Metallocene with benzododecinium derived indenyl, the retrieval method, the method of obtaining the olefin polymer and a catalyst for polymerization of olefins

 

(57) Abstract:

The proposed metallocene with benzododecinium derived indenyl as ligands, the method of their preparation and use as catalysts. A very effective system of catalysts for the polymerization of olefins comprises socializaton, preferably luminokaya, and metallocene formula I.

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where preferably M1represents Zr or Hf, R1and R2- halogen or alkyl, R3- alkyl, R4-R10is alkyl or hydrogen and R11(Sames.) alkalinity or heteroatomic bridge. 4 C. and 8 C.p. f-crystals, 3 tables.

The invention relates to new metallocenes with benzododecinium derived indenyl as ligands, which can be used preferably as a catalyst components upon receipt of polyolefins with high isotacticity, a dense distribution of molecular weight and high molecular weight.

The polyolefins of high molecular weight are important, in particular for the manufacture of films, plates or large hollow objects, such as, for example, pipes or moulds.

From the literature it is known obtaining polyolefins using rastaskivanie its Lewis acidity to turn neutral metallocene into a cation and stabilize.

As an example, was offered a special method pre-activation of metallocene alumination, which leads to a significant increase in the activity of the catalyst system and a clear improvement in the structure of the granules of the polymer (patent Germany N 3726067). Pre-activation though and increases the molecular weight, however, a significant improvement is not achieved.

Following, but not yet a sufficient increase in molecular weight was achieved by using, in particular, metallocene with colophony communication heteroatoms at the high activity of metallocene (tiled an application for a European patent N 0336128).

Along about these known catalysts based on ethylenebisacrylamide-dichloride and ethylene-up(4,5,6,7-tetrahydro-1-indenyl)carrigahorig and methylaluminoxane that by suspension polymerization can be obtained high-molecular polypropylene (J. A. Ewen et al. J. Am. Chem. Soc. 109 (1987), 6544). Despite compliance with technically relevant conditions of polymerization, the structure of the granules thus obtained polymer is unsatisfactory and the activity of the used catalyst is relatively small. Due to the high cost of the catalyst for polymerization with these systems is impossible.

In industrial production, cost-effective, it is necessary to carry out the polymerization is possible at high reaction temperatures, since at elevated temperatures the polymerization released heat of polymerization can be prevented with a small amount of cooling medium and therefore significantly reduced circulation.

In this respect, these metallocene with substituents in the 2-m or 2-m and 4-m positions in relation to the bridge at the temperature of polymerization of the 70oC are already very productive, however, the required molecular weight when technically appropriate temperature polymerization (for example, 70oC) are still very low for technical use, as, for example, in the manufacture of polymers for pipes and large hollow items and special fibers.

The goal was to find a way or catalyst system for the production of polymers with good structure granules and high molecular weight and a large output. Through the use of hydrogen in ka is the evaluation.

Unexpectedly it was found that metallocene with special derived indenyl as ligands are the perfect catalyst components of the catalyst) in the production of, in particular, isotactic polyolefins with high molecular weight.

Hence the subject of the invention are compounds of the following formula I

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where M1denotes a metal of group IVb, Vb or VIb of the periodic system,

R1and R2are the same or different and mean a hydrogen atom, a C1-C10-accelgroup, C1-C10-alkoxygroup, C6-C10-allgraph, C6-C10-alloctype, C7-C40-arylalkyl, C7-C40-alkiliruya, C8-C40-arylalkenes, the group HE or halogen atom.

The radicals R3are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-accelgroup, which can be galogenirovannami, C6-C10-allgraph, the radical-NR2, -SR, -OSiR3, -SiR3or PR2- where R is a halogen atom, a C1-C10-altergroup or C6-C10-allgroups, R4R10matter, oksanaortinska ring.

R11is

BR12,AlR12, -Ge-, -Sn-, -O-, -S-,SO,NR12,CO,PR12Ilir(O)R12,

and R12and R13are equal or different and denote a hydrogen atom, a halogen atom, a C1-C10-accelgroup, C1-C10-coralcalcium, C6-C10-allgraph, C6-C10-torridgroup, C1-C10-alkoxygroup, C2-C10-altergroup, C7-C40-arylalkyl, C8-C40-arylalkyl, C7-C40-alkiliruya or R12and R13in each case form a ring with the atoms connecting them, and M2is silicon, germanium or tin.

Alkyl is a branched or unbranched alkyl, halogen (halogenated) denotes fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

The substituents R4R10in both indenyl-ligands may be different, despite having the same designation (cf. the definition of R3).

In formula I M1is a metal of group IVb, Vb or VIb of the periodic system, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably zirconium, GAF, C1-C10preferably C1-C3-accelgroup, C1-C10-, preferably C1-C3-alkoxygroup, C6-C10-, preferably C6-C8-allgraph, C6-C10-, preferably C6-C8-alloctype, C2-C10-, preferably C2-C4-altergroup, C7-C40-, preferably C7-C10-arylalkyl, C7-C40-, preferably C7-C12-alkiliruya, C8-C40preferably C8-C12-arylalkyl or halogen atom, preferably chlorine.

The radicals R3R10are identical or different and denote a hydrogen atom, a halogen atom, preferably fluorine atom, chlorine or bromine, C1-C10-, preferably C1-C4-accelgroup, which can be galogenirovannami, C6-C10-, preferably C6-C8-allgraph, balance-NR2, -SR, -OSiR3, -SiR3or-PR2where R is a halogen atom, preferably a chlorine atom, or a C1-C10- preferably a chlorine atom, or a C1-C10-, preferably C1-C3-allgroups or C6-C10prepact the O2,NR12,CO,PR12Ilir(0)R12,

and R12and R13are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-, preferably C1-C4-accelgroup, in particular the methyl group, C1-C10-coralcalcium, preferably CF3group, a C6-C10-, preferably C6-C8-accelgroup, C6-C10-torridgroup, preferably, C1-C4-alkoxygroup, in particular, a methoxy group, a C2-C10- preferably pentafluoropropyl, C1-C10preferably C1-C4-alkoxygroup, in particular a methoxy group, a C2-C10-, preferably C2-C4-altergroup, C7-C40-, preferably C7-C10-arylalkyl, C8-C40-preferably C8-C12-arylalkyl, or C7-C40-, preferably C7-C12-alkiliruya or R12and R13form respectively a ring together with atoms connecting them.

M2represents a silicon, germanium or tin, preferably silicon and germanium.

For compounds of formula I preferably that M1The B>-altergroup or halogen atom. The radicals R3identical and denote C1-C4-altergroup. R4- R10are identical or different and denote hydrogen or C1-C4-accelgroup and R11is

< / BR>
and M2refers to silicon and R12and R13are the same go different and denote C1-C4-altergroup or C6-C10-allgraph.

Also preferred are compounds I in which the radicals R4and R10represent hydrogen and R5-R9denote C1-C4-altergroup or hydrogen.

In particular, this applies to the case when M1represents zirconium, R1and R2are the same and represent chlorine, the radicals R3are the same and denote C1-C4-accelgroup, R4and R10denote hydrogen, R5R9the same or different and denote C1-C4-altergroup group or hydrogen and R11is

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and M2silicon and R12and R13the same or different and denote C1-C4-altergroup or C6-C10-allgraph.

Especially prefocused the stands, R4R10represent hydrogen and R11is

< / BR>
and M2silicon and R12and R13the same or different and represent methyl or phenyl; in particular, the compounds I listed in the examples.

The subject of the invention is obtaining the compounds of formula I, characterized in that the compound of formula IV

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moreover, the radicals R3R11have the meanings indicated in formula I, and M3denotes an alkali metal, preferably lithium, turn with the compound of the formula V

M1X4(V)

where M1has the meaning mentioned in formula I, and X denotes a halogen atom, preferably chlorine; the resulting product was transferred to the required derivative.

Getting metallocene is known from the literature method and is depicted in the following reaction scheme (see next examples).

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Derivatives of naphthalene of the formula A are commercially available or can be obtained by known literature methods ("Friedel Crafts and Related reactions", Wiley, New York, 1964, Vol. 11, p.659-766, Bull. Soc. Chim. Belges, 58 (1949) 87, J. Amer. Chem. Soc. 89 (1967) 2411).

The conversion of compounds of formula C is known from the literature mV ethanol solutions of ethanolate sodium (J. Org. Chem. 23 (1958) 1441, J. Amer. Chem. Soc. 70 (1948) 3569).

The compounds of formula C milwauee a hydroxide of an alkali metal, such as, for example, potassium hydroxide or sodium hydroxide according to known literature methods and obtained by thermolysis of dicarboxylic acids by known literature methods decarboxylase in the compounds of formula D (J. Org. Chem. 23 (1958) 1441, J. Am. Chem. Soc. 70 (1948) 3569).

The closure ring substituted benzoindole formula E is carried out by known literature methods by transformation gloriously reagents, such as, for example, SOCl2into the corresponding acid chlorides acid and subsequent cyclization in the catalyst of the Friedel-inert solvent, such as AlCl3or polyphosphoric acid in methylene chloride or CS2(Organometallics 9 (1990) 3098, Bull. Soc. Chim. Fr. 3 (1967) 988, J. Org. Chem. 49 (1984) 4226).

The transformation in benzoindole derivative formula is carried out by known literature methods by reduction with sodium borohydride or lithium aluminum hydride, in an inert solvent, such as, for example, a simple diethyl ether or tetrahydrofuran, or by alkylation with an alkylating means of the formula F or socialmiami in appropriate Le by transformation with dehydrating substances, as, for example, magnesium sulfate or molecular sieve (Organometallics 9 (1990) 3098, Acta. Chem. Scand. B 30 (1976) 527, J. Amer. Chem. Soc. 65 (1943) 567).

Benzoindole derivatives of formula G can be synthesized also by the other, not specified in detail here the path of synthesis, based on the substituted naphthalene 4 stages of synthesis (Bull. Soc. Chem. Fr. 3 (1967) 988).

Getting ligand systems of the formula J and transformation in chiral metallocene with colophony communication formula K, as well as the selection of the desired racemic forms are in principle known (published application Australia, N 31478/89, J. were obtained. Chem. 342 (1988) 21, European patent N 0284707, European patent N 0320762). Moreover, the derivative of besondere formula G deprotonized strong base, such as, for example, butyllithium, in an inert solvent and becomes a reagent of formula H in the ligand system of the formula J. Then it deprotonized two equivalents of a strong base, such as, for example, utility, in an inert solvent (compound of formula (IV) and turn with the corresponding metalcatalyzed, such as zirconium tetrachloride in an appropriate solvent. Appropriate solvents are aliphatic and aromatic solvents, such as hexane or toluene, e is s, for example methylene chloride. Separation of racemic and metformi is carried out by extraction or recrystallization appropriate solvents.

The transformation in metallocene formula I can be carried out by known literature method, for example by transformation with an alkylating means, for example methyllithium (Organometallics 9 (1990) 1539, J. Amer. Chem. Soc. 95 (1973) 6263, European patent N 0277004).

Proposed according to the invention metallocene I are highly active components of the catalyst for polymerization of olefins.

Thus, the invention also includes a method of obtaining olefin polymer by polymerization or copolymerization of an olefin of the formula Ra-CH=CH-Rbwhere Raand Rbare identical or different and denote a hydrogen atom or a hydrocarbon radical with 1 to 14 carbon atoms, or Raand Rbmay form a ring with the atoms connecting them, at a temperature of -60 200oC, at a pressure of 0.5 to 100 bar, in solution, suspension or in the gas phase, in the presence of a catalyst which is formed from metallocene combination of transition metal and socializaton, characterized in that metallocene is a compound of formula I.

Separation of the stereoisomers, in principle, known.

According to the invention, as socializaton used preferably iluminacin formula (II)

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for the linear type and/or formula (III)

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for the cyclic type, and in formulas (II) and (III) the radicals R14may be the same or different and denote C1-C6-accelgroup, C6-C18-allgraph, benzyl or hydrogen, and p denotes an integer from 2 to 50, preferably from 10 to 35.

The radicals R14preferably are identical and represent methyl, isobutyl, phenyl or benzyl, particularly the d or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably contained in an amount of 0.01 to 40% (number of radicals R14).

Iluminacin can be obtained in various kinds of known methods. One method, for example, is that the connection aluminiumcentrum and/or connection hydrodealkylation with water (gaseous, solid, liquid or bound, for example, in the form of water of crystallization) turn in an inert solvent (e.g. toluene). To obtain iluminacin with different alkyl groups R14two different trialkylamine (AlR3+ AlR'3in accordance with the desired composition of the turn with water (compare S. Pasynkiewicz, Polyhedron 9 (1990) 429 and posted the application for the European patent N 302424).

The exact structure of alumination II and III is unknown.

Regardless of how you get the total for all aluminating solutions is changing the content neprevyshenie original aluminum compounds, which is in free form or in the form of the product of the merger.

Is possible before introduction into the polymerization reaction to pre-activate metallocene alumination formula (II) and/or (III). Thanks activating compound of the transition metal is in solution. Thus preferably metallocene in solution iluminacin dissolved in an inert hydrocarbon. As hydrocarbon suitable aliphatic or aromatic hydrocarbon. Preferably applies toluene.

Concentration iluminacin in the solution is in the range from about 1 wt. to the border of saturation, preferably from 5 to 30 wt. in each case relative to the total solution. Metallocene can be used in the same concentration, preferably still in the range from 10-1to 1 mol per mol iluminacin. Pre-activation reaches from 5 minutes to 60 hours, preferably 5-60 minutes Working at a temperature of -78oC - 100oC, preferably 0 to 70oC.

Metallocen you can also pre-polymerizate or apply to the media. For the preliminary polymerization is used, preferably the olefin (or one of the olefins used in the polymerization.

Suitable carriers are, for example, silica, aluminum oxide, solid iluminacin or other inorganic materials carriers. A suitable material carrier is also polyolefin powder fine grinding.

According to the invention,H4-xBR'4, R3CBR'3or BR'3as appropriate socialization. In these formulas, x represents a number from 1 to 4, preferably 3, the radicals R are identical or different, preferably identical, and denote C1-C10-alkyl, C6-C18-aryl or 2 radicals R form together with the atom connecting them a ring, and the radicals R' are identical or different, preferably identical, and denote C6-C18-aryl which may be substituted by alkyl, haloalkyl or fluorine.

In particular, R denotes ethyl, propyl, butyl or phenyl and R' denotes phenyl, pentafluorophenyl, 3,5-pestrepeller, mesityl, hill or tolyl (see laid out an application for a European patent N 277003, tiled an application for a European patent N 277004 and laid out an application for a European patent N 426638).

When using the above acetalization real (active) polymerization catalyst comprises the reaction product of metallocene and one of these compounds. Therefore, this first reaction product is preferably receive outside the polymerization reactor in a separate step using a suitable solvent.

Principialnosti Lewis can translate neutral metallocene into a cation and stabilize it ("unstable coordination"). In addition, acetalization or educated out of him anion should not engage in other reactions with an educated cation of metallocene (cf. published application for the European patent N 427697).

To delete present in the olefin catalyst poison preferred cleaning aluminiuim, for example AlMe3or AlEt. Cleaning can be carried out independently in a polymerization system, or the olefin prior to being fed into the polymerization system is brought into contact with the connection of aluminum and then again separated.

The polymerization or copolymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or periodically, to go one stage multi-stage at a temperature of -60 200oC, preferably 30-80oC, particularly preferably 50-80oC, polymerizers or copolymerized olefins of the formula Ra-CH=CH=Rb. In this formula, Raand Rbare identical or different and denote a hydrogen atom or an alkyl radical with 1 to 14 atoms C. However, Raand Rbcan also form a ring with the atoms connecting them C. for Example, such olefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-penten, 1-octene, norbornene mass and/or for increasing the activity served if necessary hydrogen. The total pressure in the polymerization system reaches 0.5 to 100 bar. Preferred polymerization is particularly interesting in technical terms, pressure range 5 to 64 bar.

When this is applied metallocene at a concentration corresponding to the concentration of transition metal is from 10-3up to 10-8preferably 10-4-10-7mol of transition metal per 1 DM3solvent or 1 DM3volume of the reactor. Iluminacin used in concentrations from 10-5up to 10-1mole, preferably 10-4-10-2mol per 1 DM3solvent or 1 DM3volume of the reactor. Other specified socializaton used in approximately equimolar amounts with metallocenes. However, there is also a higher concentration.

If the polymerization is carried out in suspension or in solution, is applied to the inert solvent used at low pressure. For example, the use of aliphatic or cycloaliphatic hydrocarbon; as such it may be called, for example, propane, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane.

Can be used as gasoline or gidrirovanny diesel oil fraction. Can polysoude inert solvents, the added gaseous or liquid monomers.

The duration of any polymerization, as used according to the invention the catalyst system shows only a slight time-dependent decline in polymerization activity.

Proposed invention the method is characterized by the fact that the described metallocene in a technically particularly interesting temperature range between 50 and 80oC give the opportunity to obtain polymers with high molar mass, high stereospecificity and good crystalline structure.

In particular, the proposed invention zirconocene allow to obtain polymers of high molecular weight or even surpass known from the prior art, Garrity. However, they have the disadvantage that is insignificant polymerization activity and very high cost of the catalyst, and the resulting polymers have poor structure of the powder.

Synthesis metallocenes I used in examples of the polymerization.

Example A. Synthesis of rat-dimethylanilines(2-methyl-4,5-benzhydryl)-circondariale

1. Complex diethyl ether methyl(2-naphthylmethyl)malonic acid (1)

of 5.15 g (224 mmol) intothree the aqueous diethyl ether methylmalonic acid. At 0oC solution of 50 g (217 mmol) of 2-bromoethylamine (96%) slowly drops were added to 270 ml of ethanol and heated for 4-5 hours at the boil under reflux. The mixture was poured into ice water and was extracted with acetic ether. The combined organic phases were dried with sodium sulfate and evaporated. After drying in vacuum oil vacuum pump oily residue was stirred with hexane at 0oC, and 55 g (81%) of compound I was led.

2. 2-methyl-3-naphtylpropionate acid (2)

the 33.2 g (105 mmol) of compound I mixed in 70 ml of ethanol with a solution of 23.7 g (422 mmol) of potassium chloride in 50 ml of water and heated for 4 h to reverse flow. After removal of the solvent the solid residue was combined with acetic ether, mixed with water and hydrochloric acid brought to pH 1. The aqueous phase was extracted several times with acetic ester. After drying over magnesium sulfate the combined organic phases are completely evaporated. The residue was mixed for crystallization with hexane. For decarboxylation orange solid was heated to 175oC until the evolution of gas. Received 21 g (93%) of product 2 as an orange solid.

3. 2-methyl-6,7-bentenan-1-he (3)

21 g (98 mmol) of compound 2 M. Then drove the excess thionyl chloride. The residue was quickly freed from volatile compounds in the oil of the vacuum pump and then dissolved in 25 ml of methylene chloride under Ar protection. The solution is slowly added dropwise introduced into a suspension of 26 g (196 mmol) of aluminum chloride in 60 ml of methylene chloride at room temperature and heated for further 30 minutes at boiling under reflux. The mixture was poured on ice and extracted with methylene chloride. The combined organic phases were dried with sodium sulfate and evaporated. The dark oily residue was divided into 600 g of silica gel 60 using chromatography. A mixture solvent of hexane/acetic ether (9: 3) was washed 8.6 g (45%) of compound 3 (yellow solid).

4. 2-methyl-4,5-benzoine (4)

A solution of 7.8 g (39,7 mmol) indanone3400 ml of a mixture of THF/methanol (2:1) mixed portions with 2.2 g (595 mmol) detribalized and stirred 14 h, the Solution was poured onto HCl-acidic ice and was extracted. The combined organic phase is repeatedly washed and dried with sodium sulfate. After removal of the solvent the remaining orange oil was dissolved in 240 ml of toluene and heated to 570 mg (3,15 mmol) p-toluensulfonate 15 80oC. the Solution is repeatedly washed with water at room temperature is the her. A mixture solvent of hexane/simple diisopropyl ether (20:1) was able to extract 4.7 g (65%) of the indene 4 (colorless oil).

1H-NMR spectrum (350 MHz, CDCl3): 8,02 (1, d), 7,84 (1, m) to 7.59 (1, d), 7,52 (1, d), 7,38-of 7.48 (2, m), 7,06 (1, m), 3.42 points (2, d) to 2.25 (3, d).

5. Dimetilan(2-methyl-4,5-benzhydryl)silane (5)

A solution of 4.6 g (25,5 only) of indene 4 in 50 ml of THF was mixed with 10.2 ml (255 mmol) of a 2.5 M solution of utility in hexane at room temperature and heated for 1 h at boiling under reflux. Then the red solution was added dropwise to a solution of 1.55 g (12 mmol) clear in 10 ml of tetrahydrofuran at room temperature and heated for 5-6 hours to the boil under reflux. The reaction solution was poured over ice water and was extracted several times. Dried with sodium sulfate the combined organic phases are evaporated and dried under vacuum oil vacuum pump. The residue was subjected to chromatographic separation in 300 g of silica gel 60. A mixture solvent of hexane and 3% acetic ether was first able to extract 500 mg neprevyshenie of educt 4. Then in the same solvent extracted ligand system 5. After removal of solvent, it was possible to crystallize ligand system by stirring with hexane (and the C(2-methyl-4,5-benzhydryl)circondariale (6)

A solution of 1.7 g (4.1 mmol) of the ligand system 5 in 20 ml of tetrahydrofuran at room temperature under Ar protection mixed with 4.0 ml (10.2 mmol) of a 2.5 M solution of utility and stirred 14 h at room temperature. Remaining after removal of solvent the residue was dried in an oil vacuum pump and washed with hexane. Thus obtained light brown powder was dried for several hours in vacuum oil vacuum pump at a temperature of 40-50oC and at a temperature of -78oC introduced into a suspension of 1.0 g (4.0 mmol) of zirconium tetrachloride in 25 ml of methylene chloride. After heating to room temperature the solvent was removed and the residue was extracted with 20 ml of toluene to remove mesoform of zirconocene 6. Then the remainder of the toluene extract was extracted with 40 ml of methylene chloride. The solution was concentrated to a small volume and at a temperature of -35oC was led. From several factions were able to distinguish only 970 mg (42%) of zirconocene 6 in the form of pure racemate.

1H-NMR spectrum of the racemate (300 MHz, CDCl3): 7,86 (2, m), 27,78 (2, m), 7,60 (2, d) of 7.48-7,56 (4, m), of 7.36 (2, d), 7,27 (2, S-IHd-CH3), 2,37 (6, S, Ind-CH3), 1,36 (6, S, Si-CH3). Range of weight: 574 M+correct decay, the correct model of isotopes.

1H-NMR (CDCl3, 100 MHz): to 8.57 (d, 1), 7,60 (t, 1), 7,35 (d, 1), 7,25 (s, 1), of 3.45 (q, 1), 3,40 (s, 4), 2,60-2,95 (m, 2), of 1.35 (d, 3).

2. 2-methyl-a-acenaphthen (8)

A solution of 20 g (90 mmol) of compound 7 in 250 ml of a mixture of THF/methanol (2:1) was added dropwise to a suspension of 3.8 g (100 mmol) NaBH4in 80 ml of tetrahydrofuran. The mixture was stirred at room temperature for 2 h and mixed with 100 ml of acetic ether and 100 ml slabokontsentrirovannye Hcl. Was heated for 10 min to boiling under reflux and was extracted with acetic ether. The organic phase is washed with water and dried NaSO4. When concentration is Dimetilan(2-methyl-a-acenaphthyl)silane (9)

10.8 g (a 52.4 mmol) of compound 8 was deprotonirovaniem analogously to example A/5 and transformed the clear. The organic phase is boiled away and the residue was subjected to chromatographic separation on silica gel. With hexane/4%-acetic ether were able to obtain 6.2 g (51%) of the ligand system 9.

1H-NMR (CDCl3, 100 MHz): a pair of diastereomers a 7.1 to 7.8 (m, aromatic hydrocarbons (H) 4,0 (s, CH), of 3.45 (s, CH2), 2,47 (d, CH3), is 2.40 (d, CH3), -0,25 (s, SiCH3), -0,35 (s, SiCH3), -0,37 (s, SiCH3).

4. Rat-dimethylanilines(2-methyl-a-acenaphthyl)circondariale (10)

4,9 (10.5 mmol) of the ligand system 9 was converted analogously to example A/6. The crude product, consisting of matematicheskogo connection with metformi in the ratio of 1: 1, several times recrystallize from chloroform. Obtained 1.3 g (20%) of the racemate 10 as a yellow-orange powder.

1H-NMR (CDCl3, 100 MHz): 7,0-7,8 (m, aromatic hydrocarbons-H), 3.1 to 3.4 (m, CH2), TO 2.35 (S, CH3), is 1.35 (S, SiCH3).

Example C Synthesis of rat-methylphenylethylamine(2-methyl-4,5-benzhydryl)circondariale (12)

1. Methylenebis(2-methyl-2,5-benzhydryl)silane (11)

A solution of 4.6 g (25.5 mmol) of 2-methyl-4,5-benzoine (4, example A/4 in 40 ml of THF were mixed at room the reflux condenser. Then the red solution is added dropwise at room temperature was added to a solution of 2.3 g (12 mmol) of methylphenyldichlorosilane in 10 ml of tetrahydrofuran and 8 hours was heated at the boil under reflux. Processing and purification was carried out analogously to example A/5. A mixture solvent of hexane/5% acetic acid ester can first get neprevyshenie educt, and then 1.4 g (25% relative to Si) ligand systems 11 (isomers).

2. Rat-methylphenylethylamine(2-methyl-4,5-benzhydryl)circondariale (12)

A solution of 1.3 g (a 2.71 mmol) ligand 11 in 15 ml of terriitory mixed at room temperature under Ar protection with 1.2 ml (3 mmol) of a 2.5 M solution of utility in hexane and stirred over night at room temperature. The solvent was removed, the residue, is extremely sensitive to the action of air, washed with hexane and several hours were dried in vacuum oil vacuum pump. Powder at a temperature of -78oC was added to a suspension of 680 g (2.9 mmol) ZrCl415 mg CH2Cl2. After slow warming to room temperature, stirred for another 1 h at this temperature and solvent removed. The residue is first washed with water and then was extracted with CH2Cl2. When the concentration and slowly starecheski powder). Formed then mixed fraction (racemate and 2 mesophases) able to clean the reusable by recrystallization from chloroform or toluene.

1H-NMR spectrum of the racemate: (100 MHz, CDCl3): of 6.8 to 7.9 (m, aromatic hydrocarbons (H) 7,4 (S-Ind-H), 2,4 (Ind-CH3) and 1.3 (S, Si-CH3), mass spectrum: 538 M+correct decay, the correct model of isotopes.

Example d Synthesis of rat-methylphenylethylamine(2-methyl-a-acenaphthyl)circondariale (14)

1. Methylenebis(2-methyl-a-acenaphthyl)silane (13)

A solution of 10.8 g (a 52.4 mmol) of 2-methyl-a-acenaphthylen (8, example B/2) in tetrahydrofuran was converted analogously to example A/5 53 mol of utility and 4.9 g (26 mmol) of methylphenyldichlorosilane. The reaction time was 12 hours Processing was carried out in the same way. After chromatographic separation with hexane/6% -acetic ether was obtained 6.0 g (44%) system ligand 13 (isomers).

2. Rat-methylphenylethylamine(2-methyl-a-acenaphthyl)circondariale (14)

5.0 g (9.4 mmol) of the ligand system 13 was converted analogously to example A/6 to 19.7 mmol by butyllithium and then 2.2 g (9.4 mmol) Zr-Cl4processed. The residue to remove mesoform several times recrystallize from methylene chloride. Received 1.2 g (100 MHz): 6,8-7,8 (m, aromatic hydrocarbons-H), of 3.0-3.4 (m, CH2), AND 2.4 (S, CH3), 2,1 (S, CH3) and 1.3 (S, SiCH3). Mass spectrum: 690 M+correct decay, the correct model of isotopes.

Example e Synthesis of rat-1,2-atanderson(2-methyl-4,5-benzhydryl)circondariale (15)

1. 1,2-bis(2-methyl-4,5-benzhydryl)ethane (14)

A solution of 18.0 g (100 mmol) of 2-methyl-4,5-benzoine 4 (example A/4/ in 400 ml of THF were mixed at room temperature with 40 ml (100 mmol) of a 2.5 M solution of utility in hexane and 30 min was heated to boiling under reflux. At -78oC has introduced a 9.35 g (50 mmol) of 1,2-dibromoethane. The mixture was heated overnight to room temperature, poured on ice water and hydrochloric acid were extracted simple diethyl ether. After washing with a solution of NaHCO3and drying with MgSO4the solvent was removed and the residue was subjected to chromatographic separation on silica gel 60. Using hexane/6%-acetic ether was suirable neprevyshenie educt and by-product (spirochaetaceae) 8.6 g (45%) of the ligand system 14.

2. Rat-1,2-atanderson(2-methyl-4,5-benzhydryl)-circondariale (15)

A solution of 4.2 g (10,8 mmol) ligand 14 was converted analogously to example A/6 butyllithium and ZrCl4Extraction of the remnant of claritynet in the form of a yellow microcrystalline powder.

1H-NMR spectrum (100 MHz, CDCl3): of 7.3 to 8.0 (m, aromatic hydrocarbons-H), and 7.1 (S-H), 3,4-4,1 (m, CH2CH2), 2,2 (S, CH3). Mass spectrum: 546 M+the correct model of isotopes, the correct decomposition.

Example f Synthesis of rat-1,2-mutandiro(2-methyl-4,5-benzhydryl)circondariale (17)

1. 1,2-bis(2-methyl-4,5-benzhydryl)butane (16)

18.0 g (100 mmol) of 2-methyl-4,5-benzoine (4, example A/4) was transformed with analogously to example E/1 10.7 g (50 mmol) of 1,2-dibromoethane (97%) and processed. Chromatographic separation on silica gel 60 with hexane/2% acetic ether got neprevyshenie educt and spirochaetaceae 3,9 (19%) ligand system 16 in the form of a mixture of isomers. Subsequent chromatographic separation on a long column managed using a mixture of hexane and then hexane/1-W% acetic ether to separate or enrich the individual isomers.

2. Rat-1,2-BUTADIENES(2-methyl-4,5-benzhydryl)circondariale (17)

1.0 g (2,41 mmol) ligand 16 (2 isomer) was converted analogously to example A/6 butyllithium and ZrCl4. By extraction with toluene/methylene chloride (5: 1) and slow crystallization by concentration and cooling to -35oC has received a total of 0.89 g (65%) of crystalline fractions of metallocene 17 different SOS the recrystallization could get a fraction of the racemate 17 (a pair of diastereomers). Mass spectrum: 574 M+the correct model of isotopes, the correct decomposition.

Example g Synthesis of rat-dimethylanilines(4,5-benzhydryl)circondariale (23)

1. Complex diethyl ether 2-naphthylethylene acid (18)

of 34.7 g (217 mmol) of a compound diethyl ester of malonic acid was converted analogously to example A/1 and processed. When processing hexane received 87 g of brown oil connection 18.

2. 3-naphtylpropionate acid (19)

87 g of compound treated analogously to example A/2 using KOH and subjected to thermolysis. Received 36 g (83%) of compound 19 in the form of a beige powder.

3. 6,7-bentenan-1-he (20)

33,6 (168 mmol) of the compound 19 was converted analogously to example A/3 using SOCl3and AlCl3. The reaction time of the cyclization was 15 minutes at a temperature of 40oC. After chromatographic separation received (partial decomposition on the column) 9.4 g (30%) of the indanone 20 in the form of a yellowish solid (partially oily substances).

1H-NMR spectrum (100 MHz, CDCl3): 9,15 (dd, 1, aromatic hydrocarbons-H), 7,35-81 (m, 5, aromatic hydrocarbons-H), 3,2 (m, 2, CH2), 2,80 (m, CH2).

4. 4,5-benzoine (21)

9.4 g (51.6 mmol) of indanone 20 restore the temperature of 110oC and 0.6 to 0.9 mbar missed 2,6 (30%) of the indene 21 in the form of a colorless distillate, which is hardened at room temperature.

1H-NMR spectrum (100 MHz, CDCl3): 7,35 to 8.2 (m, 7, aromatic hydrocarbons-H and CH), 6,70 (dt, 1, CH), 3,55 (t, CH2).

5. Dimetilan(4,5-benzhydryl)silane (22)

3.25 g (a 19.6 mmol) of indene 21 was converted analogously to example A/5. Chromatographic separation on 600 g silica gel 60 was obtained using hexane and hexane/acetic ether 20:1 along with the educt 1.8 g (47%) of the ligand system 22 (isomers).

1H-NMR spectrum (100 MHz, CDCl3): of 7.8 to 8.2 (m, aromatic hydrocarbons-H), 6,6-6,9 (m, CH), 3,5-4,1 (m, CH) -0,35-0,20 (multiple singlets, SiCH3).

6. Rat-dimethylanilines(4,5-benzhydryl)circondariale (23)

1.6 g (4,12 mmol) ligand 22 was converted analogously to example A/6 butyllithium and ZrCl4. After extraction with methylene chloride at a temperature of -35oC could provide 520 mg (23%) metallocene 23 in the form of a racemate (yellow-orange powder).

1NMR spectrum (100 MHz, CDCl3): 7,2-8,0 (m, aromatic hydrocarbons (H) to 7.2 (d, -CH), 6,4 (da, -CH), 1,2 (S, SiCH3).

Examples of polymerization

Examples 1 and 2. Dry reactor volume 16 DM3flushed with nitrogen and filled W the creators of toluene and the composition was stirred for 15 minutes at a temperature of 30oC. in Parallel, prepared toluene solution metallocene dimethylsilane(2-methyl-4,5-benzhydryl)circondario in one-third indicated in the table the number of MAO and after 15 min of sludge pre-activated. The solution can be activated also by stirring or shaking or ultrasonic bath. Then, this solution was applied to the reactor and start the polymerization by heating to a predetermined temperature. The process ended by cooling and relaxation in an hour. The obtained yield of polymer product and established analytical data are shown in table. 1.

Examples 3 and 4. Dry reactor volume 24 DM3washed propylene was removed air and filled with liquid propylene with a volume of 12 DM3. Then added 25 cm3toluene solution methylaluminoxane (respectively 37 mmol A1, the average degree of oligomerization p 18) and the composition was stirred at a temperature of 30oC for 15 minutes

In parallel, listed in table.2 number of metallocene rat-dimethylanilines/2-methyl-a-acenaphthene/ZrCl2dissolved in 10 cm3toluene solution methylaluminoxane (15 mmol A1), pre-activated, respectively prieuré 1. The conditions of polymerization and the results of the tests are presented in table. 2.

Examples 5 to 9. Repeated example 3. Were used metallocene table. 3. The test results are also presented in table. 3.

Example 10. Repeated example 3, only used 2.6 mg of metallocene and advanced reactor filed 2,5 bat3of hydrogen. Activity metallocene was 496 kg of PP/g of metallocene per hour, the coefficient of viscosity of 187 cm3/g ind. pl. (230/5) of 28.5 DG/min, melting point 151oC.

Example 11. Repeated example 10, only the amount of hydrogen was 25 bat3. Activity metallocene was 598 mg of polypropylene/g of metallocene per hour, the coefficient of viscosity of 105 cm3/g, melting point 149oC.

Example 12. Repeated example 3, only used a 2.8 mg metallocene rat-dimethylanilines(2-methyl-4,5-benzhydryl)zirconium dichloride and the amount of hydrogen was 15 bat3. Activity metallocene was 647 kg of polypropylene/g per hour, the coefficient of viscosity of 147 cm3/g, melting point 148oC. Examples 10-12 confirm the good agreement of hydrogen to regulate the molar mass in the proposed invention metallocenes.

Example 13. Dry Rena. Then added 35 cm3toluene solution methylaluminoxane (respectively 52 mmol A1, the average degree of oligomerization p 19). In parallel, dissolved 3.9 mg rat-dimethyl-Silantieva(2-methyl-4,5-benzhydryl)zirconium dichloride 13.5 cm3toluene solution methylaluminoxane (20 mmol A1) and after 5 min of sludge pre-activated. Then the solution was applied to the reactor and the continuous supply of 100 g of ethylene was polymerizable for 1 h at a temperature of 60oC. Activity metallocene was 40 kg of polypropylene/g of metallocene x hour, the ethylene content of the statistical copolymer amounted to 5.7 wt. The coefficient of viscosity 407 cm3/g, average molecular weight 508 500 g/mol, the molecular weight distribution of 2.4, melting point 135oC. According to the13C-NMR spectroscopy ethylene was built mostly in isolation (statistically).

Example 14. Dry reactor with a volume of 150 DM3washed with nitrogen and at a temperature of 20oC filled non-flavored gasoline by volume of 80 DM3with a boiling point 100-120oC. Then the gas chamber was washed with propylene from releasing nitrogen and filled with 50 l of liquid propylene, 64 cm3toluene solution Matilda hydrogen content in the gas chamber of the reactor was set to 0.2%, and later during the polymerization by further submission during the entire polymerization time remained constant.

(Additional testing in non-Autonomous mode by gas chromatography)

14,9 mg rat-dimethylanilines(2-methyl-4,5-benzhydryl)zirconium dichloride were dissolved in 32 cm3toluene solution methylaluminoxane (50 mmol) and filed in the reactor. In the first stage polymerization was carried out at a temperature of 65oC for 6 hours In the second stage at a temperature of 50oC quickly gave 3 kg of ethylene and after 4 h at this temperature, the polymerization was finished using gas CO2. Got 23,9 kg powder block copolymer. The coefficient of viscosity 398 cm3/g, the average weight of a mass mole 387 500 g/mol, the dispersion of the molar mass of 4.5; MEI (230/5 of 14.5 DG/min. Block copolymer contained 10.6 wt. of ethylene. Fractionation gave up 26.9 wt. ethylene/propylene-rubber. The glass temperature of the rubber was -48oC.

Example 15. Repeated example 10, was used bat 1003of hydrogen. Activity metallocene was 605 kg of polypropylene/g of metallocene per hour, the coefficient of viscosity of 17 cm3/g and a melting temperature of 150oC.

Example 15 shows that with relatively small quantities of hydrogen can be obtained even paraffins proposed invention metallocene.

1. Irani or hafnium;

R1and R2identical or different, halogen, alkyl with 1 to 10 carbon atoms or aryl with 6 to 10 carbon atoms;

R3the same or different, hydrogen or alkyl with 1 to 10 carbon atoms;

R4R10have the meanings indicated for R3or adjacent radicals R4R10together with the atoms connecting them form an aromatic or aliphatic ring;

R11the remainder of the formula M2R12R13, CR12R13or CR12R13- CR12R13where M2silicon, germanium or tin, R12and R13the same or different

hydrogen, an alkyl group with 1 to 10 carbon atoms or aryl with 6 to 10 carbon atoms.

2. The compound of formula I under item 1, characterized in that M1- zirconium or hafnium, R1and R2the same or different, - C1WITH3is an alkyl group or halogen, R3identical and denote WITH1WITH4is an alkyl group, R4- R10the same or different, hydrogen or C1- C4is an alkyl group, R11radicals of the formula

< / BR>
or

< / BR>
and M26WITH10-allgraph.

3. The compound of formula I under item 1 or 2, wherein R4and R10the hydrogen and R5R9the same or different, is hydrogen or C1WITH4is an alkyl group.

4. The compound of formula I according to one or more paragraphs.1 to 3, characterized in that M1zirconium, R1and R2identical and denote chlorine, R3identical and denote WITH1WITH4is an alkyl group, R4and R10hydrogen, R5R9the same or different, WITH1WITH4is an alkyl group or hydrogen, R11the radical of the formula

< / BR>
or

< / BR>
and M2silicon;

R12and R13the same or different, - C1WITH4is an alkyl group or6- C10-allgraph.

5. The compound of formula I according to one or more paragraphs.1 to 4, characterized in that M1zirconium, R1and R2chlorine, R3is methyl, R4R10hydrogen, R11the radical of the formula

< / BR>
and M2silicon, R12and R13identical or different, are methyl or phenyl.

6. The compound of formula I under item 1, characterized in that the compounds the compounds of the formula I according to one or more paragraphs.1 - 6, characterized in that the compound of General formula IV

< / BR>
where R3R11have the meanings specified for formula I;

M3alkali metal, preferably lithium,

enter in interaction with the compound of the formula V

M1X4,

where M1has the meaning indicated in formula I;

X is halogen, preferably chlorine,

and then, if necessary, the resulting product halogen atoms transferred into compounds in which R1and R2alkyl with 1 to 10 carbon atoms or aryl containing 6 to 10 carbon atoms.

8. The catalyst for polymerization of olefins, representing metallocene compound of titanium, zirconium or graphy, characterized in that as metallocenes compounds it contains metallocene formula I on PP.1 6.

9. The method of producing polyolefins by polymerization or copolymerization of olefins of General formula

Ra-CH=CH-Rb,

where Raand Rbthe same or different, hydrogen or alkyl with 1 to 14 carbon atoms,

at -60 200oS and 0,5 100,0 bar, in solution, suspension or gas phase in the presence of metallocenes compounds of titanium, zirconium or graphy as a catalyst and cyclizes the form catalyst under item 8.

10. The method according to p. 9, characterized in that as socializaton used iluminacin General formula II

< / BR>
for the linear type and/or General formula III

< / BR>
for the cyclic type

where R14the same or different, WITH1- C6is an alkyl group, a C6WITH18-allgraph, benzyl or hydrogen; R 2 50, an integer.

11. The method according to p. 9 or 10, characterized in that as socializaton used methylaluminoxane.

12. The method according to p. 9 or 10, characterized in that metallocene formula I before introduction into the polymerization reaction pre-activate using iluminacin formula II and/or III.

 

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