Metallocene with ligands fluoroanilino type, method of production thereof, the intermediate connection for their reception, the catalyst for polymerization of olefins containing these metallocene, the method of polymerization of olefin

 

(57) Abstract:

Describes new metallocene with ligands fluoroanilino type formula I

< / BR>
where R1is hydrogen or lower alkyl; M is Ti, Zr or Hf; R2- halogen; R3represents a radical where R4- lower alkyl or C3-C20cycloalkyl. Such metallocene applicable as components of catalysts for the polymerization of olefins, especially for high molecular weight atactic polypropylene. Describes such intermediate compounds for their preparation and catalyst for polymerization of olefins containing these metallocene, the method of polymerization of olefins. 4 C. and 7 C.p. f-crystals, 1 tab., 2 Il.

The present invention relates to compounds of series metallocenes, to a method for their production and to their use as catalyst components in ways polymerization of olefins.

In U.S. patent 4542199 disclosed catalyst system for polymerization of olefins containing bis(cyclopentadienyl)zirconium and alumoxane. As a result of polymerization of propylene carried out in the presence of such a catalyst, receive low molecular weight atactic polypropylene.

In the European patent 283739 raskrytoe polymerization of propylene, carried out in the presence of this catalyst, receive low molecular weight atactic polypropylene.

In U.S. patent 4931417 disclosed catalysts for the polymerization of olefins containing metallocene, in which two cyclopentadienyls rings linked by a moiety having an atom of germanium or silicon. Polymerization of propylene carried out in the presence of the above catalyst, partially substituted in cyclopentadienyls cycles, gives isotactic polypropylene, and in the case of applying dimethylselenide(cyclopentadienyl)zirconiated get atactic polypropylene.

In published patent application Japan N 1249782 disclosed receipt of the potassium salt of bis(fluorenyl)dimethylsilane intended for the preparation of hydrides antaninarenina compounds. The last applicable as catalysts for hydrogenation of olefins of any type and catalysts for polymerization of ethylene.

Unexpectedly discovered new metallocene, with the two linked by a bridge fluoroaniline cycle, which can be used as catalyst components for the polymerization of olefins, especially for high molecular weight atactic polypropylene.

1that are the same or different, represent hydrogen, C1-C20-alkyl, C3-C20-cycloalkyl, C2-C20alkenyl, C6-C20-aryl, C7-C20-alkylaryl or C7-C20-arylalkyl, two adjacent substituent R1may form a cycle containing 5-8 carbon atoms, and besides the substituents R1can contain atoms of Si or Ge;

M represents Ti, Zr or Hf;

the substituents R2that are the same or different, represent halogen atoms, -OH, -SH, R1, -OR1, -SR1, -NR12or PR13where R1accept above values;

the group R3select from where R1accept above values, and perhaps, when R3group both Deputy R1can form a cycle containing 3-8 atoms.

Preferred substituents R1include: hydrogen, C1-C10-alkyl, more preferably C1-C3-alkyl, C3-C10-cycloalkyl, more preferably C3-C6-cycloalkyl, C2-C10alkenyl, more preferably C2-C3alkenyl, C6-C10-aryl, C7-C10-alkylaryl or C7-C10the substituents R2include: halogen atoms or groups of R1. More preferred values of R2is chlorine or methyl.

Preferred values for R3group a more preferred group

Non-limiting of the invention examples metallocene formula (I) include:

dimethylselenide(fluorenyl)tiandihui,

dimethylselenide(fluorenyl)zirconiated,

dimethylselenide(fluorenyl)carrigahorig,

dimethylselenide(fluorenyl)titanimeteen,

dimethylselenide(fluorenyl)zirconocenes,

dimethylselenide(fluorenyl)garrigill,

isopropylidenebis(fluorenyl)tiandihui,

isopropylidenebis(fluorenyl)zirconiated,

isopropylidenebis(fluorenyl)carrigahorig,

isopropylidenebis(fluorenyl)titanimeteen,

isopropylidenebis(fluorenyl)zirconocenes,

isopropylidenebis(fluorenyl)garrigill,

dimethylgermylene(fluorenyl)tiandihui,

dimethylgermylene(fluorenyl)zirconiated,

dimethylgermylene(fluorenyl)titanimeteen,

dimethylgermylene(fluorenyl)zirconocenes,

dimethylgermylene(fluorenyl)garrigill,

dimethylchlorosilane(1-methylfluorene)carrigahorig,

dimethylselenide(1-methylfluorene)titanimeteen,

dimethylselenide(1-methylfluorene)zirconocenes,

dimethylselenide(1-methylfluorene)garrigill.

In addition, another object of the present invention is a method for metallocenes formula (I), including:

(a) reaction of compounds of formula (II):

< / BR>
where the substituents R1that are the same or different and have the abovementioned meanings, with a compound capable of forming an anion of the formula (III):

< / BR>
and then c compound of formula R3X2where R3have the above values and the substituents X, which are identical or different, represent halogen atoms, which results in the compounds of formula (IV):

< / BR>
(b) subsequent reaction of the compound of formula (IV) obtained according to paragraph (a), with a compound capable of forming dianion formula (V):

< / BR>
and then with the compound of the formula MX4where M and the substituents X have the above meanings, with the obtained compounds of formula (VI):

< / BR>
and finally,

(c) if at least one of the substituents R2in the target metallocene formula (I) is different from halogen, replace at least one Deputy X in the invention examples of the compounds capable of forming anionic compounds of formulas (III) and (V); include motility, n-utility, potassium hydride, metallic sodium or potassium.

Non-limiting examples of the invention compounds of formula R3X2include a clear, diphenyldichlorosilane, dimethyldichlorosilane, 2,2-dichloropropane. Of special interest is clear.

Non-limiting examples of the invention compounds of the formula MX4include: titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride. Of particular interest is zirconium tetrachloride.

The reaction of substitution of substituents X in the compound of formula (VI) non-halogen substituents R2carried out by generally known methods. For example, if the substituents R2- alkali, the compound of formula (VI) may be introduced into the reaction c alkylpolyglucoside (Grignard reagents) or c alkylimidazole.

According to one variant of the method of the present invention the synthesis of the ligand of formula (IV) is conveniently carried out by adding a solution of organolithium compounds in an aprotic solvent to a solution of the compounds of formula (II) in an aprotic solvent, in the recip is R3X2in an aprotic solvent.

From the solution obtained in the above way, the well-known methods allocate the ligand of formula (IV). The latter is dissolved in an aprotic polar solvent and the resulting solution was added a solution of organolithium compounds in an aprotic solvent. Received and the selected ligand of the formula (IV) is dissolved in an aprotic polar solvent, and then added to the suspension of the compounds of formula MX4in a non-polar solvent. At this point the reaction the formed solid product separated from the reaction mixture by known methods.

Throughout the process the temperature of the support in the range between -180oC and 80oC, preferably between -20oC and 40oC.

As non-polar solvents may be used hydrocarbon solvents such as pentane, hexane, benzene, etc.

Non-limiting of the invention, examples of the aprotic polar solvents include: tetrahydrofuran, dimethoxyethane, diethyl ether, toluene, dichloromethane, etc.

Another object of the present invention are the compounds of formula (IV):

< / BR>
where the substituents R1and group >different from hydrogen.

The above compounds of formula (IV) interim ligands that can be used to obtain metallocene formula (I).

Non-limiting examples of compounds of the formula (IV) of the present invention include: defenive(fluorenyl)silane, 2,2-bis(fluorenyl)propane, dimetilan(fluorenyl)germanium, dimethyl(1-methylfluorene)silane.

And another object of the present invention is a catalyst for polymerization of olefins, which is a product of a reaction between:

(A) metallocene formula (I) may be in the form of the reaction product with an ORGANOMETALLIC compound of aluminium of the formula AlR43or Al2R46where the substituents R4that are the same or different, accept the values of R1or halogen, and

(B) alumoxanes, possibly in a mixture of ORGANOMETALLIC compound of aluminium of the formula AlR43or Al2R46where the substituents R4that are the same or different, agree to the above values, or one or more compounds able to give alkyl cation of metallocene.

Used as component (B) alumoxane can be obtained is B> where the substituents R4that are the same or different and have the above values, provided that at least one R4different from halogen. In this case, the reaction is carried out at a molar ratio of Al/water in the range from 1:1 to 100:1.

The molar ratio of aluminum to metal in metallocene is 10:1 to 5000:1. preferably 100:1-4000:1.

It is especially suitable to metallocene formula (I) include those metallocene, where M = Zr, the substituents R1- hydrogen atoms, the substituents R2is chlorine or methyl and R3radical for example, dimethylselenide(fluorenyl)zirconiated.

Alumoxane used in the catalyst according to the invention, is a linear, branched or cyclic compound containing at least one group of the type:

< / BR>
where the substituents R5that are the same or different, represent R1or a group-O-Al (R5)2and maybe some of the R5can represent the atoms of halogen or hydrogen.

In particular, you can use alumoxane formula:

< / BR>
in the case of a linear structure, where n = 0 or an integer of 1 to 40, or alumoxane formula:

< / BR>
in the case of a cyclic structure, where n = 2 to 40.

Non-limiting examples of aluminum compounds of the formula AlR3or Al2R46include:

Al(Me)3, A(Et)3, AlH(Et)2, Al(ISO-Bu)3, AlH(I-Bu)2, Al(ISO-Hex)3, Al(C6H5)3, Al(CH2C6H5)3, Al(CH2CMe3)3, Al(CH2SiMe3)3, Al(Me)2ISO-Bu, Al(Me)2Et AlMe(Et)2, AlMe(ISO-Bu)2, Al(Me)2Cl, Al(Et)2Cl, AlEtCl2, Al2(Et)3Cl3where Me is methyl, Et is ethyl, ISO-Bu is isobutyl, ISO-Hex - isohexyl.

Of the above aluminum compounds are preferred trimethylaluminum and triisobutylaluminum.

Non-limiting examples of compounds able to form an alkyl cation of metallocene include compounds of formula Y+Z-where Y+is acid for a Given, is able to give a proton and to enter into an irreversible reaction with the substituent R1metallocene formula (I), and Z-is a compatible anion, which does not form coordination bonds and capable of stabilizing the active catalytic products formed in the reaction of the two compounds, and which dostatochno one or more boron atoms. The preferred anion Z-formula bar(-)3where the substituents Ar, which are identical or different, represent aryl, such as phenyl, pentafluorophenyl, bis(trifluoromethyl)phenyl. Especially preferred tetrakis(pentafluorophenyl)borate. In addition with success can be used compounds of the formula bar3.

The catalysts used in the method of the present invention can also be used on inert carriers. Catalysts of this type is obtained by applying metallocene (A) or the product of its reaction with the component (B), or component (B) and then metallocene (A) on an inert carrier, such as, for example, silicon dioxide, aluminum oxide, copolymers of styrene-divinylbenzene or polyethylene.

The resulting solid product after additional alkylamine either as such or pre-treated water, if necessary, can be successfully applied in gas-phase polymerization.

The catalysts of the present invention is applicable to the polymerization reaction of olefins.

Thus, another object of the present invention is a method for the polymerization of olefins comprising the polymerization reaction OLE is th invention can be applied with success in the reaction of homopolymerization alpha-olefins, such as ethylene, propylene or 1-butene. The interest is also the use of the catalysts of the invention in the reaction of copolymerization of ethylene with alpha-olefins such as propylene and 1-butene.

Methods of polymerization, employ catalysts of the invention may be carried out either in the liquid phase in the presence or absence of an inert aliphatic or aromatic hydrocarbon solvent such as hexane or toluene, or in the gas phase.

The temperature of polymerization in the way homopolymerization ethylene or propylene, as a rule, is in the range from -50oC to 250oC, in particular 40 - 90oC.

The molecular weight of the polymers can be changed by simply changing the polymerization temperature, the type or concentration of the catalyst components, or by using molecular weight regulators such as hydrogen.

Molecular weight distribution can be changed by the use of mixtures of different metallocene or by carrying out the polymerization in several stages, which varied the temperature of polymerization and/or concentration of a molecular weight regulator.

The yield of polymerization depends on the purity of metallocene s as such or can be subjected to cleaning.

The components of the catalyst can be mixed with each other prior to polymerization. Their contact is usually 1 to 60 minutes, preferably 5 to 20 minutes.

In Fig. 1 presents1H-NMR-spectrum dimethylpentanenitrile ligand of example 1 (A).

In Fig. 2 presents1H-NMR spectrum of dimethylselenide(fluorenyl)zirconiated of example 1 (B).

The following examples are given to illustrate, but not limit izobreteniya.

FEATURES

Characteristic viscosity () is defined in tetrahydronaphtalene at 135oC.

Molecular weight distribution determined GFH analysis on the instrument waters 150 in o-dichlorobenzene at 135oC.

Determine by the method of differential scanning calorimetry (DSC) performed on the device DSK-7 company Perkin-Elmer Ltd. according to the following procedure. Approximately 10 mg of sample was heated to 200oC at a scanning rate equal to the 20oC/minute. The sample is incubated for 5 minutes at 200oC, and then cooled at a scan speed of 20oC/minute. Then re-scan at a rate of 20oC/min, in the same mode as the first scanned>/BR>(A) Synthesis dimetilan(9-fluorenyl)silane: - (CH3)2Si(FIu)2< / BR>
To a solution obtained by dissolving 50 g (300 mmol) of fluorene in 350 ml of tetrahydrofuran (THF), under stirring at a temperature of 0oC added dropwise to 120 ml of 2.5 M solution of n-utility in hexane, maintaining the temperature at 0oC. Upon completion of addition, the solution is heated to room temperature and stirring is continued for 5 hours after cessation of gas evolution.

The resulting solution was then added dropwise to the mixed solution prepared by dissolution of 19.4 grams (0.15 mole) clear in 100 ml of THF, maintaining the temperature during the addition at 0oC. Upon completion of addition, the solution is heated to room temperature and stirring is continued for 14 hours.

The reaction mixture is neutralized with water, the organic layer separated and dried over MgSO4. The solvent is removed in vacuo and recrystallization of the residue from hexane obtain 37 g (63%) dimetallic(9-fluorenyl)silane, whose structure and chemical purity confirmed by GC-MS and1H-NMR (Fig. 1).

(B) Synthesis dimethylselenide(9-fluorenyl)zirconiabased: Me2SiFIu2ZrCl2< / BR>
To the solution, prigot the strong stirring and 0oC add 32,5 ml of 1.4 M solution metallice in diethyl ether (Et2O). Upon completion of addition, the mixture is heated to room temperature and stirring is continued for 5 hours after cessation of gas evolution. The resulting suspension is cooled to -78oC and added to the rapidly stirred suspension of 5.1 g (of 21.9 mmole) ZrCl4in 150 ml of pentane, also cooled to -78oC. Upon completion of addition, the reaction mixture is slowly warmed to room temperature and stirring is continued for 17 hours. The solvent is filtered and the collected solids washed with Et2O and then with pentane. Drying bright red complex in vacuum at room temperature until free flowing powder get 13,1 g Me2SiFIu2ZrCl2whose structure and chemical purity confirmed by GC-MS and1H-NMR (Fig. 2).

(C) Synthesis dimethylselenide(9-fluorenyl)zirconolite: Me2SiFIu2ZrMe2< / BR>
Obtained under paragraph (B) dimethylsilane(9-fluorenyl)zirconiated (6 g) is suspended in 50 ml of Et2O. To the rapidly stirred suspension added dropwise 7,29 ml of 3 M methylacrylamide in Et2O maintaining the temperature during the addition at 0oC.

the t another 17 hours. The precipitate is filtered off, washed with Et2O and pentane and dried under vacuum. Obtained 6.5 g Me2SiFIu2ZrMe2whose structure and chemical purity confirmed by GC-MS and1H-NMR.

(D) Synthesis dimethylselenide(9-fluorenyl)carrigahorig: Me2SiFIu2HfCl2< / BR>
In 150 ml of Et2O dissolve 8.5 g (of 21.9 mmole) dimetallic(9-fluorenyl)silane (see paragraph (A)) and to the solution with rapid stirring and at 0oC added dropwise with 32.5 ml of 1.4 M solution metallice in Et2O. Upon completion of addition, the solution is heated to room temperature and stirring is continued for 17 hours.

The precipitate is filtered off, washed with Et2O and re-suspended in Et2O. then Received a suspension via cannula at -78oC added dropwise to the rapidly stirred suspension of 7.01 g (to 21.8 mmole) HfCl4in 100 ml of pentane. Upon completion of addition, the reaction mixture is slowly warmed to room temperature and stirring is continued for 17 hours. The solvent is filtered and the collected solid was washed with Et2O and then with pentane. Bright orange complex is dried at room temperature under vacuum until free flowing powder. The yield of 13.1 g

(E) Synthesis of dimate dimethylselenide(9-fluorenyl)carrigahorig (see paragraph (D)) and to the suspension with rapid stirring, added dropwise 4,19 ml of 3 M solution methylacrylamide in Et2O maintaining the temperature during the addition at 0oC.

Upon completion of addition, the mixture is left to warm to room temperature and stirring is continued for another 17 hours. The precipitate is filtered off, washed with Et2O and pentane and dried under vacuum. Received a 3.9 g of an orange product. The structure and chemical cleanliness Me2SiFIu2HfMe2confirmed by GC-MS and1H-NMR.

(F) Receiving acetalization

Methylalumoxane (MAO)

Sale 30% solution of MAO in Cholula (Witco, 1400 MM), dried under vacuum until a solid glassy product, which is easily crushed and then dried in vacuum until you have deleted all volatile substances (4-6 hours, 0.1 mm Hg, 40 to 50oC) obtaining a white free flowing powder.

Isobutyryloxy (clearsea arts)

Use sales 30% solution in cyclohexane (Witco) as received.

Modified methylalumoxane (M-MAO)

Use sales solution isopar C (Ethyl) (62 g Al/l) obtained from the company.

B(C6F5)3< / BR>
Prepared according to methods which try to -78oC. To the resulting solution was slowly added 64,2 ml of utility (1.6 M in hexane), maintaining the temperature at -78oC. Upon completion of addition to the reaction mixture rapidly added 33 ml of 1 M solution of BCl3in hexane, pre-cooled to -50oC, stirred for 15 minutes and allowed to warm to room temperature. A precipitate. The stirring is continued for 16 hours then the solution is filtered and the volatile components removed under vacuum. Received to 11.31 g of white crystalline product.

Example 2. Polymerization of ethylene

In a glass autoclave Bucha capacity of 1 l, equipped with a jacket, screw stirrer and a thermocouple and connected to a thermostat for temperature regulation, after rinsing solution triisobutylaluminum Al(ISO-Bu)3and drying in a stream of nitrogen load 0.4 l of n-hexane (purified by passing through a column of alumina) under nitrogen atmosphere and the temperature was raised to 50oC.

The catalyst solution is prepared as follows. In 10 ml of toluene is dissolved 12,1 mg metallocene obtained in example 1 (B) and (112.3 mg MAO, 0.2 ml of the resulting solution is transferred into 10 ml of toluene containing 98 mg MAO, and then inject heated to 50oC arizala. Selected 9 g of polyethylene with a characteristic viscosity 10,56 dl/g

Example 3. Polymerization of ethylene

Reproduce the technique of the previous example, only the solution of catalyst was prepared as follows. In 5 ml of cyclohexane solution of suspended clearsea arts 8 mg metallocene obtained in example 1 (B). The resulting suspension (0,14 ml) was transferred into 10 ml of toluene containing 1,16 ml of the same cyclohexane solution of clearsea arts.

The resulting solution was injected into heated to 50oC autoclave together with a stream of ethylene. In the autoclave create a pressure of ethylene of 4 bar and within 1 hour of conduct polymerization. EUR 7.5 g of polyethylene with a characteristic viscosity of 10.1 dl/g

Example 4. Polymerization of propylene

Propylene (480 g) are loaded into the autoclave with a capacity of 1.4 l stainless steel jacketed, equipped with a magnetic stirrer, the vessel 35 ml stainless steel and thermocouple. The autoclave temperature is connected to thermostat. Autoclave pre-dried at 70oC in a stream of propylene. At room temperature for 5 minutes, mixed with 11.5 ml of toluene solution containing 1.5 mg Me2SiFIu2ZrCl2(see example 1 (C)), and then injected into thermostat is imago propylene pressure. After injection the temperature quickly increased to 50oC and for 1 hour at a constant temperature lead polymerization. Obtained 21 g transparent amorphous polypropylene with a characteristic viscosity of 2.28 dl/g Product is completely soluble in warm CHCl3. According GFH analysis of Min377000 and Min/Mh= 2,64 (Min- srednevekovaja molecular mass Mh- Brednikova molecular weight).

Examples 5-8. Polymerization of propylene

The polymerization is conducted according to the method of example 4. The number used Me2SiFIu2ZrCl2is 4 mg of the number of used MAO and toluene, the yield of polymerization and the characteristic viscosity of the obtained polymers are shown in table.

Example 9. Polymerization of propylene

In a stainless steel autoclave with a capacity of 2.3 liters with jacket, equipped with a magnetic stirrer, the vessel made of stainless steel 35 ml and a thermocouple, load 1 l of hexane and 270 g of propylene. To regulate the temperature of the autoclave is connected to thermostat. Autoclave pre-dried at 70oC in a stream of propylene. Then the autoclave thermostatic at 40oC. At room temperature, stirred for 5 minutes and 14.3 ml of toluene solution is up to the autoclave through a vessel of stainless steel with the use of created propylene pressure. The temperature quickly increased to 50oC and at a constant temperature for 1 hour to conduct polymerization. The reaction is stopped by adding a small amount of methanol. Transparent viscous solution of hexane is evaporated and the solid residue dried in a desiccator under vacuum at 60oC. Obtained 46 g of solid transparent amorphous polypropylene. The characteristic viscosity of the product 1,96 dl/g

Example 10. Polymerization of propylene

The polymerization is conducted according to the method of example 4, but use 3.4 ml of a solution of M-MAO containing 2 mg Me2SiFIu2ZrMe2(getting see example 1 (C). Obtained 80 g hard transparent amorphous polypropylene. The product has a characteristic viscosity of 2.1 dl/g

Example 11. Polymerization of propylene

In a glass autoclave Bucha shirt with a capacity of 1 l, equipped with a helical stirrer and a thermocouple, connected to a thermostat for temperature control, previously washed with a solution of Al(ISO-Bu)3in hexane and then dried at 60oC in a stream of nitrogen, load 0.4 l of hexane (purified by passing through a column of activated alumina) and 0,224 mmole of Al(ISO-Bu)3(0.2 M solution in hexane). After that, the autoclave thermostatic at 50oC. In the UB>5)3in hexane to 5 ml of toluene containing 0,0488 mmole of Al(ISO-Bu)3and 5.7 mg Me2SiFIu2ZrMe2(getting see example 1 (C)). Download propylene, until the pressure reaches 4 bar, and the polymerization carried out at constant pressure for 1 hour. The polymerization terminated by adding a small amount of methanol. Transparent viscous solution of hexane is evaporated and the solid residue optionally dried in a desiccator under vacuum at 60oC. Obtained 27.5 g of solid transparent amorphous polypropylene. The characteristic viscosity of the obtained product of 1.64 dl/g

Example 12. Polymerization of propylene

The polymerization is conducted according to the method of example 4, but the catalyst was prepared by dissolving Me2SiFIu2ZrCl2in toluene solution of MAO in such a way that the ratio of Al/Zr 550 molar, after which the solvent is removed under vacuum, until a light blue-green free flowing powder. The obtained powder (186 mg) is loaded into the autoclave before loading the monomer. As a result of polymerization, which are 120 minutes at 50oC, get a solid transparent amorphous polypropylene (183 g) with a characteristic viscosity 2,65 dl/g

Example 13. Polymerization of propylene
the RA. In the autoclave before creating the monomer pressure 13 bar load powder of the same catalyst as in example 12. The polymerization are 240 minutes at 50oC. 100 g of solid transparent amorphous polypropylene with a characteristic viscosity of 2.26 dl/g

Example 14. Polymerization of propylene

In 10 ml of toluene is dissolved 17,1 mg metallocene obtained in example 1 (B), and 348,5 mg MAO. The resulting solution was transferred into a 10 ml toluene solution containing 241.4 M. mg MAO, and the resulting solution was injected in the atmosphere of propylene in a glass autoclave Bucha, containing 90 ml of toluene, heated to 50oC and stir magnetic stirrer.

In the autoclave create a propylene pressure of 4 bar and leave to cure for 1 hour. After stopping the reaction by adding methanol, the polymer is coagulated by an excess of methanol, filtered, dried in vacuo, extracted with hot chloroform and dried again.

Received 4,85 g solid transparent polypropylene with a characteristic viscosity of 1.06 dl/g, not showing a method DSK no melting point. GFH analysis we obtained the following values: Min= 122000, Min/Mh= 3,7.

Example 15. Polymerization of propylene

In steletto for temperature control, after degassing hexane solution of Al(ISO-Bu)3and drying in vacuum in a stream of nitrogen load 0.4 l of hexane (purified by passing through a column of alumina) and the temperature was raised to 50oC.

The catalyst solution is prepared as follows. In 10 ml of toluene is dissolved 15.8 mg of metallocene obtained in example 1 (B), and 229,3 mg MAO. The resulting solution (3.8 ml) is transferred into 20 ml of toluene containing 1,043 mg MAO, after which the solution is injected in a stream of propylene into the autoclave. In the autoclave create a propylene pressure of 4 bar and within 30 minutes to conduct polymerization.

After coagulation in methanol and drying obtain 49 g of solid and transparent polypropylene with a characteristic viscosity of 1.41 dl/g GFH analysis, the following data: Min= 200000, Min/Mh= 3,5.

Example 16. Polymerization of propylene

In a steel autoclave with a capacity of 1.35 l, degassed under heat shock, propylene, loaded at 40oC 480 g of propylene. Using excess pressure of propylene inject 11.5 ml of toluene solution containing 174 mg MAO and 3.7 mg metallocene obtained in example 1 (B). The temperature was raised to 50oC for 1 hour to conduct polymerization reaction.

Example 17. Polymerization of 1-butene

In a steel autoclave with a capacity of 1.34 l, degassed under heat shock, propylene, at a temperature of 50oC load 560 mg of 1-butylene. Due to the excess pressure of nitrogen inject 5 ml of toluene solution containing 350 mg of MAO, then inject 10 ml of toluene solution containing 350 ml of MAO and 8.8 mg metallocene obtained in example 1 (B). The polymerization reaction are 2 hours at 50oC.

After removal of unreacted monomer and drying the product to obtain 28 g of a solid transparent poly-1-butylene, characterized by the complete amorphous, soluble in warm chloroform and a characteristic viscosity of 1.29 dl/g

Example 18. The copolymerization of propylene with 1-butylene

In an autoclave of stainless steel with a shirt with a capacity of 1.4 liters, equipped with a magnetic stirrer, the vessel made of stainless steel 35 ml and a thermocouple pre-dried at 70oC shock, propylene, at a temperature of 50oC load 330 mg of 1-butylene, and 275 g of propylene.

The solution of catalyst was prepared as follows. In 15 ml of toluene dissolve 8 mg metal is generated in a vessel of stainless steel. The polymerization is carried out in the course of 1 hour. Then the reaction stopped by the introduction of 600 cm3CO. After removal of unreacted monomer product is collected and dried at 60oC and reduced pressure of nitrogen.

Received 105 g of amorphous copolymer containing 39 wt.% links 1-butene ,Tg= -9,5 and the characteristic viscosity 2,37 dl/g

Example 19. The copolymerization of propylene with 1-hexene

I used the technique of example 18, but in the autoclave load of 120 g of propylene and instead of 1-butene in the autoclave load of 200 g of 1-hexene.

Received 67 g of amorphous copolymer containing at 55.6 wt.% links 1-hexene, Tg = -15,8 and the characteristic viscosity of 1.65 dl/g

Example 20. The copolymerization of propylene with 1-octene

Reproduce the method of example 18, but the number fed into the autoclave, propylene is 130 g, and the autoclave instead of 1-butylene load 270 g of 1-octene.

Received 75 g of amorphous copolymer containing to 66.3 wt.% links 1-octene, Tg = -32,3 and the characteristic viscosity 1,71 dl/g

Example 21. The copolymerization of propylene with 1-octene

Reproduce the method of example 20, but the number fed into the autoclave, propylene is 200 g, and the number of 1-octene - 150g

the awn of 2.15 dl/g

Example 22.The copolymerization of propylene with 1-octene

Reproduce the method of example 20, but the number loaded into the autoclave, propylene 270 g, and the number of 1-octene - 45,

Obtained 27 g of amorphous copolymer containing 12 wt.% links 1-octene, Tg = -1,6 with a characteristic viscosity 2,22 dl/g

1. Metallocene with ligands fluoroanilino type formula I

< / BR>
where R1is hydrogen or lower alkyl; M is Ti, Zr or HF;

R2- halogen;

R3represents a radical >Si(R4)2, >CR42,

where R4- lower alkyl or C3-C20cycloalkyl.

2. Metallocen under item 1, representing dimethylselenide(fluorenyl)zirconiated.

3. The method of obtaining metallocene formula I under item 1, characterized in that exercise:

(a) reaction of compounds of formula II

< / BR>
where the substituents R1that are the same or different and have the abovementioned meanings, with a compound capable of forming an anion of formula III

< / BR>
and then with the compound of the formula R3X2where R3have the above values and the substituents X, which are identical or different, represent halogen atoms, education is eat, capable to form dianion formula V:

< / BR>
and then with the compound of the formula MX4where M and the substituents X agree to the above values, which results in the compounds of formula VI

< / BR>
4. The method according to p. 3, characterized in that the compound of the formula MX4is zirconium tetrachloride.

5. The compound of formula IV

< / BR>
where the substituents R1and R3matter under item 1 and when R3- group >Si(CH3)2then at least one of the substituents R1different from hydrogen.

6. Connection on p. 5, characterized in that the group R3is radical >Si(CH3)2.

7. The catalyst for polymerization of olefins, comprising alumoxane and metallocene, characterized in that as metallocene used as a compound of formula (I) under item 1, may be in the form of the reaction product with an ORGANOMETALLIC compound of aluminium of the formula AlR43or Al2R46where the substituents R4that are the same or different, represent R1or halogen, and use alumoxane possibly in a mixture with an ORGANOMETALLIC compound of aluminium of the formula AlR43or Al2R46where the substituents R

8. The catalyst according to p. 7, characterized in that the compound capable of forming an alkyl cation of metallocene is trifoiler.

9. The catalyst according to p. 7, characterized in that it is the product of the reaction between dimethylselenide(fluorenyl)zirconiated and a compound selected from methylalumoxane and isobutylamine.

10. The method of polymerization of olefins, consisting in the wording of polymerization of olefin monomer in the presence of a catalyst, characterized in that the use of the catalyst according to PP.7 - 9, containing metallocene under item 1.

11. Metallocene under item 1 of the formula I in which the substituent R1represents hydrogen, R2represents chlorine and R3is the radical Si(CH3)2.

 

Same patents:

- olefins and method of reception" target="_blank">

The invention relates to precatalytic compositions suitable for Homo - and copolymerization of olefins and to a method for producing such composition precatalytic

The invention relates to precatalytic component of the catalytic composition of the Ziegler-Natta, suitable for the production of polymers of ethylene

The invention relates to a ball of solid catalytic components for the polymerization of olefins containing compound of titanium deposited on a magnesium halide containing more than one relationship Ti-halogen and, optionally, containing groups other than halogen, in the amount of less than 0.5 mol per 1 mol Ti

The invention relates to a method for producing olefinic polymers (this is the name used to refer to both homopolymers and copolymers of olefins by polymerization (the term used to refer to as homopolymerization and copolymerization) of olefins

The invention relates to copolymers of ethylene,-olefin containing from 3 to 18 carbon atoms, and unpaired-omega diene having at least 7 carbon atoms and having two easily curable double bonds, the number of non-conjugate diene is 0.005 to 0.7 mol

The invention relates to catalytic systems, methods for their preparation and their use in polymerization of olefins

-olefin (options)" target="_blank">

The invention relates to catalysts used for Homo - and copolymerization of ethylene and other olefin hydrocarbons

The invention relates to a method of gas-phase polymerization carried out in two vzaimosoedinenii areas polymerization, which serves one or more-olefins of General formula CH2=СНR in the presence of catalyst under reaction conditions and from which the polymer product is discharged

The invention relates to the preparation of catalyst components on the carrier, including a carrier and alumoxane, the catalysts on the media containing the metallocene compound and the ways polyaddition using these catalysts

The invention relates to a method for preventing fouling in the polymerization reactors, in particular in the reactor circulation

The invention relates to a method of continuous suspension or gas-phase polymerization of olefin(s) using as the catalyst the transition metal compounds with bulky ligand in the absence or in the presence of a small amount of the cleansing component

The invention relates to new Homo - and copolymers of ethylene having a degree of swelling at least 1,4, resistance to cracking under load at least 55 h and the flow index of at least 0.2 g/10 min

-olefin (options)" target="_blank">

The invention relates to catalysts used for Homo - and copolymerization of ethylene and other olefin hydrocarbons
Up!