Catalysts for the polymerization of alpha-olefins, a method of homo - and copolymerization of alpha-olefins and method for producing elastomeric copolymers of ethylene

 

(57) Abstract:

Describes a catalyst for the polymerization of alpha-olefins containing compound of General formula I, where X is selected from halogen, n is an integer from 2 to 18, R and R* is selected from H, alkyl radicals having from 1 to 5 carbon atoms, M represents zirconium, provided that in General formula II, the number of radicals R other than H, does not exceed 2, at least one of the two radicals R* is H, excluding the compound with n = 4, R = R* = R = N. Describes the method of Homo - and copolymerization of alpha-olefins and method for producing elastomeric copolymers. The technical result - the possibility of obtaining copolymers with acceptable application viscosity. 4 C. and 20 C.p. f-crystals, 4 PL.

The present invention relates to new catalysts metallocene type and to a method for producing (co)polymers of alpha-olefins, in particular elastomeric copolymers of ethylene alpha-olefins (in particular, copolymers of ethylene and propylene) with the use of these catalysts.

Elastomeric copolymer resins of olefins can be obtained by polymerization of ethylene and alpha-olefin, possibly in the presence of the diene. Most elastomere) and ternary copolymers of ethylene, propylene and diene (EPDM).

For the above-mentioned copolymerization constantly continue to develop complexes of zirconium or titanium with ligands bis-ingenering, bis-fluoroanilino or mixed type such as fluorenylacetamide ligands (R. C. Mohring, N. J. Coville, J. were obtained. Chem. 479, 1, 1994).

However, a disadvantage of these catalysts is the fact that do not always produce copolymers with acceptable application viscosity, in particular when receiving an elastomeric ethylene-propylene copolymer with a propylene content ranging from 40 to 65% by weight (limits, which give the best results from the point of view of the elastomeric properties).

We also know that when getting EP or EPDM copolymers copolymerization often carried out in the presence of hydrogen as molecular weight regulator.

However, the use of hydrogen sometimes creates considerable difficulties, due to the high sensitivity to hydrogen catalytic systems on the basis of metallocenes. The result is that suitable for regulating the molecular weight of the quantity of hydrogen is too small for appropriate distribution.

Now found new complexes of zirconium, of olefins.

In accordance with the present invention serves a catalytic component for the (co)polymerization of alpha-olefins, characterized in that it contains one or more compounds having a General formula I

< / BR>
where X is selected from halogen, hydride, hidrocarburos radical, alkoxide, dialkylamide, preferably from halogen, hydride, hidrocarburos radical, and even more preferably is chlorine;

n represents an integer from 2 to 18 and preferably selected from 3, 5, 6, 10;

R and R*selected from H, alkyl radicals having from 1 to 5 carbon atoms, cycloalkyl radicals having from 5 to 8 carbon atoms, aryl and alcylaryl radicals having from 6 to 8 carbon atoms, kalkilya radicals having from 7 to 9 carbon atoms;

M is zirconium,

provided that in General formula II

the number of radicals R other than H, does not exceed 2;

at least one of the two radicals R*represents H, preferably two radicals R*selected from H and C1-C3- alkyl radical;

excluding the compound with n=4, R=R*=R*=N.

Compounds of General formula I can be obtained from the derivatives cyclopent the E. the applicant.

< / BR>
What mean R and R*, typical examples of C1-C5-alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.

Typical examples cycloalkyl radicals having from 5 to 8 carbon atoms, are cyclopentyl, cyclohexyl, methylcyclopentene, methylcyclohexyl.

Typical examples of aryl and alcylaryl radicals having from 6 to 8 carbon atoms are phenyl, were, ethylphenyl, dimetilfenil.

In a preferred embodiment of the present invention R and R*selected from H and C1-C3-alkyl radicals. In an even more preferred embodiment, n is selected from 3, 5, 6, 10, R is H, R*selected from H and C1-C3-alkyl radicals.

Non-limiting examples of compounds of General formula I are:

(1) bis-(4,5,6-digidropsoralena)zirconiated;

(2) bis-(1-methyl-4,5,6-digidropsoralena)zirconiated;

(3) bis-(4-methyl-4,5,6-digidropsoralena)zirconiated;

(4) bis-(1, 4-dimethyl-4,5,6-digidropsoralena)zirconiated;

(5) bis-(5-methyl-4,5,6-digidropsoralena)zirconiated;
(8) bis-(4,5,6,7,8-pentahydrate)zirconiated;

(9) bis-(1-methyl-4,5,6,7,8-pentahydrate)zirconiated;

(10) bis-(4,5,6,7,8-hexahydroterephthalate)zirconiated;

(11) bis-(1 - methyl-4,5,6,7,8-hexahydroterephthalate) zirconiated;

(12) bis-(4,5,6,7,8,9,10,11-octahydrocyclopenta) zirconiated;

(13) bis-(1-methyl-4,5,6,7,8,9,10,11-octahydrocyclopenta)zirconiated;

(14) bis-(4,5,6,7,8,9,10,11,12,13-octahydrocyclopenta)zirconiated;

(15) bis-(1-methyl-4,5,6,7,8,9,10,11,12,13 - decahydronapthalene)zirconiated;

(16) bis(5,6-diphenyl-4,5,6,7-tetrahydroindene)zirconiated;

(17) bis-(1-phenyl-4,5,6,7,8-pentahydrate)zirconiated;

(18) bis-(1-phenyl-4,5,6,7,8,9 - hexahydroterephthalate)zirconiated;

(19) bis-(1-phenyl-4,5,6,7,8,9,10,11,12,13 - decahydronapthalene)zirconiated.

Other examples are compounds in which (again with reference to compounds 1-19) chloride is replaced by metelli, fenelli, methoxide, phenoxide.

A typical example (which is intended to be illustrative and not limiting) obtain the compounds of General formula I is SUB> according to the following scheme:

ZRb+ n-C4H9Li ---> RbLi + n-C4H10< / BR>
2RbLi + ZrCl4---> (Rb)2ZrCl2+ 2LiCl

Another object of the present invention is a method for Homo - and copolymerization WITH2-C20(preferably2-C10)-alpha-olefins using a catalyst system containing the compound having the General formula I.

When the (co)polymerization of alpha-olefins catalytic system except metallocene General formula I contains also another component (which is hereinafter referred to as socialization) selected from alumoxane and compounds having the General formula (Ra)xNH4-xB(Rd)4(III), (Ra)3PHB(Rd)4(IV) or B(Rd)3(V) that interact with metallocene General formula I are able to create a catalytic system ionic character. In the above compounds of General formula III, IV or V groups of Ra, the same or different, represent a monofunctional alkyl or aryl radicals, a Rd (same or different) represent a monofunctional aryl radicals, preferably partially or fully fluorinated, and more preferably completely fluorinated. When used the ANO in EP-A-277004, mainly consist of reaction products of one or more metallocenes General formula I, where X represents H or hydrocarbonyl radical, with any one of the compounds of General formula III, IV or V, or their mixture, and the molar ratio between the compound of General formula III, IV or V and metallocene General formula I will be in the range from 0.1 to 10, preferably from 0.5 to 3, and more preferably from 0.7 to 2.

When X is not H or hidrocarburos radical, as described in EP-A-612769, the catalytic system consists of one or more metallocenes General formula I, alkylating compounds VI, selected from trialkylamine, dialkylamino or alkylate, or other alkylating agents, well known to experts in the art, and any of compounds of General formula III, IV or V, or a mixture thereof.

The process of preparation of the catalytic system comprises pre-mixing metallocene General formula I with a suitable alkylating agent of formula VI in an aliphatic or aromatic hydrocarbon solvents or their mixtures at a temperature ranging from -20 to 100oC, preferably from 0 to 60oC, and more preferably from 20 to 50oSnout to 2 hours. The mixture is then injected into contact with the compound of General formula III, IV or V at the above temperature for a time ranging from 1 minute to 2 hours, preferably from 2 to 30 minutes, and then serve it to the reactor for polymerization.

The molar ratio of alkylating a compound of formula VI and a compound of General formula I may range from 1 to 1000, preferably from 10 to 500, and more preferably from 30 to 300.

The molar ratio between the compound of General formula III, IV or V and metallocene formula I may range from 0.1 to 10, preferably from 0.5 to 3, and more preferably from 0.7 to 2.

As for alumoxane, this connection of aluminum, which in its linear form has the General formula VII

(Re)2-Al-O-[-Al(Re)-O-]p-Al(Re)2,

and in a circular form has the General formula VIII

-[-O-Al(Re)-]p+2-,

where Rethe same or different selected from C1-C6-alkyl radicals, C6-C18-aryl radicals or H, p is an integer from 2 to 50, preferably from 10 to 35.

All Repreferably identical and selected from methyl, isobutyl, phenyl or benzyl,ethyl and hydrogen or in accordance with another variant, methyl and isobutyl, and when the number of the radicals Reis in the range from 0.1 to 40% by weight, preferably is hydrogen or isobutyl.

Alumoxane can be obtained in a variety of ways known to specialists in this field of technology. One such method, for example, includes the interaction aluminiumindustrie connection and/or aluminiumhydride with water (gaseous, solid, liquid or bound, for example, in the form of water of crystallization) in an inert solvent, for example toluene. To obtain alumoxane having different alkyl groups Recarry out the interaction of two different aluminization (AlR3+ AlR'3with water [see S. Pasynkiewich, Polyhedron 9 (1990), 429-430 and EP-A-302424].

The exact structure alumoxane unknown. You can pre-activate metallocene alumoxane before it is used in the phase for polymerization. This significantly increases the polymerization activity and improves the morphology of the particles. The above preliminary activation is preferably carried out in a solvent by dissolving metallocene in solution of an inert hydrocarbon, preferably elevationmodel from 1 mass% to the value of saturation, preferably from 5 to 30% by weight relative to the total weight of the solution. Metallocene can be used in the same concentration, but preferably it is used in an amount of from 10-4to 1 mol per mol alumoxane. The pre-activation is in the range from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The temperature is in the range from -78 to 100oC, preferably from 0 to 70oC.

The catalytic system of the present invention (catalyst having the General formula I, and socialization) can be obtained by introducing the catalyst into contact with socialization in the presence or without the polymerized monomer inside or outside the reactor.

The amount of catalyst and socializaton not particularly limited. For example, in the case of polymerization in a solvent, the amount of catalyst is preferably in the range from 10-7up to 102mmol/liter, and more preferably from 10-4to 1 mmol/liter, translated into transition metal M When using alumoxane molar ratio between the aluminum and the transition metal M is preferably above 10 and below 10000.

In addition to the catalyst and socializaton catalytic system is a, such as water, alcohols (e.g. methanol, ethanol, butanol), or electron-donating compounds such as ethers, esters, amines, compounds containing alkoxide groups, such as frivolity, dimethylethanolamine, phenylphosphate, tetraethoxysilane, diphenylmethylsilane.

The catalyst and socialization can be introduced into the reactor separately or after pretreatment with them into contact with each other. In the latter case, the contact may be carried out in the presence of monomer, which then must be cured, which represents a so-called "pre-polymerization".

To return to the copolymerization process, it is advisable to remove catalyst poisons that may be present in the monomers, in particular propylene. In this case, the treatment can be carried out by aluminiuim, for example AlMe3, AlEt3, Al(ISO-Bu)3. This cleaning can be carried out in the polymerization system or, alternatively, before the polymerization by introducing propylene into contact with aluminiuim, followed by the separation.

The catalytic system according to the present invention can be used in the polymerization is carried out without solvent (such as polymerization without solvent in the liquid phase and the polymerization in the gaseous phase), and during polymerization in solution. It is evident that the catalyst of the present invention can be applied in continuous polymerization or polymerization in a batch reactor, the.

When the polymerization is carried out in a solvent, the solvent can be used aliphatic and aromatic hydrocarbons, either separately or in mixture with each other.

Catalytic component of the General formula I can be deposited on inert carriers. Methods suitable for the application of metallocene components on a porous solid particles, for example silicon dioxide and aluminum oxide, possibly in the presence of socializaton, well known in the literature. Catalyst system supported on a carrier, can be used as such or pre-polymerized with an alpha-olefin monomers. The application provides the possibility of heterogeneous catalytic components with special morphology and degree of dispersion, particularly suitable for processes of gas-phase polymerization.

The polymerization temperature is around the s in the reaction system, even if the pressure is preferably in the range from atmospheric pressure to a gauge pressure of 50 kg/cm2. During polymerization the molecular weight can be adjusted by any known method, for example, by appropriate selection of the temperature and pressure of the polymerization or by introducing hydrogen.

The olefins which can be polymerized by the method according to the present invention are alpha-olefins (including ethylene) having from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms. Typical examples of alpha-olefins, which can be (co)polymerized by the method according to the present invention are ethylene, propylene, 1-butene, 4-methyl-1-penten, 1-hexene, 1 - octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 achozen.

Another object of the present invention is a method for elastomeric copolymers of ethylene and alpha-olefin or elastomeric ternary copolymers of ethylene, alpha-olefin and diene, preferably ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) with a propylene content ranging from 15 to 75% by weight, preferably from 25 to 70% by weight and more preferably from 40 to 60% by weight, colony Dien, preferably diluted WITH low-boiling3-C5-hydrocarbon (preferably propane), and the pressure that enables the use of this alpha-olefin in the liquefied form;

2) to the mixture obtained in stage (1), add ethylene in a quantity sufficient to maintain the desired relationship of ethylene to alpha-olefin in the liquid phase;

3) add a catalytic system containing one or more metallocenes and one or more socialization selected from alumoxane and compounds having the General formula (Ra)xNH4-xB(Rd)4(III), (Ra)3PHB(Rd)4(IV) or B(Rd)3(V) may, in the presence of alkylating compounds VI;

4) the mixture obtained in stage (3), is subjected to the reaction for a time sufficient to allow the polymerization system consisting of ethylene and alpha-olefin and possibly diene, with getting EP(D)M, having a Mooney viscosity (ML1+4when 100oC) more than 25,

characterized in that the catalytic system contains metallocene selected from metallocenes General formula I

< / BR>
where each X is independently selected from halogen, hydride, hidrocarburos radical, alkoxide, dialkylamide and predpochtite is correctly selected from 3, 4, 5, 6, 10;

R and R*selected from H, alkyl radicals having from 1 to 5 carbon atoms, cycloalkyl radicals having from 5 to 8 carbon atoms, aryl and alcylaryl radicals having from 6 to 8 carbon atoms, kalkilya radicals having from 7 to 9 carbon atoms;

M represents zirconium;

provided that in General formula II

the number of radicals R other than H, does not exceed 2;

at least one of the two radicals R*represents H, preferably two radicals R*selected from H and CH3;

excluding the compound with n=4, R=R*=N.

In a preferred embodiment, R and R*selected from H and C1-C3-alkyl radicals.

In an even more preferred embodiment, n is selected from 3, 5, 6, 10, R is H and R*selected from H and C1-C3-alkyl radicals.

Alpha-olefins which can be used in obtaining copolymers with ethylene are those described above. Typical examples of dienes that may be used to produce EPDM, are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, Dicyclopentadiene; the preferred diene is 5-ethylidene-2-norbornene.

When received the Lena is, as specified above.

The process of obtaining EP(D)M is carried out by polymerization in suspension phase of the ethylene, alpha-olefin, preferably propylene) and possible diene, optionally diluted with a low-boiling C3-C5-hydrocarbon, preferably propane.

This mixture is suspended catalytic system consisting of metallocene General formula I and socializaton selected from MAO (methylalumoxane) and compounds of General formula III, IV and V, and optionally alkylating the compound VI. This catalytic system take in quantity, ensure the receipt of a sufficient number of polymer containing the optional diene.

The concentration of the optional diene in the reactor (volume percent) is in the range from 0.05 to 10%, preferably from 0.2 to 4%.

The ethylene fed into the reactor at a pressure exceeding the pressure in the reactor. The ethylene content in the polymer is determined from the ratio between the partial pressure of ethylene and the total pressure in the reactor for polymerization. It is the partial pressure of ethylene is usually maintained within the range of from 0.5 to 50 bar (50-5000 kPa), and more preferably from 1 to 15 bar (100-1500 kPa). The temperature of the reactor support the FA-olefin and optionally a diene, polymerizes give an elastomer EP(D)M

The polymerization can be carried out suspension method, periodic or preferably continuous with a constant supply of the mixture of monomers, possibly diluted with a low-boiling hydrocarbon and catalytic systems.

Technology implementation of the method according to the present invention is (without any limitation of the scope of the present invention) is as follows.

In a reactor equipped with a mixer, continuously serving of liquid propylene with ethylene and optionally diene, possibly diluted WITH low-boiling3-C5-hydrocarbon. The reactor contains a liquid phase, mainly consisting of liquid propylene, optional diene monomers, an optional low-boiling hydrocarbon and dissolved therein gaseous ethylene, and a gaseous phase containing vapors of all components. Submitted ethylene administered either in the form of gas in the vapor phase of the reactor, or by spraying in liquid phase, as is well known to specialists in this field of technology.

The components of the catalyst system (catalyst, socialization, optional alkylating compound and the absorber) can be introduced into the reaction>/P>Polymerization occurs in the liquid phase with the formation of a copolymer insoluble in the phase and period of stay of the suspension in the reactor ranges from 10 minutes to 10 hours, and preferably from 30 minutes to 2 hours; longer periods give the final polymer with a lower content of catalytic residues.

The temperature of the reactor can be adjusted by cooling the reactor by means of a coil or jacket with circulating cooling liquid or, preferably, by evaporation and condensation of alpha-olefin (and optional low-boiling hydrocarbon) and re-feed it into the reactor.

Collected in this way the polymer is extracted, exposing his organoclay processing water in the steam flow for removal of unconverted monomers and optional diluent, and by processing in the extruder to remove the water and optional residual traces of alpha-olefins.

The following examples provide a better understanding of the present invention.

EXAMPLE 1. Synthesis of bis-(4,5,6,7,8-pentahydrate)zirconiated (compound of formula I, where n =5, R=R*=H, X=Cl).

Received an ethereal solution of 2.8 g (0.02 for the on behalf of this applicant. To the specified solution was added to 12.5 ml of a 1.6 M solution of LiMe, and there were methane, and the precipitated white solid. The mixture was left overnight to mixed, then cooled to -70oC and added to it 2.4 g (0.01 mol) of solid ZrCl4. Allowing the temperature to rise to room temperature (about 20oC, provided stirring the mixture for 4 hours and then the mixture was filtered. The residue was washed with diethyl ether and then extracted with methylene chloride (2 x 75 ml). The extract was concentrated and the resulting solid was filtered, washed with pentane and dried. Obtained 1.4 g of product (yield 33%).

Collected in this way zirconium complex had the following NMR spectra.

1H-NMR (CDCl3, M. D., skidding. TMC): 5,99 (m, 6H), to 2.65 (m, 8H), 1.91 a (m, 6H), of 1.55 (m, 2H), 1,25 (m, 4H).

13C-NMR (CDCl3, M. D., skidding. TMC): 29,06; 31,23; 32,86; 107,47; 115,9; 135,78.

EXAMPLE 2. Synthesis of bis-(4,5,6,7,8,9-hexahydroterephthalate)zirconiated (compound of formula I, where n=6, R=R*=R*=H, X=Cl).

Received an ethereal solution of 3.1 g (0,021 mol) 4,5,6,7,8,9-hexahydro-2H-Cyclopentasiloxane the method described in simultaneously considering sawk in hexane to obtain a white precipitate. The mixture was left for 4 hours to mix, then was cooled to -70oC and added to it 2.5 g (to 0.011 mol) of solid ZrCl4. Given the temperature to rise to room temperature (about 20-25oC). The mixture was filtered, washed with diethyl ether and then extracted with methylene chloride.

When the concentration was voluminous precipitate a solid, which was filtered and carefully (because of its high solubility) was washed with methylene chloride and then with hexane. Received 0.4 g of product.

When the concentration of the mother liquor also received solid, which after filtering off and washing gave 0.6 g of pure product. Thus obtained 1.0 g of pure complex compound (yield 20%).

Collected in this way zirconium complex had the following NMR spectra.

1H-NMR (CDCl3, M. D., skidding. TMC): 6,15 (t, 2H), 6,02 (d, 4H), 2,60 (m, 8H), of 1.40 (m, 16H).

13C-NMR (CDCl3, M. D. , skidding. TMC): 26,5; 27,9; 32,57; 109,1; 114,6; 134,0.

EXAMPLE 2A. Synthesis of bis-(4,5,6,7,8,9,10,11,12,13-decahydronapthalene)zirconiated (compound of formula I, where n=10, R=R*=R*=H, X= Cl).

To the ethereal solution of 4.1 g (0.02 mol) 4,5,6,7,8,9,10,11,12,13-decahydro is authorized on behalf of this applicant, and which had a purity of 81%) was added at room temperature to 12.5 ml of a 1.6 M solution of LiMe. Allocated gas and a little later precipitate white solid. The mixture was left overnight to mix. Cooled it to -70oC and added to it 2.4 g (0.01 mol) ZrCl4. Given the temperature to rise to room and left the mixture was mixed for 4 hours. The mixture was filtered, washed with diethyl ether and was extracted with methylene chloride (2 x 75 ml). The extract was concentrated, filtered and the solid is washed with pentane and dried under vacuum. Received 1.6 g (yield 28%) of product, which, as shown by NMR analysis, was clean. It should be noted that at the end of this process, the impurity originally present in the original ligand, almost completely absent.

1H-NMR (CDCl3, M. D., skidding. TMC): x 6.15 (s, 6H), 2,35 (DDD, 4H), 1.85 to a 1.5 (m, 16H), 1,5-1,1 (m, 16H).

13C-NMR (CDCl3, M. D., skidding. TMC): 23,57; 25,81; 25,95; 26,43; 30,37; 108,36; 115,32; 134,06.

EXAMPLE 2B. Synthesis of bis-(1-methyl-4,5,6,7,8,9,10,11,12,13-decahydronapthalene)zirconiated (compound of formula I, where, taking into account the formula II, n =10, R=R*=H, R*=CH3X=Cl).

7 g (to 0.032 mol) of 1-methyl-4,5,6,7,8,9,10,11,12,13-decay what about the data on behalf of the applicant, and which had a purity of 75%) was dissolved in pentane and the resulting solution was treated with 15 ml of 2.5 M solution of BuLi in hexane. After addition of THF (tetrahydrofuran) was immediately formed an abundant precipitate, which after filtering, washing with pentane and drying gave 4.3 g of the lithium salt (4.3 g, 0.019 mol).

To the lithium salt, suspended in diethyl ether and maintained at -70oC, was added 2.4 g (0.01 mol) ZrCl4. Allowing the temperature to rise to room, got a difficult mix viscous suspension.

After 2 hours exposure at room temperature, the suspension was filtered again, washed with ether and was extracted with 500 ml of methylene chloride at low heat. The mixture was concentrated to a small volume (50 ml), cooled to -20oC and filtered. The residue was washed with cold methylene chloride and then dried, resulting in 3.5 g of product. After recrystallization from methylene chloride was obtained 1.5 g of product whose characteristics are identical to the characteristics of non-crystalline product (yield 84%).

It should be noted that in this case at the end of this process, the impurity originally present in the original ligand, almost completely otsutstvuetC-NMR (CDCl3, M. D., skidding. TMC): 15,73; 23,14; 23,84; 24,47; 25,91; 25,93; 26,82; 26,97; 27,23; 27,27; 27,96; 30,36; 108,53; 109,40; 109,49; 129,76; 130,08; 131,41; 134,53; 134,79.

EXAMPLES 3-9 AND COMPARATIVE EXAMPLES Cl And C2. Synthesis of ethylene-propylene copolymers and triple propylene-ethylene-diene copolymers.

The polymerization was carried out in equipped with a magnetic anchor stirrer sealed reactor with thermostatic regulation with a capacity of 3.3 litres in accordance with the following technology.

After purging the reactor with propylene containing 5% (weight/volume) of triisobutylaluminum, and rinse with fresh propylene is served at the 23oC 2 liters of liquid propylene "polymerization grade" and optional third monomer (ENB, i.e., 5-ethylidene-2-norbornene, ENB). Then the sealed reactor is brought to a temperature for polymerization (just 45oC for tests 1 and Cl and 40oC for other tests), and enter him in hexane solution with 10% TIBA (triisobutylaluminum, CHIBA), which corresponds to 1.5 mmol Al. Then add through a submerged pipe optional hydrogen and ethylene in predetermined ratios to achieve the desired partial pressure.

The catalyst was prepared as follows.

In vitro Sinulat 30% solution methylalumoxane (MAO) in toluene (commercial product of WITCO under the name Eurocen A1 5100/30T), necessary to obtain the desired relationship Al/Zr.

The resulting solution was poured into the cylinder, under nitrogen atmosphere, and rapidly injected into a sealed reactor with excess nitrogen pressure. The pressure in the reactor to maintain a constant by feeding ethylene from a container with a controlled weight. An hour later the supply of ethylene interrupt, degenerous the remaining monomers and cooling the reactor to room temperature.

The polymer is discharged and homogenized by means of a roll mixer, and then identify.

Physico-chemical analysis and characterization.

The resulting polymer is subjected to the following measurements.

The content of propylene and ENB.

The determination is carried out by IR analysis of the polymer in the form of films with a thickness of 0.2 mm using FTIR spectrophotometer Perkin-Elmer model 1760.

Characteristic viscosity.

The measurement is carried out at 135oC with the polymer dissolved in o-dichlorobenzene. Using a viscometer of type Ubbelohde, measure the time dripping of solvent and solutions with increasing concentrations in the investigated polymer. Extrapolation of the reduced viscosity, related to no load).

Analysis was performed by the method of gel permeation chromatography in o-chlorobenzene at 135oC using chromatograph waters ALC/GPC 135. Using standard samples of monodisperse polystyrene receive a calibration curve used to calculate the molecular mass by the equation Mark-Hovinga, valid for linear polyethylene and polypropylene. Molecular weight adjusting composition using equation Solt (J. Appl. Polym. Sci. 1984, 29, p. 3363-3782).

The Mooney viscosity (1+4).

It is determined at 100oC, using a viscometer Monsanto "1500 S', in accordance with ASTM D 1646/68.

Vulcanization.

A vulcanized mixture prepared using the compositions listed in table 1.

Determination of mechanical properties.

The mechanical characteristics of the vulcanized copolymer was measured by ASTM methods listed in table 2, using samples taken from sheets, molded in a plate press at 165oC for 40 minutes at 18 MPa.

EXAMPLES of C1 And C2. Comparative examples C1 and C2 belong to the copolymerization of ethylene and propylene with bis-(tetrahydroindene)zirconiated in the presence of MAO and without controller the molecular is obtained under specified conditions using metallocenes of the present invention, in comparison with the two polymers (C1 and C2), obtained with the use of already known in the art bis-(tetrahydroindene)zirconiated.

Table 4 shows the main mechanical characteristics after vulcanization of the resulting copolymers.

Comparison of comparative examples C1 and C2 shows that in case of obtaining the EB copolymers with a propylene content greater than 40% by mass, Mooney viscosity of the polymers obtained using the catalysts of the present invention, is clearly higher than the corresponding viscosity of the copolymers obtained with the use of known catalysts.

As you can see from the physico-mechanical characteristics in table 4 and, in particular, of the values of the residual elongation, which remain low, EP copolymers, obtained with the catalysts of the present invention are elastomeric. It should be noted the value of the residual elongation is below 25% of the vulcanized product of example 6 with a high ethylene content.

Example 5 shows that the same catalytic system of examples 3 and 4 provides for the use of hydrogen as molecular weight regulator, i.e., without excessive snizhenie 9 shows the catalysts of the present invention in the presence of hydrogen contribute to the formation of the triple chain monomer ENB that gives triple EPDM copolymer having an average molecular weight with good elastic properties (see table 4).

Examples 7-9 show that another catalyst of the present invention in the polymerization behaves the same as the catalyst of examples 3-6.

In table 3 the complex And represents a catalyst bis-(tetrahydroindene)zirconiated prior art.

Complex (1) in table 3 is metallocenes used in example 1, and the complex (2) in table 3 is metallocene of example 2. In the same table the output is expressed in kilograms of polymer per gram of Zr per hour.

In conclusion, the data of tables 3 and 4 show that the catalysts of the present invention is effective in obtaining the ethylene-propylene copolymer with a propylene content of more than 40%.

In addition, using the catalysts of the present invention, it is possible to effectively receive and EP copolymers with a propylene content of less than 40%.

EXAMPLE 10. Received the ethylene-propylene copolymer using a catalyst, poluchennogo luola 0.3 g metallocene from example 2 and 10% hexane solution CHIBA so, that the molar ratio Al/Zr was set to 300.

The solution was heated for 1 hour to 40oC under stirring, then diluted with 8 ml of toluene and added with 0.2% solution of N,N-dimethylaniline(perftoralkil)borate in toluene, resulting in a molar ratio of B/Zr was equal to 2.

Then the resulting liquid was immediately submitted in a sealed reactor for testing copolymerization without MAO.

At the end of polymerization from the reactor was unloaded PEM with a propylene content of 38% by weight and a Mooney viscosity ML (1+4, 100oC) equal to 2.

The yield of polymerization was 2535 pounds per gram of zirconium per hour.

This example shows that the catalysts of the present invention provide an ethylene-propylene copolymers with high productivity when used as an alternative methylalumoxane (MAO) socializaton activator capable of creating an ionic bond by reacting with metallocene having the formula I.

1. Catalyst component for the (co)polymerization of alpha-olefins containing compound of General formula I

< / BR>
where X is selected from halogen;

n represents an integer from 2 to 18;

R and R* is selected from H, alkyl, radicalismo radicals R, other than N, not greater than 2, at least one of the two radicals R* is H, excluding the compound with n=4, R=R*=R*=N.

2. The catalytic component on p. 1, wherein n is selected from 3, 5, 6, 10.

3. Catalytic component under item 1, wherein X is selected from halogen, hydride, hydrocarbonrich radicals.

4. The catalytic component on p. 3, wherein the halogen is chlorine.

5. Catalytic component under item 1, wherein R* is selected from H and C1-C3-alkyl radicals.

6. The catalytic component on p. 2, wherein R is H, R* is selected from H and C1-C3-alkyl radicals.

7. Catalytic component under item 1, characterized in that it is a bis-(4,5,6,7,8-pentahydrate)zirconiated.

8. Catalytic component under item 1, characterized in that it is a bis-(4,5,6,7,8,9-hexahydroterephthalate)zirconiated.

9. Catalytic component under item 1, characterized in that it is a bis-(4,5,6,7,8,9,10,11,12,13-decahydronapthalene)zirconiated.

10. The catalytic component on p. 1, distinguished by the of lore.

11. The way Homo - and copolymerization WITH2-C20(in particular2-C10)- alpha-olefins in the presence of a catalytic system containing a metallocene compound, alyuminiiorganicheskikh connection and ionic boron compound, characterized in that as the metallocene compound is used as a compound of General formula I

< / BR>
where X is selected from halogen;

n represents an integer from 2 to 18;

R and R* is selected from H, alkyl radicals having from 1 to 5 carbon atoms;

M is zirconium,

provided that in General formula II, the number of radicals R other than H, does not exceed 2, at least one of the two radicals R* is H, excluding the compound with n=4, R=R*=R*=N.

12. The method according to p. 11, wherein n is selected from 3, 5, 6, 10.

13. The method according to p. 12, wherein R is H, R* is selected from H and C1-C3-alkyl radicals.

14. The method according to p. 11, wherein X is selected from halogen, hydride, hidrocarburos radical.

15. The method according to p. 14, characterized in that X represents a halogen.

16. The method of obtaining elastomeric copolymers of ethylene and alpha-olefin or elastomeric triple copolymerizing, alyuminiiorganicheskikh connection and ionic boron compound, preferably ethylene-propylene or ethylene-propylene-diene content of propylene in the range from 15 to 75 wt.%, includes the following stages:

1) in the reactor for polymerization serves alpha-olefin and optionally a diene, preferably diluted WITH low-boiling3-C5-hydrocarbon, preferably propane, at a pressure that enables the use of this alpha-olefin in the liquefied form;

2) to the mixture obtained in stage (1), add ethylene in a quantity sufficient to maintain the desired relationship of ethylene to alpha-olefin in the liquid phase;

3) add a catalytic system containing one or more metallocenes and one or more socialization selected from alumoxane and compounds having the General formula III (RAxNH4-xIn(Rd)4IV (RA)3MV(Rd)4or V(Rd)4where groups RA, the same or different, represent a multi-functional alkyl or aryl radicals, and Rd, the same or different, represent a monofunctional aryl radicals, preferably partially or fully fluorinated, possibly in the presence of alkylating solucionou at the stage (3), subjected to reaction for a time sufficient to allow the polymerization system consisting of ethylene and alpha-olefin and optionally a diene, to obtain ethylene-propylene-diene compounds having a Mooney viscosity (L1+4when 100oC) more than 25,

characterized in that, as the metallocene compound is used as a compound of General formula I

< / BR>
where X is selected from halogen;

n represents an integer from 2 to 18;

R and R* is selected from H, alkyl radicals having from 1 to 5 carbon atoms;

M is zirconium,

provided that in General formula II, the number of radicals R other than H, does not exceed 2, at least one of the two radicals R* is H, excluding the compound n=4, R=R*=R*=N.

17. The method according to p. 16, characterized in that the ethylene-propylene (EP) or ethylene-propylene-diene (EPDM) copolymers are obtained from a propylene content of 25 to 70 wt.%.

18. The method according to p. 17, wherein the content of propylene is in the range from 40 to 60 wt.%.

19. The method of obtaining elastomeric ternary ethylene-propylene-diene (EPDM) copolymers under item 16, characterized in that the content of the diene is less than 15 wt.%.

22. The method according to p. 16, wherein X is selected from halogen, hydride, hidrocarburos radical.

23. The method according to p. 22, characterized in that X represents a halogen.

24. The method according to p. 21, wherein in the General formula II, R=H, R* is selected from H and C1-C3-alkyl radicals.

 

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