%): C, 47.03; H 4.82
PRI me R 15. Polymerization.

Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer Chemical Company, LMT (mol. M. 770), (4.0 mmol) are successively added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride tsiklotetrametilensilil (cyclopentadienyl) (methylcyclopentadienyl) zirconium (0.005 mol), after which the temperature was raised ^to 30 ° C while continuously supplying propylene so that keep the total pressure of 3 kg / cm ² g and polymerized for 2 hours, then, after the completion of the reaction, decomposition of the components in the resulting catalyst was dried and polypropylene, that allows to obtain isotactic polypropylene (3.6 g). The activity of the catalyst is 3.9 kg / g h. Its mol. M. 4200.

 Example 16. Dimethylsilyl (methylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process. In a 200 ml glass reaction vessel, dimethyl (methylcyclopentadienyl) (dimethylcyclopentadienyl) silane (3.5 g, 15 mmol) in pentane (50 ml) was dissolved, then a solution (22 ml) of n-butyllithium (1.6) was slowly added dropwise. M) in hexane under ice-cooling, this mixture is stirred at room temperature for 5 hours, the solvent is distilled off to form a white solid / Li ₂ [Me ₂ Si / Me-C ₅ H ₃ // Me ₂ -C ₅ H ₂ / ] / and tetrahydrofuran (50 ml) is added to this substance, which makes it possible to obtain a tan clear liquid.

In a glass reaction vessel of 500 ml capacity was cooled zirconium tetrachloride (3.5 g 15 mmol) to ^-78 ° C after which was added tetrahydrofuran (250 ml) was slowly added dropwise the above-obtained yellow-brown transparent liquid at -78 ^C. This mixture is stirred at room temperature for 18 hours, heated under reflux for 6 hours, the solvent is distilled off from the resulting yellow solution, methylene chloride (300 ml) is added, the resulting solid is filtered off, and the resulting concentration is concentrated. fifth filtrate was added pentane, the solid formed was filtered and the solid was recrystallized from hot heptane (200 ml) to provide a yellowish-white crystals (1.08 g). The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with a KBr method and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

Elementary analysis values: C ₁₅ H ₂₀ Cl ₂ SiZr
The calculated value (%); C 46.13, H 5.16
The obtained value (%): C 46.22; H 5.16
PRI me R 17. Polymerization.

In a 1.5 L SUS autoclave, well purged with gaseous nitrogen, purified toluene (500 ml) methylaluminoxane manufactured by Toyo Staufer Chemical Company, lmt. (Molecular weight: 770) (4.0 mmol) and dimethylsilyl dichloride (sequentially) are added sequentially. methylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously introducing propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hours, then, after closure reactions produce decomposed the components of the catalyst with methanol and dried the resulting polypropylene with the formation of isotactic polypropylene (45 g). The activity of the catalyst is 49 kg / g Zr h. Its mol. M. 5600.

 PRI me R 18. Dimethylsilylbis (methylcyclopentadienyl) hafnium dichloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is dried prior to its use in this process. In a 200 ml glass reaction vessel, dimethylbis (methylcyclopentadienyl) silane (3.3, g, 15 mmol) in tetrahydrofuran (50 ml) was dissolved, then a solution (21 ml) of n-butyllithium (1.6 M) was slowly added dropwise. in hexane while cooling with ice and the mixture was stirred at room temperature for 2 hours to form a clear yellow liquid / Li ₂ [Me ₂ Si / MeC ₅ -H _3/2] /.

In a glass reaction vessel of 500 ml capacity hafnium tetrachloride was cooled to ^-78 ° C after which was added tetrahydrofuran (200 ml) was slowly added dropwise the above obtained clear yellow liquid at a temperature of ^-78 ° C, the mixture was stirred at room temperature for 17 , 5 hours, heat it under reflux for one hour, leave the resulting product to cool, remove the solvent from a yellow-orange solution containing a white precipitate, add methylene chloride (200 ml), and then dilute hydrochloric acid (100 ml), the liquid is separated, the methylene chloride layer is dried over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added, the insoluble solid is filtered off, the yellow filtrate is cooled to form yellowish-white crystals (2.02 g). The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the KBr-based method and ^I H-NMR spectra are determined using CDCl ₃ as solvent.

PRI me R 19. Polymerization. Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer Chemical Company, LMT (mol. 770) (4.0 mmol) are sequentially added to a 1.5 L SUS autoclave, well purged with nitrogen gas. chloride, dimethylsilylbis (methylcyclopentadienyl) hafnium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hours, then, after closure the reactions decompose the catalyst components and dry resulting polypropylene to form isotactic polypropylene (16 g). The activity of the catalyst is 8.9 kg / g Hf hours, and its mol. m. 66800.

 Example 20. Dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) hafnium dichloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is pre-dried before being used in the process. In a 200 ml glass reaction vessel, dimethyl (cyclopentadienyl) (methylcyclopentadienyl) silane (3.0-15 mmol) in pentane (50 ml) was dissolved, then a solution (20 ml) of n-butyllithium (1.6 M) was slowly added dropwise. in hexane under ice-cooling, this mixture was stirred at room temperature for 2 hours and the solvent was distilled off to give a white solid / Li ₂ [/ Me ₂ Si / C ₅ H ₄ // Me-C ₅ H ₃ /] /, then tetrahydrofuran (50 ml) is added to this substance, which allows to obtain a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled hafnium tetrachloride (4.8 g 15 mmol) to ^-78 ° C after which was added tetrahydrofuran (200 ml) was slowly added dropwise the above obtained clear yellow liquid at a temperature of ^-78 ° C, stirred this mixture at room temperature for 14 hours, the solvent is distilled off from a yellow solution containing a white solid, methylene chloride (200 ml) is added, then diluted hydrochloric acid (100 ml) is separated under ice-cooling, the methylene layer is dried, the methylene layer is dried chloride over anhydrous sodium sulfate, methylene chloride is distilled off, pentane is added, the resulting solid is filtered off to form a pale green solid (2.22 g) and crystals are recrystallized from hot heptane (200 ml), which allows to obtain pale yellowish-white crystals (0 94 g). The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with a method based on the use of KBr and ^I H-NMR spectra are determined using CDCl ₃ as a solvent.

PRI me R 21. Polymerization. Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer chemical company, lmt (mol. 770) (4.0 mmol) are successively added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride, dimethylsilyl (cyclopentadienyl) methylcyclopentadienyl) hafnium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hours, then after the end of the reaction decompose the components of catalysis torus using methanol and dried the resulting polypropylene with the formation of isotactic polypropylene (0.6 g). The activity of the catalyst is 0.34 kg / g Hf hours, and its mol. M. 52800.

 PRI me R 22. Dimethylsilylbis (tert-butylcyclopentadienyl) hafnium dichloride.

All reactions are carried out in an inert gas atmosphere. In addition, the reaction solvent is pre-dried before being used in the process. In a 200 ml glass reaction vessel, dimethylbis (tert-butylcyclopentadienyl) silane (4.8 g, 16 mmol) in pentane (50 ml) was dissolved, then a solution (22 ml) of n-butyl lithium (1.6) was slowly added dropwise. M) in hexane under ice-cooling, this mixture was stirred at room temperature for 4 hours, the solvent was distilled off to give a white solid / Li ₂ [MeSi / t-Bu-C ₅ H ₃ ] ₂ /, and then added to this substance tetrahydrofuran (60 ml), which allows to obtain a clear yellow liquid.

In a glass reaction vessel of 500 ml capacity was cooled hafnium tetrachloride (5.1 g, 16 mmol) to ^-78 ° C after which was added tetrahydrofuran (250 ml) was slowly added dropwise a yellow transparent liquid at -78 ^{° C,} allowed this mixture for standing in order to reach room temperature, is heated under reflux for 84 hours, the resulting material is left to cool, the solvent is distilled off from a clear yellow-orange solution, methylene chloride (300 ml) is added, and then diluted with chloride orodnuyu acid (100 ml) under ice cooling, the liquid was separated, the methylene chloride layer was dried over anhydrous sodium sulfate, distilling off methylene chloride, pentane, filtered, concentrated and the resulting yellow filtrate was cooled to give pale yellow crystals (1.41 g). The physical properties of this compound are given below. In addition, infrared spectra are determined in accordance with the method based on KBr and the ¹ H-NMR spectra are determined using CDCl ₃ as solvent.

 PRI me R 23. Polymerization.

Purified toluene (500 ml), methylaluminoxane manufactured by Toyo Staufer Chemical Company, LMT (mol. 770) (4.0 mmol) are sequentially added to a 1.5 L SUS autoclave, well purged with nitrogen gas. dichloride, dimethylsilylbis (t-butylcyclopentadienyl) hafnium (0.005 mmol), after which the temperature was raised ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hr., then, after completion of the reaction, the decomposition of the catalyst components with p using methanol and dried the resulting polypropylene with the formation of isotactic polypropylene (0.3 g). The activity of the catalyst is 0.17 kg / g Hf h. Its mol. M. 17200.

Comparative Example 4. In a 1.5 L SUS autoclave, well purged with nitrogen gas, purified toluene (500 ml), methylaluminoxane, manufactured by Toyo Staufer Kemi Kel Company, lmt. (Mol. 0 mmol) and dichloride dimethylsilylbis (cyclopentadienyl) hafnium (0.005 mmol) and then raise reaction temperature ^to 30 ° C while continuously feeding propylene so as to keep the total pressure of 3 kg / cm ² G, and polymerized for 2 hours, then after completion of the reaction, decomposition of the compone comrade catalyst with methanol and drying the resulting polypropylene to form atactic polypropylene (3.5 g). The activity of the catalyst is 2.0 kg / g Hf h

 PRI me R 24. Polymerization.

Purified toluene (500 ml), methylaluminoxane) Toyo Stauffer Chemical Co., Ltd., are sequentially charged into a 1.5 L SUS autoclave, thoroughly purged with nitrogen. (mole. m. 770, 2 mmol) and dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride (0.005 mmol) AI / M = 5000), followed by raising the temperature ^to 30 ° C, and then continuously introduced propylene with pressure maintaining of 3 kg / cm ² ( o) and polymerization for 2 hours. Then, methanol is added to decompose the catalyst components and the resulting polypropylene is dried.

 The result is isotactic polypropylene (109 g) of molecular weight 10,200, the catalyst activity of 119 kg / g Zr h

 PRI me R 25. Polymerization.

Purified toluene (500 ml), methylalumoxane (manufactured by Toyo Stauffer Co. Ltd.) (mol. M. 770, 7.6 mmol) and dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride are successively charged into a 1.5 L SUS autoclave, thoroughly purged with nitrogen. (0.005 mmol) (AI / n = 20000), followed by raising the temperature ^to 30 ° C, and then continuously introduced propylene with pressure maintaining of 3 kg / cm ² (n) and for 2 hours conduct polymerization and then adding methanol decomposed components catalyst and the resulting polypropylene is dried.

 As a result, isotactic polypropylene (137 g) mol. m. 10600, the activity of the catalyst 150 kg / g Zr h

Claims (1)

A catalyst for the polymerization of propylene containing a cyclopentadienyl compound of a transition metal and aluminoxane, characterized in that, in order to increase the activity and selectivity of the catalyst during the formation of isotactic polypropylene, the catalyst contains a compound of the general formula as a cyclopentadienyl compound of a transition metal
R $\genfrac{}{}{0ex}{}{\text{2}}{\text{2}}$ Y

M

where M is zirconium or hafnium;
Y is silicon or germanium;
R ¹ is methyl or tert-butyl, wherein the position of R ¹ in the cyclopentadienyl ring and its type correspond to a configuration in which there is no plane of symmetry, including M;
R ² is methyl or cyclotetramethylene;
n and q are integers 0 - 4, and the case when n = q = 0
or n = q = 4 are excluded,
as aluminoxane, a compound of the general formula
R $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ Al- (O

) _m -OAlR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$
or general formula

where R ³ is methyl;
m = 13.3,
with a molar ratio of aluminum to transition metal of 5000 - 20,000.