Catalytic system for producing polyolefin and a composition used for the polymerization of olefins

 

(57) Abstract:

The invention relates to a catalyst system comprising a component of the transition metal group 1V and activator component for polymerization of olefins to obtain a polymer with high molecular weight. Component of the transition metal group 1V contains one cyclopentadienyl ligand and one heteroatomic ligand, and the ligand can be linked to each other bridge the communication component of the activator contains a cation which can be acid of Branstad able to give a proton (denoted as L,-H, where L,- neutral basis for Lewis, and H is hydrogen) and is compatible with coordinationin anion. In the presence of a catalyst system according to the invention in the polymerization of olefins at temperatures of 100 - 300oC for from 1 to 10 h are polyolefin with an average mol. m from 1000 to 500000 and distribution mol. m is about 1.5 or more. 3 S. and 18 C.p. f-crystals, 1 table.

The invention relates to a catalytic system comprising the transition metal compounds of groups IV-B of the Periodic table of elements and activator, as well as to the composition using this catalytic system for obtaining polyolefins, and catalysts for homopolymerization or copolymerization of olefins. Traditional catalytic system of the Ziegler-Natta, including compounds of the transition metal and socialization-alkylamine contribute to polyolefins having a high molecular weight, but a wide distribution of molecular weight. Traditional types of catalysts of the Ziegler-Natta have a very high activity, and obtained with these catalysts polyolefins have a small amount of residual catalyst and does not require further processing for obessolivanija remainder of the catalyst.

It was later developed catalytic system type "metallocene", in which the transition metal compound has the ligands with cyclopentadienyls ring, preferably at least two rings. Such a transition metal compound, called "metallocene", catalyzes the conversion of olefinic monomers to polyolefins. Metallocene compounds of metals of group IVB in particular, bis(cyclopentadienyl) titanocene and-zirconocene, used as compounds of the transition metal in a catalytic system for the production of polyolefins and ethylene -- olefin copolymers. When the catalytic system containing such metallocene, contains as socializaton alkylamino is very low, therefore, it is not of interest for industrial applications.

It is known that metallocene you can socialservice alumoxanes, not aluminiuim, to obtain a metallocene catalyst with high activity for the production of polyolefins with a moderately high molecular weight. Unfortunately, the number alumoxanes of socializaton required to obtain metallocene component with high activity is high, and is usually located within a molar ratio of Al to transition metal. Therefore, the polyolefin obtained with such metallocene-alumoxane the catalyst may contain an undesirable amount of residue of the catalyst (ash content, as measured by the content of non-volatile aluminum and transition metal).

In the European applications 277003 and 277004 discovered a new way to activate alkyl-metallocene complexes of metals of group IVB. Improved metallocene catalysts were obtained from at least two components. The first component is biscyclopentadienyl derivative of a metal of group IVB, containing at least one ligand which will react with the cationic part of the second component. The second component is a Ki is contained in the compound of the metal of group IVB (first component), and coordinational anion, which is bulky, labile and stable. Appropriate recoordination anions disclosed in these applications include: 1) anionic coordination complexes containing a variety of lipophilic groups, covalently coordination related and protecting the Central metal carrying charge or core metalloid, and 2) anions containing many atoms of boron, for example, carborane, metallocarborane and boron. After mixing the first and second component of the cation of the second component reacts with one of the ligands of the first component, the result is an ion pair consisting of a cation of metallocene group IVB with coordination number 3 and valency 4+and mentioned coordinating anion. The disadvantage of these catalytic systems is to obtain them from the metallocene complexes of metals of group IVB, containing at least two cyclopentadienyls ligand.

The catalysts available from aluminiumgie for polymerization of olefins prepared from transition metal complexes containing less than two cyclopentadienyls rings, are poorly understood. John Bercow reported (Organometallics, 1990, 9, 867) synthesis of catalyst based on versachi. This neutral catalyst III system group elements has low activity and it is very expensive due to the high cost of scandium. There is a need in the way of receiving highly active, versatile catalysts that are free from aluminiumgie, for the polymerization of olefins, obtained from monosyllabically ligands.

The catalytic system according to the invention contains a transition metal of group IVB of the Periodic table of the elements (CRC Handbook of chemistry and physics, 68th edition, 1987-1988) and anion exchange reagent, which can be used in the polymerization in solution, suspension polymerization, gas phase polymerization or polymerization in mass, to obtain a polyolefin with a high average molecular weight and relatively narrow molecular weight distribution.

Proposed according to the present invention is a catalytic system for producing polyolefins contain interactive components: A component of the transition metal of the IVB group and B - activator. As A component it contains one of the compounds of General formula I or II:

< / BR>
where

M is zirconium, hafnium or titanium, and is in a state of higher oxidation States (4+1- C20- gidrolabilna radicals, substituted C1- C20- gidrolabilna radicals, where one or more hydrogen atoms substituted by halogen atoms, C1-C20- gidrokarbonatnye metallogenia radicals, where the metalloid atoms selected from group IVA of the Periodic table of elements, and halogen atoms, or (C5H5-y-xRx) is a cyclopentadienyls ring in which two adjacent R groups together form cycles C4-C20, resulting in the formation of polycyclic cyclopentadienyls ligand;

(JR1z-1-y) - heterogeneous ligand in which J is an element with a coordination number 3 from group VA or an element with a coordination number 2 from group VIA of the Periodic system of elements; each R1, independently, represents a radical selected from the group comprising C1- C20gidrolabilna radicals, substituted C1-C20- gidrolabilna radicals, where one or more hydrogen atoms substituted by halogen atoms, and z is the coordination num is hydrated radical, substituted hydrocarbonyl radical, in which one or more hydrogen atoms substituted electroanatomic group, in particular a halogen atom or alkoxygroup, or C1-C20- gidrokarbonatnyj metallogeny radical, where the metalloid selected from group IVA of the Periodic table of elements, provided that in the case when any of the Q denotes hydrocarbon, the radical Q is different from the group (C5H5-y-xRx), or both Q together may form alkyliden, olefin, acetylene or cyclotetrasiloxane.

y= 0 or 1, and when y=1, B is a covalent bridging group containing an element of group IVA or VA;

W is a number from 0 to 3;

L is a neutral Lewis base or L indicates the connection of the second transition metal of the same type, resulting in both the metal center M and M' are linked bridging group Q or Q', where the symbol M' are identical to the values of the symbol, and the symbol Q' are identical to the values Q, and such compounds correspond to the formula II. As component B of the catalytic system contains an activator having (1) a cation which becomes irreversible reaction with at least one ligand that is included in the mentioned coodination communication, contains many lipophilic groups, forming covalent coordination and protecting the Central carrying the charge of the atom of the metal or metalloid, or an anionic complex, containing many atoms of boron, and the specified volume of the anion is such that when the interaction of the cationic part of the activator with is able to react with reactive proton Deputy mentioned transition metal of group IVB is formed of a metal cation, this anion is sterically difficult condition for the formation of covalent coordination with a metal cation of group IVB, and mobility of the specified anion is such that the above-mentioned anion can replace with the removal from above the metal cation of group IVB unsaturated hydrocarbon, whose power base Lewis is equal to or higher than the force of ethylene, and these components interact with one another in equimolar amounts.

Preferably, if the catalytic system in the heteroatomic ligand contains an element J, which represents nitrogen, phosphorus, oxygen or sulfur.

The preferred catalyst system, where y=1, and B is a linear, branched or ciklicheskaja 1 or 2 atoms of silicon instead of carbon atoms in the chain, or alkyl substituted silanena group Si1-Si2and heteroatomic ligand element J is a nitrogen.

It is desirable that, in particular, this catalytic system had values: y= 1, and B - alkyl substituted similartony group containing 1 or 2 atoms of silicon instead of carbon atoms in the chain, or alkyl substituted silanena group Si1-Si2.

The preferred catalytic system in which the activator corresponds to the formula

[(L'-H)+]d[(M')mQ1Q2...Qn]d< / BR>
where

L' is neutral Lewis base;

H - hydrogen,

(L'-H) - acid Bronsted,

M' is a metal or metalloid selected from groups VB by VA of the Periodic table of the elements, that is, from groups VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA;

each of Q1- Qnindependently of the other represents hydrogen, dialkylamino, alkoxide, aryloxy, hydrocarbon, substituted hydrocarbon or organometalloid radical, where one, but not more than one of Q1-Qncan be a halogen;

m is an integer from 1 to 7;

n is an integer from 2 to 8;

n-m = d;

any catalyst system includes an activator corresponding to the formula

[L'-H]+[BAr
B - Bor with valence 3+;

Ar1and Ar2- same or different aromatic or substituted aromatic hydrocarbons, and these groups can be linked to each other through a stable bridging group;

X3and X4is independently hydrogen, halogen, hydrocarbon, substituted hydrocarbon or organometalloid radical.

In particular, it is desirable that the catalytic system contains an activator represented by the formula

[L H]+[B(C6F5)4]-< / BR>
where

L' is neutral Lewis base;

H is a hydrogen atom;

[L H] - acid Bronsted;

B - Bor with valence 3+,

and heteroatomic ligand element J is nitrogen.

Typically, in this catalytic system, M is zirconium or hafnium, and cyclopentadienyls ring contains four groups of R, i.e. x=4, or one group R, i.e. x=1.

The preferred catalytic system in which the activator is responsible formulas

[L - H]c[(CX)a(M X)mXb]c-,

[L'-H]d[[[(CX3)a'(M"X4)m'(X5)in']c-]2Mn+]d< / BR>
where

[L'-H] - or H+or amondarain from 1 to 20 carbon atoms, or substituted hydrocarbonyl radical containing from 1 to 20 carbon atoms, where one or more hydrogen atoms substituted by halogen atoms, postname radicals, substituted postname radicals, each having up to 3 hydrogen atoms replaced hydrocarbonyl radical containing from 1 to 20 carbon atoms, or substituted C1-C20- hydrocarbonyl radical, where one or more hydrogen atoms substituted by halogen atoms, and the like;

C - carbon atom;

M is a boron atom;

each of X, X', X", X3X4and X5is a radical selected independently from a class which includes hydrogen, halides, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, substituted gidrolabilna radicals containing 1-20 carbon atoms where one or more hydrogen atoms substituted by halogen atoms, organometalloid radicals where each hydrocarbonyl Deputy in the organic portion contains from 1 to 20 carbon atoms, and the specified metal selected from group IVA of the Periodic table of elements;

M is a transition metal atom;

each of a and b is a positive integer greater than 0;

c is an integer from 5 to 22;

each of a' and b', which may be identical or different, greater than 0;

c' is a positive integer greater than 2;

a'+b'+c' is a positive integer even number from about 4 to 8;

m' is a positive integer from 6 to 12;

n is a positive integer that 2c'-n=d;

d is a positive integer greater than or equal to 1;

or catalytic system, where the activator corresponds to the formula

[L H]+[(C2B9H11)2Co]-< / BR>
where L' is neutral Lewis base;

H is a hydrogen atom;

[L H] - acid Branstad.

The object of the present invention is a composition used for the polymerization of olefins, containing the cation of the compound of the transition metal and the anion of the activator corresponding to the formula

< / BR>
where

M is zirconium, hafnium or titanium, and is in a state of higher oxidation States (4+d0complex);

(C5H5-y-xRxx) is cyclopentadienyls ring, substituted by 0-5 groups R, x is 0,1,2,3,4 or 5 denoting the degree of substitution, and each replacement group R is independently a radical selected from the group consisting of hydrocarbonrich Radik is Orada substituted by halogen atoms, hydrocarbonoclastic metallogenic radicals C1-C20where the metalloid is selected from group IVA of the Periodic table of elements, and halogen, or (C5H5-y-xRx) is cyclopentadienyls ring in which two adjacent R groups together form cycles C4-C20to obtain polycyclic cyclopentadienyls ligand;

(JR1z-1-y) is heteroatomic ligand in which J is an element with a coordination number 3 from group VA or an element with a coordination number 2 from group VIA of the Periodic table of elements, and each R1is independently a radical selected from the group consisting of hydrocarbonrich radicals C1-C20substituted C1-C20- hydrocarbonrich radicals in which one or more hydrogen atoms substituted by a halogen atom, and z is the coordination number of the element J;

each Q may represent independently a hydrogen atom, a C1-C50- gidrolabilna radicals, substituted gidrolabilna radicals in which one or more hydrogen atoms is substituted by an electron-withdrawing group, for example, a halogen atom, or alkoxygroup, or C1-C50-gidrokarbonatnye IU the, when any Q - hydrocarbon, such Q is different from (C5H5-y-xR5), or both Q together may be alkylidene, olefin, acetylene or cyclotetrasiloxane;

y=0 or 1; when y=1, B - covalently associated bridging group comprising an element of group IVA or group VA;

L is a neutral Lewis base;

w is a number from 0 to 3;

{ A]-- labile bulk anion, which is a simple coordination complex having many lipophilic radicals, forming covalent coordination and protecting the Central carrying the charge of the atom of the metal or metalloid, or anionic complex, containing many atoms of boron.

Preferably, the group [A]-answered the following General formula

[(M')m+Q1Q2...Qn]d< / BR>
where

M' is a metal or metalloid selected from groups VB by VA of the Periodic table of elements, i.e. groups VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA;

the values of each of the characters with Q1for Qnchosen independently from a class which includes hydrogen, dialkylamino, alkoxide and aryloxides group, gidrolabilna and substituted gidrolabilna radicals, as well as ORGANOMETALLIC oven, and the values of the other characters with Q1for Qnindependently selected from the above radicals;

m is a positive integer from 1 to 7;

n is a positive integer from 2 to 8;

n-m = d; or a group [A]-meets the following General formulas

[(CX)a(M X)mXb]c-< / BR>
[[[(CX3)a'(M"X4)m'(X5)b']c-]2Mn+]d< / BR>
where

C - carbon atom;

M is a boron atom or phosphorus;

each of X, X', X", X3X4and X5is a radical selected independently from the class, which covers the atoms of hydrogen, halides, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, substituted gidrolabilna radicals, where one or more hydrogen atoms substituted by halogen atoms, and containing from 1-20 carbon atoms, organometalloid radicals where each hydrocarbonyl Deputy in the organic portion contains from 1 to 20 carbon atoms, and the specified metal selected from group IVA of the Periodic table of elements;

M is a transition metal atom;

each of a and b is a positive integer greater than 0;

x is a positive integer;
each of a' and b', which may be identical or different, greater than 0;

c' is a positive integer greater than 2;

a'+b'+c' is a positive integer even number from about 4 to 8;

m' is a positive integer from 6 to 12;

n is a positive integer that 2c'-n = d, and d is a positive integer greater than or equal to 1.

Preferably, the group [A]-answered formula

B(C6F5)-4,

or the formula

[C2B9H11)2Co]-.

Usually used for polymerization of olefin composition containing the cation of the compound of the transition metal and the anion of the activator, corresponds to the formula

< / BR>
or

.

Component IVB transition metal catalytic systems on the basis of mononitrobenzene represented by the General formula

< / BR>
where

M is Zr, Hf or Ti and is in a state of higher oxidation States (4+d0complex);

(C5H5-y-xRx)-cyclopentadienyls ring, which is substituted by from 0 to 5 groups R, x = 0,1,2,3,4 or 5 denoting the degree of substitution, and each group R is a radical independently selected from the group SOS halogen, WITH1-C20- hydrocarbonoclastic metallogenic radicals, where the metalloid is selected from group IVA metals of the Periodic table of elements, and halogen; or (C5H5-y-xRx)- cyclopentadienyls ring in which two adjacent groups R together form a C4-C20cycles to obtain polycyclic cyclopentadienyls ligand, such as, for example, derivatives of indene and fluorene;

- heteroatomic ligand in which J is an element with a coordination number 3 from group VA or an element with a coordination number 2 of group UIA Periodic table of elements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R' is independently a radical selected from the group consisting of C1-C20- hydrocarbonrich radicals, substituted C1-C20- hydrocarbonrich radicals, where one or more hydrogen atoms substituted by a halogen atom, and z is the coordination number of the element J;

each Q may be independently a hydrogen atom, a C1-C50-hydratability radicals, substituted hydratability radicals in which one or more hydrogen atoms is substituted by an electron-withdrawing group, for example, a halogen atom or alkoxy radical or a C1-C50- Gebre condition, if any Q - hydrocarbon, such Q is different from (C5H5-y-xRx), or both Q together may be alkylidene, olefin, acetylene or cyclometalation;

y is 0 or 1; when y=1;

B is a covalent bridging group containing an element of group IVA or group VA, such as dialkyl-, alkaryl or diallelic or Germany, alkyl or arylphosphonate or amine radical, or hydrocarbonyl radical, for example, methylene, ethylene, etc.;

L is a neutral Lewis base such as diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, etc;

w is a number from 0 to 3;

L can also be a second transition metal compound of the same type, with the centers of the two metals M and M' are connected bridging group Q and Q', where M' has the same value with M, and Q' have the same value of Q. Such compounds represented by formula

< / BR>
The second component is an ion-exchange compound containing the cation, which irreversibly reacts c at least one ligand contained in the compound of metals of groups IVB, and coordinational anion, which is bulky, labile and stable. When connecting the first and second components, the cation Deut the metal ion of group IVB with a formal coordination number of 3 and valency 4+and the above anion that is compatible and which coordinationin against the metal cation formed from the first component. Are given as illustrative but not restrictive examples of the cation of the second component include acid Bronsted, as, for example, ammonium ions or reducible Lewis acid, such as, for example, ions Ag+or ferrocene. The anion of the second compound must be capable of stabilizing the complex cations of a metal of group IVB without compromising the ability of the cation of a metal of group IVB or a product of its decomposition to function as a catalyst, in addition, must be sufficiently labile to replace the olefin, diolefin or acetylene-unsaturated monomer during polymerization.

The catalytic system according to the invention can be obtained if component transition metal of group IVB and ion-exchange component to be placed in the General solution of the normally liquid alkangovolo or aromatic solvent, which is suitable for use as a solvent for liquid-phase polymerization of olefin monomer. Appropriate catalysts can also be prepared by reaction of the corresponding compound is the second of these components on a substrate.

A typical method of polymerization according to the invention, for example, polymerization or copolymerization of ethylene is in the stage of contacting one of ethylene or with other unsaturated monomers, including C3- C20- olefins, C5-C20- diolefin and/or one acetylanthracene monomers or in combination with other olefins and/or other unsaturated monomers, with a catalyst containing an appropriate solvent for polymerization of the above-mentioned compounds of the transition metal of group IVB; and ion-exchange component of the activator in such amount to provide a ratio of transition metal to activator is from about 1:10 to 200:1 or more, and carrying out the reaction of this monomer in the presence of a specified catalyst system at a temperature of from about - 100oC to 300oC for from about 1 to 10 hours to obtain a polyolefin having an average molecular weight of about 1000 or less than 5000000 or more and a molecular weight distribution of about 1.5 or more.

System ion catalyst is a General method.

The method according to this invention is carried out usually with a group of catalysts which are prepared Combi the Nile and the metal of group IVB, containing at least one ligand which will be connected with the second component or at least part of it, for example cationic part. The second component is an ion-exchange compound containing the cation, which irreversibly reacts with at least one ligand contained in the compound of metals of groups IVB, and coordinational anion, which is bulky, labile and stable. When connecting the first and second components, the cation of the second component reacts with one of the ligands of the first component, forming an ion pair consisting of cations of metals of group IVB, with a total coordination number of 3 and valency 4+and the above anion that is compatible and coordinating against the metal cation formed from the first component. The anion of the second compound must be capable of stabilizing the complex cation of metals of group IVB without compromising the ability of cations of metals of group IVB or a product of its decomposition to function as a catalyst, it must be sufficiently labile to replace the olefin, diolefin or acetylene-unsaturated monomer during polymerization.

A. a Component of the catalyst is armoloy

,

in which values of the groups and radicals indicated above.

Examples of group B, which is suitable as a substitute group of the component catalytic systems based on transition metal of group IV, specified in column 1 of table I, entitled "B".

In the case when L can also be a second transition metal compound of the same type, and the centers of the two metals M and M' are connected in bridge connection Q and Q', where M' has the same meaning as M and Q' has the same meaning as Q, the compounds represented by formula

< / BR>
Examples hydrocarbonrich radikalov for Q are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl preferred. Typical substituted gidrolabilna radicals include trifluoromethyl, pentafluorophenyl, trimethylsilylmethyl and trimethoxysilylmethyl and the like. Typical gidrolabilna substituted metallogenia radicals include trimethylsilyl, trimethylgermyl, triphenylsilanol and the like. Typical alkylguanine radicals for both Q together - methylidene, ethylidene and propylidene. Examples of the group Q, which is suitable as a replacement or item run "Q".

Appropriate gidrolabilna and substituted gidrolabilna radicals which can be substituted at least by the group R in cyclopentadienyl ring, will contain from 1 to about 20 carbon atoms and include alkalemia radicals are unbranched and branched chain, cyclic hydrocarbon radicals, alkyl substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl substituted aromatic radicals. Appropriate organometallics radicals which may be substituted by a group R in cyclopentadienyl ring include trimethylsilyl, triethylsilyl, ethyldimethylamine, methyldiethylamine, triphenylene, trimethylgermyl and the like.

Examples cyclopentadienyl cyclic groups of the formula (C5H5-y-xRx), which is acceptable as a component groups component catalytic systems with transition metal of group IVB, identified in column 2 of table I under the heading "(C5H5-y-xRx)".

Appropriate gidrolabilna and substituted gidrolabilna radicals, in which at least one hydrogen atom may be substituted by a group R' in the heteroatomic ligand J, will contain from Skye hydrocarbon radicals, alkyl substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl substituted aromatic radicals. Examples of heteroatomic groups of the ligand which is suitable as a substitute group of the component transition metal of group IVB in the catalyst, is specified in column 3 of table I, entitled

Table I illustrates typical representatives of the residue component with A transition metal of group IVB", and this list is provided solely for illustrative purposes, so it is in any case not be considered as exhaustive. The number of target components can be obtained by selecting all possible combinations of different residues of the specified groups in the formula. Illustrating examples are the following compounds demethylchlortetracycline-tert. butylethylenediamine, demethylchlortetracycline-tert. butylaminoethyl, dimethylallyl-tert. butylcyclopentadienyl-tert. butylethylenediamine, dimethylallyl-tert.butylcyclopentadienyl-tert. butylmethylether, dimetyltrimetyldiizobutirat-tert. butylethylenediamine, dimethylaminostyrylmethylpyridiniumiodine-tert. butylethylenediamine, Methylpheniltiomethyldimethylaminomethyl-tert. butylaminoethyl, dimethylcyclohexylamine, diphenylpyrrolidine-tert. butylphosphate, Methylpheniltiomethyldimethylaminomethyl-tert. butylaminoethyl, demethylchlortetracycline-p-called butylbenzenesulfonamide, demethylchlortetracycline-p-N. butylphenylmethyl.

For illustration given in table I compounds do not include the ligand (L) neutral base Lewis. The conditions under which complex compounds containing neutral ligands Foundation Lewis, for example, a simple ester, or those which form dimers, are determined by the steric volume of the ligands around the metal. Similarly, due to the smaller steric volume group trimethylcyclopentanone in connection

< / BR>
compared with group tetramethylcyclopentadienyl in connection

< / BR>
the first compound is a dimer, and the latter not.

Prefer varieties compounds (y=1) with the bridge connection of the transition metal of group IVB. The preferred method of obtaining these compounds having the salt of the halide of lithium, and monoglutamates becomes covalently bound to the cyclopentadienyl compound. Then, the reaction product of substituted cyclopentadienyl reacts with the lithium salt phosphide, kisida, sulfide or amide (e.g., lithiated), after which the halogen mono-halide reaction product reacts with separation of salts of lithium halide, and the amino group of the salt Lithiania covalently bound to the remainder of the reaction product of cyclopentadienyl. Then derived aminocyclopentane reacts with alkyllithium, in which the active hydrogen atoms on the carbon atom in the cyclopentadienyl and the nitrogen atom of the amino group, is covalently linked with the foster group, react with alkyl alkylate emitting alkane and education deliciious salt cyclopentadienyl connection. Then get a different connection with a bridge connection of a transition metal of group IVB in the reaction prolonged salt of the cyclopentadienyl and the transition metal of group IVB, preferably with a halide compound of a transition metal of group IVB. The result of this transformation get dichloropropane mononitrobenzene group IVB. Then comprehensive the respective Grignard salt, lithium, sodium or potassium hidrocarburos ligand. Applied methods similar to those developed for the alkylation complex metallocene compounds of group IVB (i.e. biscyclopentadienyl systems).

Various compounds of a transition metal of group IVB without bridge connection can be obtained by reaction of the compound cyclopentadienide and lithium salts with amine with galoisienne transition metal of group IVB.

The corresponding compounds of transition metals of groups IVB, which can be used in the catalytic system according to the invention include various compounds with bridging relationship (y=1), where bridge linking group, B represents a dialkyl-, diaryl - or alkalarian, or methylene or ethylene. Examples of preferred types of compounds of transition metals of groups IVB with bridge connection are compounds with bridging communication dimethylsilane, methylphenylethyl, dietildisul, ethylvanillin, divinycell, ethylene or methylene. The most preferred types of compounds with bridge connection are compounds with dimethylsilanol, diethylsilane and methylpenicillin.

The corresponding compounds of transition metals of groups IVB without ndimethyltryptamine di tert.butyldichlorosilane, pentamethylcyclopentadienyl-di-tert. -butyldichlorosilane, cyclopentadienyl-2-methylbutadiene-titanium.

To illustrate component is A transition metal of group IVB choose any combination of flavors in table I. an Example of the type of connection with bridge connection can be dimethylcyclopentane-tert.butylenediamine; an example of a connection without bridge connection - cyclopentadienyl-decret.butylethylenediamine.

B. Component B-activator.

Compounds that can be used as component B-activator in the preparation of the catalyst according to the invention, contain a cation, which may be acid Bronsted able to give a proton, and a compatible coordinational anion, and the anion is relatively large (bulky), capable of stabilizing the active components of the catalyst (cation group IVB), which is formed when contacted two compounds, the anion should be sufficiently labile to replace olefin, diolefine and acetylanthracene grounds or other neutral Lewis bases, such as ethers, NITRILES and the like. Two classes of compatible ncoord the connections, contains many lipophilic groups, covalently coordinated and protecting the Central metal carrying charge or core metalloid, and

2) anions containing a few atoms of boron, for example, carborane, metallocarborane and boron.

Basically, activators containing simple anionic coordination complexes that can be used according to the invention can be represented by the following General formula 5.

[L'-H)+]d[M')m+Q1Q2... Qn]d< / BR>
where values of the groups and radicals indicated above.

As mentioned above, can be used any metal or metalloid capable of forming anionic compound, stable in water, or in the anion of another connection. Appropriate metals include, without limitation, boron, phosphorus, silicon and the like. Compounds containing anions, which are coordination complexes containing one atom of a metal or metalloid, are that obvious, well known, and many compounds, in particular those which contain a single boron atom in the anode part, technically available. In light of predpochtitel the public boron atom.

Preferred activators are molecules which include boron, can answer the following General formula 5A.

[L'-H]+[BAr1Ar2X3X4]-< / BR>
where

L' is neutral Lewis base;

H is a hydrogen atom;

[L' - H]+-acid Bronsted;

B is a boron atom in the trivalent state;

each Ar1and Ar2which may be identical or different, denotes an aromatic or substituted aromatic hydrocarbon radical containing from 6 to 20 carbon atoms, these radicals can be connected to each other through a stable bridging group;

X3and X4radicals chosen independently from each other from a class that includes atoms of hydrogen, halides, provided that X3and X4they are halides, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, substituted gidrolabilna radicals in which one or more hydrogen atoms substituted by halogen atoms, containing from 1-20 carbon atoms, substituted hydrocarbon metal atoms (metalloorganic radicals), in which each hydrocarbonyl Deputy and the like.

Typically, each of the Ar1and Ar2independently of one another may denote any aromatic or substituted aromatic hydrocarbon radical containing from 6 to 20 carbon atoms. To an acceptable aromatic radicals include phenyl, naphthyl and antracene, although their list is not limited. Examples of suitable substituents in the substituted aromatic radicals are gidrolabilna, organometalloid, alkoxy, alkylamino, fluorine atoms and forgetable radicals and the like, in particular the values that can be used as radicals X3and X4but their list is not limited. The substituents can be in ortho-, meta - and para-position relative to the carbon atoms connected to the boron atom. In the case where one of the radicals X3and X4or they are both hydratability radicals, each of those radicals, which may be identical or different, may represent an aromatic or substituted aromatic radical, in particular such that denoted by the symbol Ar1and Ar2or may be a straight or branched alkyl, alkenyl or alkynylaryl radionic atoms, or alkyl substituted cyclic hydrocarbon radical containing from 6 to 20 carbon atoms. X3and X4also independently of one another may represent an alkoxy - or dialkylamino, where the alkyl of the alkoxy - and dialkylamino contains from 1 to 20 carbon atoms, gidrolabilna radicals and organometalloid radicals, each containing from 1 to 20 carbon atoms, and the like. As mentioned above, the radicals Ar1and Ar2can be linked together. Similarly, any of the radicals Ar1and Ar2or they both may be associated with any of the radicals X3and X4. Finally, the radicals X3and X4can also be connected via a corresponding bridge group.

Non-limiting examples of boron compounds which may be used as activator in obtaining improved catalysts of this invention are trialkylamine ammonium salt, in particular, triethylammonium(phenyl)boron, Tripropylamine(phenyl)boron, three(n-butyl)ammoniate(phenyl)boron, trimethylammonium(p-tolyl)boron, trimethylammonium(o-tolyl)boron, tributylammonium(PE is tributylammonium(p-triptoreline)boron, three(n-butyl)ammoniate(o-tolyl)boron and the like; N,N-dialkylanilines salt, in particular, N, N-dimethylanilinium(pentafluorophenyl)boron, N,N-diethylaniline(phenyl)boron, N, N-2,4,6-pentamethylenetetrazol(phenyl)boron and the like; dialkylammonium salts, in particular di(isopropyl)ammoniate(pentafluorophenyl)boron, dicyclohexylammonium-Tetra(phenyl)boron and the like; and triarylphosphine salt, in particular, triphenylphosphite(phenyl)Bor, three(were)phosphonites(phenyl)boron, three(dimetilfenil)phosphonites(phenyl)boron and the like.

This list can continue other similar compounds whose molecules contain other metals and metalloids that can be used as activators, but this is not necessary. It should be noted that the above list should not be considered as exhaustive, as any person skilled in the art it is obvious that the above General formulas also cover other acceptable boron compounds, and compounds whose molecules contain other metals and metalloids.

Activators containing a few atoms of boron, can be represented by the following SUB>, (M"X4)m'(X5)b']c-]2Mn+]d;

in which the groups and radicals indicated above.

For illustrative but not limiting examples of second components that can be used for the preparation of the catalyst systems used in the method according to the invention, in which the anion of the second component contains many atoms metalloid (as in formulas 5 and 6) are ammonium salts, for example ammonium-1-carbamodithioate (where 1 is carbamodithioate used for illustration only, and not limitation, as the counterion for the following cations ammonium); salt monohydroxyl-substituted ammonium, for example, methylammonium-1-carbamodithioate, ethylamine-1-carbamodithioate, propylamino-1-carbamodithioate, isopropylamino-1-carbamodithioate, (n-butyl)ammonium-1-carbamodithioate, aniline-1-carbamodithioate and (p-tolyl)ammonium-1-carbamodithioate and the like; salts dihydrocarbamazepine ammonium, such as dimethylammonio-1-carbamodithioate, diethylamine-1-carbamodithioate, dipropylamino-1-carbamodithioate, diisopropylamino-1-carbamodithioate, di(n-butyl)ammonium-1-carbamodithioate, diphenylamine-1-carbamodithioate, di(p-tolyl)Amoeboceras, triethylammonium-1-carbododecaedr, Tripropylamine-1-carbododecaedr, three(n-butyl)ammonium-1-carbododecaedr, triphenylamine-1-carbododecaedr, three(p-tolyl)ammonium-1-carbododecaedr, N,N-dimethylaniline-1-carbamodithioate, N,N-diethylaniline-1-carbamodithioate and the like.

Illustrating, but not limiting examples of second compounds corresponding to the formula 5 [where (n-butyl)ammonium is used for illustration and not limitation as the counterion for the following anions] are salts of anions, for example, bis[three(n-butyl)ammonium]onabort, bis[three(n-butyl)ammonium] decaborate, bis[three(n-butyl)ammonium] undecaborate, bis[three(n-butyl)ammonium] dodecaborate, bis[three(n-butyl)ammonium]dichlorocarbene, bis(three(n-butyl)ammoniumdichromat, (three(n-butyl)ammonium-1-carbidecobalt, (three(n-butyl)ammonium-1-carboncebit, (three(n-butyl)ammonium-1-carbamodithioate, (three(n-butyl)ammonium-1-carbidecobalt, (three(n-butyl)ammonium-1-carboncebit, three(n-butyl)ammonium-1-carbamodithioate, three(n-butyl)ammonium-1-trimethylsilyl-1-carbidecobalt, three(n-butyl)ammunition-1-carbamodithioate and the like; complex compounds of borane and carboran and salt anions of borane and carboran,decaborane, dodecahydro-11-methyl-2,7-decarbonation, three(n-butyl)ammoniumbicarbonate(14), three(n-butyl)ammonium-6-carbidecobalt(12). three(n-butyl)ammonium-7-carboncebit(13), three(n-butyl)ammonium-7,8-decarbonator(12), three(n-butyl)ammonium-2,9-decarbonator(12), three(n-butyl)ammonitida-8-methyl-7,9-decarbonator, three(n-butyl)ammoniojarosite-8-ethyl-7,9-decarbonator, three(n-butyl)ammoniojarosite-8-butyl-7,9-decarbonator, three(n-butyl)ammoniojarosite-8-allyl-7,9-decarbonator, three(n-butyl)ammoniojarosite-9-trimethylsilyl-7,8-dicarbazolyl, three(n-butyl)ammoniojarosite-4,6-dibromo-7-carboncebit and the like; boron and carborane and salt Baranov and carboranes, such as 4-Carbonara(14), 1,3-dicarbonate(13), 6,9-dicarbocyanine(14), dodecahydro-1-phenyl-1,3-dicarbonate, dodecahydro-1-methyl-1,3-dicarbonate, underager-1,3-dimethyl-1,3-dicarbonate and the like.

Illustrative, but not limiting examples of second compounds corresponding to formula 7 [where three(n-butyl)ammonium is used for illustration, but not limitation as the counterion for the following ions] are salts of anions of metallacarborane and metalloboranes, for example t is carboncore)ferrate (III), three(n-butyl)ammonium(undecieded-7,8-dicarboxylato)cobaltate (III), three(n-butyl)ammonium(undecieded-7,8-dicarbonate)nicelt (III), three(n-butyl)ammonium(nonahydrate-7,8-dimethyl-7,8 - dicarboxylato)ferrate (III), three(n-butyl)ammonium(nonahydrate-7,8-dimethyl-7,8 - dicarboxylato)chromate (III), three(n-butyl)ammonium(tribromoacetic-7,8-dicarboxylato) cobalt (III), three(n-butyl)ammonium(dodecahemidodecahedron)cobalt (III), Tris[three(n-butyl)ammonium]bis(undecieded-7-carboncore)chromate (III), bis[three(n-butyl)ammonium]bis(undecieded-7-carboncore)manganate (IV), bis[three(N-butyl)ammonium] bis(undecieded-7-carboncore)cobaltate (III), bis[three(n-butyl)ammonium]bis(undecieded-7-carboncore)nicelt (IV) and the like.

As a second example of compounds that can be used include salts of phosphonium and substituted the phosphonium corresponding to the above ammonium salts and substituted ammonium.

The method of preparation of the catalyst.

The catalytic system used in the method according to the invention, contains a complex compound formed by mixing compounds of the transition metal of group IVB with underwater metal of group IVB and activator in an inert solvent, where it is possible to carry out polymerization olein method of polymerization in solution.

The catalytic system can be prepared by placing the appropriate compound of a transition metal of group IVB and the corresponding activator, in any order of addition, in alkanoyl the solvent or the solvent of the aromatic hydrocarbon, preferably toluene. The catalytic system can be prepared separately in the form of a concentrate and add the diluent to the polymerization reactor. Or, if you prefer, you can prepare the components of the catalytic system in the form of separate solutions and add in the appropriate proportions in the diluent for the polymerization in the reactor, when it is convenient for continuous polymerization reactions in the liquid phase. Examples alkanovykh and aromatic hydrocarbons, suitable as solvents for the preparation of the catalyst system and also as a diluent for the polymerization are, without limitation, hydrocarbons with straight and branched chain, for example, isobutane, butane, pentane, hexane, heptane, octane, etc., cyclic and alicyclic hydrocarbons such as cyclohexane, cyclopentane, methylcyclohexane, metals the l etc. Appropriate solvents may also be liquid olefins which may be monomers or comonomers, for example ethylene, propylene, butene, 1-hexene, etc.

Usually the best results are achieved in accordance with the invention, when the compound of the transition metal of group IVB is present in the diluent for the polymerization in a concentration of from about 0.01 to 1.0 millimoles/liter of diluent, and the activator is present in such amount to provide a molar ratio of transition metal to a component of the activator is from about 1:1 to 200:1. To ensure adequate removal of heat from the catalyst components during the reaction and achieve good mixing is necessary to apply sufficient amount of solvent.

The ingredients of the catalyst system, i.e. the components of a transition metal of group IVB and activator, and a solvent for polymerization can be added to the reaction capacity quickly or slowly. The temperature to be maintained during the contact of the catalyst components may be located in a wide range, for example, from 10o300oC. you Can also apply a higher or lower temperature. Preferably during prigotovitelno at 25oC.

The individual components of the catalytic system, as well as the catalytic system is always protected from oxygen and moisture. Therefore, the reaction is carried out in an environment free from oxygen and moisture, and when the catalyst restore separately, then restore it to atmosphere free from oxygen and moisture. Therefore, it is preferable to carry out the reaction in the presence of dry inert gas such as helium or nitrogen.

The catalytic system.

Identification and study activity

The reaction of the two components of the catalyst can be viewed as a simple reaction between acid and base, in which Q-the ligand associated with the center of the transition metal (CN)MQ2(where (CN) = Cp and J - ligands), reacts with the cation of the second component, which can be acid [L H+] [A]-(where A-- coordinational anion), to obtain the ionic catalyst [(CN)MQ+][A]-and neutral byproducts Q-H and L'. The overall catalytic activity of the catalyst depends on the choice of metal, a specific group (CN) - ligand structure and stability of the A-and the ability of the cation or base Lewis L' to form the STI if homopolymerization or statistical copolymerization, as the cation used proton donor, and Q is the ligand component of the transition metal is chosen so that: 1) a complex compound of the metal should be easily and cheaply; 2) (CN)MQ2should be quite essential in order to ensure separation of the proton from the acid to the cation component of the activator, and 3) Q-H is directionspanel radical, for example, in the case of alkane, thus, the reaction activation is irreversible. For this system (CN) M residues L' and A-component activator "regulate" the stability and General characteristics of the catalyst system. The ability of L' and A-to change the behavior of the active center of the catalyst increases the versatility of catalytic systems for polymerization, and it is an important advantage compared to conventional methods of activation (for example, socialization methylalumoxane and other aluminiumallee socializaton).

Mostly, though most of these transition metals can be used in combination with most of the above-mentioned activators to obtain an active catalyst system for the polymerization of olefins, however, to ensure continuity stages of polymerization, it is important that any cation is Also important, to the anion of the activator was resistant to hydrolysis when using ammonium salt. It is also important that the positive charge of the activator was sufficient in relation to the metal to help you transfer the necessary cation such as a proton. Join activator containing salts of aryl-ammonium, for example N, N-dimethylaniline, are more acidic than salts of trialkylamine and therefore can be used with various transition metals. The basicity of the complex compounds of metal must also be sufficient to help you transfer the required proton. In General, it can be considered that the compounds of transition metals, which can hydrolyze aqueous solutions are suitable as metallocene components for the preparation of a specified catalyst system.

With regard to the combination of the component of the transition metal component of the activator to obtain a catalytic system in accordance with the invention, it should be noted that it is necessary to choose such substituted two compounds for the preparation of the active catalyst to eliminate the transfer of part of the anion to the cation of the metal and thereby eliminate the formation of active catalyst types. It is possible to carry out estately on coordinationa anion.

When the number and size of the substituents on the components of the transition metal is reduced, you get a more efficient catalyst with an activator containing recoordination anions, which are larger and more resistant to decay. If coordinationin anion is anionic coordination complex compound, for example derived tetraphenylboron, to prevent proton transfer or all of the phenyl groups of the anion to the metal, you can use the substituents on the phenyl rings. This can be achieved by alkylation, in ortobalagang phenyl groups or better perftorirovannye anion Thus, anionic coordination complex compounds containing perftoralkil, triptoreline - or bis-triptoreline ring, are preferred for this subspecies components of the activator. When coordinational anion contains many atoms of boron, corresponding to the General formulas 6 and 7, more effective catalysts are obtained from the activator containing large anions, such as those shown in equation 7, and those that have large values of m in equation 6. In these cases, it is also preferable if you use a second , of 4 or more have acid B-H-B shares, which can also react with the formed metal cation to form a catalytically inactive connection.

Was investigated several new compositions using NMR spectroscopy in the field of high tension. In the reaction between Me2Si(Me4C5)(N-t-Bu)ZrMe2and [DMAH] [B(pfp)4] (DMAH = PhMe2NH+and pfp = C6F5in d8-toluene, get a system consisting of two phases. The top layer consists mainly of d8-toluene only, with very few present DMA (DMA - PhNMe2). The bottom layer contains an ionic catalyst, and d8-toluene. An NMR spectrum in the field of high tension 13C of the lower layer shows that the reaction proceeds so that the formed DMA-adduct with DMA, as shown below.

< / BR>
These NMR clearly show that Amin indeed forms a coordination compound with a zirconium atom, but that it is freely rotatable and probably has two coordination centres in all probability in the form of mobile isomers. Types of ionic catalysts can be recrystallized at -40oC to obtain a pale powder. An NMR spectrum of this product in the CAS d8-thf (thf - tetrahydrofuran) in the solution or on the solid product of the catalyst leads to the formation of d8-thf adduct, [Me2Si(Me4C5)(N-t-Bu)ZrMe(d8-thfx] [B(pfp)4] and free DMA. This was to be expected, since d8-thf stronger base than DMA.

Were also investigated ion activators with different basicity. Amin, which is a stronger base than DMA, for example, DMT (Me2N-p-Me-Ph), provides full coordination bond with an atom of zirconium without rotation. This catalyst was obtained by the reaction of [DMTH][B(pfp)4] Me2Si(Me4C5)(N-t-Bu)ZrMe2. An NMR spectrum13C solution of the catalyst showed very little, if any, the presence of free DMT. The use of [Bu3NH] [B(pfp)4] as activator gave the opportunity to get a more interesting result. Apparently, when [n-Bu3NH][B(pfp)4] reacts with Me2Si(Me4C5)(N-t-Bu)ZrMe2Amin is not coordinated with the zirconium atom, as shown in equation

< / BR>
The fact that Amin is not coordinated with the metal proves the fact that the chemical shift of the signals amine does not change from the free amine. From the point of view of the DMA. The opposite position in this system, and this indicates that the spatial forces dominate the chemistry of the coordination. The observation of two signals Cp-methyl and one signal Me2Si suggests that the cation is a symmetric tricoordinated the cation and the anion and amine ligand is not coordinated heavily with metal to break the plane of symmetry through the metal, Wed - centroid and silicon atom.

Also studied the reaction of Me2Si(Me4C5)(N-t-Bu)ZrMe2[DMAH][C2B9H11)2Co] using NMR spectroscopy in the field of high tension. In this case, amine, DMA does not form coordination with the metal. The fact that were awarded four signal Cp-methyl and two signal Me2Si in the range of13C-NMR suggests that metallocarborane forms a coordination bond with the Central metal. This is consistent with its high solubility and low activity with respect to system B(pfp)-4.

The method of polymerization.

In a preferred variant of the method according to the invention the catalytic system used for polymerization in the liquid phase olefin monomer. The method of polymerization in the liquid phase vkljuchaei for polymerization in the presence of catalytic systems and at a sufficient temperature to obtain a polyolefin.

The monomer for this method can only contain ethylene for the production of comopolitan or ethylene in combination with-olefin having 3-18 carbon atoms, for the production of copolymer of ethylene --olefin. Conditions most preferred for the Homo - or copolymerization of ethylene are those in which the ethylene fed to the reaction zone under a pressure of from about 0,019 lb/in2up to 50,000 lb/in2and the reaction temperature maintained within the range from about -100oC to 300oC, preferably from -10 to 220oC. the Molar ratio of the component of the transition metal to activator component is preferably from about 1:1 to 200:1. The reaction time is usually from 1 s to 1 h

An example implementation does not limit the invention, one means is the following: in the capacity of the reactor with stirring injected liquid monomer is 1-butene. The catalyst is injected through the nozzle in the vapor or liquid phase, or sprinkle in a known manner in the liquid phase. The reactor contains a liquid phase consisting essentially of liquid 1-butene together with dissolved gaseous ethylene and steam phase containing vapors of all monomers. The temperature and pressure in the reactor and can aid cooling coils, shirts, etc. regulate the Rate of polymerization depending on the speed of the additive catalyst or the concentration of the catalyst. The ethylene content in the polymer product is determined by the content of ethylene to 1-butene in the reactor, which regulate by adjusting the feed rate of these components to the reactor.

Examples.

In the examples that illustrate the application of the invention, used analytical methods of analysis of the obtained polyolefin products. The molecular weight of polyolefin products were determined by gel chromatography (GPC) according to the following procedure. The molecular weight and distribution of molecular weight was measured by gel permeation chromatograph Waters 150, equipped with a differential detector refractive index (DRI) and the photometer Chromatix KMX-6 for measuring scattered light. The system was used at a temperature of 135oC with 1,2,4-trichlorobenzene as the mobile phase. Used column 802, 803, 804 and 805 Shodex (Showa the den com America, Inc.) with polystyrene gel. This method is described in the publication "Liquid chromatography of polymers and related materials III", J. Causes, editor, Marcel Dekker, 1981, page 207. Any amendments to rachaelrayshow for polyethylene 1484 and obtained by anionic hydrogenation of polyisoprene (option copolymer ethylene-propylen) showed that such corrections on Mw/Mn (=MWD) was less than 0.05 units. Mw/Mn was calculated according to the time of elution. Numerical analyses were carried out using commercially available and manufactured in accordance with customer requirements software Beckman/CIS LALLS in combination with a standard program that run on your computer HP 1000 to determine the penetration of the gel.

The following examples are intended to illustrate a particular embodiment of the invention but not to limit the scope of the invention.

All operations were carried out in an inert atmosphere of helium or nitrogen. The choice of solvent is purely arbitrary, since, for example, in most cases, you can alternate pentane or petroleum ether 30-60. The choice between tetrahydrofuran (thf) and diethyl ether is more limited, however, in separate reactions can be applied and that and the other. Lithium amides obtained from the corresponding amines and/or h-BuLi or MeLi. Known methods for producing LiHC5-Me4described With. M Hendrika and other "Organometallics", 3, 819 (1984) and F. X. by Kohler and K. H. a$, z "Naturforsch", 376, 144 (1982). Other lithium compounds substituted cyclopentadienyl usually obtained from the corresponding cyclopentadienyls legandery the company Aldrich Chemical Company or Carat. Reagents - amine, silane, and lithium were purchased from the firm Aldrich Chemical Company or Petrarchm Sestems. The components of the activator obtained by known methods.

Examples.

Synthesis of mono-cyclopentadienyls complex compounds

1.

Part 1. Me4HC5Li (10.0 g, 0,078 mol) is slowly added in Me2SiCl2(11.5 ml, 0,095 mol in 225 ml of tetrahydrofuran - thf). The solution was stirred for 1 h to ensure complete reaction. Then tertrahydrofuran ring the solvent was removed using a vacuum to a cold trap, supported at the temperature of -196oC. To precipitate LiCl was added pentane. The mixture was filtered through a zeolite. From the filter removed the solvent. Me4HC5SiMe2Cl (15,34 g, 0,071 mol) was extracted in the form of a pale yellow liquid.

Part 2. Me4HC5SiMe2Cl (10.0 g, 0,047 mol) is slowly added to the suspension (3,68 g 0,047 mol in 100 ml of tetrahydrofuran). The mixture was stirred overnight. Then the tetrahydrofuran was removed using a vacuum to a cold trap, supported at the temperature of -196oC. was Added petroleum ether ( 100 ml) to precipitate LiCl. The mixture was filtered through a zeolite. From the filtrate the solvent was removed (11,14 g 0,044 mol) was isolated as a pale yellow W is mesh left for stirring for half an hour after the addition of MeLi. The volume of a simple ester was reduced to filtering off the product. The product was washed with several small portions of simple ether, then dried under vacuum.

Part 4. (3.0 g, to 0.011 mol) is suspended in 150 ml of Et2O. Slowly added ZrCl4(2.65 g, to 0.011 mol) and the resulting mixture left to stir throughout the night. The ether was removed using a vacuum to a cold trap, supported at the temperature of -196oC. To precipitate LiCl was added pentane. The mixture was filtered twice through a zeolite. Pentane significantly reduced in volume. The pale yellow solid was filtered and washed with solvent. Drew (1.07 g, 0,0026 mol). From the filtrate additionally removed by repeated recrystallization. The total yield was 1.94 g, 0,0047 mol.

Part 5. obtained by adding a stoichiometric amount of MeLi (1.4 M in a simple ester) suspended in a simple ether. Got a white solid with 83% yield.

2.

Part 1. MePhSiCl2(14.9 g, 0,078 mol) was diluted in 250 ml of tetrahydrofuran. Slowly added Me4C5HLi (10.0 g, 0,078 mol) as a solid. The reaction solution was left overnight for mixing. The solvent was removed using vacuo. mesh was filtered through a zeolite, and from the filtrate was removed pentane. MePhSi(Me4C5H)Cl (20,8 g of 0.075 mol) was isolated as a yellow viscous liquid.

Part 2. (4,28 g, 0,054 mol) was dissolved in 100 ml of tetrahydrofuran. Drop added MePhSi(Me4C5H)Cl (15.0 g, 0,054 mol). The yellow solution was left to stir throughout the night. The solvent was removed using vacuum. Added petroleum ether to precipitate LiCl. The mixture was filtered through a zeolite, and the filtrate is boiled away. Received (16.6 g, 0,053 mol) in the form of a very viscous liquid.

Part 3. (16.6 g, 0,053 mol) was diluted with 100 ml of a simple ester. Added slowly MeLi (76 ml, 0,106 mol, 1.4 M) and the reaction mixture left to stir for approximately 3 hours, the Volume of ether was reduced, and the lithium salt was filtered and washed with pentane, having 20,0 g of pale yellow solid having the composition:

Part 4. (5,00 g, 0,0131 mol) is suspended in 100 ml of Et2O. Slowly added HfCl4(4,20 g, 0,0131 mol) and the reaction mixture left overnight for mixing. The solvent was removed via vacuum, and added petroleum ether to precipitate LiCl. The mixture was filtered through a zeolite. The filtrate is boiled away about dryness and filtered. Filtered white toimetajale number of MeLi (1.4 M in a simple ether) to suspensions in simple ether White solid is obtained in almost quantitative yield.

The polymerization.

Example 1.

The catalyst solution prepared from 19.7 mg and 6 mg [DMAN] [B(pfp4] in 20 ml of toluene was added to the autoclave of 1 liter stainless steel containing 400 ml of hexane. The reactor was maintained at a temperature of 40oC with strong stirring, was added ethylene under a pressure of 90 lb/in2. After 30 min the reaction was stopped receiving 30 g NDRE after treatment. Analysis by gel chromatography (GPC) showed a bimodal distribution with modes centered at 900,000 and 20000.

Example 2.

The catalyst solution prepared from 28,6 mg and 9 mg [DMAN] [B(pfp4] in 20 ml of toluene, was added in a 1-liter autoclave of stainless steel, containing 400 ml of hexane. The temperature of the reactor was maintained at 50oC with strong stirring the contents, when this was added 100 ml of butene and ethylene under a pressure of 60 lb/in2. After the addition of butene and ethylene was observed instantaneous temperature rise to 90oC. After 30 min the reaction was stopped receiving 130 g waxy ethylene-butenova copolymer. Analysis by gel chromatography (GPC) showed a bimodal distribution with modes centered is lemere.

Example 3.

The catalyst solution prepared from 40 mg and 11 mg [DMAN] [B(pfp4] in 20 ml of toluene, was added in a 1-liter autoclave containing 400 ml of hexane. The temperature of the reactor was maintained at 40oC, the contents of the reactor was heavily mixed and passed under the pressure of ethylene (90 lb/in2within 15 minutes During the polymerization temperature in the reactor increased from 40 to 97oC. the Reactor is shut down and got 98 g of polyethylene having Mw= 47,7 K and MWD = 3,0.

Example 4.

The catalyst solution prepared from 50 mg 68 mg [DMAN] [C2B9H11)2Co] in 20 ml of toluene, was added in a 1-liter autoclave containing 400 ml of hexane. The reactor temperature was adjusted to 60oC, the contents of the reactor was heavily mixed and applied under pressure ethylene (120 lb/in2within 60 minutes the Reactor is shut down and got to 0.44 g of polyethylene having Mw= 538 K and MWD = 1,90.

1 1. Catalytic system for producing polyolefins containing interactive components: component a transition metal of the IVB and B - activator, characterized in that as component And it contains one of the compounds of General formula I or II 6 6 /SUB>H5-y-xRx) - cyclopentadienyls ring, which is substituted 0 to 5 radicals R, x= 0, 1, 2, 3, 4 or 5 and denotes the degree of substitution, and each replacement of the radicals R independently represents a group selected from a class which includes1- C20-gidrolabilna radicals, substituted C1- C20-gidrolabilna radicals, where one or more hydrogen atoms substituted by halogen atoms, gidrokarbonatnye metallogenia radicals WITH1- C20where the metalloid atoms selected from group IVA of the Periodic table of elements, and halogen atoms, or (C5H5-y-xRx) is a cyclopentadienyls ring in which two adjacent R-groups are joined and form a loop WITH4- C20, resulting in the formation of polycyclic cyclopentadienyls ligand; 4 heteroatomic ligand in which J is an element with a coordination number 3 from group VA or an element with a coordination number 2 from group IVA of the Periodic table of elements, each of R1, independently, represents a radical selected from the class which covers the1- C20gidrolabilna radicals, substituted C1- C20-gidrolabilna for the J; 4 Q, each independently, represents hydrogen, gidrolabilna radicals, substituted hydrocarbonyl radical, in which one or more hydrogen atoms is substituted by an electron-withdrawing group, in particular a halogen atom or alkoxygroup, or gidrokarbonatnyj metallogeny radical WITH1- C20where a metalloid selected from group IVA of the Periodic table of elements, provided that in the case when any of the Q denotes hydrocarbon, the radical Q is different from the group (C5H5-y-xRx), or both Q together may form alkyliden, olefin, acetylene or cyclotetrasiloxane, y = 0 or 1, and when y = 1, B is a covalent bridging group containing an element of group IVA or VA; 4 w is a number from 0 to 3; 4 L is a neutral Lewis base or L indicates the connection of the second transition metal of the same type, resulting in both the metal center M and M' are connected bridge groups Q and Q', where the symbol M' are identical to the values of the symbol, and the symbol Q' are identical to the values Q, and such compounds correspond to the formula II, 1 and as a component of the activator comprising (1) a cation which becomes irreversible reaction with at least one predstavljaet either a complex with one coordination bond, contains many lipophilic radicals, which form covalent coordination bond, protects the Central carrying the charge of the atom of the metal or metalloid, or an anionic complex, containing many atoms of boron, and the specified volume of the anion is such that when the interaction of the cationic part of the activator with the reactive proton Deputy mentioned transition metal of group IVB is formed of a metal cation, this anion is sterically difficult condition for the formation of covalent coordination with a metal cation of group IVB, and mobility of the specified anion is such that the above-mentioned anion can replace with the removal from the specified metal cation of group IVB unsaturated hydrocarbon, whose power base Lewis is equal to or higher than the force of ethylene, and these components interact with one another in equimolar amounts. 2 2. The system under item 1, characterized in that the element J heteroatomic ligand group is a nitrogen, phosphorus, oxygen or sulfur. 2 3. The system under item 2, wherein y = 1, and linear, branched or cyclic Allenova group containing from 1 to 6 carbon atoms, alkylamide asenna silanena group Si1- Si2. 2 4. The system under item 3, characterized in that the element J heteroatomic ligand group is a nitrogen. 2 5. The system under item 4, wherein y = 1, and - alkyl substituted similartony group containing 1 or 2 atoms of silicon instead of carbon atoms in the bridge, or alkyl substituted silanena group Si1- Si2. 2 6. The system under item 2, characterized in that the activator corresponds to the formula 6 1 where L' is neutral Lewis base; 4 N hydrogen; 4 (L' - H) - acid Bronsted; 4 M' is a metal or metalloid selected from groups VB - VA of the Periodic table of elements, i.e., from groups VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA; 4 Q1- Qneach independently represent hydrogen, dialkylamino, alkoxide, aryloxy, hydrocarbon, substituted hydrocarbon or organometalloid radicals, where one, but not more than one Q1- Qncan be a halogen; 4 m is an integer from 1 to 7; 4 n is an integer from 2 to 8; 4 n - m = d. 2 7. The system under item 6, characterized in that the activator is represented by the formula 6 1 where L' is neutral Lewis base; 4 N hydrogen; 4 [L'-H] - acid Bronsted; 4 - boron in a valence state of 3; 4 Ar1and Ar2- same or different, the scent of the C stable bridging group; 4 X3and X4is independently hydrogen, halogen, hydrocarbon, substituted hydrocarbon or organometalloid radical. 2 8. The system under item 7, characterized in that the activator is represented by the formula 6 1 where L' is neutral Lewis base; 4 N - hydrogen atom; 4 [L H] - acid Bronsted; 4 - Bor with valence 3+. 2 9. The system under item 7, characterized in that the element J of the group heteroatomic ligand is a nitrogen. 2 10. The system under item 7, wherein M is zirconium. 2 11. The system under item 7, characterized in that cyclopentadienyls ring contains four replacement group R, x = 4. 2 12. The system under item 7, wherein M is hafnium. 2 13. The system under item 7, characterized in that cyclopentadienyls ring contains one replacement group R, and x = 1. 2 14. The system under item 6, characterized in that the activator corresponds to the formula6 6 1 where [L'-H] - or H+or ammonium, or substituted ammonium cation, in which up to 3 hydrogen atoms, substituted hydrocarbonyl radical containing from 1 to 20 carbon atoms, or substituted C1- C20-hydrocarbonyl radical, where one or more hydrogen atoms substituted by halogen atoms, postname radicals, substituted postname radicals, each to - WITH20-hydrocarbonyl radical, where one or more hydrogen atoms substituted by halogen atoms, and the like; 4 - carbon atom; 4 M is a boron atom; 4 X, X', X", X3X4and X5each a radical selected independently from a class which includes hydrogen, halogen, C1- C20-gidrolabilna radicals, substituted C1- C20-gidrolabilna radicals, where one or more hydrogen atoms substituted by halogen atoms, organometalloid radicals where each hydrocarbonyl Deputy in the organic portion contains from 1 to 20 carbon atoms, and the specified metal selected from group IVA of the Periodic table of elements; 4 M is a transition metal atom; 4 a and b are each a positive integer greater than 0; 4 - a positive integer greater than 1; 4 a + b + c - a positive integer even number from 2 to 8; 4 m is a positive integer from 5 to 22; 4 each of a' and b', which may be identical or different, greater than 0; 4 c' is a positive integer greater than 2; 4 a' + b' + c' is a positive integer even number from about 4 to 8; 4 m' is a positive integer from 6 to 12; 4 n is a positive integer that 2c' - n = d; 6 1 where L' - a neutral Lewis base; 4 N - hydrogen atom; 4 [L H] - acid Branstad. 2 16. The composition used for the polymerization of olefins containing the group of the cation of the compound of the transition metal and anion activator, characterized in that these groups correspond to the formula 6 1 where M is zirconium, hafnium or titanium and is in a state of higher oxidation States (complex +4, d); 4 (C5H5-y-xRx) is cyclopentadienyls ring substituted by groups R from 0 to 5, x= 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituted group R is independent radical selected from the group consisting of C1- C20-hydrocarbonrich radicals, substituted hydrocarbonrich radicals, where one or more hydrogen atoms substituted by halogen atoms, hydrocarbonoclastic metallogenic radicals WITH1- C20where the metalloid is selected from group IVA of the Periodic table of elements, and halogen, or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups together form a loop WITH4- C20to obtain polycyclic cyclopentadienyls ligand; 4 represents a heteroatomic ligand in which J is an element with coordinats the LLC and each R' is independent radical, selected from the group consisting of C1- C20-hydrocarbonrich radicals, substituted C1- C20-hydrocarbonrich radicals in which one or more hydrogen atoms substituted by halogen atoms, and z is the coordination number of the element J; 4 Q they can each represent independently a hydrogen atom, a C1- C50-gidrolabilna radicals, substituted gidrolabilna radicals in which one or more hydrogen atoms is substituted by an electron-withdrawing group such as halogen atom or alkoxygroup or1- C50-gidrokarbonatnye metallogenia radicals, in which the metalloid is selected from group IVA of the Periodic table of elements, provided that, when any Q - hydrocarbon, such Q is different from (C5H5-y-xRx), or both Q together may be alkylidene, olefin, acetylene or cyclometalation, y = 0 or 1 when y = 1, - covalent bridging group containing a group IVA or group VA; 4 L is a neutral Lewis base; 4 w is a number from 0 to 3; 4 [A]-- labile bulk anion, which is a simple coordination complex having many lipophilic radicals, forming covalent Koordinatsionnaya many atoms of boron. 2 17. The composition according to p. 16, characterized in that the group [A]-satisfies the General formula 6 1 where M' is a metal or metalloid selected from groups VB-VA of the Periodic table of elements, i.e., groups VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA; 4 Q1- Qneach chosen independently from a class which includes hydrogen, dialkylaminoalkyl, alkoxide and aryloxides radicals, gidrolabilna and substituted gidrolabilna radicals, and organometalloid radicals and any one, but not more than one of the symbols of Q1for Qnmay denote halogen, and other symbols with Q1for Qnindependently selected from the abovementioned radicals; 4 m is a positive integer from 1 to 7; 4 n is a positive integer from 2 to 8; 4 n - m = d. 2 18. The composition according to p. 16, characterized in that [A]-meets the General formula6 6 1 where C is a carbon atom; 4 M is a boron atom or phosphorus; 4 X, X', X", X3X4and X5each a radical selected independently from the class, which covers the atoms of hydrogen, halides, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, substituted C1- C20-gidrolabilna radicals, where one likability Deputy in the organic portion contains from 1 to 20 carbon atoms, and the specified metal selected from group IVA of the Periodic table of elements; 4 M is a transition metal atom; 4 a and b are each a positive integer greater than 0; 4 x is a positive integer greater than 1; 4 a + b + c - a positive integer even number from about 2 to 8; 4 m is a positive integer from 5 to 22; 4 a' and b', which may be identical or different, each greater than 0; 4 c' is a positive integer greater than 2; 4 a' + b' + c' is a positive integer even number from about 4 to 8; 4 m is a positive integer from 6 to 12; 4 n is a positive integer that 2c' - n = d; 4 d is a positive integer greater than or equal to 1. 2 19. The composition according to p. 17, characterized in that [A]-group of the formula6 2 20. The composition according to p. 18, characterized in that [A]-group of the formula6 2 21. The composition used for the polymerization of olefins containing the group of the cation of the compound of the transition metal and anion activator, characterized in that these groups correspond to the formula 6

 

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