The method of polymerizationthe olefin and the catalyst to obtain-olefin

 

(57) Abstract:

Describes how to obtain a polyolefin, comprising the polymerization of olefin in the presence of a catalyst system containing socialization and catalyst. Describes also the catalytic Converter system, in which azamatushanov the catalyst has at least one ligand containing pyrrolidino group associated with the transition metal, which contains a nitrogen-containing 5-membered resonant ring. The technical result - the increase of catalytic activity of nitrogen-containing polymerization catalysts at high temperatures to obtain polymers with a narrow molecular weight distribution. 2 C. and 21 C.p. f-crystals.

This invention relates to zametalinism catalysts suitable for the polymerization of olefins, such as ethylene and other unsaturated monomers. In particular, the invention relates to catalysts having at least one ligand that contains pyrrolidine ring associated with the transition metal.

Until recently, polyolefins received mostly with conventional catalytic system of the Ziegler. These catalysts usually consist of compounds containing transition is of alization Ziegler, such as titanium trichloride and diethylaluminum, or a mixture of titanium tetrachloride, oxytrichloride vanadium and triethylaluminum. These catalysts are inexpensive, but they have low activity and therefore must be used at high concentrations. As a result, sometimes there is a need to remove catalyst residues from the polymer, which has increased the cost of production. The polymer should be added neutralizing agents and stabilizers in order to overcome the harmful effects of catalytic residues. The inability of the removal of catalytic residues resulted in polymers having yellow or gray color and poor stability under ultraviolet irradiation and poor long-term stability. For example, chlorine-containing residues can cause corrosion in the equipment, the processing of the polymer.

In addition, the polymers produced with the catalysts of the Ziegler had a wide molecular weight distribution, which is undesirable for some applications, such as injection molding. They were also bad at introduction-olefin comonomers. Bad introduction of comonomers is difficult, kontrolirowali is the co monomer, while many higher-olefins such as 1-octene, could be entered only at very low concentrations, if at all, could be introduced.

Although significant improvement in the catalytic system of the Ziegler has been achieved since their discovery, these catalysts are now replaced with the newly discovered metallocene catalytic systems. Metallocene catalyst usually consists of compounds of the transition metal that contains one or more cyclopentadienyls cyclic ligands. They have low activity, when used with ORGANOMETALLIC compounds, such as alkali aluminum, which are used with conventional Ziegler catalysts, but have a very high activity when used with alumoxane as socialization. The activity is usually so high that it is not necessary to remove catalyst residues from the polymer. In addition, they give polymers with high molecular weights and narrow molecular weight distribution. They also allow the well to enter-olefin comonomers. However, at elevated temperatures metallocene catalysts have a tendency to obtain low molecular weight polymers. Tack at a temperature of from about 80oC to about 95oC, but they usually don't work effectively in the polymerization of ethylene in solution at temperatures from about 150oC to about 250oC. Polymerization of ethylene in solution is desirable because it allows a wide variety in the production of polymers in a wide range of molecular weights and densities, as well as to use a large variety of different comonomers. Polymerization in solution allows to obtain polymers that are useful in many different applications, for example high molecular weight high density polyethylene film suitable as barrier films for food packaging, and copolymers of ethylene, low density, good toughness and high impact strength.

One of the features of metallocene catalysts is the presence of links between one or more cyclopentadienyls ligands containing ring, and the transition metal. These relationships are moderately strong and stable. In contrast, communication between transition metals and pyrrolidinyl ligands containing ring are relatively unstable.

Although these nitrogen-containing ligands form an unstable connection, met. Chem. 1964. 1, 471) found that pyrrolidinyl analogue of ferrocene was less stable, and showed that pyrrolidine ligands tend to education. Van Bynum et. al. got a 2.5 dimethylpyrrole derivative Zr and showed that these derivatives do not lead to the binding of Zr atoms in these compounds (Can.J.Chem. 1986. 64, 1304). Ladipo et.al. showed that indole complexes with iridium also form a connection with the transition metal (Inorgan.Chem. 1990. 29 4172). The recent debate-related paralellogram ligands (J. Zakrezewski, Heterocycles, 1990, 31, 383) re-emphasized the instability of the complexes of this type.

Database WPI AN 68-29949q, IT-A-778386 discloses N-indolyl and N-carbazol derivatives of titanium, the same titanium-tetrahalide and titanium-tetracarbonyl, and their use as catalysts for Ziegler-Natta. EP-A-0617052 reveals indolyl and carbazolyl zirconium compounds as catalysts for the polymerization of olefin with alumoxane (see S. 26 lines 52-57 and paragraph 14 of the claims). Similar calculations can be found in EP-A-0574794 (see paragraphs 1-7 of the claims, S. 5-8, lines 39-41).

In the present invention are disclosed some new azamatushanov compounds that are suitable as rolled the Dean ligand, containing pyrrolidino group which contains a nitrogen-containing 5-membered resonant ring. Pyrrolidine group can form a bond with the transition metal atom. These compounds are suitable together with socialization, which is usually alumoxane. Unexpectedly, the compounds containing pyrrolidino group, are suitable as polymerization catalysts, because in the field of catalysis is well known that nitrogen-containing compounds are often catalytic poisons. However, it was found that these compounds are not only suitable as catalysts for the polymerization of olefins, but they also have good activity at high temperatures and give high molecular weight polymers with narrow molecular weight distribution.

The catalysts of this invention allows the same way as a normal metallocene to introduction of comonomers such as butene, octene, hexene, and 4-methylpentene-1. They allow to obtain a colorless polymers having high stability with respect to UV radiation and long-term stability. In addition, the catalysts of this invention are much easier to prepare and less Dor the initial metal having a General formula

< / BR>
where L represents the ligand or mixture of ligands, each containing 4-30 carbon atoms and containing at least two condensed rings, one of which is pyrrolidinyl ring, Cp represents a ligand containing cyclopentadienyls ring, where two L ligand or L and Cp ligand can form a bond, B is a Lewis base, Y represents halogen, alkoxy with C1-C20carbon atoms, siloxy with C1-C20carbon atoms, N(R1)2, or mixtures thereof, M represents titanium, zirconium or mixtures thereof, m is from 1 to 4, preferably 2, 3 or 4, n is from 0 to 2, p is from 0 to 2, q is from 0 to 1 and m+n+q=4.

In the formula, Y is preferably a halogen and more preferably either chlorine or bromine, but alkoxy groups such as methoxy (CH3O-), ethoxy (CH3CH2O-) or siloxy (R1)3SiO-, where R1represents alkyl with C1-C20carbon atoms should also be mentioned. In addition, m is more preferably equal to 4, since such catalysts give polymers with the highest molecular weight at the highest temperature.

Examples of the L groups, which can be used include Alki,5-di-tertbutylphenol, aryl-substituted pyrrolidine rings, such as 2-phenylpyrrole, 2,5-diphenylpyrrole, indolyl, alkyl substituted indolyl.

< / BR>
such as 2-methylindole, 2-tert-boilingly, 3-boilingly, 7-methylindole, 4,7-dimethylindole, the aryl-substituted indolyl such as 2-phenylindole, 3-phenylindole, 2-pentylindol, isoindolyl and alkyl and aryl-substituted isoindoline

< / BR>
and carbazolyl and alkyl substituted carbazolyl

< / BR>
In the formulas, each R is preferably Deputy, is independently selected from hydrogen, alkyl with C1-C20and aryl C6-C10and s is 1-4. Alkyl and aryl substituents on pyrrolidino ligand containing a ring are nitrogen atom in the ring, and are on the carbon atoms of the ring. Particularly preferred ligands are carbazolyl and C1-C4alkilinity in the 2 or 7 position, or in both positions, because the alkyl in position 2 prevents the formation of dimers. Catalysts based on carbazole and indolyl give high activity and improved performance at high temperatures of polymerization, yielding high molecular weight, which imply a more durable polymer and better impact strength and l are not condensed with an aromatic ring, because such catalysts do not work successfully (see comparative examples).

Examples of Lewis bases B, which can be used in this invention include diethyl ether, disutility ether, tetrahydrofuran, and 1,2-dimethoxyethane. The Lewis base B represents the residual solvent and the relationship between B and M is not covalent.

Cp ligand can be cyclopentadienyls ring with 0-5 replacement groups

< / BR>
where each replacement group R2independently selected from C1-C20hydrocarbon group and r is from 0 to 5. In the case in which the two R2groups are adjacent, they can be associated with the formation of a ring, which is condensed with the Cp ring. Examples of alkyl substituted Cp rings include butylcyclopentadienyl, methyl cyclopentadienyl and pentamethylcyclopentadienyl. Examples of ligands condensed Cp rings include indenyl, tetrahydroindene, fluorenyl and 2-methylindenyl. While the Cp ligand can be used in combination with other ligands, it is preferable not to use them because their presence reduces the molecular weight of the polyethylene obtained at elevated temperatures.

Group, colormaterial, diphenylsilane, diethylsilane and methylpenicillin. Usually use only one bridge connection in the catalyst. I believe that the binding of the ligand changes the geometry around the catalytically active transition metal and improves the catalytic activity and other properties, such as the introduction of the co monomer and thermal stability.

The catalysts of this invention can be obtained in different ways, but the most easily obtained by using the original compounds containing the ligand. Most of the compounds used as ligands, are industrially available, including indole, pyrrole and carbazole, and some alkylidene. Substituted ligands can be obtained in various ways. Some examples include the alkylation according to Friedel-Crafts, alkylation with socialmiami, direct synthesis via the synthesis of indole Fisher and methods described Bray et.al. in J. Orq.Chem. 1990. 55, 6317. A number of other methods known to experts in this field.

In the first stage of preparation of the catalyst compound containing a ligand that interacts with a proton acceptor. Can be used in stoichiometric quantities. Examples of acceptors include protons metalman what is methylacrylamide, because it is easy to use. The reaction is preferably carried out by dissolving reactant in an organic solvent that does not contain an active proton such as tetrahydrofuran, anisole, or ethyl ether. Ether, such as diethyl ether is preferred. The solution should be concentrated as far as possible to reduce the amount of solvent that must be loaded. The reaction can take place at temperatures from about -78oC to about 50oC, but preferably the reaction is carried out at a temperature of from about -10oC to 25oC in order to avoid heating. The reaction ends when the evolution of gas ceases. For example, indole interacts with methylmagnesium with the formation of gaseous methane and mortar connection with industerial ligand in solvent:

< / BR>
In the next stage of the process for preparation of catalysts of this invention, the halide of the transition metal alkoxide or siloxy added to a solution of compounds containing the ligand, at a temperature between -100oC and about 0oC. avoid high temperatures, as they may cause decomposition of the metal-containing product.

Or azamatushanov polymerization catalysts of this invention can be obtained three-stage procedure, first the interaction of stoichiometric quantities of dialkylamide metal of group I or II with a compound of titanium or qi is>Cp) + (4-q)M R3< / BR>
where M' represents an alkaline or alkaline earth metal, preferably lithium, sodium or magnesium, as well as dialkylamide of these metals, which are easily accessible, and R3represents a halogen, preferably chloride or alkoxide with1-C8. R1(alkyl from C1to C20group is preferably C2-C6as those compounds that are more affordable. The reaction temperature is not critical and lies between -10oC and 50oC temperature such as room is suitable. The reaction ends when a by-product alkali or alkaline earth metal such as lithium chloride, precipitates. As many of tetrakis(dialkylamino)titanium or zirconium compounds are industrially available, this first reaction is not always necessary.

In the second stage the alternative procedure for preparation of the catalyst, tetrakis(dialkylamino)titanium or zirconium compound interacts with the compound containing pyrrole ring:

M(N(R1)2)4-g(Cp)q+mLH ---> (L)mM(N(R1)2)4-m-q(Cp)q+ mNH(R1)2< / BR>
This reaction, tetrahydrofuran, and dimethoxyethane, but hydrocarbon solvents such as toluene, are preferred. Preferably the reaction temperature is from about -78oC to about 50oC. On termination of the reaction is evidenced by the evolution of gas or detection of free base using nuclear magnetic resonance (NMR).

In the third stage of the alternative procedure for preparation of the catalyst, the product of the second stage interacts with the connection that replaces some or all of the remaining aminogroup halogen, alkoxy, or siloxy groups:

(L)mM(N(R1)2)4-m-q(CP)q+ nYZ --->

< / BR>
where Z represents the cationic portion of the compound YZ.

Processing palodiruyut agent replaces aminogroup halogen. Ganoderma agents include compounds such as silicon tetrachloride, hydrogen chloride, methyltrichlorosilane, boron trichloride, hexachlorethane, pentachloride phosphorus, pentachloride antimony, chlorine and the like compounds. For example, bis(carbazolyl)bis(diethylamido)zirconium two moles of silicon tetrachloride gives bis(carbazolyl)zirconium dichloride.

As the catalyst is usually used together with storim socialization. For example, if methylalumoxane (MAO) is socialization, then the solvent may be toluene, xylene, benzene or ethylbenzene. Examples of suitable socialization include MAO and the mixture MAO with other alkylamines compounds, such as triethylaluminum, ethylaluminum or diisobutylaluminum. The preferred catalyst is MAO, as it results in high catalyst activity, a good occurrence of the comonomers in the reaction, and the polymer having a narrow molecular weight distribution. Preferably not necessary to pre-mix the catalyst and socialization, as this may lead to loss of catalytic activity. Better catalyst and socialization preferably injected separately into the reactor containing the monomer, which should be polimerizuet. And preferably socialization to inject the first. The number of socializaton used with the compound of the transition metal may be in a molar ratio in the range from about 1:1 to about 15,000:1.

Can also be used catalyst and socialization on media such as silica gel, alumina, magnesium oxide or titanium dioxide. The media usually is ü may be required depending on the process, which is used. For example, the media is usually required in gas-phase polymerization and suspension polymerization processes in order to control the particle size of the polymer obtained, and in order to prevent contamination of the walls of the reactor. In order to use the carrier, the catalyst is dissolved in a solvent and deposited on the material acting as a carrier, by evaporation of the solvent. Socialization can also be deposited on the carrier, or it may be introduced into the reactor separately from the catalyst on the substrate.

As soon as the catalyst is prepared, it should be used as soon as possible, as it may lose some activity during storage. Storage catalyst must be carried out at a low temperature, such as from -100oC to 20oC. the Catalyst is used in the usual way in the polymerization of unsaturated olefinic monomers. At that time, as unsaturated monomers such as styrene, can be depolimerization using the catalysts of this invention, the catalyst is particularly suitable for the polymerization of a-olefins such as propylene, 1-butene, 1-hexene, 1-octene, and osobnymi monomers, such as 1-butene, 1 - hexene, 1-octene and the like; mixtures of ethylene and di-olefins such as 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, and the like: mixtures of ethylene and unsaturated comonomers, such as norbornadiene, ethylidenenorbornene, vinylnorbornene and the like.

The catalysts of this invention can be used in various other polymerization processes. They can be used in liquid-phase polymerization (slurry, solution, suspension(bead), in bulk or in combination of these processes), in liquid-phase processes, high pressure or gas phase polymerization processes. The processes can be used in series or as individual unit processes. The pressure in the reaction zone of the polymerization may be in the range from about 1 ATM to about 3500 ATM and the temperature can be in the range from about -100oC to about 300oC.

The following examples further illustrate this invention

Example 1

Preparation of catalyst

All stages were carried out in nitrogen atmosphere, using conventional methods with the use of shelenkov. All glassware was clean and did not contain moisture and oxygen. All solvents were of oslob the alumina collecting solvent under nitrogen by blowing with nitrogen and stored over activated molecular sieves 4A.

Indole (Aldrich Chemical Company) was recrystallized from hexane. Recrystallized indole (2,34 g) were placed in 250 ml slenk, which contained a metal rod, sealed in glass, for mixing, and slunk have sealed partition. Diethyl ether (50 ml) was added via needle with double hole for dissolution of indole. A solution of indole was cooled to 0oC in the bath with ice. Methylanisole (6,70 ml of 3.0 mol) in ether (from Aldrich Chemical Company) was slowly added under stirring with a syringe. In the process of adding the allocated gas. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was additionally stirred for 1 h at room temperature.

The zirconium tetrachloride (2,33 g) from Aldrich Chemical Company and used without further purification, was placed in a clean, dry, free from oxygen 250 ml slenk, which contained the rod for mixing. Slenk have sealed partition. Diethyl ether (100 ml) was added via needle with a double hole. This suspension within 10 min using a needle with a double hole. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was additionally stirred for 1 h at room temperature. The product was an orange suspension. The ether was removed from the suspension by evaporation in a vacuum. The product was a brown solid. Toluene (100 ml) was added to this solid substance and was stirred for 2 h at room temperature. The solution was regenerated by vacuum filtration using a glass filter SCHOTT (4 μm). The toluene was removed by evaporation in a vacuum. The product was solid, which contained 6.0 wt.% Zr. The data of elemental analysis showed the absence of a Cl.

The results of polymerization

The polymerization was carried out in a 1.7 l stainless steel autoclave with stirring at 80oC. Dry, free from oxygen toluene (840 ml) was loaded in a clean, dry, free from oxygen reactor. 6 ml of 10% MAO in toluene (from Ethyl Corporation without further purification) was added to the toluene in the reactor. To the reactor was added hydrogen or comonomer. Added a sufficient amount of ethylene to bring the reactor pressure to 1.03 mrceveli into the reactor to start the polymerization.

After 1 h the flow of ethylene was stopped and the reactor was rapidly cooled to room temperature.

The polymer was filtered from the toluene by vacuum filtration. The polymer was dried overnight in a vacuum oven and weighed. The weight of the polymer amounted to 75.2, This corresponded to the performance of the catalyst 69,9 kg/g Zr.

The properties of the polymer

The melt index of the polymer was measured according to ASTM D-1238. Condition E and Condition F. MI is the melt index measured with a weight of 2.16 kg (Condition E). HLMI is the melt index measured with a weight of 21.6 kg (Condition F). MFR is the ratio of HLMI to MI. The density of the polymer was measured according to ASTM D-1505. Molecular weight distribution of the polymer was measured using a Waters 15oC gel chromatography at 135oC with 1,2,4-trichlorobenzene as solvent. Both weight srednevekovoi molecular weight Mwand the relation of Mwto Mn(srednekamennogo molecular weight), was used to characterize the molecular mass distribution.

The melting point of the polymer was measured using a differential scanning calorimeter (DuPont Instrument 912 (DSC). Used cycles of heating and cooling. TempoC/min Between the two cycles, the sample was kept at 200oC for 10 min before cooling to 50oC.

The polymer had a value of MI 0,086 DG/min and HLMI 1,82 DG/min consistent with the MFR value of 21.2. The value of Mwequal 162000 and the ratio of MwMnequal to 2.06. This indicates a narrow molecular weight distribution, although the molecular weight was high. The density of the polymer was 0,9536 g/ml melting point according to DSC equal 136,0oC.

Example 2

This example shows that for high molecular weight polymer can be used catalyst with low concentrations of MAO. It is not necessary to use very high concentrations of MAO, usually used with metallocene catalysts. The catalyst described in Example 1 was tested under the same polymerization conditions as in Example 1, except that used was 3.0 ml of 10% MAO. Polymerization for 1 h gave the result of 26.1 g of polyethylene. The polymer had a value of MI 0,068 DG/min and HLMI 1,53 DG/min consistent with the MFR value of 22.5.

Example 3

This example shows that the catalyst can be used at high temperatures to obtain high molecular weight polymers. Kataliza used a temperature of 110oC. the Number of the obtained polyethylene was 38,9, the Polymer had a value of MI 0,90 DG/min and HLMI 15,93 DG/min consistent with the MFR value of 17.7. The value of Mwequal 102800 and the ratio of Mw/Mnwell 1,91. The density of the polymer was 0,9606 g/ml melting point according to DSC equal br135.8oC.

Example 4

This example shows the effect of higher temperatures and higher concentrations of MAO on the characteristics of the catalyst described in Example 1. The catalyst was tested under the same polymerization conditions as in Example 1, except that used a temperature of 110oC. the Number of the obtained polyethylene was 71,3, the Polymer had a value of MI 1,77 DG/min and HLMI 32,2 DG/min consistent with the MFR value of 18.2. The value of Mwequal 79600 and the ratio of Mw/Mnwell 1,68. The density of the polymer was 0,9601 g/ml melting point according to DSC equal 134,9oC.

Example 5

This example shows the effect of using different types of MAO as acetalization with the catalyst described in Example 1. The catalyst was tested under the same polymerization conditions as in Example 3, except that used 6 ml polymethylsiloxane (PMO) S2. The number of the obtained polyethylene stood at 81.9, the Polymer had a value of MI 3,69 DG/min.

Example 6

The catalyst described in Example 1 was tested under the same polymerization conditions as described in Example 4, except that of 20.0 ml of liquid 1-butene was added to the reactor. The number of the obtained polyethylene was 88,9 grams. The polymer had a value of MI to 11.79 DG/min and HLMI 233,4 DG/min, This corresponds to the value of MFR 19,8.

Example 7

Preparation of catalyst

The catalyst was prepared using the methods described in Example 1. Recrystallized indole (2,34 g) were placed in 250 ml slenk, which contained a stirring rod. Slenk have sealed partition. Diethyl ether (100 ml) was added via needle with double hole for dissolution of indole. The solution was cooled to 0oC in the bath with ice. Methylanisole in ether (6,70 ml of 3.0 molar) was dissolved in 50 ml of ether. The solution methylacrylamide was slowly added to a solution of indole with a needle with double hole under stirring. In the process of adding the allocated gas. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature perenity titanium (1,10 ml) from Aldrich Chemical Company, used without further purification, was placed in a clean, dry, free from oxygen 250 ml slenk, which contained the rod for mixing. Slenk have sealed the bulkhead and 100 ml of ether was added via needle with a double hole. This suspension was stirred at room temperature overnight to obtain a yellow solution. This solution was cooled to 0oC in the bath with ice. Product indole/methylacrylamide was added to a solution of TiCl4within 10 min using a needle with a double hole. The reaction mixture was stirred for 30 min, then bath with ice was removed and the mixture allowed to warm to room temperature. The mixture was stirred for 2 h at room temperature. The product was a black suspension. The ether was removed from the suspension by evaporation in vacuum with the release of the black solid product.

A polymerization test

A solution of the product prepared by dissolving 0,500 g of the solid in 100 ml of dry, free from oxygen toluene. After stirring for 1 h, the sample was not dissolved completely. Analysis of the liquid phase showed a concentration of Ti equal 5,01 10-3mol/liter of the polymerization Reactions was carried out as described in Example 1 for excluded is Orada. Comonomer not added to the reactor. Used 1 ml of the catalyst for the beginning of the polymerization and got to 35.1 g of the polymer after 1 h of reaction. The polymer had a value of MI 0,125 DG/min and a HLMI of 4.75 DG/min, This corresponds to the value of MFR 38,0.

Example 8

This example shows the effect of different quantities of MAO on the catalytic activity. The solid from Example 7 was dissolved in 100 ml of toluene. The polymerization conditions were identical to the conditions of Example 7, except that used was 3.0 ml of the catalyst solution and 10.0 ml of a solution of MAO. In addition, there was added 120 mmol of hydrogen. After 1 h the reaction was received with 50.1 g of polymer.

Example 9

This example shows the effect of high amounts of hydrogen and 1-butene on the catalytic activity. The polymerization described in Example 8 was repeated except that the reactor was added 12 ml of liquid 1-butene and 120 mmol of hydrogen. After 30 min the reaction was received of 55.5 g of polymer.

Example 10

This example shows the effect of the increased amount of one hydrogen on the catalytic activity. The polymerization described in Example 8 was repeated except that the added 180 mmol of hydrogen to control the molecular weight of the polymer. P is the mash was prepared using methods described in Example 1. 2-Methylindol (2.59 g) from Aldrich Chemical Company and used without further purification, was placed in a clean, dry, free from oxygen 250 ml slenk, which contained the rod for mixing. Slenk have sealed partition. Diethyl ether (70 ml) was added via needle with double hole for dissolving 2-methylindole) are studied. Methylanisole (6,70 ml to 3.0 mole) in ether was placed in 118 ml flask was added 40 ml of diethyl ether for his dissolution.

A solution of 2-methylindole was cooled in a bath of ice at 0oC. the Solution methylacrylamide was added to the indole with a needle with a double hole for 15 minutes In the process of adding the allocated gas. The reaction mixture was stirred for 30 min at 0oC. Bath with ice was removed and the mixture was heated to room temperature over 90 minutes This product was stored overnight at 10oC.

Tetrachloride titanium (1,10 ml) was placed in a clean, dry, free from oxygen 118 ml flask, which contained a rod for mixing. To the flask was added toluene (40 ml), which was then sealed by a partition. Slink containing the reaction product of 2-methylindole and methylacrylamide, cooled to 0oC in the bath is double hole. The reaction mixture was stirred for 2.5 h at 0oC. Then the bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The flask was kept at 10oC during the night. The product was a reddish-black suspension.

The ether was removed from the suspension by evaporation in a vacuum. The product was represented by the black solid. This solid matter was added to approximately 100 ml of toluene and was stirred for 1 h at room temperature. This has led to a reddish-black suspension. The solids were filtered off using a thick glass filter (SCHOTT and the solution was collected. The toluene was removed by evaporation in vacuum to obtain a solid black substance, which contained 7.9 wt.% Ti.

A polymerization test

A solution of the product prepared by dissolving 0,4501 g of substance in 100 ml of toluene. The polymerization was carried out as described in Example 1, except that was added 10.0 ml of 10% MAO in toluene as socializaton and polymerization was carried out at 80oC with the addition of 3 moles of hydrogen. Used 3 ml of the catalyst for the beginning of the polymerization and obtained 12.5 g of the polymer after 1 h of reaction. The polymer had vicopisano in Example 11, repeated, except that the used amount of the catalyst was 1.5 ml of a solution of catalyst in the reactor was added 180 mmol of hydrogen. After 1 h the reaction was obtained 14.4 g of polymer. The polymer had a value of MI 0,393 DG/min and HLMI 7,78 DG/min, This corresponds to the value of MFR 19,8.

Example 13

Preparation of catalyst

The catalyst was prepared using the methods described in Example 1. 2-Methylindol (2,69 g) from Aldrich Chemical Company and used without further purification, were placed in a 250 ml slenk, which contained the rod for mixing. Slenk have sealed partition. Diethyl ether (40 ml) was added via needle with double hole for dissolving 2-methylindole) are studied. Methylanisole (6,70 ml to 3.0 mole) in ether was placed in 118 ml flask was added 30 ml of diethyl ether for his dissolution.

A solution of 2-methylindole was cooled in a bath of ice at 0oC. the Solution methylacrylamide was added to the indole with a needle with a double hole for 10 minutes In the process of adding the allocated gas. The reaction mixture was stirred for 2 h at 0oC. Bath with ice was removed and the mixture was stored overnight at 10oC.

Tetrachloride zirconium (2,30 g diethyl ether (120 ml) and the flask was sealed with septum. The contents of the flask was stirred for 2 h at room temperature and then was cooled to 0oC in the bath with ice.

The reaction product 2-methylindole and methylacrylamide was added to the suspension ZrCl4using a needle with a double hole for about 20 minutes under stirring. This reaction resulted in the formation of a yellow suspension which was stirred for 2 h at 0oC. Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The ether was removed from the suspension by evaporation in a vacuum. Was added toluene (100 ml) to this solid product was stirred for 3 h at room temperature, which gave the resulting reddish suspension. The solids were filtered off using a thick glass filter SCHOTT. The product was isolated from the toluene solution by evaporation of the toluene under vacuum. The product was a dark red solid, which contained 12.2 wt.% Zr.

A polymerization test

A solution of the product prepared by dissolving 0,3440 g of substance in 100 ml of toluene. The polymerization was carried out as described in Example 1, except that was added 10.0 ml of 10% MAO in toluene as socializaton and polymers the Ala polymerization and obtained 11.1 g of the polymer after 1 h of reaction. The polymer had a value of MI 0,082 DG/min and HLMI 4,51 DG/min consistent with the MPR value of 54.8.

Example 14

This example shows the effect of increased amounts of hydrogen on catalytic activity. The polymerization described in Example 13 was repeated except that the reactor was added 180 mmol of hydrogen. The amount of polymer obtained after 1 h the reaction was 7.3, the Polymer had a value of MI 0,071 DG/min and HLMI 2,90 DG/min, This corresponds to the value of MFR 41,0.

Example 15

This example shows the effect of hydrogen and 1-butene on the catalytic activity. The polymerization described in Example 13 was repeated except that the reactor was added 120 mmol of hydrogen and 20 ml of liquid 1-butene. The amount of polymer obtained after 1 h the reaction was 8.5, the Polymer had a HLMI value of 1.05 DG/min.

Example 16

Carbazole (1,67 g from Aldrich Chemical Company) was recrystallized from ether and placed in 250 ml slenk, which contained the rod for mixing. Slenk have sealed partition. Ether (100 ml) was added via needle with a double hole. The solution was cooled to 0oC in the bath with ice. Methylanisole (3,30 ml to 3.0 mole) in ether (from Aldrich Chemical Company) was slowly added with pouchenie 1 h Bath ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was additionally stirred for 1 h at room temperature.

Tetrachloride zirconium (1,16 g) from Aldrich Chemical Company (used without further purification) was placed in a clean, dry, free from oxygen 250-ml slenk, which contained the rod for mixing. Slenk have sealed partition. 50 ml of ether was added via needle with a double hole. This suspension was cooled to -78oC in a bath of dry ice/isopropanol. Product carbazole/methylacrylamide was added to the suspension ZrCl4within 10 min using a needle with a double hole. The reaction mixture was stirred for 1 h Bath was removed and the mixture allowed to warm to room temperature with stirring. The mixture was stirred additionally for 1 h under stirring. The product was a yellow-orange suspension.

The ether was removed from the suspension by evaporation in a vacuum. Toluene (100 ml) was added to this solid substance and was stirred for 2 h at room temperature. The solution was regenerated by vacuum filtration using a dense (4 μm) glass filter SCHOTT. Toluene prowess of the>The results of polymerization

Polymerization was performed in a mix of 1.7 l stainless steel autoclave at 80oC. Dry, free from oxygen toluene (840 ml) was loaded in a clean, dry, free from oxygen reactor and 6.0 ml of 10% methylalumoxane (MAO) in toluene (from Ethyl Corporation and used without further purification) was added to the toluene in the reactor. To the reactor was added hydrogen or comonomer. Added a sufficient amount of ethylene to bring the reactor pressure up to 10.5 ATM. The catalyst solution was prepared by dissolving 0,1090 g of product in 100 ml of toluene. The polymerization was started by injection of 1.0 ml of this solution.

After 1 h the flow of ethylene was stopped and the reactor was rapidly cooled to room temperature. The polymer was filtered from the toluene by vacuum filtration. The polymer was dried overnight in a vacuum Cabinet and weighed. The weight of the polymer was 26.8, This corresponded to the performance of the catalyst 304 kg/g Zr. The polymer had a value of MI 0,136 DG/min and a HLMI of 1.30 DG/min consistent with the MFR value of 9.6. This indicates a narrow molecular weight distribution, even if the molecular weight was high.

Example 17

The catalyst described in Example 16, was and is Isadora was diluted in 100 ml of toluene. This diluted solution (1.0 ml) was used under the same conditions as in Example 16. After 1 h of polymerization got to 38.3 g of polyethylene. This was in line with the performance of the catalyst 1,737 kg/g Zr. The polymer had a value of MI 0,142 DG/min and a HLMI of 1.45 DG/min consistent with the MFR value of 10.2. The density of the polymer was 0,9599 g/ml.

Example 18

The catalyst described in Example 16 was tested under the same polymerization conditions as described in Example 17, except that added 20 ml of 10-butene as co monomer. 41,0 g of the obtained polyethylene match the performance of the catalyst 1,859 kg/g Zr. The polymer had a value of MI 0,154 DG/min and HLMI 1,71 DG/min consistent with the MFR value of 11.1. The density of the polymer was 0,9411 g/ml.

Example 19

The catalyst described in Example 16 was tested under the same polymerization conditions as described in Example 17, except that the reactor was added 30 mmol of hydrogen. 7,8 g of the obtained polyethylene match the performance of the catalyst 354 kg/g Zr. The polymer had a value of MI 197 DG/min Density of the polymer was higher than at 0.9700 g/ml.

Example 20

Preparation of catalyst

The catalyst was prepared using the SP is then ZrCl4. The product was represented by the black solid, which consisted of 8.7 wt.% Ti.

Polymerization test

A solution of the product prepared by dissolving 0,1065 g of substance in 100 ml of toluene. The polymerization was carried out as described in Example 16. The polymerization was started, using 1.0 ml of a solution of the catalyst, and got to 18.1 g of the polymer after 1 h of reaction. This was in line with the performance of the catalyst 196 kg/g Ti. The polymer had a value of M1 0,150 DG/min and HLMI 1,60 DG/min consistent with the MFR value of 10.7.

Example 21

The catalyst described in Example 20 was tested under the same polymerization conditions as in Example 16, except that 25 ml of the catalyst was diluted in 100 ml of toluene. 1.0 ml of this diluted solution was used under the same conditions as in Example 17. 1 h polymerization gave 10.0 g of polyethylene. This was in line with the performance of the catalyst 432 kg/g Ti. The polymer had a value of MI 0,200 DG/min and a HLMI of 1.64 DG/min consistent with the MFR value of 8.2.

Example 22

The following example illustrates the preparation of bis(carbazolyl)zirconium dichloride way interaction tetrakis(diethylamido)zirconium with carbazole, followed by chlorination tetrachloride kraanium conventional methods using shelenkov. All glassware was clean and did not contain moisture and oxygen. All solvents were freed from moisture, air and other impurities.

Carbazole (1,874 g from Aldrich Chemical Company) was added at room temperature to a solution of 2.0 g of tetrakis(diethylamido)zirconium, dissolved in 40 ml of toluene. It was added over a 10 minute period and stirred for 3 h at room temperature. Volatiles were removed in vacuum. The resulting residue was dissolved in 30 ml of toluene. Silicon tetrachloride (0,954 g) in 5.0 ml of toluene was added at room temperature. The mixture was stirred for 4 h at room temperature. At the end of this period greenish-yellow solid was isolated from the original brown solution. After removal of the volatile allocated 1,43 g solids. This substance was used without further purification.

The results of polymerization

Polymerization was performed in a mix of 1.7 l stainless steel autoclave at 80oC. Dry, free from oxygen toluene (840 ml) was loaded in a clean, dry, free from oxygen reactor. 6 ml of 10% methylalumoxane (MAO) in toluene (Albemarle Corporation, used without further purification) was added to the toluene in d in order to bring the reactor pressure up to 10.5 ATM. The catalyst solution was prepared by dissolving 0,2508 g of product in 100 ml of toluene. To start the polymerization was injected 2.0 ml of this solution into the reactor. After 1 h the flow of ethylene was stopped and the reactor was rapidly cooled to room temperature. The polymer was filtered from the toluene by vacuum filtration. The polymer was dried overnight in a vacuum Cabinet and weighed. The weight of the polymer was 9.1, This corresponded to the performance of the catalyst 9,88 kg/g Zr. The polymer had a value of MI to 0.060 DG/min and a HLMI of 0.36 DG/min, This corresponds to the value of the MFR of 6.0 and pointed to a narrow molecular weight distribution, although the molecular weight was very high.

Example 23

The catalyst described in Example 22, was tested under the same polymerization conditions as in Example 22, except that used 4,0 ml of catalyst. One hour of polymerization resulted in the receipt of 9.3 g of polyethylene. This was in line with the performance of the catalyst of 5.05 kg/g Zr. The polymer had a value of MI 0,0031 DG/min and HLMI 0,097 DG/min consistent with the MFR value of 31.4.

Comparative Example 1

The preparation of the catalyst.

The catalyst was prepared using the methods described in Example 1. Pyrrole (Ald is for mixing. Slenk have sealed partition. Diethyl ether (50 ml) was added via needle with double hole for dissolving pyrrole. The solution was cooled to 0oC in a bath of ice and 6,70 ml of a 3.0 molar methylmagnesium in ether was slowly added to slink using a syringe with stirring. In the process of adding the allocated gas. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was additionally stirred for 1 h at room temperature.

Tetrachloride zirconium (2,33 g) were placed in a clean, dry, free from oxygen 250 ml slenk, which contained the rod for mixing. Slenk have sealed the bulkhead and 100 ml of ether was added via needle with a double hole. This suspension was cooled to 0oC in the bath with ice. Product pyrrole/methylacrylamide was added to the suspension ZrCl4within 10 min using a needle with a double hole. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was stirred additionally for 1 h at room temperature. The product of t is s brown solid. 100 ml of toluene was added to this solid substance and was stirred for 2 h at room temperature. The solution was regenerated by vacuum filtration using a dense (4 μm) glass filter SCHOTT. The toluene was removed by evaporation in a vacuum. The number of selected solids was 0,453 g and it contained 15,1 % Zr. The data of elemental analysis showed the absence of a Cl.

A polymerization test

A solution of the product prepared by dissolving 0,3201 g of substance in 100 ml of toluene. The polymerization was carried out as described in Example 1, except that added to 6.0 ml of 10% solution of MAO in toluene as socializaton and polymerization was carried out at 110oC. Hydrogen or comonomer not added to the reactor. To start polymerization used in 5.0 ml of catalyst and received a 24.3 g of the polymer after 1 h of reaction. The polymer had a value of MI 1,20 DG/min and HLMI 27,86 DG/min consistent with the MFR value of 23.2.

Comparative Example 2

This example shows the low catalytic output and low activity in the polymerization process, which are the result of the use of derivatives of pyrrole, which do not contain condensed aromatic stake is imerpial (1.90 g, 99% from Aldrich Chemical Company) was placed in a clean, dry, free from oxygen 118 ml flask, which contained a rod for mixing and germetizirovany rubber septum. Ether (50 ml) was added via syringe. The solution was cooled to 0oC in the bath with ice. Methylanisole (6,7 ml of a 3.0 molar) in ether (from Aldrich Chemical Company) were placed in a separate 113,5 g flask and was dissolved in 50 ml of ether. This solution methylacrylamide/ether was slowly added to a solution of 2,5-dimethylpyrrole using needles with double hole under stirring. In the process of adding the allocated gas. The reaction mixture was stirred for 1 h Bath with ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was additionally stirred for 1 h at room temperature.

Tetrachloride zirconium (2,32 g from Aldrich Chemical Company was used without further purification) and placed in a clean, dry, free from oxygen 250 ml slenk, which contained the rod for mixing. Slenk have sealed partition and added 70 ml of dry, free from oxygen ether with a syringe. This solution was cooled to oC in the bath with ice. The product 2,5-dimethylpyrrole/methylacrylamide was stirred for about 2 hours Bath ice was removed and the mixture allowed to warm to room temperature with stirring. The mixture was stirred additionally for 1H at room temperature. The ether was removed by evaporation and allocated reddish-brown solid product.

Toluene (100 ml) was added to this solid product was stirred for 3 hours at room temperature. The solution was regenerated by vacuum filtration using a dense (4 μm) glass filter SCHOTT. The dissolved product was besieged from solution by addition of 700 ml of hexane. The solid products were isolated by vacuum filtration using a glass filter SCHOTT. Allocated approximately 0.06 g of light-yellow solid product.

The results of polymerization

The polymerization was performed using the procedure described in Example 1. In this example, 10 ml of 10% methylalumoxane (MAO) in toluene (from Ethyl Corporation, used without further purification) was added to the toluene in the reactor. To the reactor was added hydrogen (180 mmol) was not added comonomer. The catalyst solution was prepared by dissolving 0,050 g of product in 100 ml of toluene. To start the polymerization was injected 3.0 ml of this solution into the reactor and received 2.0 g of the polymer.Tetrachloride titanium (1,10 ml of Aldrich Chemical Company) was dissolved in 30 ml of toluene in a clean, dry, free from oxygen 118 ml bottle, which contained a rod for mixing. The flask was sealed with septum. A solution of TiCl4added to the product of the pyrrole/methylacrylamide at 0oC for 20 min using a needle with a double hole. The reaction mixture was stirred for about 2 hours Bath with ice was removed and the mixture allowed to warm to room Temperley evaporation, and provided a dark brown solid product.

Toluene (100 ml) was added to this solid product was stirred for 2 h at room temperature. The solution was regenerated by vacuum filtration using a glass filter. The dissolved product was isolated by evaporation of the toluene.

The results of polymerization

The polymerization was performed using the procedure described in Example 1, except that 10 ml of 10% methylalumoxane (MAO) in toluene was added to the reactor together with 180 mmol of hydrogen, but without the co monomer. The catalyst solution was prepared by dissolving 0,0960 g of product in 100 ml of toluene. To start the polymerization was injected 3.0 ml of this solution into the reactor and after one hour of reaction was obtained 3.4 g of polymer.

1. The method of producing polyolefin, comprising the polymerization of olefin in the presence of a catalyst system containing socialization and catalyst with the formula

< / BR>
where L is the ligand or mixture of ligands, each of which has 4 to 30 carbon atoms and contains at least two condensed rings, one of which is pyrrolidinyl ring, and the other is aromatic;

Cp - ligand containing cyclopentadienyls group, where the ligands L or ligand L and Cp can form on and from C1to C20siloxy (R1)3SiO, N(R1)2and mixtures thereof;

M is selected from the group consisting of titanium, zirconium and mixtures thereof;

R1is alkyl from C1to C20;

m = 2 to 4, n = 0 or 1, p = 0 to 2, q = 0 - 1, m + n + q = 4, m + q = 3 or 4.

2. The method according to p. 1, wherein M is titanium.

3. The method according to p. 1, wherein M is zirconium.

4. The method according to p. 1, wherein Y is halogen.

5. The method according to p. 4, wherein Y is chlorine.

6. The method according to p. 1, characterized in that L is indolyl or substituted indolyl and has the formula

< / BR>
where each R independently is selected from hydrogen, alkyl from C1C10and aryl C6C10s = 1 - 4.

7. The method according to p. 1, characterized in that L is carbazolyl or substituted carbazolyl and has the formula

< / BR>
where R is independently selected from hydrogen, alkyl from C1C10and aryl C6C10s = 1 - 4.

8. The method according to p. 1, characterized in that m = 3.

9. The method according to p. 1, characterized in that m + q = 3.

10. The method according to p. 1, characterized in that socialization is ORGANOMETALLIC.

11. The method according to p. 10, characterized in that h is m what olefin will polimerizuet with one or more monomers that can dry out.

13. The method according to p. 12, characterized in that the monomer is ethylene.

14. The method according to p. 1, characterized in that the olefin will polimerizuet at a temperature of 80 - 110oC.

15. The catalyst for use in obtaining polyolefins containing socialization and catalyst with the formula

< / BR>
where L is the ligand or mixture of ligands, each of which has 4 to 30 carbon atoms and contains at least two condensed rings, one of which is pyrrolidine ring, and the other is aromatic;

Cp - ligand containing cyclopentadienyls group, where two of the ligand L or ligand L and Cp can form a bridge connection;

B represents a Lewis base;

Y is selected from the group consisting of halogen, alkoxy from C1to C20siloxy (R1)3SiO, N(R1)2and mixtures thereof;

M is selected from the group consisting of titanium, zirconium and mixtures thereof;

R1is alkyl from C1to C20;

m = 2 to 4, n = 0 or 1, p = 0 to 2, q = 0 - 1, m + n + q = 4, m + q = 3 or 4.

16. The catalyst according to p. 15, wherein M is titanium.

17. The catalyst according to p. 15, S="ptx2">

19. The catalyst p. 18, wherein Y is chlorine.

20. The catalyst according to p. 15, characterized in that L is indolyl or substituted indolyl and has the formula

< / BR>
where each R independently is selected from hydrogen, alkyl from C1WITH10and aryl C6C10s = 1 - 4.

21. The catalyst according to p. 15, characterized in that L is carbazolyl or substituted carbazolyl and has the formula

< / BR>
where each R independently is selected from hydrogen, alkyl from C1WITH10and aryl from C6WITH10s = 1 - 4.

22. The catalyst according to p. 15, characterized in that m is equal to 3.

23. The catalyst according to p. 15, characterized in that m + q is equal to 3.

 

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