A solid component catalyst system for the (co) polymerization of ethylene, method thereof, a catalytic system for the (co)polymerization of ethylene (co) polymerization of ethylene

 

(57) Abstract:

Offers a solid component catalyst system for the (co)polymerization of ethylene containing inorganic carrier, metallocene transition metal, the ionizer and the compound of the metal of group VIB of the Periodic system of elements, the method of obtaining a solid component of a catalytic system in which the gain of the first stage solid mass containing inorganic carrier and a compound of the metal of group VIB, at the second stage in it enter the connection, which consists mainly of metallocene transition metal, and the connection, which consists mainly of the ionizer; catalytic system for the (co)polymerization of ethylene, obtained by bringing into contact the above solid catalyst component with an ORGANOMETALLIC compound, a method of polymerization of olefins, in which are using this catalytic system. The use of a new solid component catalytic system makes it possible to obtain a polyethylene with a broad molecular weight distribution and a relatively high ratio of yield strength, which is suitable for subsequent easy use in such methods as injection molding, etc. 4 C. and the second system for the (co) polymerization of ethylene, contains both metallocene and a catalyst based on a metal of group VIB of the Periodic system of elements, particularly chromium. It relates, furthermore, to a method for producing this solid component catalyst system, catalyst system for the (co) polymerization of ethylene comprising this solid component, and the method of (co) polymerization of ethylene using the catalyst system.

For the polymerization of ethylene are known various types of catalysts, such as catalysts based on chromium catalysts based on titanium or metallocene, and characteristics (properties) of the resulting polyethylene is determined especially by the nature of the used catalyst.

In order to obtain a copolymer of alpha-olefins with a wide molecular weight distribution, in the patent application PCT-And - 92/15619 has already been proposed to use two-stage method, in which the first stage will polimerizuet at least two alpha-olefin using metallocene and alumoxane, and in the second stage, continuing the polymerization in the presence of the polymer obtained in the first stage. In this known method it is necessary to use a complicated setup involving two reachingout to use the catalyst, including:

(a) a chromium compound deposited on a porous carrier of inorganic oxide;

(b) a compound of a transition metal (such as for example biscyclopentadienyl); and

(C) alumoxane,

to obtain polyethylene with a broad molecular weight distribution. The use of this known catalyst for the polymerization of ethylene has the disadvantage that in certain conditions, receive a polyethylene with too little flow index, so they can be used in such methods as injection molding, blowing, etc.

The aim of the present invention is to avoid the above disadvantages through the application of new solid catalytic component system, allowing to obtain a polyethylene with a broad molecular weight distribution and a relatively high ratio of yield strength, which is suitable for subsequent easy use in such methods as injection molding, etc.

Thus, the invention relates to a solid component catalyst system for the (co) polymerization of ethylene, comprising at least one inorganic carrier, at least as group VI of the Periodic system of elements.

The essential feature of the invention is the combination of two well-known catalysts of different nature in one solid component catalyst system, namely metallocene based on transition metal (which is ionized by the action of ionizer) and catalyst based on a metal of the group VI of the Periodic system of elements. The applicant has found that these two catalyst compatible so that they can be simultaneously activated one in the presence of another for (co) polymerization of ethylene.

One of the essential characteristics of the invention consists in the use of the ionizer, which is used for ionization metallocene and makes it so active in the (co)polymerization of ethylene. The applicant has found that the use of metallocene in the ionized state (arising due to the impact ionizer) in combination with a catalyst based on chromium typically produces polyethylene with a higher yield (and therefore more easy to use) as compared with the known catalysts of this type, in which metallocene not ionized when they are used in the same conditions of polymerization.

According to the invention, under ionizator able to ionize metallocen in cationic metallocene, and the second fragment, which is inert with respect to the ionized metallocene and which is able to stabilize the ionized metallocene.

The ionizer can be ionic compound comprising a cation which has the properties of a Lewis acid and the anion, forming the second of the above fragment of the ionizer. Anions, leading to very good results are boron anions. The term "organoboron anion" understand derived from boron anion, in which the boron atom is associated with 4 organic substituents. Examples of cationic Lewis acids are carbocation, sulfone, hydronium, aniline, ammonium and lithium cation. Preferred carbocation. As examples of ionic ionizer can be called triphenylcarbenium - tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, three(n-butyl) ammonium tetrakis (pentafluorophenyl)borate and tetrakis(pentafluorophenyl) borate and lithium.

Alternatively, the ionizer may be non-ionic compound capable of converting metallocen in ionized metallocene. In this case, the ionizer itself turns into an anion which is inert to the cationic metallocene and which is capable of stabr, trimethylol, three (trimethylsilyl) borate and organobromine.

Ionizer preferably selected from triphenylcarbenium(pentafluorophenyl)borate and three (pentafluorophenyl)boron. Particularly well suitable triphenylcarbenium - tetrakis(pentafluorophenyl)borate.

In the solid component of the catalytic system according to the invention metallocen usually chosen among compounds of the formula

(Cp)a(Cp')bMXxZz,

where Cpand Cp'each represent an unsaturated hydrocarbon moiety coordinated to the Central atom M, and group Cpand Cp'can be linked by covalent bridge;

M denotes a transition metal chosen from groups V, IVB, VB and VIB of the Periodic system of elements;

"a", "b", "x" and "z" denote integers such that (a+b+x+z)=m;, x > 0; "Z" 0 and "a" and/or "b" 0;

"m" denotes the valence of the transition metal M;

X denotes halogen; and

Z denotes a hydrocarbon radical, which if necessary may include oxygen, or a silyl radical of the formula (Rt-Si-R R"R"'),

where R denotes alkyl, alkenylphenol, aryl, CNS or cycloalkyl group, in case neophilologica, each, halogen or alkyl, alkenylphenol, aryl, CNS or cycloalkyl group, if necessary substituted and containing up to 20 carbon atoms; t represents 0 or 1.

Preferably, the transition metal is selected from a scandium, titanium, zirconium, hafnium and vanadium. Particularly well suited Zirconia.

Group Cpand Cp'each represent preferably a mono - or polycyclic group, if necessary substituted and containing 5-50 carbon atoms, linked conjugated double bonds. As typical examples, cyclopentadienyls, intenally or fluorenyl radical or a substituted derivative of this radical. Substituted groups may be selected from hydrocarbon radicals containing up to 10 carbon atoms. One of the groups WITHpand Cp'or both groups may also denote a radical derived from VA element of the Periodic system of elements, such as nitrogen or phosphorus.

As examples metallocene formula (Cp)a(Cp')bMXxZzwhen "Z" is 0, you can call metallocene scandium, mono - and dihalogenoalkane, such as chlorine-di(Cyclops the EOS-three(pentamethylcyclopentadienyl) titanium, dibromo-di (methylcyclopentadienyl) titanium and trichloro(cyclopentadienyl) titanium; mono-, di - and trihalomethane metallocene zirconium, such as dichloro-di (cyclopentadienyl) zirconium, iodine-three (cyclopentadienyl) zirconium disarm(cyclopentadienyl-1-indenyl) zirconium, trichloro(fluorenyl) zirconium; mono-, di - and trihalomethane metallocene hafnium and mono-, di - and trihalomethane metallocene vanadium, such as chlorine-three (cyclopentadienyl) vanadium, dichloro - di(ethylcyclopentadienyl) vanadium and trichloro(ethylidene) vanadium.

When "Z" is other than zero, and Z is a hydrocarbon radical, metallocen formula

(Cp)a(Cp')bMXxZz< / BR>
can be selected from, for example, chloro (cyclopentadienyl) scandium, dibromo- (methylcyclopentadienyl)butylsilane, chlorine(indenyl)-isopropyl-titanium and dichloro (fluorenyl)hexylsilane.

When "Z" is other than zero, and Z denotes a silyl radical of the formula (Rt-Si-R R"R"'), metallocene formula (Cp)a(Cp')bMXxZzcan be selected, for example, from metallocenes, including as a radical silyl, allylimidazole, allylmethylamine, 5-(dicyclo trimethoxysilyl and diphenyldichlorosilane.

Metallocene containing covalent bridge that links the two groups WITHpand Cp'can contain as colophony group alkylenes group, which, if necessary, may include oxygen, alkynylamino group, arylalkylamine group, alkylsilane group, arylalkylamine group, if necessary halogenated, or a radical derived from an element selected from elements of groups IIIA, IV, VA and VI of the Periodic system of elements, such as boron, aluminum, silicon, germanium, tin, nitrogen, phosphorus, and sulfur. Particularly well suitable ethylene, dimethylsilane, dimethylmethylene.

The preferred metallocene formula (Cp)a(Cp')bMXxZzare those in which the group Cpand Cp'choose from cyclo - pentadienyl, indanilnykh and fluorenyl radicals. Good results were obtained with metallocene, in which group Cpand Cp'linked covalent bridges alkalinous type. Very well suitable metallocene, in which a transition metal selected from titanium, zirconium and hafnium. Particularly satisfactory results are achieved with metallocene derived from zirconium.

In a solid the s is preferably chromium. The chromium compound may be selected from inorganic or organic chromium compounds in which the chromium is in the hexavalent state, trivalent or divalent state. As an example, chromium compounds can be called chromium oxides and salts of chromium, such as chromium acetate, chromium chloride, chromium sulfate, chromium, bichromate or chromium acetylacetonate. For example, we can talk about the compounds hexavalent chromium, obtained by oxidation of chromium compounds in which the chromium is in restored condition, and, if necessary, the oxidation can be carried out in the presence of inorganic media. Also we can talk about the connections of three - and divalent chromium, obtained by the reduction of compounds of hexavalent chromium, if necessary in the presence of inorganic media.

In the solid component of the catalytic system according to the invention the number of metallocene and metal link band VI of the Periodic system of elements depend on the desired characteristics of the (co) polymer of ethylene. When you wish to obtain a (co) polymer of ethylene having properties similar to the properties that reach in the case of catalysts h is was high. On the contrary, if it is desirable to achieve properties close to the properties acquired in the application of metallocenes, it is preferable that this ratio was negligible. Metallocene and the compound of the metal of group VIB are usually present in such quantities that the molar ratio of the metal of group VIB/transition metal is at least about 0.001, in particular at least 0,01, with the most preferred ratio of at least 0,1. The molar ratio of the metal of group VIB/transition metal often is at most 100, more precisely, at most 50, and the recommended ratio of at most 10, such as about 1 to 3.5.

Inorganic solid media component catalytic system according to the invention, for example, may be selected from metal halides such as magnesium chloride; metal oxides, such as oxides of silicon, aluminum, titanium, zirconium, thorium, their mixtures and mixed oxides of these metals, such as aluminum silicate and aluminum phosphate. The media, if necessary, can be processed by persediaan. Well suited silicon dioxide, aluminum oxide, magnesium chloride, aluminum phosphate and mixtures of silicon dioxide, aluminum oxide and phosphate, alue (Z), in particular such that the molar ratio (X): (Y):(Z) which is(10-95): (1-80): (1-85), more precisely(20-80) : (1-60) : (5-60).

The media usually has a grain size distribution characterized by a mean diameter D of at least 10 μm, in particular at least 20 μm, and the most common diameters equal to at least 40 microns. The diameter is usually at most 1000 μm, typically at most 500 μm, and the recommended value of at most 200 μm. Often the grading, in addition, is characterized by a standard deviation of at least 10 μm, predominantly at least 20 μm. The standard deviation is usually at most 50 μm, preferably at most 40 μm.

The carrier preferably has a specific surface area determined volumetric BET according to the standard UK BS 4359/1 (1984), at least 100 m2/g, mostly at least 180 m2/g, and most preferred value of at least 220 m2/g Specific surface area is usually at most 800 m2/g, often at most 700 m2/g, and a favorable value of at most 650 m2/,

In most cases, the media, moreover, x is the most common size of at least 2.2 cm3/g pore Volume is usually at most 5.0 cm3/g, preferably at most 4.5 cm3/g, with recommended values of at most 4.0 cm3/g pore Volume represents the amount of pore volume, measured by the method of penetration of nitrogen (BET) according to the volumetric method described in the rate of UK BS 4359/1 (1984), and pore volume, measured by the method of mercury penetration using porosimetry type PORO 2000, manufactured in the sale of the company CARLO ERBACO, according to the norm Belgium NBN In 05-202 (1976).

A solid component of a catalytic system according to the invention preferably includes a carrier in the amount of at least 0.01 wt.%, calculated on the total weight of the inorganic carrier and a compound of metal of group IVB, preferably at least 0.1 wt.%, the most usual amount constituting at least 0.2 wt.%; the number of media usually does not exceed 2 wt.%, in particular 1.5 wt.%, with the recommended value of at most 1 wt.%.

Needless to say, a solid component catalytic system according to the invention may include more than one metallocene, more than one ionizer, more than one carrier and/or more than one compound of a metal of group VIB.

A solid component of a catalytic system according to the invention can be obtained by any known method. In particular, a solid component catalytic system according to the invention is manufactured using the method, according to which, in the first stage, get a solid mass containing inorganic carrier and a compound of the metal of group VIB, and in the second stage include the connection on the basis of metallocene and the connection on the basis of the ionizer.

In the method according to the invention, the solid mass comprising a carrier and a compound of the metal of group VIB, may be obtained by any known appropriate method. For example, it can be obtained by impregnation of the carrier water or inorganic concrete the SQL connection metal of group VIB, choose from soluble salts, such as acetate, chloride, sulphate (in particular, when the metal is chromium, chromates and bichromate), in aqueous solution, or as acetylacetonate in organic solution. After impregnation of the carrier with the compound of the metal of group VIB, the impregnated carrier is preferably activated by heating it at a temperature of 400-1000oC to convert at least part of the metal in the hexavalent metal. Then hexavalent metal, if necessary, can be restored, at least partially, by using a reducing agent such as, for example, carbon monoxide or ethylene. Used compound of the metal of group VIB can also be terpolymerization.

Solid mass comprising a carrier and a compound of the metal of group VIB, preferably can be obtained by mechanical mixing of the carrier with a solid compound of a metal of group VIB in the absence of a liquid, for example a metal acetylacetonate. Then this mixture is preferably productiviteit at a temperature below the melting temperature of the compound of metal of group VIB before its activation, as described above.

Alternatively, the compound of the metal of group VIB is also possible VC"ptx2">

In the solid mass comprising a carrier and a compound of the metal of group VIB metal is typically present in amount of at least 0,05 wt.%, calculated on the total solid weight, in particular at least 0.1 wt.%, the most preferred values of at least 0.25 wt.%. The proportion of metal usually amounts to at most 10 wt.%, calculated on the total solid weight, more particularly at most 5 wt.%, the most usual size at most 2 wt.%.

In the second stage of the method according to the invention the inclusion of compounds on the basis of metallocene and the inclusion of compounds on the basis of the ionizer can be performed simultaneously or separately. In this latter case, the connection on the basis of metallocene and the connection on the basis of the ionizer can be added in any order.

In the second stage of the method according to the invention, the introduction can be implemented by any known appropriate method. When you add a connection on the basis of metallocene and the connection on the basis of the ionizer, the addition preferably takes place by mixing with a solid mass containing a carrier and a compound of the metal of group VIB, in a heterogeneous environment. Under heterogeneous environment," see, SOA group VIB, the connection on the basis of metallocene and connection-based ionizer, where (environment) at least 80% (preferably at least 95%) of at least one of these last two connections and at least 80% (preferably at least 95%) of a solid mass containing a carrier and a compound of the metal of group VIB, are in the solid state. Such a heterogeneous environment is essentially solid and get it by mixing, in the absence of fluid, the two above-mentioned compounds in the solid state with a solid mass containing a carrier and a compound of the metal of group VIB, usually in powder form. Alternatively, heterogeneous environment may contain a liquid phase and to provide a suspension comprising an organic liquid in which at least 80% (preferably at least 95%) of at least one of the two connections (connection-based metallocene and connection-based ionizer) and at least 80% (preferably 95%) of a solid mass containing a carrier and a compound of the metal of group VIB, insoluble. As the organic liquid can be used aliphatic hydrocarbons chosen from linear alkanes (such as n-butane, n-hexane and n-heptane), razwell entan and cyclohexane). Also suitable monocyclic aromatic hydrocarbons such as benzene and its derivatives, such as toluene, polycyclic aromatic hydrocarbons, and each cycle can be replaced, unless they are in a heterogeneous environment, such as the above. It is also possible to use aliphatic halogenated hydrocarbons, such as chlorinated alkanes, such as CH2Cl2or Cl4. Preferred aromatic hydrocarbons and chlorinated alkanes. When the connection is based on metallocene and connection-based ionizer add separately, the inclusion of the first compounds is preferably carried out in a heterogeneous environment, in which at least 80% (preferably 95%) of a solid mass containing a carrier and a compound of the metal of group VIB, are in the solid state. The inclusion of the second connection is then preferably carried out in a heterogeneous environment, in which at least 80% (preferably 95%) of either the first or the second, or both compounds, and at least 80% (preferably 95%) of a solid mass containing a carrier and a compound of the metal of group VIB, are in the solid state. Heterogeneous environment can be mostly solid the connections on the basis of the ionizer can be done, for example, in the mixer, equipped with a mixer, a reactor with a rotating layer, or in a reactor with stirring or fluidized bed, or even in a rotating reactor. Usually in the case where the addition is carried out in the absence of organic liquid, it may be desirable to carry out the mixture of compounds based on metallocene and connections on the basis of the ionizer with a solid mass containing a carrier and a compound of the metal of group VIB, by their joint grinding. Preferably operate in a rotating reactor or mixer equipped with a mixer.

In a particularly preferred variant of the method according to the invention, the second stage is carried out by first mixing the solid mass containing a carrier and a compound of the metal of group VIB, with the connection based on metallocene, in the absence of a liquid and then by impregnating the thus obtained mixture, a solution of compounds on the basis of the ionizer. The mixture in the absence of a liquid is preferably carried out in pseudorandom layer. This embodiment is also suitable for solid components of catalytic systems without connection of the metal of group VIB, namely solid components of catalytic systems, with the second metal and at least one ionizer. In this case, the receiving is carried out by first mixing the carrier with the connection based on metallocene in the absence of a liquid and then by impregnating the thus obtained mixture, a solution of compounds on the basis of the ionizer.

In the method of receiving according to the invention, metallocene and ionizer identical to those described above.

Under "connection-based metallocene" understand net metallocene or mixture, including metallocene and at least one other solid substance, other than metallocene and ionizer and inert with respect thereto.

Under "connection-based ionizer" see clean the ionizer or the mixture containing the ionizer and at least one other solid substance, other than ionizer and metallocene and inert towards them. These solids can be polymer type (such as polyolefins) or inorganic type (such as oxides and halides of metals). These are the appropriate mixture can be obtained, for example, by mechanical mixing in the solid state metallocene or ionizer solid. Alternatively, they can be obtained by impregnation of a solid solution metallocene, respectively OI the deposits on the basis of metallocene and connection-based ionizer, used in the method of receiving according to the invention, generally such that the molar ratio metallocen/ionizer is at least 0.5, especially at least 1. The molar ratio metallocen/ionizer usually does not exceed 2. Preferably the molar ratio equal to 1.

The temperature at which carry out the introduction to the second stage of the method according to the invention, can be any temperature below the decomposition temperature of the medium, the compounds of the metal of group VIB, connection-based metallocene and connections on the basis of the ionizer.

The temperature depends on the nature of these components; usually it is at least equal to the 0oC, preferably 20oC; the most common values, the maximum is 250oC, most preferred are temperatures below 200oC, for example 150oC. In case of a heterogeneous environment is a suspension comprising an organic liquid, the temperature should be such that at least 80% (preferably 95%) of a solid mass containing a carrier and a compound of the metal of group VIB, and, preferably, at least 80% (preferably at least 90%) at least one of the TLD the cooling fluid. The introduction can be performed at a constant temperature or by changing the temperature, continuously or periodically.

In the second stage of the method according to the invention, the time during which an introduction should be sufficient for the maximum homogenization of the mixture. This time depends on the mixer. It usually takes at least 1 minute, preferably 5 hours; for reasons of economy it is desirable that this time did not exceed 100 hours, particularly 50 hours. Especially well suited to a duration of approximately 24 hours.

In a particular form of implementation of the method according to the invention, the connection-based metallocene and/or connection-based ionizer contain additional media as a solid substance that is different from metallocene and/or ionizer. The carrier is identical to the above media. The number of media in the connection-based metallocene or in connection on the basis of the ionizer is such that the mass ratio of the carrier to the connection on the basis of metallocene (or on the basis of the ionizer) is at least equal to 0.05, preferably 2; preferably it does not exceed 1000, in particular 100, being what the shadow is used for (co)polymerization of ethylene, in combination with socialization.

The invention relates to a catalytic system for the (co)polymerization of ethylene, obtained by bringing into contact of the solid component of the catalytic system according to the invention, such as the above, with socialization selected from ORGANOMETALLIC compounds of a metal selected from elements of groups IA, IIA, IIB, IIIA and IVA of the Periodic system of elements.

In the catalytic system according to the invention socialization, for example, may be selected from ORGANOMETALLIC compounds of lithium, magnesium, zinc, aluminum or tin. The best results are achieved with alyuminiiorganicheskikh compounds containing at least one link aluminum - carbon and, if necessary, which may include oxygen and/or halogen. As examples trialkylaluminium compounds, halogenated alkylamine connection and alkylamine compounds containing at least one CNS group. Alyuminiiorganicheskikh compounds preferably correspond to General formula Al-TT'T", where T, T' and T" represent, each, alkyl, alkenylphenol, aryl or CNS group, think what propyl-, triisopropyl, tributyl, triisobutyl, tridecyl-, trioctyl and tridodecyl - aluminum. Particularly well suited trimethylaluminum. You can also use criativo, by itself or in a mixture with alyuminiiorganicheskikh connection, such as described above.

In the catalytic system according to the invention the number of socializaton may vary within wide limits. It typically is such that the molar ratio of socializaton to metallocene at least equal to 5. However, in practice it does not matter the value above 5000, and recommended values below 2000. Usually well-fit values close to 10 of 500, when a catalyst system intended for the polymerization of olefins.

The catalytic system according to the invention can be used to homopolymerization and copolymerization of ethylene with one or more comonomers. The comonomers can be a different matter. They can be monoolefinic, which may contain up to 8 carbon atoms, such as 1-butene, 1-penten, 3-methyl-1-butene, 1 - hexene, 3 - and 4-methyl-1-pentene and 1-octene. One or more diolefins containing 4-18 carbon atoms, also megalonychidae (asparaginic) diolefines, such as 4-vinylcyclohexane and 1.5 - hexadiene; alicyclic diolefins containing industrijski bridge, such as Dicyclopentadiene, methylene - and ethylene-norbornene; and aliphatic conjugated diolefins, such as 1,3-butadiene, isoprene and 1,3-pentadiene.

The catalytic system according to the invention proves to be particularly successfully applied to obtain homopolymers of ethylene and copolymers of ethylene containing at least 90 wt.%, preferably at least 95 wt.%, of ethylene. Preferred comonomers of ethylene are propylene, 1-butene, 1-hexene, 1-octene and 1.5-hexadiene and mixtures thereof. Particularly preferred comonomers are 1-butene and 1-hexene.

The present invention also relates to a method of (co) polymerization of ethylene, which is used catalytic system according to the invention, such as the above.

According to a particularly preferred variant of the method of polymerization according to the invention, first, a mixed ethylene with socialization and then to the thus obtained mixture of the solid component of the catalyst system. In this preferred embodiment, the method of polymerization according to image Levoberezhny the diluent may be selected from aliphatic hydrocarbons, such as linear alkanes (such as n-butane, n-hexane and n-heptane), branched alkanes such as isobutane, isopentane, isooctane and 2,2-DIMETHYLPROPANE) and cycloalkanes such as cyclopentane and cyclohexane). Preferably operate in isobutane and hexane.

In this preferred embodiment, the method of polymerization according to the invention, since, when the solid component of the catalyst system is introduced into contact with a hydrocarbon diluent, socialization and ethylene react to turn metallocen in the catalytically active substance in the ionized state.

In a particularly preferred form of this variant of the method of polymerization according to the invention, when provided the copolymerization of ethylene with at least one of the co monomer, ethylene and comonomer (comonomers) is injected at the same time or different time in the polymerization reactor before adding the solid precursor of a catalytic system.

In the polymerization method according to the invention the polymerization can be performed in solution, in suspension or in the gas phase, and it can be implemented continuously or periodically, e.g., by sueli in the gas phase in two consecutive reactors. Alternatively, it is also possible to carry out the polymerization in several, arranged in a row, the reactor, and the temperature and/or pressure and/or concentration of co monomer in the first reactor are different from those prevailing in other reactors. If necessary during polymerization it is possible to use a molecular weight regulator such as hydrogen or diethylzinc.

In the case of suspension polymerization, it is carried out in a hydrocarbon diluent at a temperature such that at least 80% (preferably at least 95%) of the resulting (co) polymer in it insoluble. The hydrocarbon diluent may be selected from among aliphatic, cycloaliphatic and aromatic liquid hydrocarbons. Preferred diluents are linear alkanes such as n-butane, n - hexane and n-heptane, or branched alkanes such as isobutane, isopentane, isooctane and 2,2-DIMETHYLPROPANE, or cycloalkanes such as cyclopentane and cyclohexane, or mixtures thereof. The temperature is usually at least equal to the 20oC, preferably at least 50oC; it is usually a maximum of equal to 200oC, most preferably 100oC. the Partial pressure of olefin often klaineana 5 MPa, preferably 2 MPa, for example 1.5 MPa.

The following examples serve to illustrate the invention. In these examples, a solid component catalytic system according to the invention was produced using the method according to the invention and then used for polymerization of ethylene.

The meaning of the symbols used in these examples, the units expressing the above values, and methods of measurement of these quantities are explained below.

MI2= the index of the fluidity of the molten polymer at 190oWith measured under a load of 2.16 kg and expressed in g/10 min, according to the standard ASTM D1238 (1990).

MI5= the index of the fluidity of the molten polymer at 190oC, measured under a load of 5 kg and expressed in g/10 min, according to the standard ASTM D1238 (1990).

HLMI = index of the fluidity of the molten polymer at 190oC, measured under a load of 21.6 kg and expressed in g/10 min, according to the standard ASTM D1238 (1990).

MVS = standard density of the polymer, expressed in kg/m3and measured according to the standard ASTM D1928.

S = the proportion of oligomers in the polymer, expressed in grams of oligomers per kilogram of polymer and measured by extraction for 2 hours using hexane when it is used filler has a height of 30 mm and an inner cross-section of 2 mm

o/2= the ratio between the viscosities measured at velocity gradient of 1-1and the velocity gradient of 100 s-1. Used filler has a height of 30 mm and an inner cross-section of 2 mm

Mn= Brednikova molecular weight, as measured by spatial exclusion chromatography implemented in 1,2,4-trichlorobenzene at 135oC chromatograph firm WOUTERSE, type 150C. This mass is expressed in daltons.

Mw= srednevekovaja molecular weight, as measured by spatial exclusion chromatography implemented in 1,2,4 - trichlorobenzene at 135oC chromatograph firm WOUTERSE, type 150C This mass is expressed in daltons.

Mz= average molecular weight of the polymer, defined by the ratio:

MZ= (WiM2i)/(WiMi)

where "Wi" indicates the weight of the polymer with a molecular mass Mi. The value of MZmeasured by spatial exclusion chromatography implemented in 1,2,4-trichlorobenzene at 135oC chromatograph firm WOUTERSE, type 150C. This weight is expressed in daltons.

Example 1 (according to the invention)

a). Preparation of a solid component, including ratio) containing 0.7 wt.% chromium calcined at 815oC by blowing dry air. After 16 hours, the catalyst Recuperat.

b). Introduction metallocene (dicyclopentadienyl - dichloro - Zirconia)

9,451 g catalyst activated in the above stage (a), is mixed with 0,207 g dicyclopentadienyl-dichloro-zirconium at 70oC for 16 hours under nitrogen atmosphere.

in). The introduction of the ionizer (triphenylcarbenium-tetrakis - pentafluorophenyl-borate)

4,158 g of the mixture prepared during stage (b), add to 0,281 g triphenylcarbenium-tetrakis(pentafluorophenyl) borate. The whole mass is stirred at room temperature for 15 hours. A solid component catalytic system then Recuperat.

g). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, enter trimethylaluminum (TMA) in the form of a solution in hexane and 1 l of isobutane. The autoclave is heated to the desired temperature, which is maintained for the entire duration of the experience. When they reach the desired temperature in the autoclave introducing ethylene at a partial pressure of 10 bar. Also introducing hydrogen at a partial pressure specified in the table below. Then into the autoclave together with 100 ml of isobutane at a pressure of 40 bar, AI (). In the reaction, the total pressure support by adding in an autoclave with ethylene. After 1 hour, the polymerization stop by degassing and cooling of the autoclave.

The following table 1 TMA indicates the number of ml of hexane solution containing 50 g/l of trimethylaluminum; temperature (Temp) is specified in theoC; the partial pressure of hydrogen (H2) is indicated in the bars; the entered quantity of the catalyst (cat-R) is specified in mg, and the amount of polyethylene (PE) is given in grams.

Example 2 (according to the invention)

a). The preparation of the solid catalytic component system

Repeat the operation of example 1 (a) - (C) so as to obtain a molar ratio of Cr/Zr = 3,3.

b). Polymerization of ethylene.

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, injected 1.5 ml hexane solution containing 50 g/l of trimethylaluminum, and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the experience. When the desired temperature is reached, the autoclave is injected ethylene and hydrogen at a partial pressure of 10 bar and 0.2 bar. Then in the autoclave together with 100 ml isobune stage (a). In the reaction, the total pressure support by adding in an autoclave with ethylene. After 1 hour, the polymerization stop by degassing and cooling of the autoclave. Obtain 41 g of polyethylene. Characteristics of the polymer are the following:

MI2< 0.1 g/10 min; MI5< 0.1 g/10 min;

HLMI < 0.1 g/10 min; MVS = 960,9 kg/m3; S = 32 g/kg;

Mn= 1420; Mw= 349000; Mz= 2930000.

Example 3 (according to the invention)

a). The preparation of the solid catalytic component system

Repeat the operation of example 1 (a) - (C) so as to obtain a molar ratio of Cr/Zr = 0,95.

b). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, injected 1.5 ml hexane solution containing 50 g/l of trimethylaluminum, and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the experience. Ethylene and hydrogen is introduced into the autoclave at a partial pressure of 10 bar and 0.2 bar. Then in the autoclave together with 100 ml of isobutane at a pressure of 40 bar is administered 160 mg of the solid component of the catalyst system prepared in the above stage (in). In the reaction, the total pressure support due to D. what are square-149 g of polyethylene. Characteristics of the polymer are the following:

MI2= 40 g/10 min; MI5= 126 g/10 min; HLMI > 500 g/10 min; MVS = 971,2 kg/m3; S = 20 g/kg; Mn= 2230; Mw= 115000; Mz= 2380000.

Example 4 (according to the invention)

a). Preparation of a solid mass, including the media and the chromium compound

15 g of the carrier composition AlPO4/SiO2/Al2O3= 47,5/50,4/2,1 (molar ratio) is mixed with chromium acetylacetonate in such quantity that the mixture contains 1 wt.% chromium. Then thus obtained mixture is treated in the fluidized bed at 150oC for 2 hours while purging with dry air. After that its calcined at 815oC all the time by blowing dry air. After 16 hours at 815oC catalyst Recuperat.

b). Introduction metallocene (dicyclopentadienyl - dichloro - Zirconia)

13,2 g obtained in the above stage (a) solid mixed with 0,371 g dicyclopentadienyl-dichloro-zirconium at 70oC for 16 hours under nitrogen atmosphere.

in). The introduction of the ionizer (triphenylcarbenium-tetrakis-pentafluorophenyl-borate)

4.4 g obtained in stage (b) mixture is added to 0,390 g triphenylcarbenium-tetrakis(pentafluorophenyl) borate in 25 ml of CH2Cl2oC.

g). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, enter trimethylaluminum in the form of a solution in hexane and 1 l of isobutane. The autoclave is heated to the desired temperature, which is maintained for the entire duration of the process. When the desired temperature is reached in the autoclave introducing ethylene at a partial pressure of 10 bar. Hydrogen is also introduced at a partial pressure specified in the table below. After that, the autoclave together with 100 ml of isobutane at a pressure of 40 bar enter the specified amount of solid component of a catalytic system prepared during the above stage (in). In the reaction, the total pressure support by adding in an autoclave with ethylene. Polymerization stop by degassing and cooling of the autoclave.

The following table 3 TMA indicates the number of ml of hexane solution containing 50 g/l of trimethylaluminum; temperature (Temp.) specified inoC; the partial pressure of hydrogen (H2) is given in bars; duration of polymerization (time) is specified in minutes; put amount of catalyst (cat-R) is specified in mg; and the resulting number Eday mass, including the media and the chromium compound

20 g of the carrier composition AlPO4/SiO2/Al2O3= 47,5/50,4/2,1 (molar ratio) containing 0.7 wt. % chromium, annealed at 815oC by blowing dry air. After 16 hours of solid mass Recuperat.

b). Introduction metallocene (dicyclopentadienyl-dichloro - Zirconia)

13,4 g obtained above in stage (a) solid mass is mixed with 0,264 g dicyclopentadienyl-dichloro-zirconium at 70oC for 16 hours under nitrogen atmosphere. The thus obtained mixture is further referred to as a mixture of 5B.

in). The introduction of the ionizer (triphenylcarbenium-tetrakis (pentafluorophenyl) borate)

2.7 g of a mixture of 5B add to 0,169 g triphenylcarbenium-tetrakis (pentafluorophenyl) borate in 15 ml of toluene. The toluene is then removed by distillation under reduced pressure at room temperature. Then the solid component catalytic system Recuperat.

g). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, injected 1.5 ml hexane solution containing 50 g/l of trimethylaluminum, and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration about the accordingly, 10 bar and 0.2 bar. Then in the autoclave together with 100 ml of isobutane at a pressure of 40 bar enter 198 g of the solid component of the catalyst system prepared in the above stage (in). In the reaction, the total pressure support by adding in an autoclave with ethylene. After 2 hours the polymerization stop by degassing and cooling of the autoclave. Obtain 124 g of polymer. Polyethylene is characterized MI2= 2.6 g/10 min and HLMI = 240 g/10 min.

Example 6 (according to the invention)

a). Preparation of a solid mass, including the media, the chromium compound and metallocen

0.6 g of the mixture 5 is placed in kondicionirovaniya flask with a nitrogen atmosphere, then pre recover under the current ethylene for 15 minutes at room temperature.

b). Introduction metallocene (triphenylcarbenium - tetrakis - pentafluorophenyl-borate)

Obtained in the above stage (a) compound is mixed with 0,0378 g triphenylcarbenium-tetrakis(pentafluorophenyl) borate in 5 ml of toluene. The toluene is then removed by distillation under reduced pressure at room temperature. After that Recuperat component catalytic system.

in). Polymerization of polyethylene

In the autoclave with a capacity of 3 l, pre visudyne. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the process. When the temperature of polymerization is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. 170 ml of a solid component of a catalytic system prepared in the above stage (b), then enter in the autoclave together with 100 ml of isobutane at a pressure of 40 bar. In the reaction, the total pressure support by adding ethylene to the autoclave. After 90 minutes, the polymerization stop by degassing and cooling of the autoclave. Obtain 106 g of polymer. Polyethylene is characterized MI2= 0.1 g/10 min and HLMI=46,8 g/10 min.

Example 7 (according to the invention)

a). Preparation of a solid mass, including the media and the chromium compound

15 g of the carrier composition AlPO4/SiO2/Al2O3= 47,5/57,4/2,1 (molar ratio) containing 0.7 wt.% chromium calcined at 815oC by blowing dry air. After 16 hours Recuperat thus obtained solid mass.

b). Introduction metallocene (dicyclopentadienyl-dichloro-Zirconia)

13,77 g solid mass obtained in the above stage (a), is mixed with 0,2977 g dicyclomine further referred to as a mixture of 7b.

in). The introduction of the ionizer (triphenylcarbenium - tetrakis (pentafluorophenyl) borate)

3.5 g of a mixture of 7b add to 0,2288 g triphenylcarbenium - tetrakis (pentafluorophenyl) borate. The totality is stirred for 15 hours at room temperature. A solid component catalytic system then Recuperat.

g). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, injected 1.5 ml hexane solution containing 50 g/l of trimethylaluminum, and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the process. When the desired temperature is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. After that, the autoclave together with 100 ml of isobutane at a pressure of 40 bar enter 251,9 mg of solid component of a catalytic system prepared in the above stage (in). In the reaction, the total pressure support by adding in an autoclave with ethylene. After 1 hour the polymerization stop by degassing and cooling of the autoclave. Get 22 g of polyethylene. Characteristics of the polymer are the following:

MI2= 0.21 g/10 min; MI5= 2.6 g/10 min; HLMI = 9 4760000.

Example 8 (shown for comparison)

In this example, preparing the catalyst described in European patent application EP-A-339571. Then it is used for polymerization of ethylene.

a). Preparation of catalyst

Into the flask containing 3.3 grams of a mixture of 7b, add 10 ml of anhydrous toluene and 8.8 ml of toluene solution containing 315,9 g methylalumoxane per litre. The mixture was then stirred for 15 minutes on a rotary evaporator, and then the toluene is removed by evaporation in vacuum at 40oC.

b). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, enter 1 l of isobutane. The autoclave is heated to a temperature of 60oWith that support throughout the duration of the process. When the desired temperature is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. Then in the autoclave together with 100 ml of isobutane at a pressure of 40 bar enter 339,8 mg of the catalyst prepared in the above stage (a). In the reaction, the total pressure support by adding in an autoclave with ethylene. After 1 hour the polymerization stop by degassing and cooling of the autoclave. Get 15 grams of polyethylene is kg/m3; S= 18 g/kg; Mn= 6630; Mw= 680000; Mz= 3850000.

Comparing the results of example 8 with example 7 shows that the catalyst described in European patent application EP-A-339571, in the same conditions of polymerization results in a significantly lower flow index (HLMI < 0.1 g/10 min) than the catalytic system according to the invention (HLMI = 98 g/10 min).

Example 9 (according to the invention)

a). Preparation of a solid mass containing a carrier and a chromium compound

15 g of the catalyst HA30W produced in the sale of the company Grace Davison and containing 1% chromium, calcined at 815oC by blowing dry air. After 16 hours Recuperat 12.7 g of a solid mass.

b). Introduction metallocene (dicyclopentadienyl-dichloro - Zirconia)

12.7 g of the solid mass obtained in stage (a) above mixed with 0,2614 g dicyclopentadienyl-dichloro-zirconium at 70oC for 16 hours under nitrogen atmosphere. The thus obtained mixture is further referred to as a mixture of 9b.

C) Introduction of the ionizer (triphenylcarbenium-tetrakis (pentafluorophenyl) borate)

3.5 g of a mixture of 9b add to 0,230 g triphenylcarbenium-tetrakis (pentafluorophenyl) borate. The totality is stirred for 13 hours at com">

g). Polymerization of ethylene

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, enter 321 mg of the solid component of the catalyst system prepared in the above stage (C), and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the process. When the desired temperature is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. After that, the autoclave together with 100 ml of isobutane at a pressure of 40 bar inject 0.3 ml hexane solution containing 50 g/l of trimethylaluminum. In the reaction, the total pressure is maintained by adding in an autoclave with ethylene. After 2 hours the polymerization stop by degassing and cooling of the autoclave. Get 374 g of polymer. Polyethylene is characterized MI5= 0.1 g/10 min and HLMI = 1.7 g/10 min.

Example 10 (according to the invention)

a). The preparation of the solid catalytic component system

2.1 g of a mixture of 9b mixed with 0,137 g triphenylcarbenium - tetrakis(pentafluorophenyl) borate in 10 ml of CH2Cl2. After stirring for 10 minutes CH2Cl2is removed by distillation under reduced pressure and at komnatnaya

In the autoclave with a capacity of 3 l, pre-dried and equipped with a stirrer, enter 343 mg of the solid component of the catalyst system prepared in the above stage (a), and 1 l of isobutane. The autoclave is heated to a temperature of 60oC, which is supported throughout the duration of the process. When the desired temperature is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. After that, the autoclave together with 100 ml of isobutane at a pressure of 40 bar inject 0.3 ml hexane solution containing 50 g/l of trimethylaluminum. In the reaction, the total pressure support by adding in an autoclave with ethylene. After 2 hours the polymerization stop by degassing and cooling of the autoclave. Obtain 110 g of polymer. Polyethylene is characterized HLMI = 0.6 g/10 min.

Example 11 (according to the invention)

a). The preparation of the solid catalytic component system

1.7 g of a mixture of 9b mixed with 0,111 g triphenylcarbenium - tetrakis(pentafluorophenyl) borate in 10 ml of toluene. After stirring for 10 minutes, the toluene is removed by distillation under reduced pressure and at room temperature. A solid component catalytic system Recuperat.

oC, which is supported throughout the duration of the process. When the temperature of polymerization is reached, the autoclave is injected ethylene and hydrogen at a partial pressure 10 bar and 0.2 bar. After that, the autoclave together with 100 ml of isobutane at a pressure of 40 bar inject 0.3 ml hexane solution containing 50 g/l of trimethylaluminum. In the reaction, the total pressure support by adding in an autoclave with ethylene. After 2 hours the polymerization stop by degassing and cooling of the autoclave. Obtain 114 g of polymer. Polyethylene is characterized MI2< 0.1 g/10 min and HLMI = 18,9 g/10 min

1. A solid component catalyst system for the (co)polymerization of ethylene containing inorganic carrier and a compound of the metal of group VIB of the Periodic system of the elements, characterized in that it contains metallocene transition metal and ionizer.

2. A solid component of the catalytic system under item 1, wherein the ionizer is triphenylcarbenium(pentafluorophenyl)borate.

3. Solid is

(Cp)and(Cp')bMX,

in whichp1and Cpeach denotes cyclopentadienyls radical coordinated to the Central atom M, and group Cpand Cp1can be linked by covalent bridge;

M denotes a transition metal chosen among the elements of group VIB of the Periodic system of elements,

a, b and x denote integers such that (a + b + x) = m x > 0 and a and/or b 0;

m represents a valence of the transition metal M;

X denotes halogen.

4. A solid component of a catalytic system according to one of paragraphs.1 to 3, characterized in that the metal of group VIB of the Periodic system is chrome.

5. A solid component of a catalytic system according to one of paragraphs.1 to 4, characterized in that metallocen and the compound of the metal of group VIB is present in such quantities that the molar ratio of the metal of group VIB/transition metal is 0.001 - 100.

6. A solid component of a catalytic system according to one of paragraphs.1 to 5, characterized in that the medium is selected from silicon dioxide and mixtures of silicon dioxide, aluminum oxide and aluminum phosphate.

7. A method of obtaining a solid component catalyti the Assu, containing inorganic carrier and a compound of the metal of group VIB of the Periodic system of elements, wherein the first stage is carried out by mechanical mixing inorganic carrier with a solid compound of a metal of group VIB in the absence of fluid with subsequent predictively mixture at a temperature below the melting temperature of the compound of metal of group VIB and activating by heating predictivemodel mixture at a temperature of 400 - 1000oC to convert at least part of the metal in the hexavalent metal, then carry out the second stage by mixing solid mass, connection-based metallocene transition metal and compounds on the basis of the ionizer.

8. The method according to p. 7, characterized in that the connection on the basis of metallocene and connection-based ionizer injected sequentially, first mixing the solid component containing a carrier and a compound of the metal of group VIB with a compound based on metallocene in the absence of a liquid, and then impregnated with the resulting mixture with a solution of compounds on the basis of the ionizer.

9. Catalytic system for the polymerization of ethylene, which is the product of interaction of (a) a solid component and b) socializational component according to any one of paragraphs.1 - 7.

10. The catalytic system under item 9, characterized in that as alyuminiiorganicheskikh compounds it contains trimethylaluminum.

11. The method of polymerization of ethylene, characterized in that the use of the catalytic system under item 9 or 10.

 

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