A solid component of catalyst for the (co)polymerization of ethylene and c2- c6-alpha-olefins, process for its production, the catalyst for the (co)polymerization with2- c6-alpha-olefins and a method of producing polyolefins

 

(57) Abstract:

The invention relates to a solid component of catalyst, the method of its preparation and its use. A solid component of catalyst for the (co)polymerization of C2- C6alpha-olefins containing magnesium-carboxylate communication and the transition metal carboxylate obtained by the sequential interaction of compounds of magnesium with a compound of the transition metal and alkylhalogenide and can be represented by the formula MgXn(RCOO)2-nwhere X is fluorine, chlorine or bromine; R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 4 carbon atoms to 25; n = 0 - 1, and as the transition metal carboxylate of General formula MXm(RCOO)4-mwhere m = 0 to 2; M is at least one metal selected from titanium, vanadium, zirconium and hafnium. In the following is described the preparation of solid catalyst component (1) and its use in methods (co)polymerization of C2- C6alpha-olefins. 4 C. and 3 h.p. f-crystals, 3 tables.

The invention relates to a solid component of catalyst, the method of its preparation and its use in methods (co)polymerization of C2-C6

Also known solid components of catalysts of the Ziegler-Natta, which contain a transition metal (usually titanium), ferrous metal (usually magnesium), halogen (usually chlorine), and possibly electron donor. These solid components are used in combination with an ORGANOMETALLIC compound of aluminum, to form active catalysts for the (co)polymerization of ethylene in the processes carried out at low temperature and pressure. For example, in U.S. patent N 3642746 described solid catalyst component obtained by contacting compounds of the transition metal halide of the divalent metal processed by the electron donor. According to the U.S. patent N 4421674 a solid component of catalyst is obtained by contacting compounds of the transition metal with the product obtained by spray drying of a solution of magnesium chloride in ethanol.

In accordance with the United Kingdom patent N 1401708 solid component cat is agenda aluminum. In the U.S. patents NN 3901863 and 4292200 described solid component of catalyst obtained by bringing into contact dehalogenated compounds of magnesium with negligently compound of a transition metal and a halide of aluminum.

In U.S. patent N 4843049 and application Europatent (published) N 243327 described solid components of catalyst which contains titanium, magnesium, aluminum, chlorine and alkoxygroup, which has high activity in the processes (co)polymerization of ethylene is carried out at low pressure and temperature, respectively, in tanks or tubular reactors. These solid components are usually obtained by spray drying of a solution of magnesium chloride in ethanol to obtain an active medium, which further interacts with tetraethoxide titanium or titanium tetrachloride and alkylamine chloride, respectively.

Now in accordance with the present invention found that by introducing relations magnesium carboxylate and the transition metal carboxylate usually get advanced solid components of catalyst compared with those of the prior art in relation to their very high activity in the process (with)polymerizate, improving the nature of the thus obtained polymers.

In accordance with this first aspect of the present invention relates to a solid component of catalyst for the (co)polymerization of ethylene and alpha-olefins, which contains a magnesium carboxylate communication and the transition metal carboxylate and may be represented by formula

M1Mg(0,3-20)X(2-60)Al(0-6)(R-COO)(0,1-3)(I)

in which M is at least one metal selected from titanium, vanadium, zirconium and hafnium;

X halogen except iodine;

R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing at least 4 carbon atoms.

According to one variant embodiment of the invention, the metal M in the formula (I) represents titanium or titanium and another metal selected from zirconium and hafnium, and the atomic ratio between the titanium and the other metal is from 0.25 to 1 to 2.0 to 1 and preferably from 0.33 to 1 to 1 to 1.

In another preferred variant of embodiment, the halogen X in the formula (I) is a chlorine atom or bromine, and preferred is chlorine.

The maximum number of carbon atoms in the radical R in SPECT the present invention relates to a method for producing a solid catalyst component (I), which includes:

a) formation of a solution in an inert organic solvent, of a magnesium carboxylate or halide carboxylate magnesium

MgXn(R-COO)2-n(II)

and at least one transition metal carboxylate or halide of at least one transition metal carboxylate

MXm(R-COO)4-m(III)

in which M is at least one metal selected from titanium, vanadium, zirconium and hafnium;

X halogen except iodine;

R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing at least 4 carbon atoms, up to about 25 carbon atoms;

n from O to 1;

m from 0 to 2,

and in which the atomic ratio between the magnesium in the formula (II) and the transition metal in the formula (III) is in the range from 0.3 1 to 20 1;

b) adding to the solution of stage a) of alkylhalogenide having the formula

< / BR>
in which X is halogen except iodine;

R' is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 20 carbon atoms, and

in which the ratio between the atoms of halogen in the formula (IV) and the amount of carboxyl groups in formulas (II) and (III) ranges from 0.3 1 to the NTA of the catalyst from the products of the reaction stage b).

The solvent used to prepare the solution at the stage a) of this method may be any organic solvent that is inert (not reactive) towards the other components. Preferred solvents for this purpose are aliphatic, cycloaliphatic, or aromatic hydrocarbon solvent, liquid under the operating conditions, such as hexane, heptane, octane, Nanan, decane, undecane, cyclopentane, cyclohexane, benzene, toluene, xylenes and mesitylene.

Examples of the carboxyl group R-COO in formulas (II) and (III) are those in which:

the radical R is a linear alkyl containing at least 9 carbon atoms, for example, n-decanoate, n-undecanoate and n-dodecanoate group;

the radical R in branched alkyl product, with branching at the second carbon atom in the alpha position relative to the carboxyl group

< / BR>
in which the sum of carbon atoms in the radicals R1and R2equal to at least two; for example, isobutyrate group, 2-methylbutyrate group and 2-ethylhexanoate group;

the radical R in branched alkyl having two branching at the tertiary carbon atom in the alpha position relative SUP>3, R4and R5equal to at least three; for example, 2,2-dimethylpropanoate and versata group;

the radical R in the alkyl having branching at the second carbon atom in the beta position relative to the carboxyl group

(R6R7) > CH-COO -,

in which the sum of carbon atoms in the radicals R6and R7equal to at least 4; for example, 3-ethylpentane and citronella group;

the radical R is cycloalkyl, cicloanelor, alquilercochelujo or alquilercochelujo

R8-(CH2)s-COO,

in which the radical R8represents cycloalkyl or cycloalkenyl part, or monocyclic, or multiple condensed or unfused cycles, and s varies from 0 to 10; for example, naftanaila group;

the radical R is an alkyl, substituted aryl in the alpha position relative to the carboxyl group

(R9R10) > C-COO,

in which the radical R9is aryl, such as phenyl, and

R10is alkyl containing at least one carbon atom; for example, 2-phenylbutyrate group.

In accordance with one embodiment of the invention, the metal M in the formula (III) pedo titanium and the other metal is from 0.25 to 1 1 to 2 and preferably from 0.33 to 1 to 1 to 1.

In another preferred variant of embodiment X in formulas (II) and (III) represents a chlorine atom or bromine, the preferred form is chlorine.

In accordance with an additional variant embodiment, n in formula (II) has a value of at least 0.1 and preferably at least 0.5 to 1, and m in the formula (III) has a value of at least 0.1 and preferably at least 0.2 to 2.

At the stage a) it is convenient to mix a solution of compound (II) in the selected solvent with a solution of the compound (III) in the same solvent or another solvent, operating at room temperature (20 25oC) or close to the temperature. Solutions of the compounds (II) and (III) in similar solvents can be obtained in an easy and convenient in practice the methodology that will be described below and illustrated in the examples.

At the stage b) of the method is added to the aluminum halide (IV), which interacts with the solution prepared in stage a). The preferred aluminum halides are chloride and bromides of aluminum, in which the alkyl contains from 1 to 6 carbon atoms. Even more preferred halides of aluminum are ethylaluminum dichloride, diethylaluminium chloride, Eid aluminum may be added as such or in the form of a solution in an inert organic solvent, selected from those used in the preparation of the solution of stage a).

At the stage b) it is convenient to operate at temperatures varying from 20 to 120oC during the period, which depends on the selected temperature, and can vary from 0.5 to 8 o'clock In the preferred method, the aluminum halide is added to a solution of compounds (II) and (III) at room temperature (20 - 25oC) or close to the temperature, and the resulting mixture is heated to a temperature varying from 50 to 100oC during the period from 45 to 180 minutes

Working under such conditions, get a solid component of catalyst in the form of powdered sediment with a particle size of from 10 to 40 μm. When M is titanium, receive the catalysts (I), in which the ratio of titanium in the trivalent state and the amount of titanium in the trivalent and tetravalent States usually varies from 0.9 to 1 to 1 to 1.

The thus obtained solid component of catalyst is separated from the suspension on stage), using conventional techniques, such as decantation, filtration or centrifugation, washed with hydrocarbon solvent and possibly dried.

As discussed previously, the compounds (II) and (III) can b is (II) can be obtained by reacting carboxylic acid R-COOH (where R corresponds to the above designation) with the halide of magnesium MgX2(where X has the above meaning) in accordance with the following reaction:

MgX2+ (2-n)R-COOH__ MgXn(R-COO)(2-n)+(2-n)HCl

Similarly, compound (III) can be obtained by reacting carboxylic acid R-COOH (in which R has the above meaning) with a halide of the metal M (MX4where X has the above meaning) in accordance with reaction

MgX4+ (4-m)R-COOH__ MgXm(R-COO)(4-m)+(4-m)HCl.

Examples of suitable acids R-COOH are n-cekanova, n-undecanoate, n-dodecanoate, 2-ethylhexanoate, versatilely, citronella, naphthenic and 2-fenilalanina acid.

Used for this purpose, the magnesium halide can be:

vysokochastotnom a magnesium halide with a particle size of not more than 100 μm and a water content of preferably less than 0.2 wt. or

partially or fully amorphous magnesium halide, such as that which can be obtained by prolonged grinding of crystalline magnesium halide or by spray drying of aqueous solutions or solutions of magnesium halide in an organic solvent.

Among all of the halides of magnesium, it is preferable to use amorphous magnesium chloride obtained pute">

The interaction between the halogen magnesium, or a halide of the metal M, and acid R-COOH is conveniently carried out in an inert organic solvent and preferably aliphatic, cycloaliphatic or aromatic solvent by removal of halogen acid which is released as a by-product of the reaction, for example, by ozonation flow of inert gas, such as nitrogen. At the end of the reaction the solution of the magnesium-halide carboxylate or carboxylate metal (M)-halide get dissolved in the solvent used as reaction medium. Obviously, the solvent can be chosen in such a way as to have the maximum solubility of the reactants and reaction products. Therefore, paraffin solvents are preferred when using aliphatic acids R-COOH and aromatic solvents when using aromatic and substantially aromatic acids R-COOH. The use of mixed solvents, obviously, is not excluded. In any case, it may be allocated to any possible insoluble material by filtration or decantation. In the preparation of compound (II) it is convenient to operate with concentrations MgX2from 0.1 to 0.7 mol/l in St the St side, the concentration of compounds MX4in the preparation of the compounds of formula (III) is not particularly critical. If there is excess acid R-COOH in the mixture at the end of the reaction, there is no need to separate it, provided that the free carboxyl group does not exceed 100% of the total content of carboxyl groups in a solid. If this takes place at the stage b) methods of preparation of solid catalyst component, the amount of carboxyl groups is the same, which are derived from compounds (II) and (III), and those that appear from the free acid R-COOH.

When at the stage a) is used magnesium chloride obtained by spray drying an alcohol solution, in particular ethanol solution, the solid catalyst component (I) is optionally contain alkoxy groups, and in particular ethoxy group, but in an amount not more than 25% relative to the amount of carboxy-groups.

In a preferred variant embodiment of the invention, the solution used in stage a) of the method of preparation of the solid component of catalyst is obtained by reacting solution containing as MgX2and MX4with the necessary amount of acid R-COOH. Typically, however, is predpochtu to obtain the catalyst components with different recipes.

An additional aspect of the present invention relates to catalysts for (co)polymerization of ethylene and alpha-olefins, which are formed from the solid components of the above-described catalyst in combination with an ORGANOMETALLIC compound of aluminum (acetalization), which can be selected from trialkyl aluminum halides (such as chlorides) aluminiumgie containing from 1 to 6 carbon atoms in the alkyl function. Among them, preferred are trialkyl aluminum, such as triethylaluminium, tri-n-butylamine, triisobutylaluminum and tridecylamine. In the catalysts of the present invention, the atomic ratio between aluminum (socializaton) and titanium (solid catalyst component) typically varies from 1 to 3 1500 1 and is preferably from 5 1 to 200 1 depending on the specific polymerization system and its purity.

The present invention also relates to methods of polymerization and copolymerization of ethylene and alpha-olefins using the above catalyst. Usually alpha-olefins are those containing from 3 to 15 carbon atoms, such as propylene, butene-1, 4-methylpentene-1, hexene-1 and octene-1.

In custodiam molecular weight, that have the desired combination of characteristics, such as melt index, sensitivity to shear and the relationship between the average molecular weight (MW) and srednekislovsky molecular weight (PM). In this case, it is convenient to operate, using the technique of suspension in an inert diluent under the following normal conditions: temperature from 60 to 95oC, a pressure of from 6 to 20 kg/cm2and the ratio of partial pressures of hydrogen and ethylene, from 0 to 5. If homopolymerization of ethylene and copolymerization of ethylene with propylene, butene-1 or hexene-1, to obtain a polyethylene with a narrow distribution of molecular weight (MV/PM from 3 to 6), it is preferable to use a solid component of catalyst with a reduced content of magnesium and halogen, in which M is titanium (1A)

M1Mg(0,3-2,0)X(2,0-6,0)Al(0,1-0,5)(R-COO)(1.5 to 3).

These solid components of catalyst can be obtained as a result of work under normal conditions the above methods when used on stage a) the atomic ratio between magnesium and transition metal with a tendency to lower limits, such as for example from 0.3 to 1 2.0 to 1, and the ratio between the atoms of halogen and carboxy groups in the study is imerissia of ethylene with alpha-olefins, especially with propylene, yielding copolymers with characteristics of elastomers. In this case, it is convenient to use the method in suspension or solution at a temperature of from 20 to 60oC and a pressure of from 4 to 25 kg/cm2.

If necessary, obtain a (co)polymer of ethylene with a wide distribution of molecular weight in the two-layer method in suspension advantageous to use solid components of catalyst with an average content of magnesium and halogen, in which M is preferably titanium (1B)

M1MD(1,0-3,0)X(4.5-12)Al(0,5-15)(R-COOH)(0.5 to 1.0).

These solid components of catalyst can be obtained as a result of work under normal conditions the above methods and use of stage a) of the nuclear relationship between magnesium and transition metal 1.0 1 3.0 1 and the relationship between atoms of halogen and carboxy groups at the stage b) near the lower limit, such as from 1.2 1 to 4.0 1. In this case it is convenient to operate at temperatures from 70 to 90oC in the first stage when the General directions from 8 to 12 kg/cm2and temperatures from 70 to 90oC in the second stage when the total pressure of 4 to 8 kg/cm2and when the relationship between the partial pressures of hydrogen and ethylene, equal ostalinom method in suspension, it is advisable to use a solid component of catalyst, in which M represents a transition metal, preferably titanium and zirconium or hafnium with atomic ratios of titanium, zirconium or titanium, hafnium from 0.33 1 to 1 1 (1C)

M1Mg(0,5-2,5)X(5-10)Al(0-1)(R-COO)(0,1-0,4).

This bimetallic catalyst can be easily obtained using at the stage a) methods of solution of titanium-haritchabalet and solution of zirconium chloride or hafnium-haritchabalet. The polymerization is conveniently carried out in one stage using the suspension method at temperatures from 70 to 95oC, pressures from 6 to 15 kg/cm2and when the relationship between the partial pressures of hydrogen and ethylene equal to from 0 to 5.

The distribution of molecular weight polyethylenes obtained by one-step method, can be adjusted by changing the composition of the bimetallic catalyst component in the above limits and/or through the introduction of the Foundation Lewis, as described in the patent application Italy N 22115 A/88, 1988.

A solid component of catalyst of the present invention is also highly active in ways copolymerization of ethylene with alpha-olefins, which are carried out at high temperature and pressure is tnost from 0,915 up to 0.900 g/ml) and VLDPE (density of 0.900 for up to 0,870 g/ml). In these methods typically operate at temperatures from 90 to 280oC, pressures from 800 to 2000 kg/cm2and time from 15 to 90 in the case of tubular reactors and at temperatures from 140 to 280oC, pressures from 800 to 2000 kg/cm2and time from 45 to 180 s in the case of capacitive reactors. In these methods, the polymerization is preferably used a solid component of catalyst with a high content of magnesium and halogen, in which M is preferably titanium or titanium and hafnium. When M is titanium, a solid component of the catalyst may be indicated by the formula (1D)

M1Mg(7-20)X(15-60)Al(0-6)(R-COO)(0,4-3).

When M is titanium, and hafnium, in the atomic ratio from 0.33 to 1 to 1 1, the formula of the preferred catalyst may be indicated (1E)

M1Mg(2-3,5)X(8-120)Al(0-2)(R-COO)(0,1-0,4).

It was found that the solid components of catalysts (1D) and (1E) are active catalysts in which the atomic ratio between aluminum (socializaton) and titanium (solid catalyst component) is unusually low, and in particular in the range from 3 to 10, and they are able to produce copolymers of ethylene with butene-1 and SS="ptx2">

Finally, a solid component of catalyst of the present invention has a high activity in the way homopolymerization alpha-olefins, such as propylene, butene-1, 4-methyl-pentan-1, hexene-1 and octene-1, with the formation of poly(alpha-olefins) with high performance and high molecular weight, which is associated with its own composition. In particular, in order to obtain poly(alpha-olefins) with high performance, it is advantageous to use solid components of catalysts with a high content of magnesium, in which M is titanium (1F)

M1Mg(7-20)X(15-60)Al(0-4)(R-COO)(0,4-3).

In order to obtain poly(alpha-olefins) with high molecular weight, the metal M in the above formula (1F) can be a hafnium or zirconium. In both cases, the polymerization is carried out in suspension at temperatures in the range from 20 to 90oC.

Presented in the following comparative examples and examples of the preparation of the catalyst, and examples of polymerization designed for better illustration of the present invention. In comparative examples 1 cf 19 cf uses magnesium chloride, which is obtained by spray drying an ethanol solution knosti about 0.4 g/ml; the surface area of 3 m2/g, a porosity of 0.7 ml/g and a content of hydroxyl groups of the alcohol to about 10 wt. (based on the weight of ethanol). This magnesium chloride was obtained in accordance with example 1 of U.S. patent N 4843049. The following comparative examples 1 cf 19 cf

Comparative example 1 cf. the Preparation of versatate magnesium chloride.

10.7 g of the carrier (100 mmol), obtained as described above, suspended in 250 ml of n-decane, working in the reactor (1000 ml) with stirring. The suspension is heated to 100oC and while stirring, slowly add 35 g (a 38.5 ml, 200 mmol) versational acid (average mol.m. 175, density of 0.91 g/ml, the molar ratio versatilely acid/magnesium chloride is 2.0). At the end add bubbled through the suspension nitrogen for 5 h, and the temperature of the support is equal to 100oC to facilitate removal of the formed chloride-hydrogen acid. After this period, the suspension is cooled to room temperature (20 25oC), and the residue is filtered on a filter of melted glass.

The soluble product in the filtrate according to chemical analysis, see: 384 Mg mmol/l, Cl 466 mmol/l, and the atomic ratio of chlorine/magnesium is 1.2.

The output of the th example 2 cf. Cooking versatate magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of the medium, 250 ml of n-decane, 43,75 g (250 mmol) versational acid (48,07 ml, average mol.m. 175, density of 0.91 g/ml). Therefore, polar ratio versatilely acid/magnesium chloride equal to 2.5.

The soluble product in the filtrate according to chemical analysis contains: Mg 551,1 mmol/l, Cl 674,8 mmol/l, and the atomic ratio of chlorine/magnesium is 1.2.

The output versatate magnesium chloride equal to 95%, based on all loaded magnesium chloride.

Comparative example 3 cf. the Preparation of versatate magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of carrier 300 ml of n-decane, 52,5 g (300 mmol) versational acid (57,7 ml, average mol.m. 175, density of 0.91 g/ml). Therefore, the molar ratio versatilely acid/magnesium chloride is 3.0.

The soluble product in the filtrate according to chemical analysis contains: 360 Mg mmol/l, Cl 455 mmol/l, and the atomic ratio of chlorine/magnesium equal to 1.26 in.

Output warrior 4 cf. Cooking versatate magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of media, 350 ml of n-decane, 70 g (400 mmol) versational acid (76,92 ml, average mol.m. 175, density of 0.91 g/ml). Therefore, the molar ratio versatilely acid/magnesium chloride is equal to 4.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 380,7 mmol/l, Cl 464 mmol/l, and the atomic ratio of chlorine/magnesium is 1.2.

The output versatate magnesium chloride equal to 100%, based on all loaded magnesium chloride.

Comparative example 5 cf. the Preparation of citronellate magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of the medium, 250 ml of n-decane, to 34.06 g (200 mmol) citronella acid (37,02 ml, average mol.m. 170,03, a density of 0.92 g/ml). Therefore, the molar ratio of citronella acid/magnesium chloride is 2.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 300,6 mmol/l, Cl 349,75 mmol/l, and the atomic ratio of chlorine/magnesium equal to 1.1.

In the comparative example 6 cf. Preparation of citronellate magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of carrier 300 ml of n-decane, 51,09 g (300 mmol) citronella acid (55,5 ml, average mol.m. 170,03, a density of 0.92 g/ml). Therefore, the molar ratio of citronella acid/magnesium chloride is 3.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 320,6 mmol/l, Cl 396,1 mmol/l, and the atomic ratio of chlorine/magnesium is 1.2.

The output of citronellate magnesium chloride equal to 100%, based on all loaded magnesium chloride.

Comparative example 7 cf. the Preparation of (2-ethylhexanoate) magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of the medium, 250 ml of n-decane, 28.8 g (200 mmol) of 2-ethylhexanoic acid (31.8 ml, average mol.m. 144,22, density 0,906 g/ml). Therefore, a molar ratio of 2-ethylhexanoate acid/magnesium chloride is 2.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 330,66 mmol/l, Cl 343,1 mmol/l, and the atomic ratio of chlorine/magnesium R is magnesium.

Comparative example 8 cf. the Preparation of (2-ethylhexanoate) magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of carrier 300 ml of n-decane, 43,26 g (300 mmol) of 2-ethylhexanoic acid (47,7 ml, average mol.m. 144,22, density 0,906 g/ml). Therefore, a molar ratio of 2-ethylhexanoate acid/magnesium chloride is 3.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 340,7 mmol/l, Cl 333,2 mmol/l, and the atomic ratio of chlorine/magnesium equal to 0.97.

Output 2-ethylhexanoate magnesium chloride equal to 100%, based on all loaded magnesium chloride.

Comparative example 9 cf. the Preparation naphthenate, magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of media, 350 ml of n-decane, of 52.8 g (200 mmol) of naphthenic acid (54,48 ml, average mol.m. 264,22, the density of 0.97 g/ml). Therefore, the molar ratio of naphthenic acid/magnesium chloride is 2.0.

The soluble product in the filtrate according to chemical analysis contains: 350 Mg mmol/l, Cl 360,3 mmol/l, and nuclear soo the military magnesium chloride.

Comparative example 10 cf. the Preparation naphthenate, magnesium chloride.

Used the same methodology as that described in comparative example 1 Wed, when loaded into the reactor: 10.7 g (100 mmol) of carrier 300 ml of n-decane, 79,26 g (300 mmol) of naphthenic acid (81,72 ml, average mol.m. 264,22, the density of 0.97 g/ml). Therefore, the molar ratio of naphthenic acid/magnesium chloride is 3.0.

The soluble product in the filtrate according to chemical analysis, see: Mg 310,6 mmol/l, Cl 306,6 mmol/l, and the atomic ratio of chlorine/magnesium is 1.0.

The output naphthenate, magnesium chloride equal to 100%, based on all loaded magnesium chloride.

Comparative example 11 cf. the Preparation of 2-phenylbutyrate magnesium chloride.

5,52 g media (51.6 mmol), obtained as described above, is suspended in 300 ml of toluene, working in the reactor (1000 ml) with stirring. While mixing, slowly add to 16.9 g (103,2 mmol) 2-phenylalkanoic acid, dissolved in 150 ml of anhydrous toluene (molar ratio fenilalanina acid/magnesium chloride is 2.0), to the resulting suspension, maintained at room temperature. At the end add bubbled through the suspension nitrogen for 3 h

Output 2-phenylbutyrate magnesium chloride equal to 90,5% (based on all loaded magnesium chloride.

Comparative example 12 cf. the Preparation of versatate chloride titanium.

Tetrachloride titanium (5,69 g, 30 mmol, 3.3 ml, the density of the cash consideration of USD 1,726 g/ml) dissolved in 200 ml of n-decane in the reactor (500 ml) with stirring. To the solution, heated to 80oC, while mixing, slowly add the 10.5 g (11.5 ml, 60 mmol) versational acid (average molecular weight of 175, a density of 0.91 g/ml, the molar ratio versatilely acid/chloride titanium is 2.0). At the end add bubbled through the suspension nitrogen for 5 h, and the temperature of the support is equal to 100oC to facilitate removal of the formed chloride-hydrogen acid. After this period, the suspension is cooled to room temperature (20 25oC) and you get the solution, which according to chemical analysis, see: Ti 146,1 mmol/l, Cl 226 mmol/l, and the atomic ratio of chlorine/titanium equal to 1.56.

Comparative example 13 cf. the Preparation of citronellate chloride titanium.

Used the same methodology as that described in comparative example 12 cf, is) citronella acid (11,1 ml, average mol.m. 170,03, density 0,922 g/ml). Therefore, the molar ratio of citronella acid/chloride titanium is 2.0.

The resulting solution of the product according to chemical analysis, see: Ti 153,64 mmol/l, Cl 248,2 mmol/l, and the atomic ratio of chlorine/titanium equal to 1.61.

Comparative example 14 cf. the Preparation of (2-ethylhexanoate) chloride titanium.

Used the same methodology as that described in comparative example 12 Wed, when loaded into the reactor: 5,69 g (30 mmol, 3.3 ml, the density of the cash consideration of USD 1,726 g/ml) of titanium tetrachloride, 200 ml of n-decane, 8.6 g (60 mmol) of 2-ethylhexanoic acid (9.6 ml, average mol.m. 144,22, density 0,906 g/ml). Therefore, a molar ratio of 2-ethylhexanoate acid/chloride titanium is 3.0.

The resulting solution of the product according to chemical analysis, see: Ti 239,0 mmol/l, Cl 392,6 mmol/l, and the atomic ratio of chlorine/titanium is 1,64.

Comparative example 15 cf. the Preparation of naphthenate chloride titanium.

Used the same methodology as that described in comparative example 12 Wed, when loaded into the reactor: 5,69 g (30 mmol, 3.3 ml, the density of the cash consideration of USD 1,726 g/ml) of titanium tetrachloride, 200 ml of n-decane, 15,8 g (60 mmol) of naphthenic acid (16.3 m the deposits equal to 2.0.

The resulting solution of the product according to chemical analysis, see: Ti 223,3 mmol/l, Cl 432,2 mmol/l, and the atomic ratio of chlorine/titanium equal to 1.9.

Comparative example 16 cf. the Preparation of versatate chloride vanadium.

Used the same methodology as that described in comparative example 12 Wed, when loaded into the reactor: 3,86 g (20 mmol, 2,12 ml, density 1,816 g/ml) vanadium tetrachloride, 200 ml of n-decane, 7 g (40 mmol) versational acid (7.7 ml, average mol.m. 175, density of 0.91 g/ml). Therefore, the molar ratio versatilely acid/vanadium is 2.0.

The resulting solution according to the chemical analysis are: V 68,5 mmol/l, Cl 116,4 mmol/l, and the atomic ratio of chlorine/vanadium is 1.7.

Comparative example 17 cf. the Preparation of versatate hafnium chloride.

Hafnium tetrachloride (a 8.34 g, 26 mmol) are suspended in 250 ml of n-decane in the reactor (500 ml) with stirring. To the solution at room temperature and stirring slowly add to 9.1 g (10 ml, 52 mmol) versational acid (average mol.m. 175, density of 0.91 g/ml, the molar ratio versatilely acid/hafnium tetrachloride is 2.0). At the end of the addition, the suspension is heated to 100oC and Basle this period, the suspension was filtered in hot condition receive a solution, in which according to chemical analysis contains: Hf 103,1 mmol/l, Cl 214,4 mmol/l, and the atomic ratio of chlorine/hafnium is 2. The content of hafnium in the solution is 85,3% in the calculation of its initial amount.

Comparative example 18 cf. the Preparation of versatate chloride of zirconium.

Used the same methodology as that described in comparative example 17 Wed, when loaded into the reactor: 8,49 g cases (36.4 mmol) of zirconium tetrachloride, 200 ml of n-decane, 12.7 g (72,8 mmol) versational acid (14,0 ml, average mol.m. 175, density of 0.91 g/ml). Therefore, the molar ratio versatilely acid/vanadium is 2.0.

The resulting solution according to the chemical analysis are: Zr 81,3 mmol/l, Cl to 126.8 mmol/l, and the atomic ratio of chlorine/zirconium equal to 1.56.

The zirconium content in the solution is 87,7% in the calculation of its initial amount.

Comparative example 19 cf. the Preparation of 2-phenylbutyrate hafnium chloride.

Hafnium tetrachloride (16,4 g of 51.1 mmol) is suspended in 200 ml of toluene in the reactor (500 ml) with stirring. To the suspension at room temperature and stirring is 16.8 g (102,2 mmol) 2-phenylalkanoic acid, dissolved vne at room temperature through a mixture bubbled nitrogen for 3 h, to facilitate removal of the formed chloride-hydrogen acid. After this period, the suspension is filtered while hot, and get the solution, which according to chemical analysis are: Hf 812 mmol/l, Cl 1476 mmol/l, and the atomic ratio of chlorine/hafnium equal to 1.8.

The content of hafnium in the solution is 95.1% in the calculation of its initial amount.

Below are the main examples 1 43 describing the preparation of the catalyst component.

Example 1. Preparation of catalyst component

Ti1Mg16,3Cl36,2Al1,9R-COO0,76.

Loaded into the reactor with a mixer (capacity 2000 ml) 238,1 mmol (620 ml solution in n-decane) versatate magnesium chloride, prepared as described in comparative example 1 cu (atomic ratio of chlorine/magnesium 1,2), and then 14.9 mmol (102 ml of solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cu (atomic ratio of chlorine/titanium 1,56).

At operating temperature 30oC dropwise added slowly 139,5 g (565,5 mmol) ethylamine of sesquichloride (the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1), Joe substance is filtered on a porous filter made of fused glass.

Thus obtain 27.5 g of the solid component of the catalyst which is washed with three portions of n-heptane, 100 ml For the solid component of catalyst is found to have the following features:

The titanium content, wt% 2,5

The content of magnesium, by weight. 20,7

The aluminium content, wt. 2,7

The chlorine content, wt. 67,2

The content of the organic part ( organic part consists mainly of residues versational acid), wt. 6,2

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,98

Surface area, m2/g 40

Porosity, about. 70

In terms of components as the ratio of their atomic parts of the solid component of the catalyst may be represented by formula

Ti1Mg16,3Cl36,2Al1,9R-COO0,76.

Example 2. Preparation of catalyst component

Ti1Mg4,1Cl12,2Al0,36R-COO0,27.

Loaded into the reactor with a mixer (capacity 2000 ml) 160 mmol (250 ml solution in n-decane) versatate magnesium chloride, prepared as described in reference example 1, and then 40 mmol (286 ml solution in n-decane) versatate titanium chloride, prepared as described in smmol) ethylamine of sesquichloride (the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carbonyl groups is equal to 3/1), diluted n-decane to 345 ml At the end of the addition, the suspension is heated to 90oC for 2 h and then the solid is filtered on a porous filter made of fused glass.

Thus obtain 24.5 g of the solid component of the catalyst which is washed with three portions of n-heptane, 100 ml For the solid component of catalyst is found to have the following features:

The titanium content, wt. 7,5

The content of magnesium, by weight. the 15.6

The aluminium content, wt. 1,5

The chlorine content, wt. 68,0

The content of organic parts, by weight. 7,4

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent state 0,98

In terms of components as the ratio of their atomic parts of the solid component of the catalyst may be represented by formula

Ti1Mg4,1Cl12,2Al0,36R-COO0,27.

Example 3. Preparation of catalyst component

Ti1Mg7,6Cl17,65Al0,87R-COO0,49.

Using the same technique as in example 1, but with different amounts of added components: 160 mmol (416 ml solution in n-decane) versatate magnesium chloride, prepared as described in relatively eunicella example 12 cf; 98,8 g (400 mmol) ethylamine of sesquichloride (diluted n-decane to 313 ml); the ratio between the atoms of chloride in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

Data analysis:

The titanium content, wt. 5,0

The content of magnesium, by weight. 18,9

The aluminium content, wt. 2.4GHz

The chlorine content, wt. 64,7

The content of organic parts, by weight. 9,0

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,98,

the formula Ti1Mg7,6Cl17,65Al0,82R-COO0,49.

Example 4. Preparation of catalyst component

Ti1Mg10,6Cl25,8Al2,1R-COO0,64.

Use the same technique as in example 1, but with different amounts of added components: 100 mmol (106 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 Wed; 10 mmol (144 ml solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cf; of 60.5 g (245 mmol) ethylamine of sesquichloride (diluted n-decane to 190 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxyl is C. 18,5

The aluminium content, wt. 4,1

The chlorine content, wt. 65,9

The content of organic parts, by weight. 8,0

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,99,

the formula Ti1Mg10,6Cl25,8Al2,1R-COO0,64.

Example 5. Preparation of catalyst component

Ti1Mg16,6Cl38,6Al2,6R-COO1,13.

Use the same technique as in example 1, but with different amounts of added components: 160 mmol (170 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 Wed; 10 mmol (11,7 ml solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cf; 78,4 g (316 mmol) ethylamine of sesquichloride (diluted n-decane up to 250 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups equal to 2.5/1.

Data analysis:

The titanium content, wt. 2,3

The content of magnesium, by weight. 19,3

The aluminium content, wt. 3,3

The chlorine content, wt. 65,6

The content of organic parts, by weight. 9,5

The ratio of titanium in trehu the Cl38,6Al2,6R-COO1,13.

Example 6. Preparation of catalyst component

Ti1Mg16,6Cl40Al3,3R-COO1,1.

Use the same technique as in example 1, but with different amounts of added components: 160 mmol (170 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 Wed; 10 mmol (11,7 ml solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cf; 62,7 g (253,3 mmol) ethylamine of sesquichloride (diluted n-decane up to 250 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 2/1.

Data analysis:

The titanium content, wt. 2,2

The content of magnesium, by weight. 18,8

The aluminium content, wt. 4,1

The content of chloride, wt. 66,1

The content of organic parts, by weight. 8,8

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,98,

the formula Ti1Mg16,6Cl40Al3,3R-COO1,1.

Example 7. Preparation of catalyst component

Ti1Mg18Cl39,3Al3R-COO1,25.

ol (230 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 Wed; 10 mmol (11,7 ml solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cf; 47 g (190 mmol) ethylamine of sesquichloride (diluted n-decane 150 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is 1.5/1.

Data analysis:

The titanium content, wt. 2,2

The content of magnesium, by weight. 20

The aluminium content, wt. 3,7

The chlorine content, wt. 64,8

The content of organic parts, by weight. 10

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,97,

the formula Ti1Mg18Cl39,3Al3R-COO1,25.

Example 8. Preparation of catalyst component

Ti1Mg19Cl43Al4,8R-COO1,25.

Use the same technique as in example 1, but with different amounts of added components: 160 mmol (230 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 Wed; 10 mmol (11,7 ml solution in n-decane) versatate titanium chloride, prepared as described in compare the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

Data analysis:

The titanium content, wt. 2

The content of magnesium, by weight. 18,9

The aluminium content, wt. 6

The chlorine content, wt. 64

The content of organic parts, by weight. 9,1

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 1,

the formula Ti1Mg19Cl43Al4,8R-COO1,25.

Example 9. Preparation of catalyst component

Ti1Mg18Cl39,3Al3R-COO1,4.

Use the same technique as in example 1, but with different amounts of added components: 131 mmol (190 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 cf; 8,2 mmol (9.6 ml of a solution in n-decane) versatate titanium chloride, prepared as described in comparative example 12 cf; of 36.4 g (233,3 mmol) isobutylamine dichloride (diluted n-decane of 110 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is 1.5/1.

Data analysis:

The titanium content, wt. 2,2

The content of magnesium, by weight. 20

The aluminium content, wt. 3,7

The chlorine content, wt. 64,8

Containing the x - and tetravalent States 0,97,

the formula Ti1Mg18Cl39,3Al3R-COO1,4.

Example 10. Preparation of catalyst component

Ti1Mg16,4Cl37,2Al3,5R-COO1,1.

Use the same technique as in example 1, but with different amounts of added components: 174 mmol (550 ml solution in hydrocarbon) citronellate magnesium chloride, prepared as described in comparative example 6 Wed; to 10.8 mol (70 l of a solution in n-decane) of citronellate titanium chloride, prepared as described in comparative example 6 cf; 145,3 g (587,1 mmol) ethylamine of sesquichloride (diluted n-decane up to 460 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carbonyl groups is equal to 3/1.

Data analysis:

The titanium content, wt. 2,3

The content of magnesium, by weight. 19,3

The aluminium content, wt. 4,6

The chlorine content, wt. 64,6

The content of organic parts, by weight. 9,2

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,98,

the formula Ti1Mg16,4Cl37,2Al35R-COO1,1.

Example 11. Preparation of catalyst component

Ti1Mg16,2Cl

Data analysis:

The titanium content, wt. 2,5

The content of magnesium, by weight. 20

The aluminium content, wt. 2.4GHz

The chlorine content, wt. 66

The content of organic parts, by weight. 9,1

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,99,

the formula Ti1Mg16,2Cl36Al1,7R-COOfor 0.6.

Example 12. Preparation of catalyst component

Ti1Mg16,2Cl38,3Al2R-COO1,3.

Use the same technique as in example 1, but with different amounts of added components: 200 mmol (580 ml solution in hydrocarbon) 2 ethylhexanoate magnesium chloride, prepared as described in comparative example 8 cf; 12.5 mmol (52 ml solution in n-decane) 2 ethylhexanoate titanium chloride, prepared as described is the relation between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

Data analysis:

The titanium content, wt. 2,3

The content of magnesium, by weight. 19,1

The aluminium content, wt. 2,6

The chlorine content, wt. 66,8

The content of organic parts, by weight. 9,2

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,98,

the formula Ti1Mg16,2Cl38,3Al2R-COO1,3.

Example 13. Preparation of catalyst components

Ti1Hf1,93Mg8Cl32,7Al3R-COO0,8.

Loaded into the reactor with a mixer (capacity 2000 ml) 70 mmol (148 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 3, Wed; 10 mmol (37,5 ml solution in hydrocarbon) versatate titanium chloride, prepared as described in comparative example 12 Wed, 30 mmol (300 ml solution in hydrocarbon) versatate hafnium chloride, prepared as described in comparative example 17 cf.

Working at room temperature, dropwise added slowly 84,1 g (840 mmol, diluted with n-decane to a volume of 290 ml) ethylamine of sesquichloride (the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups equally the Ute on a porous filter made of fused glass.

Thus obtain 19.5 g of the solid component of the catalyst which is washed with four portions of n-heptane, 100 ml For the solid component of catalyst is found to have the following features:

The titanium content, wt. 2.4GHz

The content of hafnium, wt. 17,5

The content of magnesium, by weight. 9,9

The aluminium content, wt. 4,1

The chlorine content, wt. 59,1

The content of organic parts, by weight. 7,0

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,92.

In terms of components as the ratio of their atomic parts component of the catalyst may be represented by formula

Ti1Hf1,98Mg8Cl32,7Al3R-COO0,8.

Example 14. Preparation of catalyst component

Ti1Zr1,2Mg8Cl29,8Al1,6R-COO0,8.

Use the same technique as in example 13, but with different amounts of added components: 80 mmol (148 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 3, Wed; 10 mmol (37,5 ml solution in hydrocarbon) versatate titanium chloride, prepared as described in comparative example niteline example 18 cf; and 84,1 g (340 mmol) ethylamine of sesquichloride (diluted n-decane to 290 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carbonyl groups is equal to 3/1.

So give 19.5 g of the solid catalyst component with the following characteristics:

The titanium content, wt. 3,1

The zirconium content, wt. 7.2V

The content of magnesium, by weight. 12,8

The aluminium content, wt. 2,9

The chlorine content, wt. 65

The content of organic parts, by weight. 9,0

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,92,

the formula Ti1Zr1,2Mg8Cl29,8Al1,6R-COO0,8< / BR>
Example 15. Preparation of catalyst component

Ti1Mg1,1Cl4,5Al0,22R-COOa 1.8.

Use the same technique as in example 1, but on the basis of: 85.6 mmol (155 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 2, cf; 85.6 mmol (100 ml solution in hydrocarbon) versatate titanium chloride, prepared as described in comparative example 12 cf; 36,7 g (304,6 mmol) diethylaluminium of monochloride (diluted n-decane up to 250 ml); the ratio is pensio heated to 60oC for 1 h, cooled and filtered through a porous filter.

So get a solid catalyst component with the following characteristics:

The titanium content, wt. 8,6

The content of magnesium, by weight. 4,8

The aluminium content, wt. 0,82

The chlorine content, wt. 25

The content of organic parts, by weight. 60,8

The ratio of titanium in the trivalent state and the amount of titanium in the three - and tetravalent States 0,9,

the formula Ti1Mg1,1Cl4,5Al0,22R-COOa 1.8.

Example 16. Preparation of catalyst component

V1Mg2,1Cl5,3R-COOof 0.2.

Use the same technique as in example 1, but on the basis of: 100 mmol (210 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 cf; 50 mmol (635 ml solution in hydrocarbon) versatate vanadium chloride, prepared as described in comparative example 16 cf; 80.4 g (325 mmol) ethylamine of sesquichloride (diluted n-decane up to 235 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3.1/1.

The suspension is heated to 90oC for 2 h, cooled and pilot three portions of heptane, 100 ml This component of the catalyst had the following characteristics, wt.

The vanadium content 16

Magnesium content of 15.2

Chlorine 59

The organic part of 9.8,

formula V1Mg2,1Cl5,3R-COOof 0.2.

Example 17. Preparation of catalyst component

V1Mg6,2Al2,0Cl15,5R-COO0,5.

Use the same technique as in example 16, but on the basis of: 240 mmol (505 ml solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 cf; 30 mmol (381 ml solution in hydrocarbon) versatate vanadium chloride, prepared as described in comparative example 16 cf; 148,5 g (600 mmol, 471 ml hydrocarbon solution) ethylamine of sesquichloride (diluted n-decane at 253 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

So get component of the catalyst, which has the following characteristics, wt.

The vanadium content of 5.7

The content of magnesium 17

The aluminium content of 9.1

The chlorine content of 62

The content of organic parts of 9.5,

formula V1Mg6,2Al2,0Cl8Ala 0.1R-COOof 0.15.

Use the same technique as in example 1, but on the basis of: 200 mmol (476 ml of solution in hydrocarbon) versatate magnesium chloride, prepared as described in comparative example 1 cf; 200 mmol (540 ml solution in hydrocarbon) versatate hafnium chloride, prepared as described in comparative example 17 cf; 210,4 g (850 mmol) ethylamine of sesquichloride (diluted n-decane to 668 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

So get component of the catalyst, which has the following characteristics, wt.

The content of hafnium 44,4

The content of magnesium 6.0

The content of aluminium 0,7

The chlorine content of 42.3

The content of organic parts 6,6,

the formula Hf1Mg1Cl4,8Ala 0.1R-COOof 0.15.

Example 19. Preparation of catalyst component

Hf1Mg1,7Cl9,1Al0,7R-COOfor 0.3.

Use the same technique as in example 1, but on the basis of: 16 mmol (20 ml solution in toluene) 2-phenylbutyrate magnesium chloride, prepared as described in comparative example 11 cf; 16 mmol (20 ml solution in toluene) 2-Fe is glevodorodnogo solution) ethylamine of sesquichloride (diluted n-decane up to 235 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

So get component of the catalyst, which has the following characteristics, wt.

The hafnium content of 28,9

Magnesium content of 6.7

The aluminium content of 3.0

The chlorine content 52,3

The content of organic parts 9,1,

the formula Hf1Mg1,7Cl9,8Al0,7R-COOfor 0.3.

Example 20. The components of the catalysts of examples 1 to 12 are used in the test polymerization of ethylene under the working suspension method, in a solvent. More specifically, in the reactor (5 l) with a stirrer download the following products in the specified sequence: 1900 ml of anhydrous n-heptane, 0,228 g triethylaluminum and 5.5 mg of solid catalyst component. The reactor is heated to a temperature of 85oC and presoviet its hydrogen at a pressure of 3.2 kg/cm2. Then loaded into the reactor ethylene to a pressure of 9 kg/cm2and this pressure is maintained for the following 2 h with continuous feeding of ethylene. At the end of this period the polymerization stopped, and charged to the reactor 20 ml alcohol 10% solution of BHT.

Identified the following values:

yhod, expressed as kg of polyethylene obtained per 1 g of titanium in the solid component of catalyst;

the melt index (MI at 190oC and a load of 2.16 kg) of the obtained polyethylene, determined in accordance with ASTM-D 1238 E, expressed in g/10 min;

sensitivity to shear (SS ratio between the indices of melt flow and measured with a 21.6 and 2.16 kg) of the obtained polyethylene, determined in accordance with ASTM-D 1238 E.

The results are shown below in table. 1.

Example 21. In the reactor (5 l) with a stirrer download the following products in the order listed: 0.6 g of triisobutylaluminum and 36 mg of solid component of catalyst prepared as described in example 13. The reactor is heated to a temperature of 85oC and presoviet its hydrogen at a pressure of 7.7 kg/cm2. Then loaded into the reactor ethylene to a pressure of 11 kg/cm2and this pressure is maintained for the following 2 h with continuous feeding of ethylene ratio (hydrogen/ethylene equal to 2.3). At the end of this period the polymerization stopped, and charged to the reactor 20 ml alcohol 10% solution of BHT.

Get a polyethylene with a capacity of 14.2 kg per 1 g of solid component of catalyst; exit politicalmath to shift equal to 92 (ASTM-D 1238 (E).

Example 22. Use the same technique as in example 21, with the catalyst of example 13; the ratio of hydrogen/ethylene is 0,57.

Get a polyethylene with a capacity of 25.2 kg per 1 g of solid component of catalyst; output polyethylene 1050 kg per 1 g of titanium in the solid component. The polyethylene had a melt index equal to 0.2 g/10 min, and sensitivity to shift equal to 15 (ASTM-D 1238 (E).

Example 23. Use the same technique as in example 21, with the catalyst of example 14; the ratio of hydrogen/ethylene is 1,94.

Get a polyethylene with a capacity of 12.4 kg per 1 g of solid component of catalyst; output polyethylene 400 kg per 1 g of titanium in the solid component. The polyethylene had a melt index equal to 5.2 g/10 min, and sensitivity to shift equal to 60 (ASTM-D 1238 (E).

Example 24. Use the same technique as in example 20, with the use of 16.9 mg of solid component of catalyst of example 15, the polymerization temperature 90oC, total pressure of 10 kg/cm2and the ratio of hydrogen/ethylene equal to 0.71.

Get a polyethylene performance 23.3 kg per 1 g of solid component of catalyst; output polyethylene 294 kg per 1 g of the se, equal to 29.5 (ASTM-D 1238 (E).

Example 25. Into a reactor (capacity 1 l) with stirring load in the specified order: 500 ml of anhydrous n-heptane, 0.1 g of triisobutylaluminum (0.5 ml of 1 molar solution). The reactor is heated to a temperature of 50oC and presoviet its propylene at a pressure of 4 kg/cm2. Upon reaching the phase equilibrium supply of propylene stop, and the inside of the reactor enter a solid component of catalyst of example 15 in the amount of 2.8 mg with the flow of ethylene to a pressure of 5 kg/cm2. Polymerization is continued for 0.5 h, and stop introducing into the reactor 20 ml alcohol 10% solution of BHT.

Get an ethylene-propylene copolymer with access 159,2 kg per hour per 1 g of titanium in the solid component of catalyst. This copolymer had a characteristic viscosity, defined in decaline at 135oC, equal to 3.3 DL/g According to nuclear magnetic resonance copolymer has the following composition: 37 wt. propylene units (28,7 mol.) and of 62.4 wt. ethylene units (from 71.3 mol.).

Example 26. Use the same technique as in example 20, with a solid component of catalyst of example 16 (16.2 mg) and 0.6 g of triisobutylaluminum (3 mmol) under the following conditions: temperature 80oC, total giving is part of 0.33 kg to 1 g of solid component of catalyst; the yield of polyethylene 5,77 kg per 1 g of vanadium in the solid component. The polymer had a melt index is 0.135 g/10 min and a sensitivity shift, equal to 17 (ASTM-D 1238 (E).

Example 27. Use the same technique as in example 20, with a solid component of catalyst of example 17 (11.6 mg) and 0.16 g of triisobutylaluminum (0.8 mmol) under the following conditions: temperature 80oC, a pressure of ethylene of 3 kg/cm2; reaction time 2 h

Get a polyethylene with a capacity of 3.5 kg per 1 g of solid component of catalyst; output polyethylene 61,8 kg per 1 g of vanadium in the solid component.

Example 28. Use the same technique as in example 20, using the solid component of catalyst of example 18 under the following conditions: temperature of polymerization equal to 85oC, pressure of 11 kg/cm2and the ratio of hydrogen/ethylene is equal to 1.3.

Get a polyethylene with a capacity of 5.4 kg per 1 g of hafnium in the solid component.

Example 29. Use the same technique as in example 20, using 141 mg of solid component of catalyst of example 19 under the following conditions: temperature of polymerization equal to 85oC, the total pressure of 11 kg/cm2and sootnosheniem component.

Example 30. Use a solid component of catalyst prepared as described in example 1 in test and copolymerization of ethylene with butene-1, working continuously at elevated pressure and temperature.

More specifically, used reaction vessel with a capacity of 0.5 l, equipped with a turbine stirrer, a feed water temperature control and cooling system. On the top of the reactor serves the following threads:

the flow of ethylene and butene-1 (weight ratio of 32:68) obvej a rate of 25 kg/h;

the solution triethylaluminum in hexane (concentration of 9 mmol/l) in an amount of about 0.06 mmol of triethylaluminum for every kilogram amounts of gases (ethylene and butene-1);

suspension in vaseline and paraffin oil solid component of catalyst prepared in example 1 in the amount of 6.3 µmol titanium for every kilogram amounts of gases.

The temperature of the incoming reactants is equal to 60oC, the temperature of polymerization 230oC; stirrer speed is 1700 rpm./min, the average residence time of the reactants in the reactor is about 40 at a pressure of 1200 kg/cm2.

The copolymerization product is continuously removed from the bottom part of the reactor and subjected to initial a single evaporation separator high the deposits (1 to 5 kg/cm2). At the reactor exit enter deactivator catalytic system (glycerin). Unreacted monomers selected when processing a single evaporation, after cleaning and re-mixing with fresh monomers return to the reactor. The copolymer allocate using an extruder connected to the low pressure separator.

Working continuously for 48 hours, get the following results: the degree of conversion of monomer for the passage of 15.2 wt. average hourly productivity of the copolymer of ethylene-butene-1 3.8 kg/h; index melt flow of the copolymer (190oC, load of 2.16 kg) 4,2 DG/min (ASTM-D 1238 (E); the sensitivity of the copolymer to shift 33 (ASTM-D 1238 (E); the density of the copolymer, measured at 23oC 0,9244 g/ml; output copolymer 500 kg per 1 g of titanium.

Example 31. Use the same technique as in example 30 at the temperature of polymerization 210oC and the weight ratio 32 68 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 8.

The degree of conversion of monomers for the passage equal to 12.8 wt. get a copolymer of ethylene-butene-1 with a capacity of 3.2 kg/h, with a yield of 700 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 1.7 DG/min, custo in example 30 at the temperature of polymerization 240oC and the weight ratio 32 68 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 5.

The degree of conversion of monomers for the passage equal to 16.4 wt. get a copolymer of ethylene-butene-1 performance 4.1 kg/h; 420 kg per 1 g of titanium. Index melt flow copolymer 6.5 DG/min, density copolymer 0,9211 g/ml.

Example 33. Use the same technique as in example 30, at the temperature of polymerization 225oC and a weight ratio of 20 to 80 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 5.

The degree of conversion of monomers for the passage equal to 14.4 wt. get a copolymer of ethylene-butene-1 with a capacity of 3.6 kg/h; 400 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 7.8 DG/min, sensitivity to shear 38, the density of the copolymer 0,9060 g/ml.

Example 34. Use the same technique as in example 30 at the temperature of polymerization 214oC and a weight ratio of 22 78 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 6.

The degree of conversion of monomer for the passage equal to 12.0 wt. get a copolymer of ethylene-butene-1 with proizvoditelnee 0,9079 g/ml.

Example 35. Use the same technique as in example 30 at the temperature of polymerization 211oC and a weight ratio of 20 to 80 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 5.

The degree of conversion of monomers per pass is equal to 13.2 wt. get a copolymer of ethylene-butene-1 with a capacity of 3.3 kg/h; 893 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 2.7 DG/min, density copolymer 0,9014 g/ml.

Example 36. Use the same technique as in example 30 at the temperature of polymerization 205oC and a weight ratio of 13 87 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst equal to 4.

The degree of conversion of monomers for the passage equal to 12.4 wt. get a copolymer of ethylene-butene-1 performance 3.1 kg/h; 575 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 1.7 DG/min, density copolymer 0,8897 g/ml.

Example 37. Use the same technique as in example 30 at the temperature of polymerization 205oC and a weight ratio of 8 92 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 5.

The degree of conversion of monomers for the and. Index melt flow of the copolymer is equal to 22.8 DG/min, density copolymer 0,8760 g/ml.

Example 38. Use the same technique as in example 30, using a solid component of catalyst of example 13 at a temperature of polymerization 230oC and a weight ratio of 28 72 incoming ethylene and butene-1; the atomic ratio of aluminum/titanium in the catalyst is equal to 8.

The degree of conversion of monomers for the passage equal to 12.8 wt. get a copolymer of ethylene-butene-1 with a capacity of 3.2 kg/h; with the release of 450 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 0.5 DG/min, sensitivity to shear 45, the density of the copolymer 0,921 g/ml.

Example 39. Use a solid component of catalyst prepared as described in example 1, in the test copolymerization of ethylene with propylene-1, working continuously at elevated pressure and temperature.

More specifically, apply the same methodology described in example 30, feeding a stream of ethylene and propylene (the weight ratio of 35 to 65) with a speed of 30 kg/h and the inlet temperature 60oC.

The polymerization is carried out at a temperature of 220oC and the atomic ratio of aluminum/titanium in the catalyst is equal to 6.

The degree priihoda 550 kg per 1 g of titanium. Index melt flow of the copolymer is equal to 15 DG/min, density copolymer 0,895 g/ml.

Example 40. Into a reactor (capacity 1 l) with stirring load 400 ml of anhydrous n-heptane containing 0,158 g triisobutylaluminum (0.8 ml 1 molar solution). The reactor is heated to a temperature of 65oC and the inside of the reactor is injected to 7.6 mg of solid catalyst component prepared in example 1 with the flow of propylene to a pressure of 5 kg/cm2. This pressure support, feeding propylene for 4 hours At the end of this period stop polymerization, introducing into the reactor 20 ml alcohol 10% solution of BHT.

Receive polypropylene with a capacity of 7.0 kg per 1 g of solid component and 278,9 kg/h per 1 g of titanium in the solid catalyst component.

Example 41. Into a reactor (capacity 0.5 l) with stirrer download the following products in the specified sequence: 300 ml n-heptane, 30 g (46 ml) 4 methylpentene-1 and 0,109 g triisobutylaluminum. The reactor is heated to a temperature of 60oC and enter to 17.3 mg of the solid catalyst component prepared in example 1. The polymerization is conducted for 1 h and then stop loading in the reactor 20 ml alcohol 10% solution of BHT.

Get poly-(4-methylpentan-1) with p the home component. The polymer had a characteristic viscosity, defined in decaline at 135oC, equal to 5.7 DL/g

Example 42. Use the procedure described in example 41, loading into the reactor a solid component of catalyst (17.3 mg) prepared in example 3.

Get poly-(4-methylpentan-1) performance 1,21 kg per 1 g of solid component of catalyst; the polymer yield 24,2 kg per 1 g of titanium in the solid component. The polymer had a characteristic viscosity, defined in decaline at 135oC, 5.9 DL/g

Example 43. Into a reactor (capacity 0.5 l) with stirrer download the following products in the specified sequence: 300 ml n-heptane, 35 g of 1-hexene and 0,099 g triisobutylaluminum. Then at a temperature of 25oC type of 19.2 mg of solid catalyst component prepared in example 1. The polymerization is conducted for 1 h and then stop loading in the reactor 20 ml alcohol 10% solution of BHT.

Get poly-(hexane-1) with a capacity of 1.28 kg per 1 g of solid component of catalyst; the polymer yield 50,8 kg per 1 g of titanium in the solid component. The polymer had a characteristic viscosity, defined in decaline at 135oC, equal to 2.1 DL/g

Comparative PDA from: 176,8 mmol (18,9 g) media, magnesium chloride, having the features specified in the description; 11.0 mmol (13 ml) solution of versatate titanium chloride, prepared as described in comparative example 12 cf; 16,3 (66,2 mmol) ethylamine of sesquichloride (diluted n-decane to 52 ml); the ratio between the chlorine atoms in ethylaluminum sesquichloride and the alkoxide and carboxylate groups is equal to 3/1.

Get a solid catalyst component with the following characteristics:

The titanium content, wt. 2.4GHz

The content of magnesium, by weight. 20,8

The aluminium content, wt. 2,7

The chlorine content, wt. 72

The content of organic parts, by weight. 2,1

the formula Ti1Mg17Cl39,9Al2.

This solid component of catalyst used in the test polymerization of ethylene in the polymerization conditions of example 20.

Identified the following values: performance of 16.0 g of polyethylene per 1 g of solid component of catalyst; exit 666 kg of polyethylene per 1 g of titanium in the solid component of catalyst; a melt index 1.0 g/10 min (ASTM-D 1238 E); sensitivity to shear 36 (ASTM-D 1238 (E).

The following are comparative examples 45 to 48.

Comparative example 45. Prepare a solid component of catalyst, based on the chlorite is application Europatent N 243327.

This solid component of catalyst used in the test polymerization of ethylene in the polymerization conditions of example 20.

Identified the following values: performance 18,1 kg of polyethylene per 1 g of solid component of catalyst; output 604 kg of polyethylene per 1 g of titanium in the solid component of catalyst; a melt index of 1.1 g/10 min (ASTM-D 1238 E); sensitivity to shear 35 (ASTM-D 1238 (E).

Comparative example 46. Prepare a solid component of catalyst based on magnesium chloride, obtained by spray drying an ethanol solution of Tetra-n-butyl and diethylaluminium-chloride, in accordance with U.S. patent N 4843049.

Formula:

Ti1Mg0,96Cl3,96Al0,46(ethyl+o-methyl+o-butyl)2,23.

This solid component of catalyst used in the test polymerization of ethylene in the polymerization conditions of example 24.

Get a polyethylene with a capacity of 12.1 kg per 1 g of solid component of catalyst; output 100 kg of polyethylene per 1 g of titanium in the solid component of catalyst. This polyethylene had a melt index of 6.6 g/10 min and sensitivity to shear 27,2 (ASTM-D 1238 (E).

Comparative example 47. Prepare a solid component is; 4.6 mmol (16.3 g) of Tetra-n-butyl hafnium; 184 mmol (19,7 g) chlorine-containing carrier having the features specified in the description; and 68.5 g (276,4 mmol) ethylamine of sesquichloride (the ratio between the chlorine atoms in ethylaluminum sesquichloride and alkoxide groups is equal to 3/1).

So get a solid catalyst component with the following characteristics:

The titanium content, wt. 2,9

The content of hafnium, wt. 16,3

The content of magnesium, by weight. 12,7

The aluminium content, wt. 0,8

The chlorine content, wt. 58,2

The content of organic parts, by weight. 9,1

formula: Ti1Hf1,5Mg8,6Cl27Al0,5.

This solid component of catalyst used in the test polymerization of ethylene was carried out in the polymerization conditions of example 21, working with a ratio of hydrogen/ethylene 2,35.

Identified the following values: performance 3.2 kg of polyethylene per 1 g of solid component of catalyst; exit 111 kg of polyethylene per 1 g of titanium in the solid component of catalyst; a melt index of 0.05 g/10 min (ASTM D 1238 (E); sensitivity to shear 222 (ASTM-D 1238 (E).

Comparative example 48. Use a solid component of catalyst prepared with known pospatany copolymerization of ethylene with butene-1, working at the temperature of polymerization 235oC, the flow of ethylene and butene-1 in a weight ratio of 32 68 and the atomic ratio between the aluminium in socializaton and titanium in the solid component of catalyst is equal to 23.

The following results were obtained: degree of conversion of monomers to 13.2 wt. performance copolymer of ethylene-butene-1 3.4 kg/h; output copolymer 221 kg per 1 g of titanium. Index melt flow of a copolymer of 4.2 DG/min, the sensitivity of the copolymer to the offset of 30 and a density 0,9235 g/ml.

The test was repeated at the operating temperature of 210oC. the following results Were obtained: degree of conversion of monomers to 10.4 wt. performance copolymer of ethylene-butene-1 2.6 kg/h; output copolymer 322 kg per 1 g of titanium. Index melt flow of a copolymer of 1.1 DG/min, the sensitivity of the copolymer to shift 31 and density 0,9214 g/ml.

In conclusion, the attached table. 2, reflecting different molar ratios between the ingredients used in the examples to obtain a solid component of catalyst. It should be noted that in table. 2 data related aluminum compounds, related to the effective number of moles of aluminum. Also in the table. 3 contains data that autosattlerei, in example 1 indicated that 76 moles of aluminum compounds to 1 pray compounds of the transition metal (even if in example 1 is used 38 moles ethylaluminum of sesquichloride), because ethylaluminum sesquichloride contains two atoms of aluminum per mole.

This is confirmed by the fact that really relevant for the invention is the molar ratio of transition metal:magnesium:aluminum in the ingredients, not the ratio of used connections.

From the data given in table. 2, we can conclude that the ratio of transition metal compounds:compound of magnesium, alkylamine chloride to obtain a solid component of catalyst is from 1 to 1 and 3,5 16,1 - 109 (M/Mg/Al).

From the data given in table. 3, it can be concluded that the ratio between trialkylaluminium and solid component of catalyst (in terms of the transition metal) ranges from 1 to 2.7 872. These values underpin claimed in patent formula components.

1. A solid component of catalyst for the (co)polymerization of ethylene and C2- C6-alpha-olefins, including magnesium and transition metal obtained by the sequential interaction of compounds of magnesium with a compound of the transient the interactions, obtained using as compounds of magnesium carboxylate of General formula

MgXn(RCOO)2-n,

where X is fluorine, chlorine or bromine;

R is aliphatic, cycloaliphatic or aromatic4- C25is a hydrocarbon radical;

n 0 1,

and as the compound of the transition metal is at least one carboxylate of General formula

MXm(RCOO)4-m,

where M is a metal selected from the group comprising titanium, vanadium, zirconium and hafnium;

X is fluorine, chlorine or bromine;

R is aliphatic, cycloaliphatic or aromatic4- C25is a hydrocarbon radical;

m 0 2,

and contains 1 atom of the transition metal 1 19 atoms of magnesium, and 4.5 43.0 atoms of halogen and 0.15 1,80 carboxyl groups.

2. Component under item 1, characterized in that it comprises 0.1 to 4.8 atoms of aluminum per 1 atom of transition metal.

3. A method of obtaining a solid component of catalyst for the (co)polymerization of ethylene and C2WITH6alpha-olefins sequential interaction of compounds of magnesium with a compound of the transition metal and alkylhalogenide, characterized in that the connection quality using magnesium dissolve the

as compounds of the transition metal solution in an inert organic solvent at least one carboxylate of General formula

MXm(RCOO)4-m,

where M is a metal selected from the group comprising titanium, vanadium, zirconium and hafnium;

X is fluorine, chlorine or bromine;

R is aliphatic, cycloaliphatic or aromatic4- C25is a hydrocarbon radical;

n 0 1;

m 0 2,

and the process is carried out at a molar ratio of the compound of the magnesium compound of the transition metal 1,0 16,1 1.0 and alkylaminocarbonyl compound of the transition metal 3,5 109,0 1.

4. The catalyst for the (co)polymerization WITH2WITH6alpha-olefins comprising a solid component containing magnesium and a transition metal, obtained by the interaction of the compounds of magnesium with a compound of the transition metal, and three WITH2WITH4-alkylamino, characterized in that it contains a solid component, which is a product under item 1 with the following molar ratio of the components:

A solid component in terms of the transition metal 1

Three-C2WITH4-alkylamine 27,0 87,2

5. The catalyst p. 4, characterized in that it includes a solid component, what liberizatsii2- C6-alpha-olefins or copolymerization of them together in the presence of a catalyst comprising a solid component comprising magnesium and a transition metal, and obtained by the interaction of the compounds of magnesium with a compound of the transition metal, and three WITH2WITH4-alkylamine, characterized in that use the catalyst as a solid component comprising the product of the interaction under item 1 of the formula.

7. The method according to p. 6, characterized in that use the catalyst as a solid component containing the product of the interaction, including 0,1 4,8 aluminium atoms 1 atom of transition metal.

 

Same patents:
The invention relates to methods of producing stabilized polypropylene and can be used in the plastics industry

The invention relates to catalysts for (co)polymerization of olefins and method () polymerizatio olefins

The invention relates to catalysts suitable for the stereospecific polymerization of propylene, the way to obtain this solid substance and method of polymerization of propylene in the presence of this solid

The invention relates to a catalyst containing product ways, including:

a) processing an inert inorganic substrate to remove surface hydroxyl groups;

b) interactions treated in a similar manner to the substrate with a soluble hydrocarbon compound magnesium;

C) interaction of the product of stage b) with a modifying compound selected from the halides of silicon, boron, aluminum, alkylsilane and hexadecylamine, or mixtures thereof;

g) the interaction of the product of stage b) with a compound of vanadium structural formula V(O)S X'4-Swhere X1halogen and S is 0 or 1; the first compound of titanium with the structural formula Ti(OR2)nX2mwhere R2hydrocarbon radical, X2halogen, n is the target number from 1 to 4, and m is 1 or 0, or an integer from 1 to 3 provided that the sum of n and m is 4; a second compound of titanium with the structural formula TIX3p(OR3)qwhere R3hydrocarbon radical, X3halogen, R is an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4, and these first and second titanium compounds are not identical

The invention relates to a titanium containing catalyst component for the polymerization of ethylene, which in large polymerization activity can be obtained a polymer of ethylene with a narrow size distribution of particles, the catalyst for polymerization of ethylene comprising this titanium containing component and the polymerization of ethylene using a specified catalyst for polymerization of ethylene

The invention relates to the field of polymer chemistry and relates to a method of obtaining a solid component of catalyst for the (co)polymerization of ethylene

The invention relates to a method for producing alpha-olefin polymers, in particular homopolymers of ethylene and copolymers of ethylene and higher alpha-olefins, to a method for producing alpha-olefin polymers in solution, where the alpha-olefin monomer is subjected to polymerization in the presence of heat treated complex catalyst, which can be used at relatively high polymerization temperatures, especially at temperatures above 150oC
The invention relates to the field of polymers and relates to a method of obtaining a solid component of catalyst for the (co)polymerization of ethylene, the solid component of catalyst, catalyst for (co)polymerization of ethylene and method of (co)polymerization of ethylene
The invention relates to a solid component of catalyst, the method of its production and its use in the polymerization of ethylene and copolymerization of ethylene with alpha-olefins

The invention relates to methods of producing ultra-high molecular weight polyethylene (UHMWPE), i.e. polyethylene with srednevozrastnoe molecular weight of 1-6 million (characteristic viscosity in decaline at 135oWith 10-30 DL/g), high output, adjustable particle size and improved properties for processing

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

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