Titanium containing catalyst component for the polymerization of ethylene, the catalyst for polymerization of ethylene and the method of polymerization of ethylene using the catalyst

 

(57) Abstract:

The inventive titanium containing catalyst component for the polymerization of ethylene is produced by interaction /A/ solid magnesium aluminum complex containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol having at least 6 carbon atoms, and /B/ the tetravalent titanium compounds. The solid magnesium aluminum complex /A/ receive interaction (a-1) magnesium solution formed from halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and the hydrocarbon solvent, and (a-2) alyuminiiorganicheskikh connection. It is also proposed a method of polymerization of ethylene, comprising the polymerization of ethylene or copolymerization of ethylene and alpha-olefin having from 3 to 20 carbon atoms, in the presence of a catalyst for polymerization of ethylene, which consists of /I/ the above titanium containing catalyst for polymerization of ethylene and /II/ component-based alyuminiiorganicheskikh connection. 3 S. and 4 C.p. f-crystals, 6 tab., 1 Il.

The invention relates to a titanium containing catalyst component for the polymerization of ethylene, which in large polymerization activity can floor the mu this titanium containing component and the polymerization of ethylene using a specified catalyst for polymerization of ethylene.

Known methods of making ethylene polymers are copolymerized ethylene with alpha-olefins or polymerization of ethylene in the presence of a catalyst of Ziegler. When implementing this method is widely used polymerization in solution at high temperature, in which process the reaction is carried out in a medium of hydrocarbon solvent at a temperature higher than the melting temperature of the formed polymer. However, if you want to obtain a polymer with a high molecular weight, the concentration of polymer in the polymer solution must be reduced, because the viscosity of the polymer solution increases with molecular weight. As a result, the problem of low polymer yield.

On the other hand, when carrying out the polymerization process using a paste-like catalyst for other problems, namely due to the fact that the resulting polymer is easily swells in the solvent used in the polymerization process. In the end, it is difficult to increase the concentration of pasta and hardly possible to conduct long-term and continuous processes.

In light of the problems encountered in the known methods of polymerization, as indicated above, the authors investigated and developed terjadi component of the catalyst has excellent qualities for use in the processes of conducting the polymerization pasty on the catalyst and enables the processes of polymerization at high concentrations paste. This catalyst based on titanium more than 70 wt. the titanium atoms restored to trivalente state. When using this titanium containing component with a high degree of activity of the catalyst to obtain the ethylene polymer (copolymer), which is characterized by excellent compositional uniformity.

As indicated above, when using the catalytic component described in [1] with a high degree of activity of the catalyst to effect polymerization of ethylene, and in addition, it is possible to obtain copolymers of ethylene, characterized by high compositional homogeneity and excellent morphology. However, it is necessary to develop a titanium containing catalyst component for the polymerization of ethylene in which the ethylene polymer can be obtained with a higher degree of activity in the polymerization.

Further, in the Japan patent [2] describes a method of obtaining titanium containing solid catalyst component. In this method, titanium containing solid catalyst component is produced by interaction of the magnesium-aluminum complex, which is formed by the interaction of alcohol solution halogenated derivatives of magnesium with aluminiurn this method titanium containing solid catalyst component has a good distribution of particle sizes and therefore, polymers, obtained using a catalyst comprising this solid titanium containing catalyst component, also have a good distribution of particle sizes. However, it is necessary to develop solid titanium containing component of a catalyst which has high activity in the polymerization of ethylene.

Further, posted in the patent application of Japan [3] are:

solid titanium containing catalyst component, which is obtained by introducing the product formed by the reaction product (a-1) interaction of the halogen derivatives of magnesium with alcohol and alyuminiiorganicheskikh compounds into contact with a halogen-containing compound of titanium, with a specified solid titanium containing component of the catalyst has a molar ratio of alkoxy groups and/or alcohol to the titanium, not more than 0.25;

solid titanium containing catalyst component, which is obtained by introducing the product formed by the reaction product (a-1) interaction of the halogen derivatives of magnesium with alcohol and alyuminiiorganicheskikh compounds into contact with a halogen-containing compound of titanium, and then, entering the compound obtained into contact with a halogen derivatives alyuminiiorganicheskikh connection (palodiruyut agent), and/or alcohol to Titan no more 0,9; and

solid titanium containing catalyst component, which is obtained by introducing the product formed by the reaction product (a-1) interaction of the halogen derivatives of magnesium with alcohol and alyuminiiorganicheskikh compounds in contact with halogenated derivatives of alyuminiiorganicheskikh connection (palodiruyut agent), and then introducing the compound obtained into contact with a halogen derivatives of titanium, and re-entering the compound obtained into contact with a halogen derivatives alyuminiiorganicheskikh connection (palodiruyut agent) with a specified solid titanium containing component of the catalyst has a molar ratio of alkoxy groups and/or alcohol to the titanium, not more than 0.9.

In the specified titanium containing solid component of catalyst molar ratio Ti3+/Ti4+lies in the range from 2.0 to 10.0, and most of the atoms are tetravalent titanium restored to the trivalent state. When using this catalyst it is possible to conduct the polymerization of ethylene with high polymerization activity. However, it is necessary to develop a titanium containing solid catalyst component for polymerization of ethylene, which has a narrow distribution of particles and by which it is washed titanium containing solid catalyst component, which is obtained by interaction

a solid magnesium-aluminum complex is formed by contacting of the solution derived from halogenated derivatives of magnesium, alcohol and hydrocarbon solvent, and alyuminiiorganicheskikh connection,

tetravalent compounds of titanium in liquid form and

vanadium compounds, zirconium or hafnium.

In this application [4] is given as a comparison example, in which the tetravalent titanium chloride is used 2-ethylhexyloxymethyl and not used connection vanadium.

In such solid titanium containing catalyst component most of the titanium atoms is restored to the trivalent state and the catalytic component exhibits low activity in the polymerization of ethylene. Therefore, the titanium containing solid catalyst component, which has significantly greater activity when carrying out the polymerization of ethylene.

The aim of the invention is a titanium containing catalyst component for the polymerization of ethylene, which with high polymerization activity can be obtained a polymer of ethylene with a narrow size distribution h of ethylene, using a specified catalyst for polymerization of ethylene.

Titanium containing catalyst component of the present invention is a titanium containing component of the catalyst for polymerization of ethylene, which is produced by interaction

/A/ solid magnesium aluminum complex containing magnesium, halogen, aluminum, and alkoxy group and/or alcohol having at least 6 carbon atoms, with the specified complex is produced by interaction

(a-1) magnesium solution formed from halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and the hydrocarbon solvent, with

(a-2) alyuminiiorganicheskikh connection, and

/B/ tetravalent compounds of titanium,

in which the majority of titanium atoms, included in a titanium containing catalyst component is in the tetravalent state, and the molar ratio of alkoxy groups and/or alcohol to titanium (EO/Ti) lies in the range from 0.26 to 6.0.

This titanium containing catalyst component for the polymerization of ethylene contains as main components magnesium, halogen, aluminum, alkoxy group and/or alcohol having at least 6 carbon atoms, and titanium.

The first polymerization catalyst of the present invention contains titanium containing component of the catalyst /I/ and alyuminiiorganicheskikh connection /II/.

The second polymerization catalyst of the present invention consists of terpolymerization titanium containing component of the catalyst /I/, and alyuminiiorganicheskikh connection /II/.

The method of polymerization of ethylene according to the present invention consists in the polymerization of ethylene or copolymerization of ethylene with alpha-olefin containing from 3 to 20 carbon atoms, in the presence of a catalyst for polymerization of ethylene.

The drawing shows the stage of the process of obtaining titanium containing catalyst component for polymerization of ethylene according to the present invention.

Further details of such component of the catalyst for polymerization of ethylene according to the present invention, the catalyst of ethylene, comprising a titanium containing catalyst component and a method of (co)polymerization of ethylene using titanium containing catalyst component.

The meaning of the term "polymerization" in this case is not limited to "homopolymerization", and also includes the term "copolymerization". Similarly, LVEF">

The drawing schematically shows one example of a method of obtaining titanium containing catalyst component of the present invention.

Titanium containing catalyst component of the present invention obtained when the interaction.

/A/ solid magnesium aluminum complex containing magnesium, halogen, aluminum, and alkoxy group and/or alcohol having at least 6 carbon atoms, with the specified complex is produced by interaction

(a-1) magnesium solution formed from halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and the hydrocarbon solvent, with

(a-2) alyuminiiorganicheskikh connection, and

/B/ the tetravalent titanium compounds.

First we explain the method of obtaining the solid magnesium aluminum complex /A/, containing magnesium, halogen, aluminum, alkoxy group and/or alcohol having at least 6 carbon atoms.

The solid magnesium aluminum complex /A/ receive interaction

(a-1) magnesium solution formed from halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and the hydrocarbon solvent, with

(a-2) alyuminiiorganicheskikh is evom complex /A/ typically lies in the range from 0.05 to 1, preferably from 0.08 to 0.7, and even more preferably from 0.12 to 0.6. The content of the alkoxy group and/or alcohol having at least 6 carbon atoms, usually in relation to 1 teaspoon of magnesium, 0.5 to 15 o'clock by weight, preferably from 2 to 13 o'clock by weight, and still more preferably from 5 to 10 p.m weight. The value of the atomic ratio x1/Mg (x1- halogen) usually lies in the range from 1 to 3, preferably from 1.5 to 2.5.

Preferably, the solid magnesium aluminum complex /A/ was a dispersed substance, the value of the diameter of the solid particles magini-aluminium compound, preferably lying in the range from 1 to 200 μm, more preferably in the range from 2 to 100 μm. With regard to the distribution of particles of complex /And/ in size, the value of the geometric standard deviation should preferably lie in the range from 1.0 to 2.0, most preferably in the range from 1.0 to 1.8.

Specific examples of halogen derivatives of magnesium to use the magnesium solution (a-1) of the present invention include:

-magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride;

-alkoxysilylated, such as methoxyphenylacetonitrile, such as proximinality and methylenebisacrylamide;

alkoxysilane derivatives, such as dioxirane, di-isopropoxide, dobutamine and doktorskini;

arylacetamide derivatives, such as deferoxamine and dimethylethanolamine; and

the carboxylates of magnesium such as magnesium laurate and magnesium stearate.

These compounds can be used in the form of complex compounds or double salts with other metals or as mixtures with other derivatives of metals.

Of these preferred compounds are magnesium halides and alkoxyamine halides, more predpochtitelnye are magnesium chloride and alkoxysilane, and most preferred is magnesium chloride.

These compounds can be used both individually and in combination with each other.

The solution of the magnesium compound (a-1) used in the present invention in liquid form, derived from halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and hydrocarbon solvent.

Specific examples of the alcohol having at least 6 carbon atoms, for use in the present Istana, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecanoyl alcohol, undecanol, oleic alcohol and stearyl alcohol;

aromatic alcohols such as benzyl alcohol, methylbenzylamine alcohol, ISO-propylbenzyl alcohol, alpha-methylbenzylamine alcohol and dimethylbenzylamine alcohol; and

alifaticheskie alcohols containing alkoxy group, such as n-butylcellosolve and 1 butoxy-2-propanol.

Preferred are alcohols containing at least 7 carbon atoms. The most preferred one is 2-ethylhexanol.

These alcohols can be used both individually and in combination with each other.

When halogenated derivatives of magnesium, the alcohol having at least 6 carbon atoms, and a hydrocarbon solvent to come into contact with each other halogenated derivatives of magnesium dissolved in the hydrocarbon solvent, forming a magnesium solution.

Specific examples of the hydrocarbon solvent are:

aliphatic hydrocarbons, such as propane, butane, n-pentane, ISO-pentane, n-hexane, ISO-hexane, n-heptane, n-octane, ISO-octane, n-decane, n-dodecane and kerosene.

-alicyclic hydrocarbons such as cyclopentane, methylcyclo is R>
galoidoproizvodnykh hydrocarbons, such as dehority methylene chloride, ethyl, dehority ethylene and chlorobenzene.

Of these the most preferred solvents are aliphatic hydrocarbons, particularly those containing from 3 to 10 carbon atoms.

These hydrocarbons can be used both individually and in combination with each other.

The interaction of halogen derivatives of magnesium, an alcohol containing at least 6 carbon atoms, and the hydrocarbon solvent is usually carried out at a temperature not lower than room temperature, preferably at temperatures below 65oC, more preferably from about 80 to 300oC, and most preferably from about 100 to 200oC, during the time from 15 minutes to 5 hours, mostly from 30 minutes to 3 hours, although these conditions may vary depending on the connection and alcohol etc.

Alcohol is usually used in an amount of not less than 1 mole, preferably from about 1.5 to about 20 moles, and more preferably from about 2.0 to about 12 moles per 1 mole of the halogen derivatives of magnesium, although this number can vary depending on epalzeorhynchos compounds (a-2) get a solid magnesium-aluminum complex /A/.

Mainly used in the present invention alyuminiiorganicheskikh compounds (a-2) are, for example, alyuminiiorganicheskikh compounds of General formula:

RanAIX3-n(iV)

where

Rahydrocarbon group containing from 1 to 12 carbon atoms, X a halogen atom or hydrogen, and n is a natural number from 1 to 3.

Hydrocarbon group containing from 1 to 12 carbon atoms, alkyl group includes, cycloalkyl group and aryl group. Examples of such groups are methyl group, ethyl group, n-sawn group, ISO-sawn group, ISO-bucilina group, pencilina group, exilda group, anjilina group, cyclopentenone group, tsiklogeksilnogo group, phenyl group and toluylene group.

Specific examples alyuminiiorganicheskikh compounds (a-2) are:

trialkylaluminium compounds such as trimethylaluminum, triethylaluminum, tri-ISO-Propylamine, tri-ISO-butylamine, trioctylamine, and Tris(2-ethylhexyl)aluminum;

alkanolamine compounds such as ISO-propanolamine;

halides dialkylamines compounds, such as dimethylammoniumchloride, diethylaluminium spodnie alkylaromatic compounds, such as methylaluminoxane, ethylaminoethanol, ISO-propyl-aluminiumanschlag, ethylaluminum;

dehalogenation alkylaromatic compounds, such as methylaluminoxane, ethylaminoethanol, ISO-properlyinstalled and ethylaluminum; and

alkylhalogenide, such as diethylaluminum and di-ISO-butylaldehyde.

Can also be used as alyuminiiorganicheskikh compounds, compounds having the General formula;

RaAlY3-n(v)

where

Rameans the same as in the formula (iv); n is an integer from 1 to 2; and Y group is-ORb(where the radicals Rb, Rc, Rdand Rneach is a methyl group, ethyl group, ISO-sawn group, ISO-butilkoi group, tsiklogeksilnogo group or phenyl group; the radical Reis a hydrogen atom, methyl group, ethyl group, ISO-sawn group or trimethylsilyloxy group; and the radicals Rfand Rgeach is methyl group or ethyl group.

Specific examples of such alyuminiiorganicheskikh compounds include:

(1) compounds of General formula RanAI(OSiRb)3-nsuch soup formula, RanAI(OSiRc3)3-nsuch as Et2Al(OSiMe3), (iso-Bu)2Al(OSiMe3and (iso-Bu)2Al(OSi Et3);

(3) compounds of General formula RanAI(OAIRd2)3-nsuch as Et2AlOAlEt2and (iso-Bu)2AlOAl(iso-Bu)2;

(4) compounds of General formula RanAI(NRe2)3-nsuch as Me2AlNEt2Et2AlNHMe, Me2AlNHEt, Et2AlN(Me3Si)2and (iso-Bu)2AlN(Me3Si)2;

(5) compounds of General formula RaAI(SiRf3)3-nsuch as (iso-Bu)2AlSiMe3;

(6) compounds of General formula RanAI[N(Rg)AIRn2]3-nsuch as Et2AlN(Me)AlEt2and (iso-Bu)2AlN(Et)Al(iso-Bu)2.

Further, as alyuminiiorganicheskikh compounds (a-2) can be used integrated alkylates, which are formed from metals of group I of the Periodic system and aluminum, these complex alkylates can be represented by the following formula:

MIAIRj4< / BR>
where

MIIs Li, Na or K, and Rjhydrocarbon group containing from 1 to 15 carbon atoms.

Specific examples of such complex alkylates are LiAl (the compounds are preferably used trialkylaluminium connection halide derivatives dialkylamines compounds, dialkylamide and dialkylaminoalkyl. Of these compounds the most preferred are trialkylaluminium connection, in particular, triethylaluminium, because by using them we can get the favorable catalyst forms.

These alyuminiiorganicheskikh compounds can be used both individually and in combination with each other.

To obtain the solid magnesium aluminum complex /A/ alyuminiiorganicheskikh compound (a-2) is mainly used in such quantity that the value of the molar ratio (ROH/Al) alcohol ( ROH), having at least 6 carbon atoms and used to obtain the magnesium solution (a-1) to the aluminum atom (Al) contained in alyuminiiorganicheskikh the compound (a-2) was approximately from 0.5 to 7, mainly from 1 to 5.

The interaction of the magnesium solution (a-1) with alyuminiiorganicheskikh compound (a-2) exercise, slowly, dropwise adding with stirring alyuminiiorganicheskikh compound (a-2) to the magnesium solution (a-1), preferably having a concentration of 0.005 to 2 mol/l, more preferably from 0.05 to 1 mol/l Specified S="ptx2">

The value of the temperature during the interaction of the magnesium solution (a-1) with alyuminiiorganicheskikh compound (a-2) is usually in the range from -50 to 150oC, mainly from -30 to 100oC.

Obtained in this way a solid magnesium aluminum complex /A/ does not contain organic groups having reducing properties, and, thus, does not have regenerative properties.

Titanium containing catalyst component polymerization /I/ of the present invention, obtained when the interaction of the above solid magnesium aluminum complex /And/ and tetravalent compounds of titanium /B/.

Used a combination of tetravalent titanium /B/ is mainly a compound represented by the following formula:

Ti(OR2)gX4-g(ii)

where

R is a hydrocarbon group, X a halogen atom, and

0g3

Specific examples of tetravalent titanium compounds /B/ are:

tetrachloride titanium, such as TiCl4, TiBr4and TiI4;

alkoxy-substituted trigalogenmetany titanium, such as connections

Ti(OCH3)Cl3,

Ti(OC2H5)Cl3,

< / BR>
dialkoxybenzene dehalogenation titanium, such as

Ti(OCH3)2CL2,

Ti(OC2H5)2Cl2,

Ti(On-C4H9)2Cl2,

Ti(OC2H5)2Br2;

dialkoxybenzene monohalogenated titanium, such as

Ti(OCH3)3Cl

Ti(OC2H5)3Cl

Ti(On-C4H9)3Cl

Ti(OC2H5)3Br

Of the above compounds are preferably used tetrachloropropane titanium, and most preferably is titanium tetrachloride.

These compounds can be used both individually and in combination with each other.

Tetravalent compound titanium /B/ is used in such quantity that the value of the atomic ratio (Ti/Mg+Al), titanium (Ti) contained in the connection /B/, magnesium and aluminum contained in the solid magnesium aluminum complex /A/, lying in the range 0.005 to 18, mostly in the range of from 0.01 to 15.

The interaction of solid magnesium aluminum complex /And/ and tetravalent compounds of titanium /B/ mainly carried out in a hydrocarbon solvent. As S="ptx2">

The interaction in accordance with the present invention is carried out usually at a temperature of from 0 to 150oC, preferably from 50 to 130oC, and even more preferably from 50 to 120oC.

Titanium containing catalyst component for polymerization of ethylene according to the present invention can be obtained by the above method, and it contains as main components magnesium, halogen, aluminum, alkoxy group and/or alcohol having at least 6 carbon atoms, and titanium. Titanium contained in titanium containing component of the catalyst is almost completely in the tetravalent state, namely: more than 90% of predominantly greater than 95% and even more mainly 100% of the titanium atoms are tetravalent state.

The value of the atomic relations Ti/Mg titanium containing catalyst component lies usually in the range of from 0.01 to 1.5, mostly from 0.05 to 1.0.

The value of the atomic relations Al/Mg titanium containing catalyst component lies usually in the range from 0.1 to 2.0, preferably from 0.13 to 1.5, and still more preferably from 0.15 to 1.2.

The value of the molar ratio of the alkoxy group and/or alcohol to the titanium (OR)/Ti titansoderzhashchego from 0.26 to 5.0, and most preferably from 0.26 to 4.0.

The number of alkoxy groups and/or alcohol having at least 6 carbon atoms is usually from 0.1 to 15 weight. hours, preferably from 0.3 to 10.0 weight.h. and even more preferably from 0.5 to 6 weight. including with respect to 1 weight. including magnesium.

It is desirable that titanium containing catalyst component consisted of a dispersed substance, the value of the diameter of its particles preferably lying in the range from 1 to 200 μm, more preferably in the range from 2 to 100 μm. The value of the geometric standard deviation of particle titanium containing component of the catalyst should preferably lie in the range from 1.0 to 2.0, most preferably in the range from 1.0 to 1.8.

Terpolymerization titanium containing component of the catalyst /I/' polymerization of ethylene according to the present invention is produced by terpolymerization of olefin and catalyst, including /I/ the above titanium containing catalyst component and (II) specified alyuminiiorganicheskikh connection.

The olefins which will polimerizuet with titanium containing component of the catalyst /I/ include ethylene and the alpha-olefins containing 3 to 20 carbon atoms.

Another catalyst for the polymerization of ethylene according to the present invention includes

/I/' above terpolymerization titanium containing component of a catalyst for polymerization of ethylene and

/II/ above alyuminiiorganicheskikh connection.

According to the method of polymerization of ethylene according to the present invention, the ethylene will polimerizuet or copolymerized with an alpha olefin containing from 3 to 20 carbon atoms in the presence of a catalyst for polymerization of ethylene formed by /I/ the above titanium containing component of the catalyst for polymerization of ethylene and /II/ above component-based alyuminiiorganicheskikh connection.

Examples of alpha-olefins containing from 3 to 20 carbon atoms, which may copolymerisate with ethylene are propylene, 2-methylpropene, 1-buten, 1-hexane, 1-penten, 4-methyl-1-penten, 3-methyl-1-penten, 1-octene, 1-none, 1-mission 1-undecene and 1-dodecene. The alpha-olefins can copolymerisate with polyene. Examples of polyene include butadiene, isoprene, 1,4-hexadiene, Dicyclopentadiene and 5-ethylidene-2-norbornene.

Obtained in this way copolymers of ethylene and alpha-alcoho compounds for use in the polymerization process can be applied already considered alyuminiiorganicheskikh compounds (a-2), used to obtain a titanium containing catalyst component (I) in the polymerization of ethylene.

In the implementation process for the polymerization reaction of titanium containing catalyst component (I) in the polymerization of ethylene is typically used in the amount of approximately from 0.00001 to about 1 mmol, mostly from 0.0001 to about 0.1 mmol, counting on the titanium atoms, per 1 liter of reaction volume during polymerization.

Alyuminiiorganicheskikh connection /II/ is used depending on the required number from 1 to 1000 mol, mostly from 2 to 500 mol, per 1 g-atom of titanium contained in the titanium containing catalyst component (I) in the polymerization of ethylene.

Titanium containing catalyst component for the polymerization of ethylene may be supported on a carrier. Examples of such carriers are Al2O3, SiO2B2O3, MgO, CaO, TiO2, ZnO, Zn2O, SnO2, BaO, ThO and resins such as a copolymer of styrene/divinylbenzene.

Further, the above-mentioned catalyst for the polymerization of ethylene can be terpolymerization with ethylene.

In the polymerization process, hydrogen can be used, it is possible to regulate the molecular weight of the obtained poly is for example, the reaction solution polymerisation or polymerization in suspension or in the gas phase. Furthermore, the polymerization can be carried out both portions, and semi-continuous and continuous.

When conducting polymerization using a paste of the catalyst, it is possible to use ethylene and any inert solvent which is liquid under the reaction conditions of the polymerization.

Examples of such inert solvents are aliphatic hydrocarbons, such as propane, butane, n-pentane, ISO-pentane, n-hexane, ISO-hexane, n-heptane, n-octane, ISO-octane, n-decane, n-dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, Methylcyclopentane, cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. These solvents can be used individually or in combination with each other.

The temperature of the polymerization reaction is usually from 20 to 150oC, preferably from 50 to 120oC, and even more preferably from 70 to 110oC; the pressure of the polymerization reaction is usually from 1 to 10000 kg/cm2mainly from 2 to 40 kg/cm2.

The copolymerization reaction can be conducted motilin, and static or block copolymer of ethylene and alpha-olefin, however, preferred is a homopolymer of ethylene and a statistical copolymer of ethylene and alpha-olefin.

Most preferably the present invention receive a homopolymer of ethylene or copolymer of ethylene/alpha-olefin, having a density of from 0.900 for up to 0,970 g/cm2mainly from 0.910 to 0,970 g/cm2. The specified density value is determined in accordance with standard ASTM d 1505.

In accordance with the present invention, as mentioned previously, the ethylene can cure with a high polymerization activity, moreover, the ethylene may polymerization of alpha-olefins containing from 3 to 20 carbon atoms.

(Co)polymers of ethylene of the present invention are formed in the form of particles, and these particles usually have a diameter in the range from 10 to 1500 μm, predominantly from 10 to 1000 microns.

Standard geometricheskoe deviation of the particles is from 1.0 to 2.0, mostly from 1.0 to 1.8.

(Co)polymers of ethylene, obtained by the present method have a narrow interval of the distribution of particles by size.

Preferably, powdered (co)polymer according nastoiashaia 0,8 wt. and even more preferably not more than 0.5. the content of particles with a diameter of not more than 100 μm was not more than 7.0 wt. preferably not more than 5.0 wt. and even more preferably not more than 3.0 wt. and the content of particles with a diameter from 100 to 500 μm is not less than 85 wt. preferably at least 90 wt. the total weight of all the polymer particles.

Obtained according to the present invention (co)polymers of ethylene may contain various additives, such as stabilizers against heat, from weathering stabilizers, antistatic agents, plasticizers, nucleating agents, deblokiruyuschee agents, pigments, dyes, inorganic fillers and organic fillers.

In titanium containing catalyst component for the polymerization of ethylene according to the present invention, the halogen-containing compound of titanium is applied on the solid magnesium aluminum complex, and titanium contained in this component of the catalyst is in the tetravalent state. Thus, the use of titanium containing component of the catalyst allows for the polymerization of ethylene with a high polymerization activity, moreover, in the case where the ethylene will copolymerized with alpha CLASS="ptx2">

Further, the use of titanium containing catalyst component for the polymerization of ethylene allows to obtain a copolymer with a narrow distribution of particle size, with particles having a very small size, are formed only in small quantities.

The method of (co)polymerization of ethylene according to the present invention carried out using the above-mentioned titanium containing catalyst component, with the aim of obtaining high polymerization activity (co)polymer of ethylene having a narrow distribution of particle size and excellent morphology. When carrying out the polymerization process over a pasty catalyst ensures good digestibility of the polymerization process.

Examples. Analysis of the catalyst for polymerization of ethylene and measuring the distribution of particle size and the standard geometric deviation is carried out as follows.

1. Mg, Al, Ti

Determination of magnesium, aluminum and titanium performed by atomic adsorption at excitation inductively coupled plasma (ICP) instrument ICP F1000TR company Shimazu Seisakusho K. K.

2. Cl

The determination of the content of chlorine is carried out by the method of titration solution nsim way.

Well the dried catalyst was added to the acetone solution containing 10 wt. water to conduct hydrolysis and highlight ROH, the content of which is determined by gas chromatography.

4. Determination of the distribution of particle size and geometric standard deviation.

Determination of the distribution of particle size and geometric standard deviation are using vibrator company Iida Seisakusho K. K. and set of sieves (stretched on frame sieves JIS-Z-8801 company Iida, the inner diameter of 200 mm).

Example 1. (Receiving component catalyst)

4.8 g of the purchase of anhydrous magnesium chloride, 19.5 g of 2-ethylhexanol and 200 ml of decane is heated at a temperature of 140oC for 3 h before formation of a homogeneous solution containing magnesium chloride. To the resulting solution are added dropwise at 20oC and stirring for 30 min a solution of 60 mmol of triethylaluminum in 52 ml of the Dean. Then the temperature of the mixture gradually over 2 hours up to 80oC and stirred at this temperature for 2 hours Cooled, the solid precipitate is filtered and washed once with 200 ml of decane, getting a solid magnesium-aluminum complex.

Received toflorida titanium and conduct reaction at 80oC for 2 hours the reaction Product is well washed with hexane and receive a suspension of the solid catalyst in hexane. The composition of the solid catalyst are given in table. 2.

A portion of the suspension of the solid catalyst (corresponding to 5 g of the solid catalyst) are placed in a reactor with a capacity of 300 ml equipped with a stirrer made of Teflon. Then add 0.5 g of liquid paraffin and mix the contents of the reactor. The reactor is placed in a bath with a temperature of 40oC and let a stream of nitrogen at 80 l/h to evaporate the hexane. After evaporation of the hexane get powdered titanium containing catalyst component containing approximately 10% of liquid paraffin.

/Polymerization/

In the autoclave of 2 l in the atmosphere of nitrogen was placed 1 liter of pre-purified hexane. Suspended in hexane 1.0 mmol of triethylaluminum obtained above and powdered titanium containing component and 0.1 mmol (counting on the titanium atoms) resulting suspension contribute to the reactor. The system temperature was raised to 80oC, serves hydrogen under pressure 4 kg/cm2and then served continuously for 2 h ethylene so that the total pressure is maintained at 8 kg/cm2. The temperature during polymailer ethylene is separated from the solvent and dried.

The results of determination of the properties of the polymer of ethylene is shown in table. 3.

The output of powdery polymer was 227 g, an MFR value for him is 2.7 g/10 min, the value of the bulk density of 0.33 g/cm2.

Data on the distribution of particle size of powdered polymer are shown in table. 1.

Example 2. Preparation of the catalyst component and the polymerization carried out analogously to example 1, except that the used amount of 2-ethylhexanol is not 19.5 g, and 16.3 g, and the amount of trimethylaluminum reduced from 60 to 46 mmol mmol.

The results of determination of the properties of the polymer of ethylene is shown in table. 3.

Example 3. Preparation of the catalyst component and the polymerization carried out analogously to example 2, except that the temperature of the reaction mixture after addition of 400 mmol of titanium tetrachloride maintained at the level not 80oC, and 100oC.

The results of determination of the properties of the polymer of ethylene is shown in table. 3.

Example 4. Preparation of the catalyst component and the polymerization carried out analogously to example 1, except that the amount used is about from 60 to 43 mmol mmol.

The results define the properties of a polymer of ethylene presents and table. 3.

Example 5. Preparation of the catalyst component and the polymerization carried out analogously to example 1, except that the used amount of 2-ethylhexanol is not 19.5 g, 15.3 g, and the amount of trimethylaluminum reduced from 60 to 41 mmol mmol.

The results of determination of the properties of the polymer of ethylene is shown in table. 3.

Comparative example 1.

4.8 g of the purchase of anhydrous magnesium chloride, 19.5 g of 2-ethylhexanol and 200 ml of decane is heated at a temperature of 140oC for 3 h before formation of a homogeneous solution containing magnesium chloride. To the resulting solution are added dropwise at 20oC and stirring for 30 min a solution of 52 mmol of triethylamine in 45 ml of decane. Then the temperature of the mixture gradually over a period of 2.5 h was raised to 80oC and stirred at this temperature for 1 h after completion of the reaction yield of the mixture to cool, the liquid above the precipitate is drained and the residue containing the reaction product, add 200 ml of decane, and 50 mmol of chloride diethylamine and again carry out the reaction at 80oC for 1 h, the Solid part of the mass part of the th group, possessing regenerative ability.

Obtained in this way a solid component again suspended in 200 ml of decane, and to the resulting suspension was added 25 mmol of titanium tetrachloride and spend interaction at 80oC for 2 h

The resulting reaction, the solid is separated by filtration and washed 5 times with hexane, getting a titanium containing catalyst component.

Carry out the polymerization of ethylene as in example 1, using the above titanium containing catalyst component.

The results of determination of the properties of the polymer of ethylene is shown in table. 3.

Comparative example 2.

/Catalyst/

30 mmol purchase of anhydrous magnesium chloride are suspended in 150 ml of n-decane. To the resulting suspension is added dropwise under stirring for 1 h, 120 mmol of n-butanol, and then carry out the reaction at a temperature of 80oC for 3 hours To the resulting suspension is added dropwise at room temperature and with stirring, 240 mmol of monochloride diethylaluminum and conduct the reaction at a temperature of 90oC for 3 hours Cooled, the solid precipitate is filtered and washed, and then suspended in the and carry out the reaction at 25oC for 10 minutes

The composition of the obtained catalyst are given in table. 4.

/Polymerization/

Steel autoclave with a capacity of 2 liters of well rinsed with nitrogen and placed in 1 l of hexane and heated to 50oC. Then added 1.0 mmol three-ISO-butylamine, 0.5 mmol ethylene chloride and 0.02 mmol (counting on the titanium atoms) obtained earlier catalyst. After sealing the autoclave, it serves hydrogen, so that the reading on the manometer was 4.5 kg/cm2and then served ethylene, so that the reading on the gauge was 8 kg/cm2. The temperature in the reaction system for 2 h support at level 80oC and continuously serves ethylene so that the total gauge pressure was 8 kg/cm2.

The yield of polyethylene is 316, This number corresponds to the polymerization activity 16800 g of polyethylene per 1 g of catalyst.

Example 6. /Terpolymerization/

In a flask with a capacity of 400 ml equipped with a stirrer, was placed 200 ml of purified hexane, 6 mmol of triethylaluminum and 2 mmol (counting on the titanium atoms) suspension in hexane powdered titanium containing catalyst component obtained in example 1. Then, into the flask over 3 hours with a speed of 1.74 l/h n polyethylene is 5 g per 1 g of catalyst.

/Polymerization/

In the autoclave of 2 l in the atmosphere of nitrogen was placed 1 liter of pre-purified hexane. In an autoclave was placed 1.0 mmol of triethylaluminum and 0.01 mmol (counting the atoms of the titanium component of the catalyst, terpolymerization, as described previously, and the system temperature was raised to 80oC. Serves hydrogen under pressure 4 kg/cm2and then served continuously for 2 h ethylene so that the total pressure is maintained at 8 kg/cm2. The temperature of the polymerization process is 80oC.

After completion of the polymerization process, the polymer of ethylene is separated from the solvent and dried.

The results of determination of the properties of the polymer of ethylene is shown in table. 5.

Comparative example 3. 4-throat flask suspended 30 mmol of anhydrous magnesium chloride in 150 ml of n-decane. To the resulting suspension is added dropwise under stirring for 1 h, 180 mmol of ethanol, and then conduct the reaction at room temperature for 1 h In the reaction of the swollen magnesium chloride forms a white powder. To the resulting suspension is added dropwise at room temperature 84 mmol of monochloride diethylaluminum and spend the reaction is imaut temperature up to 80oC and carry out the reaction at this temperature for 3 h under stirring. Cooled, the solid precipitate is filtered off and washed with 2 l of n-decane.

/Polymerization/

2-liter steel autoclave thoroughly rinsed with nitrogen, placed in 1 l of hexane and heated to 50oC. Then added 1.0 mmol three-ISO-butylamine, 0.5 mmol ethylene chloride and 0.02 mmol (counting on the titanium atoms) obtained earlier catalyst and the autoclave is pressurized. In the autoclave serves hydrogen, so that the reading on the manometer was 4.5 kg/cm2and then served ethylene, so that the reading on the gauge was 8 kg/cm2. Within 2 hours at a temperature of 80oC continuously served the ethylene so that the total gauge pressure is maintained at 8 kg/cm2.

The results of determination of the properties of the polymer are shown in table. 6.

1. Titanium containing catalyst component for the polymerization of ethylene, obtained by the sequential interaction of the alcohol solution of sodium halide with trialkylaluminium in the environment of the hydrocarbon solvent by heating with the formation of the solid magnesium aluminum complex containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which a fact, that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, the alcohol contains at least 6 carbon atoms.

2. Component under item 1, characterized in that it is produced in the interaction of the solid magnesium aluminum complex with a combination of tetravalent titanium in a hydrocarbon solvent at 50 120oC.

3. Terpolymerization titanium containing catalyst component for the polymerization of ethylene, obtained by terpolymerization of olefin to catalyst consisting of (I) titanium containing catalyst component for the polymerization of ethylene, obtained by the sequential interaction of the alcohol solution of magnesium halide with trialkylaluminium in the environment of the hydrocarbon solvent by heating with the formation of the solid magnesium aluminum complex containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which is treated with a combination of tetravalent titanium in a hydrocarbon solvent by heating, characterized in that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, the alcohol contains at least 6 carbon atoms, and (II) alyuminiiorganicheskikh connection.

4. The catalyst for polymerization of ethylene, comprising esteem alcohol solution of magnesium halide with trialkylaluminium in the environment of the hydrocarbon solvent by heating with the formation of a solid magnesium-aluminum complex, containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which is treated with a combination of tetravalent titanium in a hydrocarbon solvent by heating, characterized in that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, the alcohol contains at least 6 carbon atoms, and (II) alyuminiiorganicheskikh connection.

5. The catalyst for polymerization of ethylene, comprising (A) terpolymerization titanium containing catalyst component for the polymerization of ethylene, obtained forpolymerization of olefin to catalyst consisting of (I) titanium containing catalyst component for the polymerization of ethylene, obtained by the sequential interaction of the alcohol solution of magnesium halide with trialkylaluminium in the environment of the hydrocarbon solvent by heating with the formation of the solid magnesium aluminum complex containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which is treated with a combination of tetravalent titanium in a hydrocarbon solvent by heating, characterized in that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, and the alcohol contains at least 6 carbon atoms, and (II) alyuminiiorganicheskikh joint is ethylene or the copolymerization of ethylene with alpha-olefin, containing 3 to 20 carbon atoms, in the presence of a catalyst for polymerization of ethylene consisting of (I) titanium containing catalyst component for the polymerization of ethylene, obtained by the sequential interaction of the alcohol solution of magnesium halide with trialkylaluminium in the environment of the hydrocarbon solvent by heating with the formation of the solid magnesium aluminum complex containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which is treated with a combination of tetravalent titanium in a hydrocarbon solvent by heating, characterized in that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, the alcohol contains at least 6 carbon atoms, and (II) alyuminiiorganicheskikh connection.

7. The method of polymerization of ethylene, comprising the polymerization of ethylene or copolymerization of ethylene with alpha-olefin containing 3 to 20 carbon atoms, in the presence of a catalyst for polymerization of ethylene, comprising (A) terpolymerization titanium containing catalyst component for the polymerization of ethylene, obtained by terpolymerization of olefin to catalyst consisting of (I) titanium containing catalyst component for the polymerization of ethylene, obtained Polidoro solvent by heating with the formation of a solid magnesium-aluminum complex, containing magnesium, halogen, aluminium and alkoxygroup and/or alcohol, which is treated with a combination of tetravalent titanium in a hydrocarbon solvent by heating, characterized in that the molar ratio of alkoxygroup and/or alcohol to the titanium 0,26 6,0, the alcohol contains at least 6 carbon atoms, and (II) alyuminiiorganicheskikh connection, (B) alyuminiiorganicheskikh connection.

 

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