RU2073018C1 - Coordination metallic complex, catalyst for ionic- coordination polymerization, and process for ionic- coordination polymerization - Google Patents

Abstract

FIELD: catalyst for ionic coordination polymerization. SUBSTANCE: claimed invention describes coordination metallic complex of general formula:

wherein Z is

Description

 The invention relates to metal coordination complexes with a stressed structure. The invention also relates to some new addition polymerization catalysts containing such metal complexes with a stressed structure, as well as to polymerization methods of monomers involved in the addition polymerization, and to the resulting polymers.

 Due to the unique arrangement of the active metal center of the metal coordination complex with a stressed structure, the catalysts obtained from them have unique properties. Under certain conditions, the catalysts of the invention make it possible to obtain new olefin polymers with previously unknown characteristics due to their ability to polymerize alpha olefins, lyolefins, hindered vinylidene aliphatic monomers, vinylidene aromatic monomers and mixtures thereof.

Many metal coordination complexes are known to those skilled in the art, including complexes containing monocyclopentadienyl groups and substituted monocyclopentadienyl groups. The considered metal coordination complexes differ from those previously known in that the metal is bonded to a substituted fragment with a delocalized π-bond in such a way that a stressed structure is formed near the metal. Preferably, the metal is bound to cyclopentadienyl substituted by cyclopentadienyl or a similar group in both η ⁵ bonds, and the bridging bond includes the remaining metal ligands. These complexes also preferably include metals having suitable catalytic properties. Transition metal coordination complexes, known as tucked complexes, were also previously known. Such complexes are described in Organometallics, 6, 232-241 (1987).

 From US patent N 4680353, C 08 F 112/08, 1985, a method is known for producing a polymer, including polystyrene, by polymerization in the presence of a catalyst of a metal complex, in particular titanium and an aluminum-organic cocatalyst.

 U.S. Application No. 8800, filed January 30, 1987 (published in equivalent form as EP 277004) discloses certain bis (cyclopentadienyl) metal compounds obtained by reacting bis (cyclopentadienyl) metal complexes with Bronsted acid salts containing non-coordinating compatible anions. The references disclose the fact that such complexes have been successfully used as catalysts in the polymerization of olefins. The above catalysts are not considered particularly effective olefin polymerization catalysts.

Past attempts to produce vinylidene aromatic monomer copolymers with alpha olefins, in particular styrene-ethylene copolymers, have been unsuccessful either due to the impossibility of substantially incorporating vinylidene aromatic monomer, or due to the production of low molecular weight polymers. In Polymer Bulletin, 20, 237-241 (1988), a random copolymer of styrene and ethylene is disclosed containing 1 mol of styrene. The yield of said polymer was 8.3 x 10 ^-4 g of polymer per micromole of titanium used.

 It was found that previously known addition polymerization catalysts are not capable of high activity and polymerization of many monomers due to the fact that they do not have a stressed structure.

 One aspect of the invention relates to a metal coordination complex with a stressed structure. More specifically, it relates to such coordination complexes that are successfully used in combination with activating cocatalytic compounds or mixtures of compounds to form a catalytic system that can be used in the polymerization of addition of polymerizable monomers, especially ethylenically unsaturated monomers.

 In yet another aspect of the invention, it relates to a process for the preparation of addition polymers, especially homopolymers and copolymers of olefins, diolefins, hindered aliphatic vinyl monomers and mixtures of the above monomers, and to the resulting polymers.

где R' в каждом случае представляет собой водород или метил или смежная пара R'-групп образует гидрокабонильное кольцо, соединяющееся в циклопентадиенильную часть;
Х представляет собой в каждом случае хлорид, метил, бензил или О-(N,N-диметиламино)бензил;
Y является -О-, -NR*- и -PR*-, где R* в каждом случае представляет собой водород или часть, выбранную из группы алкила, арила или их комбинаций, содержащих до 20 неводородных атомов;
М представляет собой титан, цирконий или гафний;
Z представляет собой Si(CH₃)₂, -Si(CH₃)₂Si(CH₃)₂-, -CH₂-СН₂- или -CH₂CH(CH₃)-;
n представляет собой целое число 1 или 2.In accordance with the invention proposed a metal coordination complex corresponding to the formula

where R 'in each case represents hydrogen or methyl, or an adjacent pair of R'-groups forms a hydrocarbonyl ring joined to the cyclopentadienyl moiety;
X is in each case chloride, methyl, benzyl or O- (N, N-dimethylamino) benzyl;
Y is —O—, —NR * - and —PR * -, where R * in each case is hydrogen or a part selected from the group of alkyl, aryl or combinations thereof containing up to 20 non-hydrogen atoms;
M represents titanium, zirconium or hafnium;
Z is Si (CH ₃ ) ₂ , —Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ -, —CH ₂ —CH ₂ -, or —CH ₂ CH (CH ₃ ) -;
n is an integer of 1 or 2.

Also proposed is a catalyst suitable for ion coordination polymerization containing the following components:
a) the metal coordination complex of the invention, preferably corresponding to formula I, and an activating cocatalyst selected from the group consisting of methylaluminoxane, aluminum alkyls and Lewis acids in a molar ratio complex cocatalyst (1 1) (1 10000).

Further, in accordance with the invention, a polymerization process is provided, comprising contacting one or more of the monomers polymerized by addition under addition polymerization conditions with a catalyst comprising:
a) a metal coordination complex of the invention, preferably corresponding to the formula, and an activating cocatalyst. The process is carried out at 80 160 ^o C and pressure from atmospheric to 3100 kPa.

Further, in accordance with the invention, there is provided a polymer comprising a polymerizable form of one or more of the addition-polymerisable monomers obtained by contacting a polymerisable-addition monomer or mixture of monomers under addition polymerization conditions with a catalyst containing:
a) a metal coordination complex, preferably corresponding to formula I, and an activating cocatalyst.

 In a further embodiment, EIPE polymers of high elasticity, interpolymers of ethylene and one or more of olefins other than ethylene are provided.

 In addition, pseudostatic polymers of alpha-olefin, in particular ethylene and a vinylidene aromatic monomer: a difficult aliphatic vinylidene monomer or mixtures thereof, are proposed.

 The complexes of the invention are conveniently used as cocatalysts for addition polymerization to produce polymers that are suitable as molded products, packaging films, foamed cushioning materials, and for the modification of synthetic and natural resins. These complexes can also be used as hydrogenation catalysts, cracking catalysts, and other industrial processes.

In FIG. 1 to 5 are computer models of complexes with the stressed structure of the invention, constructed on the basis of x-ray data of single crystals; in FIG. 6 and 7 are computer models of metal complexes calculated on the basis of X-ray diffraction analysis of single crystals, which are less stressed than the models of FIG. 15; in FIG. 8 13 calculated and observed distributions of styrene, ethylene, “reverse” styrene moieties in ethylene-styrene copolymers corresponding to pseudostatic inclusion in accordance with the invention; in FIG. 14 lack of correspondence between the calculated and observed distribution of styrene, ethylene and reverse styrene fragments in ethylene-styrene copolymers, if the rules of statistical inclusion are fully observed; in FIG. 15 typical rheological curves of EIPE resins according to the method of the invention. The viscosity of the complex η ^* and tan d are presented as a function of shear rate for the resin; in FIG. 16 is a typical curve of the modulus of elasticity versus melt index for the EIPE resins of the invention; in FIG. 17 typical rheological curves of a polyethylene resin obtained in the usual way. The viscosity of the complex η ^* and tan d are presented as a function of shear rate for the resin.

 An exemplary arrangement of complex atoms according to x-ray diffraction data for a single crystal is shown in FIG. 1 7.

In FIG. 1 shows the structure of / 4-methylphenylamido / dimethyl / -tetramethyl-η ⁵ -cyclopentadienyl / silantitane dichloride, determined from a crystal X-ray crystallography. The angle formed by the centroid of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), a titanium atom (T11) and a nitrogen atom N 14 is 105.7 ^o .

In FIG. 2 shows the structure of (tert.-butylamido) dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silanzirconium dimethyl, determined on the basis of x-ray crystallography of a single crystal. The angle formed by the centroid of the cyclopentadienyl ring (C2, C3, C3 *, C5 and C5 *), a zirconium atom (ZRI) and a nitrogen atom (N 9) is 102.0 ^° .

In FIG. Figure 3 shows the structure of (phenylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl) silantitane dichloride determined based on x-ray crystallography of a single crystal. The angle formed by the centroid of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), a titanium atom (T11) and a nitrogen atom (N 14) is 106.1 ^o .

In FIG. 4 shows the structure of (tert-butylamido / dimethyl-η ^5- cyclopentadienyl) silanzirconium dichloride, determined on the basis of x-ray crystallography of a single crystal. The structure suggests that this molecule crystallizes as a dimer with two bridging chlorides. The angle formed by the centroid of the cyclopentadienyl ring (C2, C3, C5 and C6), the zirconium atom (ZRI) and the nitrogen atom (N 10), or the angle formed by the centroid of the cyclopentadienyl ring (C102, C103, C104, C105 and C106), zirconium atom (ZR101) and a nitrogen atom (N 110), is 99.1 ^o .

In FIG. 5 shows the structure of (tert.-butylamido) dimethyl- / tetramethyl-η ⁵ -cyclopentadienyl / silanzirconium dichloride. The angle formed by the centroid of the cyclopentadienyl ring (C1, C2, C3, C4 and C5), zirconium atom (ZR) and nitrogen atom (N) is 102.0 ^o .

In FIG. Figure 6 shows the structure of (tert-butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl) silanzirconium dichloride, determined on the basis of single-crystal X-ray crystallography. The relatively long disilyl linking group of the amide ligand allows the nitrogen atom to be less stressed. The angle formed by the centroid of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), zirconium atom (ZRI) and nitrogen atom (N 17) is 118.0 ^o .

The activity of this catalyst in the polymerization of olefins is noticeably lower compared to the similar monosilane linking group in (tert.-butylamido / dimethyl-η ⁵ -cyclopentadienyl / silanzirconium dichloride (Fig. 5).

In FIG. Figure 7 shows the structure of (tert-butylamido / tetramethyl / tetramethyl-η ^5- cyclopentadienyl / disilantitane dichloride determined by single crystal X-ray crystallography. The relatively long disilyl linking group that connects the cyclopentadienyl ring to the nitrogen atom of the amide ligand provides a lower tension to the nitrogen atom. formed by the centroid of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and nitrogen atom (N 17) amounts to 120,5 ^o. Accordingly, the activity of catalysis ora polymerization of olefins in significantly lower compared to a similar group in the bridging monosilanovoy tert-butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silanetitanium.

 The term “activating cocatalyst” as used herein refers to a secondary component of a catalyst that is capable of increasing the efficiency of a metal-containing complex as an addition polymerization catalyst or, in another embodiment, balancing the ionic charge of a catalytically activated sample. Examples of the above activating cocatalysts for use in the invention include aluminum compounds including an Al — O bond such as alkylaluminoxanes, especially methylaluminoxane, aluminum alkyls, aluminum halides, aluminum alkyl halides, Lewis acids, ammonium salts, non-competing oxidizing agents such as silver salts, iron ions, etc., as well as mixtures of the above compounds.

где R означает каждый встречающийся C_1-10 алкил или аралкил;
Х" является галоидом;
n равно 1, 2 или 3.Additional suitable activating cocatalysts include compounds of the formula

where R is each occurring C _1-10 alkyl or aralkyl;
X "is a halogen;
n is 1, 2 or 3.

 Most preferred are cocatalysts such as trialkyl aluminum compounds, in particular triethyl aluminum.

“Addition polymerization monomers” include, for example, ethylenically unsaturated monomers, acetylene compounds, conjugated or non-conjugated dienes, polyenes, carbon monoxide, etc. Preferred monomers include C _2-10 alpha olefins, especially ethylene, propylene, isobutylene, 1-butene , 1-hexene, 4-methyl-1-pentene and 1-octene. Other preferred monomers include styrene, halo- and alkyl-substituted styrene, vinyl chloride, acrylonitrile, methyl acrylate, temlmethacrylate, tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinylbenzenecyclobutane and 1,4-hexadiene.

By the term “hindered aliphatic vinylidene compounds” is meant adduct polymerizable vinylidene monomers according to the formula
CG ₂ G'R ",
where R "is a bulky aliphatic substituent containing up to 20 carbon atoms;
G independently in each case is hydrogen or methyl;
G 'in each case is independently hydrogen or methyl, or another embodiment;
G 'and R "together form a cyclic system.

 By the term “sterically bulky” is meant that a monomer with a substituent which is usually not capable of participating in the addition polymerization with conventional Ziegler-Natta polymerization catalysts at a rate comparable to that of ethylene polymerization. Preferred sterically hindered aliphatic vinylidene compounds are monomers in which one of the carbon atoms containing ethylene unsaturation is three or four-substituted. Examples of such substituents include cyclic aliphatic groups such as cyclohexanes, cyclohexenes, cyclooctenes or cyclic alkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl, etc. The most preferred hindered aliphatic vinylidene compounds are various isomeric vinyl cyclic substituted and cyclic substituted derivatives cyclohexenes and 5-ethylidene-2-norbornenes. Most suitable are 1-, 3- and 4-vinylcyclohexenes.

By the term "hindered vinylidene compounds" is meant polymerized by the addition of vinylidene monomers corresponding to the formula:
CG ₂ CG'R '",
where R '"is either R" or an aryl substituent containing up to 20 carbon atoms;
G and G 'have the previously indicated meanings.

Thus, for example, in addition to hindered aliphatic vinylidene compounds, hindered vinylidene compounds also include vinylidene aromatic monomers. By the term "vinylidene aromatic monomers" is meant involved in the polymerization of the addition corresponding to the formula
CG C (G) Ph,
where G independently in each case is hydrogen or methyl;
Ph is phenyl, or a halo or C _1-4 alkyl substituted phenyl group.

 Preferred vinylidene aromatic monomers are those corresponding to the above formula, wherein G in each case is hydrogen. The most preferred vinylidene aromatic monomer is styrene.

By the term "alpha olefin" is meant ethylene and C _3-10 olefins containing ethylene unsaturation in the alpha position. Preferred alpha olefins are ethylene, propylene, butene, styrene, 4-methyl-1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinylbenzocyclobutane.

Preferred complexes are those that contain delocalized η ⁵ linked groups, which are cyclopentadienyl or substituted cyclopentadienyl groups that form cyclic structures with metal atoms. Preferred fragments with a delocalized n-bond are the groups of cyclo-pentadienyl, indenyl and fluorenyl, as well as their saturated derivatives, which form a cyclic structure with a metal atom. Each carbon atom in the cyclopentadienyl radical may be substituted or unsubstituted, and the substituents may be the same or different and selected from the group consisting of hydrocarbon radicals, substituted hydrocarbon radicals, substituted hydrocarbon radicals in which one or more of the hydrogen atoms is replaced by a halogen atom, hydrocarbon substituted metalloid radicals in which the metalloid is selected from group 14 of the Periodic table of the elements, and halide radicals. In addition, two or more of these substituents may together form a fused ring system. Suitable hydrocarbon and substituted hydrocarbon radicals which may be substituted by at least one hydrogen atom in the cyclopentadienyl radical may contain 1 to 20 carbon atoms and include branched and unbranched alkyl radicals, cyclic hydrocarbon radicals, alkyl substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl substituted aromatic radicals. Suitable organometallic radicals include mono-, di- and tri-substituted organometallic radicals of group 14 elements, where each hydrocarbon group contains 1 to 20 carbon atoms. More specifically, suitable organometallic radicals include trimethylsilyl, pentadimethylsilyl, methyldephenylsilyl, triphenylsilyl, triphenylgermyl, trimethylgermyl, and the like.

 In the previously disclosed formula, I X represents chloride, methyl, benzyl, or O (N, N-dimethylamino) benzyl.

где R' в каждом случае является водородом или метилом, или сложную пару R'-группа образует гидрокарбонильное кольцо, соединяющееся в циклопентадиенильной части;
Y является -O-, -NR*-, -PR*-;
M представляет собой титан, цирконий или гафний;
Z является Si(CH₃)₂, -Si(CH₃)₂Si(CH₃)₂-, -CH₂-CH₂- или -CH₂CH(CH₃)-; R* в каждом случае является водородом или фрагментом, выбранным из группы, состоящей из алкила, арила, силила, галоидированного алкила, галоидированного арила и их сочетаний (например, аралкил, алкарил, галоидалкарил и галоидаралкил), содержащих вплоть до 20 неводородных атомов.The most preferred metal coordination complexes correspond to the formula

where R 'in each case is hydrogen or methyl, or a complex pair of the R'-group forms a hydrocarbonyl ring, connecting in the cyclopentadienyl part;
Y is -O-, -NR * -, -PR * -;
M represents titanium, zirconium or hafnium;
Z is Si (CH ₃ ) ₂ , —Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ -, —CH ₂ —CH ₂ - or —CH ₂ CH (CH ₃ ) -; R * in each case is hydrogen or a fragment selected from the group consisting of alkyl, aryl, silyl, halogenated alkyl, halogenated aryl and combinations thereof (e.g., aralkyl, alkaryl, haloalkaryl and haloalkyl) containing up to 20 non-hydrogen atoms.

 It should be noted that since formula I and the following formulas indicate a cyclic structure for the catalyst, it is more correct to call the bond between M and Y the coordinate-covalent bond. It should also be noted that the complex can exist in the form of a dimer or higher oligomers.

Further, it is preferable that at least one of R ', Z or R * be an electron-donating fragment. Thus, it is particularly preferred that Y be a nitrogen or phosphorus group corresponding to the formula —N (R ″ ″) - or —P (R ″ ″) -, where R ″ is C _1-10 alkyl or aryl, i.e. an amido - or a phosphido group.

где М является титаном, цирконием или гафнием, связанными по типу η⁵ с циклопентадиенильной группой;
R' каждый являются водородом или метилом, или соседняя пара R' групп образует углеводородное кольцо, конденсированное с циклопентадиенильным фрагментом;
Е является кремнием или углеродом;
Х принимает значения, указанные выше;
m равно 1 или 2;
n равно 1 или 2 в зависимости от валентности М.The most preferred complex compounds are amidosilane or amidoalkanediyl compounds of the formula

where M is titanium, zirconium or hafnium, connected by type η ⁵ with a cyclopentadienyl group;
R 'each is hydrogen or methyl, or an adjacent pair of R' groups forms a hydrocarbon ring fused to a cyclopentadienyl moiety;
E is silicon or carbon;
X takes the meanings indicated above;
m is 1 or 2;
n is 1 or 2 depending on the valency of M.

Examples of the above most preferred metal coordination complexes include compounds in which the R 'at the amide group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl, etc. the cyclopentadienyl group is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc. R 'in the above cyclopentadienyl groups is each time hydrogen, methyl, and X is chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl, etc. Specific compounds include: (tert.-Butylamido // tetramethyl-η ⁵ -cyclopentadienyl / -1,2-ethanediylzirconium dichloride, (tert.-Butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyl titanedichloride, (methylamido) (tetramethyl-η ^5- cyclopentadienyl / -1,2-ethanediyl zirconium dichloride, (methylamido // tetramethyl-η ⁵ -cyclopentadienyl / -1,2-ethanediyl titanedichloride, (ethylamido // tetramethyl-η ^5- cyclopentadienyl / -methylene-tert-butylamide / tetramethyl-η ⁵ -cyclopentadienyl / silanetitanium dichloride, (tert. -butilamido) (dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / B antsirkoniydibenzil, (benzylamide / dimethyl / tetramethyl-η ⁵ -tsiklopentadientil / silanetitanium (fenilfosfido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantsirkoniydibenzil and t. d.

 Suitable catalysts for use in the polymerization process of the invention are prepared by combining the metal coordination compound and the activating cocatalyst in any order and by any suitable method. Preferably, the ratio of the coordination complex to the cocatalyst is (1 1) (1 10000) (based on mole). It should, of course, be borne in mind that the catalyst system can also be obtained in situ if its components are added directly during the polymerization and a suitable solvent or diluent, including a condensed monomer, is used in the polymerization process. Suitable solvents include toluene, ethylbenzene, alkanes, and mixtures thereof. In some cases, the catalysts can be isolated from the solution and stored in an inert atmosphere until use. The components of the catalyst are sensitive to both moisture and oxygen, and it is necessary to work with them and transfer them in such an inert atmosphere as nitrogen, argon or helium, or in vacuum.

The polymerization is usually carried out by known methods for the Ziegler-Natta or Kaminsky-Sinn polymerization types. That is, the monomer (s) and the catalyst are reacted at a temperature of 80-160 ^° C. from atmospheric pressure to 3100 kPa. The polymerization is carried out in an inert atmosphere, which may be a gas such as nitrogen, argon, hydrogen, ethylene, etc., or in vacuum. Additionally, hydrogen can be used to control molecular weight due to chain termination, as is known to those skilled in the art. The catalyst can be used either as it is or on a suitable support, such as alumina, MgCl ₂ or silica, to produce a heterogeneous supported catalyst. If desired, a solvent may be used. Suitable solvents include toluene, ethylbenzene and an excess of vinylidene aromatic or olefin monomer. The reaction can also be carried out in solution or in suspension using perfluorinated hydrocarbons or a similar liquid in the gas phase, i.e. using a fluidized bed reactor, or in the solid phase (powder polymerization). A catalytically effective amount of the catalyst and cocatalyst in question are any amounts that result in successful polymer production. Such amounts can be easily determined in conventional experiments known to those skilled in the art. Preferred amounts of catalyst and cocatalyst are sufficient to provide an equivalent ratio of addition-polymerized monomer catalyst from about 1 x 10 ¹⁰ 1 to 100 1, preferably (1 x 10 ⁸ 1) (500 1), more preferably (1 x 10 ⁶ 1) (1000 1). The cocatalyst is usually used in an amount providing an equivalent ratio of the cocatalyst catalyst (10000 1) (1 1), and preferably (1000 1) (1 1).

 It should be borne in mind that the metal complex can undergo various transformations or form intermediate products before or during the polymerization process. So, it is possible to imagine other precursors to achieve the same catalytic samples that are presented here, without going beyond the scope of the invention.

 The resulting polymer product is isolated by filtration or other known methods. Additives and adjuvants may be included in the polymers of the invention to provide the desired characteristics. Suitable additives include pigments, UV stabilizers, antioxidants, blowing agents, lubricants, plasticizers, photosensitizers and mixtures thereof.

 In the preparation of copolymers containing vinylidene aromatic or hindered aliphatic vinyl monomers, it is desirable to use a comonomer, i.e. an alpha olefin, which is not partially sterically hindered. Without pretending to any specific theory, it can be assumed that this is due to the fact that the active site will be blocked when the hindered vinyl compound is turned on, which will make it unlikely that another hindered vinyl compound will be included in the polymerization as the next monomer in the sequence. After the inclusion of one or more of the olefins other than the hindered vinyl compound, the active site once again becomes available to include the hindered vinyl monomer, but in a limited amount. A vinylidene aromatic monomer or a sterically hindered vinyl monomer can be incorporated into the polymer chain in the reverse order, that is, in such a way that two methylene groups exist between the substituted polymer fragments of the polymer chain.

Preferred are such polymers, mol. m of which would be more than 13,000, more preferably more than 20,000 and most preferably more than 30,000. It is also preferable that such polymers have a melt index I ₂ ASTM D-1238 procedure A, conditions E, less than 125, more preferably 0.01 100 and most preferably 0.1 to 10.

 Due to the use of the previously mentioned catalytic systems containing a coordination complex with a stressed structure, it is possible to obtain copolymers that include relatively bulky or hindered monomers in a practically statistical manner at low concentrations, and at high concentrations in accordance with the logic of ordered inclusion. The copolymers of alpha-olefins, especially ethylene and hindered aliphatic vinylidene compounds or vinylidene aromatic monomers, can be further described as “pseudo-statistical”, i.e. there will be no well-defined blocks of any monomer in the copolymers, however, the corresponding monomers are limited by certain inclusion rules.

These rules were derived from some experimental details resulting from polymer analysis. These polymers were investigated by ¹³ C NMR spectroscopy at 130 ^° C on a Varian-VXR-300 spectrometer at 75.4 MHz. Samples of 200 250 mg polymer were dissolved in 15 ml of hot orthodichlorobenzene (1,1,2,2-tetrachloroethane-d ₂ ) of approximately 70/30 volume / volume, which was approximately 0.05 M in chromium (III) Tris / acetylacetonate, and part of the resulting solution was introduced into a 10 mm NMR ampoule. The shooting conditions were as follows: spectral width of 16500 Hz, accumulation time of 0.090 s, pulse width of 36 ^o , delay of 1.0 s, and during the delay, the decapler is disabled, size FT 32K, number of scans over 30,000, broadening 3 Hz. As a reference, tetrachloroethane-d ₂ (d / 73.77 million dollars in the TMS scale).

где j, k и l≥1.So, without being bound by any particular theory, we can say that the results of the above procedure indicate that a specific distinguishing feature of pseudostatic copolymers is the fact that all phenyl or bulky hindered groups substituted on the polymer chain are separated by two or more methylene in groups. In other words, polymers containing the hindered monomers of the invention can be described by the following general formula (using styrene as an illustration of the hindered monomer):

where j, k and l≥1.

Во время реакции полимеризации этилен может быть включен в любое время. После включения затрудненного мономера "хвост к хвосту", следующий мономер должен быть этиленом, так как включение другого затрудненного мономера в этом месте приведет к сближению затрудненных заместителей ближе, чем их минимальное разделение как было описано ранее.Explaining further the above experimental and theoretical results and without being bound by any particular theory, it can be assumed that during the polymerization of the addition using the proposed catalysts, if the hindered monomer is included in the growing polymer chain, the next included monomer should be ethylene or hindered monomer, which included in reverse order or tail to tail. This is further illustrated for the hindered vinyl monomer, where M is the metal center of the catalyst, HG is the hindered group, and P is a growing polymer chain:

During the polymerization reaction, ethylene can be included at any time. After turning on the tail-to-tail hindered monomer, the next monomer should be ethylene, since the inclusion of another hindered monomer at this location will bring the hindered substituents closer together than their minimum separation as described previously.

 A consequence of these polymerization rules is that the catalyst of the invention does not homopolymerize styrene to any significant degree, while a mixture of ethylene and styrene polymerizes quickly and the styrene content may be high (up to 50 mol. Styrene) in the copolymers.

As a further illustration of the description of the alpha-olefin / hindered monomer copolymer of the invention, a computer model of the polymerization reaction was used to calculate the expected ¹³ C NMR spectrum of the polymer product. The computer program used a random number generator to select the inclusion of either an alpha olefin or a hindered monomer in the growing polymer chain, then calculated the number of ¹³ C signals for each type resulting from this inclusion. The polymers were calculated by repeating this process for 10,000 or more monomeric inclusions, and the calculated data for the ¹³ C NMR spectrum were compared with the actual experimental ¹³ C NMR spectrum for the pseudo-statistical ethylene-styrene copolymers of the present invention.

Computer simulation of the polymer and the obtained ¹³ C NMR spectra of the calculated pseudo-statistical ethylene styrene copolymers were carried out using the assumption that if the styrene monomer is included in the growing polymer chain, the next included monomer must be ethylene or styrene, which is included in the reverse order or tail-to-tail. The optimal agreement between the experimental and calculated spectra was observed for the case where approximately 15 styrene inclusions were obtained by the tail-to-tail method. The observed and calculated ¹³ C NMR spectra for such pseudo-statistical ethylene-styrene copolymers containing 1.4, 4.8, 9.0, 13, 37 and 47 mol. styrene shown in FIG. 8 13. In each case, the spectra observed in the calculation are in good agreement.

Then a computer simulation of the polymer and the corresponding ¹³ C NMR spectrum was carried out for fully statistical alpha-olefin / hindered monomer copolymers without using the assumptions about the inclusion of the hindered monomer. In other words, the hindered monomer was included in the growing polymer chain after the previous inclusion of the hindered monomer, if the random number generator chose the hindered monomer as the next monomer to be included. The calculated spectra for such completely statistical copolymers do not agree with the observed ¹³ C NMR spectra, as can be seen in FIG. 14 for 37 mol. styrene in an ethylene / styrene copolymer.

 Before polymerization according to the method of the invention, the monomers and solvents, if used, can be purified by vacuum distillation or by using molecular sieves, silica or alumina to remove impurities. In addition, compounds such as trialkyl aluminum compounds, alkali metals, metal alloys, especially Na / K, can be used to remove impurities.

Suitable vinylidene aromatic monomers that can be used in accordance with the method of the invention include styrene, as well as alpha-methylstyrene, C _1-4 alkyl, phenyl, cyclic substituted styrene derivatives such as ortho-, meta- and para-methylstyrene or mixtures thereof , cyclic halogenated styrenes, vinylbenzenecyclobutane and divinylbenzene. Styrene is the preferred vinylidene aromatic monomer.

When polymerizing vinylidene aromatic monomers or hindered aliphatic vinylidene compounds and olefins, the monomers are preferably combined in such a proportion as to achieve a vinylidene aromatic monomer (or hindered aliphatic vinylidene compound) content of at least 1.0 mol. in the obtained polymer, more preferably from 1.5 to less than 50 mol. and most preferably from 1.5 to less than 50 mol. and most preferably from 5.0 to 48 mol. and most preferably from more than 8.0 up to 47 mol. Preferred operating conditions for such a polymerization reaction are atmospheric to 1000 atm pressure. and temperatures of 30,200 ^° C. Polymers obtained at temperatures above the autopolymerization temperature of the respective monomers may contain small amounts of homopolymer products resulting from free radical polymerization.

Some polymers obtained by the method of the invention, especially copolymers of ethylene and alpha-olefins other than ethylene, are characterized by unique rheological properties. In particular, it was found that polymers (hereinafter referred to as elastic polyethylenes or EIPE) are less Newtonian than the linear polyethylene resins with a similar olefin content that are conventionally prepared. These polymers also have higher elastic moduli, especially at high melt indices compared to those for conventional polymers. This property makes the resin particularly useful in producing films of foamed materials and woven products, for example, obtained by blow molding. The above phenomenon is more specifically defined with reference to FIG. 15, where the viscosity of the η ^* complex, measured in poises at 190 ^° C., is plotted as a function of shear rate w measured in radians per second for typical EIPE ethylene and 1-octene copolymers according to the method of the invention. The slope of this curve indicates that the melt is highly Newtonian. The actual values of η ^* and ω used on the graph are presented in table. one.

 In FIG. 15 such values of tan δ are postponed for the same EIPE polymer. This value is dimensionless and is calculated by dividing the viscosity modulus by the elastic modulus. The actual values of tan δ and w used on the graph are presented in table. 2.

 For improved performance in blow molding applications, it is preferred that tan δ is from 0.1 to 3.0 for shear rates between 0.01-100 rad / s.

The following property of EIPE polymers is illustrated in Fig. 16: modulus of elasticity in dyne / cm ² , G, at 0.1 rad / s and 190 ^o C for several ethylene / -1-octene EIPE resins are constructed as a function of melt index. Resins used include those of Examples 11, 12, 14 16, 18 22, 24-26, 30 and 31.

 The values of the melt indices and elastic moduli used in the construction of the graph are given in the following table. 3.

Typical characteristics η ^* for a polyethylene resin obtained in the usual way are shown for comparison in FIG. 17.

It is easy to see that EIPE resins have higher modulus of elasticity in the melt. In particular, EIPE resins have a melt index (I ₂ ), ASTM D-1238 procedure A, conditions E, less than 200, preferably less than 125, and more preferably less than 50, and an elastic modulus of more than 1000 dyne / cm ² , more preferably more than 2000 dyne / cm ² . All of the above rheological measurements were carried out according to standard procedures described by HA Barnes et al. Introduction to Rheology, Elsevior publishing, Inc. 1989.

Densities are usually in the range of 0.85 to 0.97 g / ml, preferably 0.89 to 0.97 g / ml. Molecular weight distribution (Mv / Mch) more than 2.0, preferably 3.0 to 10.0. Typically, melting points are in the range of 50 135 ^o C.

Preferred polymers further demonstrate the properties of homogeneous polymers as described in US Pat. No. 3,645,992, i.e., ethylene copolymers have a substantially statistical distribution within a given molecule and substantially the same ethylene / copolymer ratio between molecules. Polymers obtained at elevated temperatures, especially at temperatures exceeding 130 ^° C., can produce a heterogeneous melt curve. Further, the polymers of the invention are distinguished by better optical properties, especially low haze in contrast to conventional ethylene polymers, which makes them particularly suitable for the manufacture of films and injection molded products.

 In addition, these polymers containing olefin and vinylidene aromatic monomer, especially ethylene and styrene, were surprisingly found to have the properties of elastomers. So, such polymers are surprisingly suitable for use as thermoplastic elastomers, such as impact resistant modifications of thermoplastic and thermoset polymers, including bitumen, adhesives, elastomeric products, etc.

 The polymers of the invention can be modified by conventional grafting, crosslinking, hydrogenation, functional groups or other reactions well known in the art. With particular regard to polymers containing vinylidene aromatic compounds, vinylcyclohexane and / or 1,4-hexadiene functional groups, they can be easily sulfonated or chlorinated to obtain functional derivatives obtained by standard procedures. In addition, polymers based on vinylcyclohexane are easily crosslinked by the interaction of unsaturated functional groups of the cycle.

 The polymers of the invention, regardless of whether they are modified or not, can be mixed with synthetic or natural polymers to obtain mixtures with the desired properties. In particular, polyethylene, ethylene / alpha-olefin copolymers, polypropylene, polystyrene, styrene / acrylonitrile copolymers (including resins modified by their derivatives), syndiotactic polystyrene, polycarbonate, polyamide, aromatic polyester, polyisocyanate, polyurethane, polyacrylonitrile polyethylene, silicone and mixed with the polymer compositions of the invention. The polymer modifier uses 0.1 to 99.0, preferably 0.5 to 50 wt.

 In the most preferred embodiment of the invention, polymers containing ethylene and styrene are elastomeric according to the definition of elastomeric substances in ASTM Special Technical Bulletin No. 184, as a substance that can be stretched to a double length at room temperature and it will return to its original length upon release.

 In addition to modifying synthetic thermoplastics, these polymers can also be used as modifiers for asphalt or bitumen compositions. Thus, it is desirable to use styrene / ethylene polymers.

The term "bitumen" usually defines mixtures of hydrocarbons of natural or pyrogenic origin or a combination of both of them, often accompanied by their non-metallic derivatives, which may be gaseous, liquid, semi-solid or solid and which are usually soluble in carbon disulfide. For the purposes of the invention, bitumen may be used in liquid, semi-liquid or solid form. From a commercial point of view, bitumen is usually divided into asphalts, peaks and tar. The list of various bituminous materials that can be used in the invention include the following:
1. Asphalts.

 I. Oil asphalts.

 A. Directly restored asphalts.

 1. Recovery in air or under reduced pressure.

 2. Precipitation by solvent, for example propane.

 B. Thermal asphalts as residues from cracking of petroleum feed.

 C. Oxidized asphalts.

 1. Direct oxidation.

 2. "Catalytic" oxidation.

2. Natural asphalts:
A. With a mineral content below 5
1. Asphalts, such as gilsonite, graphite and pure asphalt.

 2. Bermuda and other natural deposits.

B. With a mineral content above 5
1. Natural asphalts.

 2. Trinidad and other natural deposits.

 II. Tar and derivatives.

 1. The remains of coal tar processing.

 A. Coal tar, restored to the "float" degree of purity, as road tar for asphalting.

 B. Pitches from coal tar, restored to the point of softening.

 2. Residues from other pyrogenic distillates, for example, from wood, peat, bone, shale, tar and fatty acids tar.

As it is easy to understand for specialists, the weight average molecular weight of various bitumens can vary over a wide range, for example 500 to 10000. In addition, the softening points of various types of asphalts also vary 10 - 205 ^o C.

 Of all the types of asphalts that can be used, oil and natural are preferred. Of petroleum, thermal asphalts are preferred.

 The amount of bitumen used in the compositions of the invention is preferably in the range of 65 to 99 wt. hours and preferred amounts are in the range of 80 to 98 wt. h

 Describing the invention using the following examples, they are offered as an additional illustration and should not be construed as limiting. If there are no conflicting indications, parts and percentages are given by weight.

Example 1. Obtaining (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclo-pentadienyl) silanzirconium dichloride.

To 0.443 g (1.90 mmol) of ZrCl ₄ , 8 ml of diethyl ether was added to the flask, followed by 15 ml of tetrahydrofuran (THF). A solution of 0.500 g (1.90 mmol) of dilithium (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silane in 15 ml of THF is slowly added to the resulting suspension. The resulting yellow solution is stirred for several days. The solvent was removed to give an adhesive residue, which was extracted with a mixture of 5 1 (v / v) ethyl pentane and filtered off from a white precipitate. The solvent was removed from the yellow filtrate to give a light yellow powder. Recrystallization from pentane ether (5 1) gave the product (C ₅ Me ₄ (Me ₂ Si-N-tert-Bu) ZrCl ₂ ) as a crystalline, almost white substance. Yield 0.2207 g (28.2). The product is identified by ¹³ C and ¹ H NMR spectra.

 Polymerization.

A. Five ml of a 1.009 M solution of methylaluminoxane (MAO) in toluene is added to a reactor containing 25 ml of 5-methyl-1-pentane. A catalytic solution is prepared by adding 500 ml of a 0.01172 M solution of C ₅ Me ₄ (Me ₂ Si-N-tert-Bu) ZrCl ₂ in toluene to 2 ml of toluene in a second reactor. Both reactors are sealed and transferred from a glove box to a stainless steel autoclave. The autoclave is pumped out and purged with argon.

A solution of 4-methyl-1-pentene / toluene / MAO was added to the autoclave and heated to 89 ^° C. under an ethylene pressure of 620 kPa (6.88 kg / cm ² ) with stirring. After adding a catalytic solution to the 4-methyl-1-pentene / MAO / ethylene mixture, the ethylene pressure was increased to 1240 1275 kPa (12.66 13.00 kg / cm ² ). After 2 hours, the solution was cooled to 30 ^° C. and opened to atmosphere. The polymer yield after drying under reduced pressure at 100 ^° C. overnight gives 10.0 g.

¹³ C NMR analysis of the polymer shows that a random copolymer of ethylene with 4-methyl-1-pentene is obtained.

 B. Polymerization.

Polymerization A is generally repeated, except that instead of 4-methyl-1-pentene, 50 ml of 1-hexene is used and the concentration of the catalyst in toluene is 0.01012 M. The catalyst solution is added to a mixture of 1-heesene (MAO) ethylene and pressure ethylene is increased to 1240 1275 kPa (12.66 13.00 kg / cm ² ). After adding a catalytic solution, the temperature of the reaction mixture rises to 139 ^o C. After 30 minutes the solution is cooled to 100 ^o C. Heating and blowing of ethylene is stopped and the solution is cooled and opened to atmosphere. The polymer yield after drying under reduced pressure at 100 ^° C. overnight is 36.8 g. ¹³ C NMR analysis of the polymer indicates that the product is a statistical copolymer of ethylene with 1-hexene (8 per mole).

 B. Polymerization.

Polymerization A is generally repeated except that 213 μl of a catalytic solution (0.01172 M in toluene) and 143 mg of solid MAO are used. Olefin is not added. When a metal solution is added to the reactor, the temperature rises to 109 ^o C due to the exothermicity of the polymerization reaction. The reaction is stopped after an hour by cooling and opening the reactor to the atmosphere. The yield of polyethylene after drying under reduced pressure at 100 ^° C. overnight was 11.0 g.

G. 130 ml of toluene is placed in an autoclave used in polymerization A, then 100 g of propylene are added. A solution of 0.828 g of MAO in toluene (8 ml) is added, followed by 2130 μm of catalytic solution. The mixture is reacted for 3.0 hours at 8 ^° C. The reaction is quenched with acidified methanol to give 0.38 g of a white adhesive.

¹³ C NMR analysis indicates that it is atactic polypropylene.

Example 2. Obtaining (tert-butylamido) dimethyl (tetramethyl-η ^5- cyclopentadienyl) - silantitanedichloride.

 (a) (Chlorine) (dimethyl) tetramethylcyclopentadi-2,4-enyl) silane.

To a solution of 21.5 g (167 mmol) of dimethyldichlorosilane in 150 ml of THF cooled to -40 ^° C, a solution of 8.00 g (55.6 mmol) of 1,2,3,4-tetramethylcyclopentadienide sodium in 80 ml of THF is slowly added . The reaction mixture was allowed to warm to room temperature and was stirred overnight. The solvent was removed, the precipitate was extracted with pentane and filtered. Pentane was removed under reduced pressure to give the product as a pale yellow oil.

 Yield 10.50 g (88.0).

¹ H NMR (C ₆ D ₆ ) d 2.89 (s, 1H), 1.91 (s, 6H), 1.71 (s, 6H), 0.14 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 137.8; 131.5; 56.6; 14.6; 11.4; 0.81.

 (b) (tert-butylamino) (dimethyl) tetramethylcyclopentadi-2,4-enyl) silane.

 A solution of 11.07 g (151 mmol) of tert-butylamine in 20 ml of THF is added over 5 minutes to a solution of 13.00 g (60.5 mmol) of (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 300 ml of THF. A precipitate forms immediately. The suspension is stirred for 3 days, then the solvent is removed, the residue is extracted with pentane and filtered. Pentane was removed under reduced pressure to give the product as a pale yellow oil.

 Yield 14.8 g (97.2).

MS: 251, ¹ H NMR (C ₆ D ₆ ) d 2.76 (s, 1H), 2.01 (s, 6H), 1.84 (s, 6H), 1.09 (s, 9H), 0.10 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d / 135.4; 133.2; 57.0; 49.3; 33.8; 15.0; 11.2; 1.3.

 (c) Dilithium (tert-butylamido) (dimethyl) -tetramethylcyclopentadienyl) silane.

To a solution of 3.00 g (11.98 mmol) (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 100 ml of ether, 9.21 ml of 2.6 M (23.95 mmol) of butyl lithium mixed with C ₆ aliphatic solvents are slowly added . A white precipitate formed and the reaction mixture was stirred overnight, then filtered. The solid residue is washed several times with ether, then dried under reduced pressure to give the product as a white powder.

 Yield 3.134 g (99.8).

(g) (tert-butylamido) (dimethyl) (tetramethyl-η ⁵ -cyclopentadienyl) -silantitane dichloride.

0.721 g (3.80 mmol) of TiCl _{4 was} added to 30 ml of frozen THF (-196 ^° C). The mixture was allowed to warm to -78 ^o C (bath of dry ice). A solution of 1.00 g (3.80 mmol) of dilithium (tert-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silane in 30 ml of THF is slowly added to the resulting yellow solution. The solution was allowed to warm to room temperature with stirring overnight. The solvent is removed from the resulting very dark solution. The residue was extracted with pentane and filtered. Cooling in the refrigerator causes the separation of a very soluble dark red-brown substance and light yellow-green crystalline. The solid is filtered and recrystallized from pentane to give an olive green product.

 Yield 0.143 g (10.2).

¹ H NMR (C ₆ D ₆ ) d 2.00 (s, 6H), 1.99 (s, 6H), 1.42 (s, 9H), 0.43 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 140.6, 137.9, 104.0, 62.1, 32.7, 16.1, 13.0, 5.4.

 Getting 2.

In a dry chamber, 4.00 ml of a 2 M solution of isopropyl magnesium chloride in diethyl ether is introduced into a 100 ml flask with a syringe. The ether is removed under reduced pressure, leaving a colorless oil. Add 20 ml of a mixture of 4 1 (by volume) THF toluene, then 0.97 g of (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane. The solution was heated under reflux. After 8-10 hours, a white precipitate begins to form. After heating under reflux for 27 hours, the solution was cooled and the volatiles removed under reduced pressure. The white solid was washed with pentane and filtered to give a white powder (1.23 g, yield 62) Me ₄ C ₅ SiMeN-t-BuMg ₂ Cl ₂ (THF) ₂ .

0.50 g of TiCl ₃ (THF) ₃ in 10 ml of THF are suspended in a dry chamber. 0.69 g of solid Me ₄ C ₅ SiN-t-BuMg ₂ Cl ₂ (THF) _{2 was} added, resulting in a color change from pale blue to dark purple. After 15 minutes, 0.35 g of AgCl was added to the solution. The color immediately begins to brighten to light green-yellow. After 1 1/2 hours, THF was removed under reduced pressure to give a yellow-green solid. Toluene (20 ml) was added, the solution was filtered, and toluene was removed under reduced pressure to obtain a yellow-green fine crystalline precipitate, 0.51 g (quantitative yield). The product (tert-butylamido) (dimethyl) (tetramethyl-η ⁵ -cyclopentadienyl) silantitane dichloride was identified by a ¹ H NMR spectrum (C ₆ D ₆ ): d 1,992 (s), 1,986 (s), 1,414 (s), 0,414 (s )

 Getting 3.

TiCl ₄ 0.72 g (3.80 mmol) was added to 35 ml of frozen THF (-196 ^° C) in a flask. The mixture was heated to -78 ^° C. A solution of 1.0 g (3.80 mmol) of dilithium (tert-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silane in THF was slowly added. The resulting yellow solution was warmed to room temperature and stirred overnight. The solvent was removed to give a dark residue, which was extracted with pentane and filtered. The product (C ₅ Me ₄ (Me ₂ SiN-t-Bu) TiCl ₂ ) was obtained as a dark green-yellow crystalline substance after double recrystallization from pentane at (-35) (-40) ^o C. The product was identified by ¹³ C spectra. and ¹ H NMR.

 Getting 4.

TiCl ₃ (THF) ₃ (2.0 g, 5.40 mmol) is suspended in 40 ml of THF in a dry chamber. Dilithium (tert-butylamido) (dimethyl) -tetramethylcyclopentadienyl) silane (1.42 g, 5.39 mmol) is then added, as a result of which the color immediately darkens to dark blue. After 1 1/2 hours stirring, AgCl (0.84 g, 5.86 mmol) was added. The color immediately begins to brighten to red-orange. After 1 1/2 hours stirring, THF was removed under reduced pressure. Diethyl ether (50 ml) was added, the solution was filtered and the volatiles removed under reduced pressure. The yield of (tert-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silantitane dichloride 1.91 g.

¹ H NMR (C ₆ D ₆ ) d 1.992 (s), 1.987 (s), 1.415 (s), 0.415 (s).

 Polymerization.

The styrene / ethylene mixture was polymerized by combining 1.65 ml of a 10 solution of MAO in toluene with a solution of 45 ml of toluene and 50 ml of styrene in a stainless steel reactor. 250 ml of a 0.010 M solution of (tert-butylamido) dimethyl (tetramethyl-η ^5- cyclopentadienyl) silantitane dichloride are added to 2.5 ml of toluene in a second reactor. Both reactors are clogged, transferred from a glove box to a 600 ml stainless steel autoclave. The autoclave is pumped out and purged with argon. The styrene (toluene) MAO solution is added to the autoclave and heated to 89 ^° C. under an ethylene pressure of 620 kPa (6.33 kg / cm ² ) with stirring. At the same time, a catalytic solution is added and the pressure is increased to 1275 kPa (13.00 kg / cm ² ), the pressure is regulated within 1240 1275 kPa (12.66 13.00 kg / cm ² ). The temperature rises in the exothermic reaction to 95 ^o C. The temperature is reduced to 90 ^o C and regulated within 90 to 92 ^o C until the end of the reaction. After 1 h, ethylene supply was stopped. The reaction mixture was opened to atmosphere and cooled to 30 ^° C. while methanol was added. The product was collected, washed with methanol and the remaining solvent was removed under reduced pressure at 120 ^° C. The result was 9.02 g of material. ¹³ C NMR analysis shows that the product is a statistical copolymer of styrene (15.2 per mol) and ethylene, three peaks are attributed to polystyrene.

 Example 3 (polymerization of olefins).

Ethylene is polymerized by combining 5 ml of a 1 M solution of triethylaluminum in a mixture of C ₆ aliphatic solvents and 0.5 ml of a 0.01 M solution of (tert-butylamido) dimethyl (tetramethyl-η ⁵ - cyclopentadienyl) silantitane dichloride in toluene in a stainless steel reactor (HC ) A solution of a titanium catalyst and triethylaluminum cocatalyst is added under pressure in a 3 L HC autoclave containing 2 L of a mixture of aliphatic solvents (Isopar E, obtained from Exxon Chemicals, Inc.) under a pressure of 3100 kPa (31.64 kg / cm) created by ethylene at a temperature 150 ^° C. The reaction temperature was maintained at 150 ^° C. for 10 minutes. The ethylene pressure is also kept constant and the flow meter detects an increase of ethylene by 15.7 g. Then the polymer solution is poured out of the autoclave and the polymer is obtained after drying under reduced pressure at 90 ^° C. overnight.

 Yield 15.7 g.

 Example 4

 (Copolymerization of olefins).

In a glove box in an argon atmosphere, 5.0 ml of a 1.0 M solution of methylaluminoxane (MAO) in toluene and 50 ml of 1-octene are poured into a stainless steel reactor (HC) having a float valve on both sides. In another HC reactor, 50 ml (5.06 mmol) of a 0.0101 M solution of (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride in toluene are added to 2 ml of toluene. The reactors are hermetically sealed by transferring an autoclave from a glove box into a 600 ml HC. The autoclave is pumped out and purged with argon. A solution of 1-octene and MAO are added to the autoclave. The solution was heated to 89 ^° C. under an ethylene pressure of 620 kPa (6.33 kg / cm ² ) with stirring. At the same time, a catalytic solution is added. The temperature of the exothermic reaction rises to 142 ^o C. the Ethylene pressure is maintained between 1310 and 1345 kPa (13.36 13.71 kg / cm ² ).

After 0.5 h, ethylene supply was stopped. The reactor is cooled to 30 ^o C, open to the atmosphere and quench the reaction with methanol. The product is collected on a porcelain filter and washed with methanol. The remaining solvents are removed under reduced pressure and 110 ^° C., whereby 35 g of material are obtained. ¹³ C NMR analysis indicates that 1-octene is incorporated into the polymer in an amount of 7.8 mol. Differential scanning calorimetry (DSC) shows T _p 100 ^o C.

 Density 0.895 g / ml, M.w. 44,000, M.V. / M.h. 6.8.

 Example 5

 (Copolymerization of olefins).

Basically, the procedure of example 4 is repeated, except that 1-hexene is used instead of 1-octene. The reaction temperature is maintained at 133-140 ^° C. The polymer yield is 37 g. The incorporation of 1-hexene in the copolymer is 8 mol. 21 wt.

 Example 6

 (Homopolymerization of a-olefin).

A. 4-methyl-1-pentene (6.0 ml, 4.0 g) is added to 1.0 ml of a 1.0 M solution of MAO in toluene in a 20 ml ampoule (crimp-top). 100 ml of a 0.01172 M toluene solution of the zirconium complex catalyst of Example 4 are added thereto. The ampoule is sealed, shaken and left at room temperature (approximately 20 ^° C) for 16 hours, then heated to 48 ^° C for another 24 hours. A viscous polymer solution is precipitated by the addition of methanol. The resulting polymer was collected, and the volatile components were removed under reduced pressure and 100 ^° C. for 4 hours to obtain 3.8 g of pure polymer (yield 95).

¹³ C NMR analysis indicates that the polymer is atactic poly-4-methyl-1-pentene.

B. Basically repeat the polymerization procedure A. 3.4 g of 1-hexene, 1 ml of MAO solution and 100 μl of the catalytic solution are placed in a 20 ml ampoule in a dry chamber, purged with argon. The ampoule is sealed and heated at 50 ^° C. overnight. After quenching the reaction with acidified ethanol and drying, 3.0 g of poly (1-hexene) is obtained.

 Example 7

 (Homopolymerization of ethylene).

A stainless steel reactor was charged with 500 μl (5.0 μmol) of a 0.010 M solution of (tert-butylamido) dimethyl (tetramethyl-η ^5- cyclopentadienyl) silantitanedichloride in toluene and 2.5 ml of toluene in a glove box filled with argon. 5.0 ml of a 1.0 M solution of MAO in toluene are added to 92 ml of toluene in the second HC reactor. Both reactors are sealed and transferred from a glove box to a 600 ml autoclave. The autoclave is pumped out, purged with argon and then filled with ethylene. The cocatalyst solution is added to the autoclave and heated to 89 ^° C. under an ethylene pressure of 620 kPa (6.33 kg / cm ² ). At this time, a catalyst solution is added to the reactor. As a result of the exothermic reaction, the temperature rises to 109 ^o C in a few seconds. The ethylene pressure is regulated between 1240 and 1275 kPa (12.66 13.00 kg / cm ² ). After 0.5 hours, the temperature of the reactor was raised to 110 ^° C. and the ethylene supply was increased. After an hour, the ethylene supply was stopped, the reactor was opened to the atmosphere and allowed to cool. The autoclave was opened, the reaction was quenched with methanol and the polymer was separated. After removal of volatile components, the yield of polyethylene is 24 g.

 Example 8. Polymerization of a substituted vinyl aliphatic monomer.

4-vinylcyclohexene is purified by vacuum distillation over a Na / K alloy. Basically, the procedure of Example 4 is repeated using 50 ml of 4-vinylcyclohexene and 5.0 ml of a 1.0 M solution of MAO catalyst in toluene in one reactor and 500 ml of a 0.010 M solution of (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl ) silanzirconium dichloride in toluene with 2 ml of toluene in another reactor. The temperature rises to 114 ^o C due to an exothermic reaction. Ethylene supply was stopped after 1.0 h, cooled and the reactor was opened to atmosphere, the reaction was quenched with acidified methanol. 12.6 g of substance are obtained.

¹³ C NMR analysis indicates that vinylcyclohexene forms a polymer in an amount of 1.5 mol.

 Example 9. Copolymerization of ethylene / styrene.

The polymerization procedure described above is generally repeated, except that the reaction temperature is 90 ^° C. The reactor is filled with 150 ml of a mixture of aliphatic solvents, 500 ml of styrene and 8 ml of a 15 solution of MAO in toluene (1000 Al Ti). The reactor is filled with ethylene up to 1240 kPa (12.66 kg / cm ² ) and 20 μmol [(C ₅ Me ₄ ) SiMe ₂ -N-phenyl)] TiCl ₂ ethylene is fed up to 1240 kPa (12.66 kg / cm ² ). After 60 minutes, the solution is drained from the reactor into a container that contains a small amount of antioxidant. The polymer is dried under vacuum. The polymer yield is 26.6 g, the melting index (I ₂ ) is 26.6. ¹³ C NMR analysis indicates that the polymer contains 47 mol. styrene (76 wt.). Isotactic, atactic, or syndiotactic sequences are not observed.

 Example 10. The copolymerization of ethylene / styrene.

The reaction conditions of Example 9 are generally repeated in the preparation of styrene / ethylene copolymers differing in styrene content. The catalyst is (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silantitane dichloride instead of the above. The MAO cocatalyst is added in an amount that provides a ratio of Al M 1000 1. The reaction conditions are contained in table. 4.

Examples 11 32. In these examples, 2000 ml of a solvent from a mixture of alkanes (Isopar-E) with various amounts of 1-octene are charged into a four-liter autoclave. The catalyst is (tert.-Butylamido) dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitane dichloride dissolved in toluene. As a cocatalyst, a 10 solution of MAO in toluene is used. If desired, hydrogen is added by expanding from a 100 ml vessel under the pressure indicated above to the operating pressure of the reactor. The reactor is filled with solvent, 1-octene and MAO, heated to the reaction temperature, then the pressure is increased to 3100 kPa (450 psi) with ethylene until the solution is saturated. Hydrogen (if used) is expanded into the reactor, and then a catalyst solution is added. After 10 minutes, the solution was drained from the reactor into a container containing a small amount of an antioxidant (Iroanox 1010®, supplied by Tsiba-Geigy). The polymer is dried in vacuo. The results are shown in table. 5.

 Examples 33 42. The procedure of Examples 11 32 is repeated, except that the catalyst is (tert.-butylamido / dimethyl / tetramethyl-cyclopentadienyl / silanzirconium dichloride. The results are shown in Table 6.

Examples 43 57. Repeat the procedure of examples 11 32, except that they use a two-liter reactor, and (tert.-butylamido) dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitanedichloride (2 ml of a 0.005 M solution in toluene, 10 μmol). 15 MAO in toluene (2 ml, 500 Al Ti) was used as cocatalyst.

 The results are shown in table. 7.

 Examples 58 77. Polymerization of olefins.

Ethylene and / or ethylene / 1-octene are polymerized respectively as a homopolymer or copolymer by adding a solution of the corresponding catalyst in combination with MAO or triethylaluminum co-catalyst to a three-liter SS autoclave containing a mixture of C ₆ alkanes as solvent (1-octene) (in various ratios) under a pressure of 3100 kPa (450 psi) of ethylene at 150 ^o C for 10 minutes The ethylene pressure is kept constant, and a mass flow meter controls the flow of ethylene. The resulting polymer was recovered from the reactor and dried under reduced pressure at 90 ^° C. overnight. The results are shown in table. eight.

Example 78. Obtaining supported on a substrate (tert.-butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitane dichloride.

0.100 g of dehydroxylated silica (—OH concentration of about 1 mmol / g SiO ₂ ) is suspended in 20 ml of a solvent of a mixture of C ₆ alkanes in a nitrogen atmosphere in a dry box under stirring in a 50 ml Erlenmeyer flask. From this suspension, 1.0 ml was withdrawn with a syringe and combined with 1.10 ml of a 0.011 M solution in toluene (tert-butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitanedichloride in a 5 ml round bottom flask and stirred for 12 hours. After of this period of time, 6.7 ml of a 10 (w / w) solution of methylaluminoxane (MAO) in toluene is added to the solution containing silica.

 Polymerization.

The polymerization is carried out by adding under pressure the above suspension of titanium / silicon dioxide / MAO into a three-liter autoclave containing 2 L of a mixture of alkanes solvent, at a pressure of 3100 kPa (450 psi) of ethylene at 150 ^° C for 10 minutes. The ethylene pressure is kept constant and the ethylene flow rate according to the mass flow meter is 26.7 g. Then, the polymer solution is removed from the reactor and the polyethylene is isolated after drying under reduced pressure at 90 ^° C. overnight. Yield 30.0 g.

Example 79. Obtaining / 2-methoxyphenylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

 (a) ((Tetramethylcyclopentadienyl / dimethylsilyl / 2-methoxyphenyl / amine.

 To 1.3 g (5.9 mmol) of ((tetramethylcyclopentadienyl / dimethylsilyl / chloride in 50 ml of tetrahydrofuran (THF) was added 0.86 (5.9 mmol) of sodium-2-methoxyanilide. The resulting mixture was stirred overnight. The solvent was removed. under reduced pressure, and the residue was extracted with pentane.The pentane extracts were filtered, combined and concentrated to give a pale yellow liquid.

 Yield 1.4 g (79).

¹ H NMR (benzene-d ₆ ) d 6.91 (m, 2.2), 6.74 (m, 1.1), 6.57 (d, 1.1 J 9), 4.25 (s , 1), 3.32 (s, 3.7), 1.93 (s, 6.7), 1.80 (s, 6.8), 0.13 (s, 6.3).

(b) Dilithium / tetramethylcyclopentadienyl / dimethylsilyl / - 2-methoxyphenyl / amide /
3.9 ml of 2.5 M butyllithium (9.8 mmol) in hexane is added dropwise to 1.4 g (4.6 mmol) of ((tetramethylcyclopentadienyl / dimethylsilyl // 2-methoxyphenyl / amine in diethyl ether). A white precipitate forms. Pentane is added to the mixture, the resulting suspension is filtered, and the solid is washed with pentane.

(c) / 2-methoxyphenylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

To 1.6 g of dilithium // tetramethylcyclopentadienyl / dimethylsilyl- / 2-methoxyphenyl / amide suspended in toluene, 0.85 g of TiCl _{4 was} added. The resulting mixture was stirred for three days and the solvent was removed in vacuo under reduced pressure. The residue was suspended in pentane and filtered to give a dark powder.

 Yield 0.77 g (41).

¹ H NMR (benzene-d ₆ ) d: 4.10 (s, 3), 2.20 (s, 6.4), 1.99 (s, 6.6), 0.40 (s, 6, 3).

Example 80. Obtaining (4-fluorophenylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

 (a) ((Tetramethylcyclopentadienyl) dimethylsilyl) (4-fluorophenyl) -amine.

 Equimolar amounts of ((tetramethylcyclopentadienyl) dimethylsilyl / chloride and lithium 4-fluoroanilide were combined in THF and the resulting mixture was stirred overnight. The solvent was removed under reduced pressure.

¹ H NMR (benzene-d ₆ ) d: 6.79 (m, 2.5), 6.33 (m, 2.4), 2.95 (s, 1), 2.90 (s, 1) 1.87 (s, 6.9), 1.79 (s, 6.9), 0.2 (s, 5.8).

 (b) Dilithium // tetramethylcyclopentadienyl / dimethylsilyl / 4-fluorophenyl / amide.

 // Tetramethylcyclopentadienyl / dimethylsilyl / -4- / 4-fluorophenylamine in a solvent diethyl ether and butyl lithium 2.5 M in hexane are combined in equivalent amounts. A white precipitate forms. Pentane is added to the suspension. The precipitate was filtered, washed with pentane and dried.

¹ H NMR (THF-d ₈ ) d: 7.28 (m, 2.0), 6.77 (m, 2), 3.27 (s, 2.7), 2.05 (s, 5, 2), 2.01 (s, 5.2), 0.44 (s, 4.6).

(c) (4-fluorophenylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride
0.50 g (1.7 mmol) of dilithium // tetramethylcyclopentadienyl / dimethylsilyl / -4-fluorophenyl / amide are added to 0.59 g (1.6 mmol) of TiCl ₃ , ETHF in 50 ml of THF. After 0.5 h, 0.25 g (1.8 mmol) of AgCl are added. After two hours, the solvent was removed under reduced pressure. The residue was extracted with diethyl ether. The ether extracts are filtered, combined and concentrated under reduced pressure to obtain a red glassy solid. After dissolution in toluene and re-concentration, a waxy solid is obtained. This solid product is extracted into pentane. The pentane extracts are filtered, combined and concentrated to a waxy solid. It is suspended in a small amount of pentane (2 ml) and filtered to obtain a red powder. The yield is 0.18 g (28).

¹ H NMR (benzene-d ₆ ) d 7.10 (t), 6.80 (t), 2.00 (s), 1.97 (s), 0.35 (s).

 Polymerization.

The polymerization procedure of Examples 11 32 was used using 1000 ml of a solvent of a mixture of alkanes, 200 ml of 1-octene and 5 ml of 15 MAO in toluene (1280 Al Ti), and the reaction temperature was 130 ^o C. Hydrogen was supplied from a 75 ml pressure vessel 3450 kPa (psi), until an overpressure of 345 kPa (psi) is obtained, 10 μl of the above complex is added in order to start polymerization. Ethylene consumption is provided at the rate of 3100 kPa (psi). The polymer yield is 12.8 g, MW 103000, MW / MW 4.77, density 0.9387, melt index 6.37.

 Example 81

Obtaining / 4-methoxyphenylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

To 0.73 g of TiCl ₄ , 2 THF in 30 ml of toluene add 0.7 g of dilithium / tetramethylcyclopentadienyl / dimethylsilyl // 4-methoxyphenyl / amide /, obtained by the method of example 81. The resulting mixture was stirred for two days and concentrated under reduced pressure. The residue was suspended in pentane and filtered to give a red powder cake. Yield 0.61 g (67).

¹ H NMR (benzene-d ₆ ) d 7.28 (d, 2, J 8.8), 6.78 (2, J 8.9), 3.27 (s, 2.8), 2.05 (s, 5.6), 2.01 (s, 5.6), 0.44 (s, 4.8).

 Polymerization.

 By the method of example 80, using 10 μmol of the above complex, polymerization is carried out. The polymer yield was 7.2 g. MW 79.800, MW / MW 21.5. Melt index 2.90.

Example 82. Obtaining 1- / tert-butylamide / -2- / tetramethyl-η ⁵ -cyclopentadienyl / - 1,1,2,2-tetramethyldisilantitane dichloride.

 (a) 1-chloro-2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane.

 To a solution of 4.802 g (25.7 mmol) of 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 ml of dimethyl ether is slowly added a solution of 2.285 g (12.8 mmol) of sodium-1,2,3,4 Tetramethylcyclopentadiene in 30 ml of dimethyl ether. The reaction mixture was stirred for several hours, then the solution was removed, the residue was extracted with pentane and filtered. Pentane is removed under reduced pressure to give the product as a pale yellow oil.

 Mass spectrum: m / e 272 (8).

¹ H NMR (C ₆ D ₆ ) d 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 ( s, 6H)
¹³ C NMR (C ₆ D ₆ ) d 135.8, 134.0, 54.4, 14.6, 11.4, 3.2 2.4.

 (b) 1- (tert-butylamino) -2- (tetramethylcyclopentadienyl) -1,2,2,2-tetramethyldisilane.

 To a solution of 3.0 g (II mmol) of 1-chloro-2- / tetramethylcyclopentadienyl / -1,1,2,2-tetramethyldisilane in 50 ml of ether, 2.422 g (33.1 mmol) of tert-butylamine are added. A precipitate forms quickly. The resulting suspension was stirred for several days at room temperature, then carefully heated to complete the reaction, the aminohydrochloride was filtered off and pentane was removed under reduced pressure to obtain the product as a yellow oil.

 Yield 3.150 (92.5).

 Mass spectrum: m / e 309.

¹ H NMR (C ₆ D ₆ ) d 2.75 (s, 1H), 1.95 (s, 6H), 1.82 (s, 6H), 1.08 (s, 9H), 0.51 ( s, 1H), 0.24 (s, 6H), 0.16 (s, 6H)
¹³ C NMR (C ₆ D ₆ ) d 135.2, 134.4, 55.2, 50.3, 34.1, 14.9, 1.7, 3.3 1.4.

 (c) Dilithium-1- (tert.-butylamido / -2- / tetramethyl-cyclopentadienyl / -1,1,2,2-tetramethyldisilane.

To a solution of 3.0 g (9.72 mmol) of 1- / tert.-butylamido / -2- / tetramethylcyclopentadienyl / -1,1,2,2-tetramethyldisilane in 100 ml of ether, 7.70 ml, 2.60 are slowly added. M (20.2 mmol) of butyl lithium in a solvent is a mixture of C ₆ alkanes. The resulting suspension was stirred for several hours, then filtered and washed with ether, then dried under reduced pressure, whereby the product was obtained in the form of a white powder. Yield 2.918 g (93.4).

¹ H NMR (THF-d-8) d 2.05 (s, 6H), 1.91 (s, 6H), 0.87 (s, 9H), 0.25 (s, 6H), 0.03 (s, 6H).

¹³ C NMR (THF-d-8) d 117.3, 113.6, 53.5, 38.4, 34.1, 11.3, 8.4, 2.2.

(d) 1- / tert-butylamido / -2- / tetramethyl-η ⁵ -cyclopentadienyl / -1,1,2,2-tetramethyldisilantitane dichloride
A suspension of 0.75 g (2,333 mmol) of dilithium-1- (tert-butylamide-2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane and 0.779 g (2,333 mmol) of TiCl ₄ (THF) ₂ and 50 ml of toluene stirred for several days. The red-orange reaction mixture is filtered and the solvent removed to give a sticky red solid. It is extracted with pentane and filtered. After concentration and cooling at -35 ^° C in a freezer, the red microcrystalline product is collected on a frit and washed with cold pentane for removing dark red oily mater Yala Yield 0.3643 g, 36
¹ H NMR (C ₆ D ₆ ) d 2.20 (s, 6H), 1.94 (s, 6H), 1.48 (s, 9H), 0.44 (s, 6H), 0.43 ( s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 137.7, 135.5, 112.7, 65.9, 35.4, 16.6, 12.5, 2.8, 2.1.

 Polymerization.

 According to the method of example 81, using 10 μmol of the above complex, carry out the polymerization. The polymer yield is 12.1 g, Mv 62400, Mv / Mch of 8.45. The melt index is 6.14. Density 0.9441.

 Example 83

Receive / tert. -butylamido // dimethyl // tetramethyl-η ⁵ - cyclopentadienyl / silanzirconium dimethyl.

A solution of 0.5 g (1.215 mmol) (tert.-butylamido)) (dimethyl) / (tetramethylcyclopentadienyl / silanzirconium dichloride in 35 ml of ether is cooled to -40 ^o C. To this suspension 1.41 ml of a solution of methyl lithium (1.72 M (2.43 mmol). The reaction mixture was allowed to stir at room temperature for several hours. The solvent was removed and the residue was extracted with pentane and filtered. The resulting filtrate was concentrated and cooled to -40 ^° C. The resulting colorless crystals were isolated by decanting the supernatant.

Yield 0.2215 g, 49.2
¹ H NMR (C ₆ D ₆ ) d 1.97 (s, 6H), 1.91 (s, 6H), 1.40 (s, 9H), 0.46 (s, 6H), 0.00 ( s, 6H).

¹³ C NMR (C ₆ D ₆ ) d / 130.2, 125.3, 95.7, 35.4, 34.0, 13.9, 10.9, 6.2.

Example 84. Obtaining (tert.-Butylamido / dimethyl / η ⁵ -cyclopentadienyl / - silanzirconium dichloride.

To 0.6747 g (2.90 mmol) of ZrCl ₄ , 4 ml of diethyl ether was slowly added to the flask, then 4 ml of THF. Excess solvent is removed in vacuo to obtain a solid product, which is triturated. This solid product was combined with 0.6008 g (2.90 mmol) of dilithium (tert.-butylamido // cyclopentadienyl // dimethyl / silane obtained according to the method of Example 87 and 75 ml of toluene. The resulting suspension was stirred for several days after whereupon the colorless solution is filtered, the solvent is removed under reduced pressure and the residue is suspended in pentane. This product is collected on a frit and dried under reduced pressure.

 Yield 0.6186 g (60.0).

¹ H NMR (C ₆ D ₆ ) d 6.43 (t, 2H), 6.08 (t, 2H), 4.17 (br s, 6H), 1.27 (s, 9H), 1, 03 (br s, 6H); 0.22 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 122.0, 121.4, 109.5, 57.2, 32.8, 25.2, 0.7.

 The structure was determined crystallographically using x-rays: in the solid state, the compound is a dimer (bridged chlorides).

Example 85. Obtaining (anilido) (dimethyl) (tetramethyl-η ⁵ - cyclopentadienyl / silanzirconium dichloride.

To 0.6905 g (2.963 mmol) of ZrCl ₄ , 3 ml of diethyl ether was slowly added to the flask, then 4 ml of THF. Excess solvent is removed under reduced pressure to obtain a solid product, which is triturated. The solid product is combined with 0.8044 g (2.963 mmol) of dilithium / anilido / dimethyl / - / tetramethylcyclopentadienyl / silane and 70 ml of toluene. In a few minutes, the suspension turns pale yellow-green. The suspension is stirred for several days, after which the solution is filtered, the solvent is distilled off under reduced pressure, and the residue is suspended in pentane. A very pale yellowish product is collected on a frit and dried under reduced pressure.

¹ H NMR (C ₆ D ₆ ) d 7.21 (t, 2H), 7.1 (t, 1H), 6.97 (m, 2H), 2.50 (s, 3H), 2.46 ( s, 3H), 1.87 (s, 3H), 1.85 (s, 3H), 0.53 (s, 3H), 0.40 (s, 3H).

Example 86. Obtaining
(a) (Para-toluidino) (dimethyl) tetramethyl-η ⁵ - cyclopentadienyl / silanzirconium dichloro / para-toluidino // dimethyl / / tetramethylcyclopentadienyl / silane.

To a solution of 2.0 g (9.302 mmol) (chlorine) (dimethyl) (2,3,4,5-tetramethylcyclopentadienyl / silane in 70 ml of THF, 1.259 g (9.302 mmol) of lithium-para-toluidide (0.3 ether) are slowly added. adduct according to ¹ H NMR). The reaction mixture was stirred overnight. The completion of the reaction was monitored by gas chromatography. Additional lithium-para-toluidine was added in small portions (0.725 g, 14.7 mmol total). The solvent was removed, the residue was extracted with pentane and filtered. Pentane is removed under reduced pressure to give the product as a yellow oil. Yield 2.456 g ( 92.5).

 Mass spectrum m / e 285 (22).

¹ H NMR (C ₆ D ₆ ) d 6.96 (d, 2H), 6.57 (d, 2H), 3.07 (s, 1H), 3.01 (s, 1H), 2.17 ( s, 3H), 1.91 (s, 6H), 1.80 (s, 6H), 0.08 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 145.0, 136.2, 132.7, 130.2, 126.9, 116.9, 55.2, 20.5, 14.3, 11.3 2 , 2.

 (b) Dilithium (para-toluidine) (dimethyl / tetramethylcyclopentadienyl / silane.

To a solution of 2.233 g (7.82 mmol) of (para-toluidino / (dimethyl / tetramethylcyclopentadienyl) silane in 65 ml of ether, 6.17 ml of 2.60 M (16.0 mmol) of butyl lithium in a solvent of a mixture of C ₆ alkanes was slowly added. Not the reaction mixture containing the precipitate was stirred overnight.The solvent was removed under reduced pressure The resulting white solid was suspended in pentane, collected on a frit, washed with pentene and dried under reduced pressure to obtain the product as a white powder.

 Yield 2.34 g (100%).

¹ H NMR (THF d-8) d 6.42 (d, 2H), 6.18 (d, 2H), 2.09 (s, 6H), 2.01 (s, 3H), 1.94 ( s, 6H), 0.36 (s, 6H).

¹³ C NMR (THF d-8) d 160.8, 129.1, 121.3, 115.9, 115.2, 112.2, 106.2, 20.8, 14.7, 11.7, 5.2.

(c) / para-toluidino / dimethyl // tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

Suspension of 1.00 g (3.363 mmol) of dilithium / paratoluidino / - (dimethyl) (tetramethyl-η ^5- cyclopentadienyl / silane and 1.123 g (3.363 mmol) of TiCl ₄ (THF) ₂ in 70 ml of toluene.The reaction mixture was stirred for several days, then filtered and the solvent removed. The resulting solid was suspended in pentane and the resulting product was collected on a frit and dried under reduced pressure. The yield of the product as an olive brown powder was 0.7172 g (53%).

¹ H NMR (C ₆ D ₆ ) d 7.26 (d, 2H), 7.01 (d, 2H), 2.08 (s, 3H), 2.04 (s, 6H), 2.00 ( s, 6H), 0.45 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 150.3, 141.7, 137.5, 133.9, 130.0, 129.7, 119.6, 21.0, 20.6, 16.4, 16.0, 13.3, 12.8, 2.8 2.6.

(d) (para-toluidino) (dimethyl) (tetramethyl-η ⁵ - cyclopentadienyl / silanzirconium dichloride.

To 0.7836 g (3.363 mmol) of ZrCl ₄ , 3 ml of diethyl ether was slowly added to the flask, then 4 ml of THF. Excess solvent is removed under reduced pressure to obtain a solid product, which is triturated. The solid is combined with 1.0 g (3.363 mmol) of dilithium / para-toluidino) (dimethyl) - (tetramethyl-η ^5- cyclopentadienyl) silane in 70 ml of toluene. The resulting suspension is stirred for several days. The initial yellow color of the suspension turns into brown. The yellow solution was filtered, the solvent was removed under reduced pressure, and the solid was suspended in pentane. The pale yellow product was collected on a frit and dried under reduced pressure.

 Yield 0.8854 g (69.1).

¹ H NMR (C ₆ D ₆ ) d 7.06 (q, 2H), 6.87 (q, 2H), 2.50 (s, 3H), 2.47 (s, 3H), 2.21 ( s, 3H), 1.89 (s, 3H), 1.88 (s, 3H), 0.51 (s, 3H), 0.41 (s, 3H).

 According to x-ray crystallography, the structure was determined as ZiCl containing a dimer with bridged chlorides.

Example 86 ^a . Preparation of (benzylamido / dimethyl / tetramethyl-η ⁵ - cyclopentadienylsilantitane dichloride.

 (a) (Benzylamino) dimethyl / tetramethylcyclopentadienyl / silane.

 To a solution of 1.0 g (4.651 mmol) (chlorine) (dimethyl // tetramethylcyclopentadienyl / silane in 70 ml of ether, 0.526 g (4.601 mmol) of lithium benzylamide are slowly added.The reaction mixture is stirred overnight, then the solvent is removed, the residue is extracted with pentane and filtered Pentane is removed under reduced pressure to give the product as a yellow oil.

 Yield 1.234 g (93.3).

 Mass spectrum 285 (18).

¹ H NMR (C ₆ D ₆ ) d 7.0 7.24 (m, 5H), 3.71 (d, 2H), 2.73 (br s, 1H), 1.88 (s, 6H) 1.76 (s, 6H); 0.43 (br t, 1H); 0.07 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 144.3, 135.7, 132.0, 128.5, 127.3, 126.7, 56.7, 46.4, 14.6, 11.4 2 , 3.

 (b) Dilithium / benzylamido / dimethyl / tetramethylcyclopentadienyl / - silane.

To a solution of 1.091 g (3.836 mmol) of (benzylamino) (dimethyl) / tetramethylcyclopentadienyl / silane in 70 ml of ether, 3.1 ml of 2.60 M (8.06 mmol) of butyl lithium in a solvent of a mixture of C ₆ alkanes were slowly added. Simultaneously with the appearance of sediment, a pale pink color appears. The reaction mixture was stirred overnight. The solvent is removed under reduced pressure. The resulting solid was suspended in pentane, collected on a frit, washed with pentane and dried under reduced pressure to obtain the product as a pale pink powder.

 Yield 1.105 g (96.9).

¹ H NMR (THF d-8), d 7.15 (m, 4H), 7.00 (m, 1H), 4.02 (s, 2H), 2.04 (s, 6H), 1.79 (s, 6H); 0.15 (s, 6H).

¹³ C NMR (THF) d-8) d 152.1, 128.1, 127.9, 125.0, 115.8, 111.9, 108.3, 54.0, 15.0, 11.2 4.6.

(c) (benzylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl) -silantitanedichoride.

A suspension of 0.5052 g (1.699 mmol) of dilithium (benzylamido / dimethyl // tetramethyl-η ^5- cyclopentadienyl / silane and 0.5673 g (1.699 mmol) of TiCl ₄ (THF) ₂ in 40 ml of toluene is stirred for several days. the brown reaction mixture was filtered and the solvent was removed.The dark oily precipitate was suspended in pentane and the resulting product was collected in frit and washed with cold pentane to remove the dark oily material to give the product as a greenish-yellow powder.

 Yield 0.2742 g (40.1).

¹ H NMR (C ₆ D ₆ ) d 7.19 (m, 2H), 7.02 (m, 3H), 5.37 (s, 2H), 1.99 (s, 6H), 1.98 ( s, 6H), 0.03 (s, 6H).

¹³ C NMR (C ₆ D ₆ ) d 141.4, 140.9, 135.8, 129.0, 128.8, 126.9, 126.6, 126.3, 103.6, 59.3, 15.6, 12.4, 1.7.

 Polymerization.

 The polymerization is carried out according to the method of example 80, using 10 μmol of the above complex. The polymer yield is 14.4 g. MW mv / mh 5.0. Melt index 251, density 0.969.

Example 87. Preparation of (benzylamido) dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silanedicirconium dichloride.

0.393 g (1.687 mmol) of ZrCl ₄ , 0.5015 g (1.687 mmol) of dilithium / benzylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienylsilane and 40 ml of toluene are combined in a flask. The brownish-yellow suspension was stirred for several days, and then filtered and the solvent was removed under reduced pressure. The wet brownish residue was suspended in pentane and the resulting product was collected on a frit and dried under reduced pressure.

 Yield: 0.2873 g (38.2).

¹ H NMR (C ₆ D ₆ ) d 7.51 (d, 2H), 7.23 (t, 2H), 7.09 (t, 1H), 5.48 (d, 1H), 5.00 ( d, 1H), 2.45 (s, 6H), 2.05 (s, 3H), 2.01 (s, 3H), 2.01 (s, 3H), 0.34 (s, 3H), 0.20 (s, 3H).

¹³ C NMR (C ₆ D ₆ ) d 145.2, 135.1, 132.2, 131.8, 129.4, 129.0, 128.9, 128.8, 127.0, 126.6, 126.3, 16.6, 57.2, 16.0, 15.6, 12.5, 11.8, 2.6.

Example 88. Obtaining (phenylphosphido) dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silantitane dichloride.

 (a) (Phenylphosphino // dimethyl // tetramethylcyclopentadienyl / - silane.

To a solution of 1.5 g (6.983 mmol) (chlorine)) dimethyl // tetramethylcyclopentadienyl / silane in 55 ml of THF was added 1.1248 g (7.665 mmol) of toluene in excess, since according to gas chromatography, reaction 11 was incomplete. Lithium phenyl phosphide (0.4 ether adduct according to ¹ H NMR spectroscopy). The reaction mixture was stirred for several days, then the solvent was removed, the residue was extracted with pentane and filtered. Pentane is removed under reduced pressure to give the product as a yellow oil.

 Yield 1.985 g (98.5).

 (b) Dilithium / phenylphosphido / dimethyl / tetramethylcyclopentadienyl / silane.

To a solution of 1.858 g (6.451 mmol) (phenylphosphino // dimethyl / - / tetramethylcyclopentadienyl / silane in 65 ml of ether, slowly add 5.21 ml of 2.60 M (13.55 mmol) of butyllithium in a solvent of a mixture of C ₆ alkanes, whereby a yellowish precipitate.The reaction mixture was stirred overnight.The product was collected in frit and washed with pentane, then dried under reduced pressure to obtain the product as a white powder. Yield (0.5 ether adduct according to ¹ H NMR) 2.0845 g (95, 8).

(c) Phenylphosphido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / - silantitane dichloride.

The flask combines 0.9 g (2.668 mmol) of dilithium (phenylphosphido / dimethyl // tetramethyl-η ⁵ -cyclopentadienyl / silane (0.5 ether adduct) and 0.8907 g (2.668 mmol) of TiCl ₄ (THF) ₂ in 75 ml of toluene.The color changes strongly to dark green-black with the addition of toluene.The reaction mixture is stirred for several days, then filtered and the solvent removed.The dark residue is extracted with pentane and filtered until a green-brown product remains on frit (0.2477 g ) and a black glassy product after removal of pentane from the filtrate.

 Polymerization.

 The polymerization is carried out according to the method of example 80, using 10 μmol of the above complex. The polymer yield was 14.4 g. MW 27700, MW / Mh 5.0, melt index 251, density 0.9690.

Example 89. Obtaining (phenylphosphido / dimethyl / tetramethyl-η ⁵ - cyclopentadienyl / silanzirconium dichloride.

To 0.6217 g (2.668 mmol) of ZrCl ₄ , 3 ml of diethyl ether was slowly added to the flask. Excess solvent is removed in vacuo to obtain a solid product, which is crushed into powder. The solid is combined with 0.9 g (2.668 mmol) of dilithium / phenylphosphido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silane and 75 ml of toluene. The color changes to dark red-orange with the addition of toluene. The reaction mixture was stirred for several days, then the orange solution was filtered from a small amount of dark insoluble material and the solvent was removed. The residue was suspended in pentane and filtered. The brown solid was collected in frit and dried under reduced pressure.

 Example 90

 Preparation (tert.butylamido / dimethyl // indenyl / - silantitanedichloride.

 a) (Tert.butylamido / dimethyl / indenyl / silane.

 To a solution of 5.255 g (71.8 mmol) of tert-butylamine in 75 ml of ether was added 3.0 g (14.4 mmol) of 9- (chlorodimethylsilyl / -indene. A precipitate formed a few minutes after the start of addition. The resulting suspension was stirred for overnight, the solvent was removed, the residue was extracted with pentane and filtered.The pentane was removed under reduced pressure to obtain a pale yellow oily product as a mixture of two isomers. Yield 3.313 g (93.9).

 (b) Dilithium (tert.butylamido (dimethyl / indenyl / silane.

To a solution of 3.125 g (12.73 mmol) (tert. Butylamino / dimethyl / indenyl / silane in 75 ml of ether, 10.28 ml of 2.60 M (26.73 mmol) of butyl lithium in a solvent of a mixture of C ₆ alkanes are slowly added. without precipitate, it darkens slightly and turns orange. The reaction mixture is stirred for several days, then the solvent is removed. Fluffy glassy material is mixed with pentane. Powder lumps are together. Pentane is decanted and the washing is repeated several times, then the solid part is dried under reduced pressure.

 Yield 2.42 g (73.9).

 (c) (Tert.butylamido / dimethyl / indenyl / silantitane dichloride.

The flask combines 1.0 g (3.887 mmol) of dilithium / tert.butylamido // dimethyl / indenyl / silane and 1.298 g (3.887 mmol of TiCl _4. (THF) ₂ with 70 ml of toluene. Instantly the color turns red.

 The reaction mixture was stirred for three days, then filtered and the solvent removed. The residue was extracted with pentane and filtered to give the product as a red microcrystalline material.

 Yield 0.4917 g (34.9).

 Polymerization.

 The polymerization is carried out according to the method of example 80, using 10 μmol of the above complex. The polymer yield of 14.8 g.

 Example 91

 Preparation (tert-butylamido / dimethyl / indenylsilane zirconium dichloride.

To 0.9057 g (3.887 mmol) of ZrCl ₄ in a flask, 2 ml of THF were slowly added. Excess THF is removed in vacuo to obtain a solid product, which is pulverized. 1.0 g (3.887 mmol) of dilithium / tert.butylamido / dimethyl / indenyl / silane are added together with 70 ml of toluene. The resulting suspension was stirred for several days, after which the solution was filtered and the solvent was removed under reduced pressure. The residue was suspended in pentane, filtered and dried under reduced pressure.

 The yield of brown-beige product is 0.5668 g (36.0).

 Example 92

Preparation of 1- / tert.butylamido / -2- / tetramethyl-η ⁵ - cyclopentadienyl / ethanediyl titanedichloride.

 (a) Ethyl 2- / tetramethylcyclopentadienyl / acetate.

A solution of 3.822 g (22.89 mmol) of ethyl bromoacetate in 25 ml of THF is cooled to -78 ^° C. and 3.00 g (20.80 g) of sodium tetramethylcyclopentadienyl in 50 ml of THF are slowly added thereto. The resulting suspension was allowed to warm to room temperature and stirred overnight. The solvent was removed, the residue was extracted with pentane and filtered. Pentane is removed to obtain a mixture of isomers.

 Yield 3.733 g (86.3).

 Mass spectrum m / e 208 (41).

 (b) -2- (tetramethylcyclopentadienyl) tert-butylacetamide.

 16.35 ml of 2.00 M (32.7 mmol) of trimethylaluminum in toluene add 2.39 g (32.7 mmol) of tert-butylamine in 50 ml of toluene. The solution was stirred for 45 minutes, then 3.40 g of ethyl 2-tetramethylcyclopentadienyl acetate was added. The reaction mixture is stirred for several days with gentle heating. After water treatment of the obtained amide, a mixture of three isomers is obtained in the form of an orange semi-crystalline paste.

 Mass spectrum m / e 235 (21).

 (c) 1- / tert. butylamino / -2- / tetramethylcyclopentadienyl / ethane.

 The amide mixture was dissolved in 120 ml of ether and 0.830 g (21.8 mmol) of lithium aluminum hydride was added. The reaction mixture was stirred overnight with gentle warming. Control by gas chromatography indicates that the reaction is not complete. The ether is replaced with THF, more lithium aluminum hydride is added and the resulting solution is refluxed for several days. After water treatment, three isomers of 1- / tert. Butylamino / -2- / tetramethylcyclopentadienyl / ethane are obtained.

 Mass spectrum mt 221 (11).

(d) Dilithium-1- / tert-butylamido / -2- / tetramethyl-η ⁵ - cyclopentadienyl / ethane.

To a solution of 2.00 g (9.05 mmol) (tert.butylamino / -2- / tetramethylcyclopentadienyl) ethane isomers (67 1- / tert. Butylamino / -2- / 2,3,4,5-tetramethylcyclopentadiene-2, 4-enyl / ethane according to gas chromatography, 1.34 g (6.06 mmol) in 50 ml of ether was slowly added 6.09 ml of 2.60 M (15.8 mmol) of butyllithium in a solvent of a mixture of C ₆ alkanes with the formation of a yellowish Precipitate The reaction mixture was stirred for three days and then filtered.The pale yellow powder was washed several times with ether, then dried under reduced pressure.

 Yield 0.7908 g (55.9).

¹ H NMR (THF-d-8) d 2.43 (br m 4H), 1.85 (s, 6H), 1.83 (s, 6H), 1.0 (s, 9H).

¹³ C NMR (THF d-8) d 109.5. 107.3, 106.3, 50.5, 45.4, 29.4, 28.2, 20.2, 10.9, 10.8.

(e) 1-tert. butylamido / -2- / tetramethyl-η ⁵ -cyclopentadienyl / - ethanediyl titanedichloride
In the flask, 0.3650 g (1.565 mmol) of dilithium-1- / t. butylamido / - 2- / tetramethylcyclopentadienyl / ethane and 0.5799 g (1.565 mmol) of TiCl ₃ (THF) ₃ are combined with 60 ml of THF. The solution quickly turns green. The reaction mixture was stirred overnight, then 1.121 g (7.82 mmol) of AlCl were added. In a few minutes, the color begins to change to brown-orange. The suspension is stirred for two days and the solvent is taken up under reduced pressure. The residue was extracted with toluene, the solution was filtered and the solvent was removed. The residue was extracted with pentane, filtered, concentrated and cooled to -30 ^o C. The bright orange product was collected on a frit, washed with a small amount of cold pentane, dried under reduced pressure.

 Yield 0.1904 g (36.0).

¹ H NMR (C ₆ D ₆ ) d 4.01 (t, J 7.2, 2H), 2.58 (t, J 7.2, 2H), 2.02 (s, 6H), 1.89 (s, 6H); 1.41 (s, 9H).

¹³ C NMR (C ₆ D ₆ ) d 138.0, 129.3, 128.6, 69.1, 62.7, 28.6, 24.9, 13.0, 12.3
Polymerization 1.

 The polymerization is carried out according to the method of example 80, using 10 μmol of the above complex. The polymer yield is 64.3 g, melt index 3.21, density 0.9262.

 Polymerization 2.

The above polymerization procedure, except that it is repeated that 0.95 μmol -1- / tert.butylamido / -2- / tetramethyl -η ⁵ -cyclopentadienyl / ethanediyl titanedichloride is added to initiate the polymerization. The polymer yield of 11.4 g, the melt index is less than 0.1, the density of 0.9119.

 Polymerization 3.

The above polymerization is repeated, except that 2.5 μmol of 1- / tert. Butylamido / -2-tetramethyl-η ⁵ - cyclopentadienyl / ethanediyl titanedichloride is added to initiate the polymerization. In addition, I use 300 ml of octene and 900 ml of isopar, but without hydrogen. The polymer yield of 36.2 g, the melt index of 0.21, the density of 0.9190.

 Polymerization 4.

The conditions of the above polymerization 1 are repeated, except that the temperature is 90 ^° C.

 The polymer yield of 66.7 g, the melt index of 0.16.

- циклопентадиенил/этандиилцирконийдихлорида.Example 93. Obtaining 1- / tert.butylamido / -2- / tetramethyl-

- cyclopentadienyl / ethanediylzirconium dichloride.

In a flask, 0.3862 g (1.657 mmol) of ZrCl ₄ and 0.3866 g (1.657 mmol) of dilithium / -1- / t. butylamido-2- / tetramethyl-η ⁵ - cyclopentadienyl / ethane / is combined with 50 ml of toluene. After stirring for several days, 1 ml of THF was added, and the resulting suspension was stirred for several more days, after which the solution was filtered and the solvent was removed under reduced pressure. The solid was suspended in pentane, collected on a frit and dried under reduced pressure. The yield of pale yellow product of 0.6307 g (99.8%).

1 H NMR (C ₆ D ₆ ) d 2.75 (etc. 1H), 2.38 (m, 2H), 2.11
(s, 6H), 2.03 (s, 3H), 2.00 (s, 3H), 1.75 (etc. 1H),
1.08 (s, 9H)
₁₃ C NMR (C ₆ D ₆ ) d 131.5, 128.7, 126.8, 126.5,
126.2, 56.9, 50.9, 27.9, 23.1, 13.4, 13.2,
12.6, 12.5.

Example 94. Polymerization of terpolymer. We carried out the polymerization of mixtures of ethylene, styrene and another additional polymerizable monomer using (tert. Butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitane dichloride complex and MAO cocatalyst in an amount providing atomic ratio AI / Ti 1000: 1. Reaction conditions and results obtained are given in table 9.

Example 95. Suspension polymerization. The following example illustrates the use of the catalyst of the present invention in suspension polymerization conditions. Practically repeat the procedures of examples 11-32, except that the reaction is carried out under conditions when the polymer is insoluble in the reaction medium and precipitates from the reaction mixture as it is formed. A temperature of 70 ^° C., 10 ml of octene, 1190 ml of a solvent mixture of alkanes, and 5 ml of 15% MAO in toluene (1280 AI: Ti) were used. After 20 minutes, the reactor was freed to obtain 4.6 g of polymer. An additional solvent is added to the reactor and heated to 170 ^° C. to remove the polymer, which forms long strands and twists around the stirrer. The melt index is 0.28.

Example 96. Obtaining / tert.butylamido / dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silantitane (III) chloride. In a chamber with a desiccant, 0.24 g of TiCl ₃ (THF) ₃ and 0.33 g of Me ₄ C ₅ SiMe ₂ N-t-BuMg ₂ Cl ₂ (THF) _{2 are} mixed. Add 15 ml of THF, get a dark purple color. After 30 minutes, volatile materials were removed under reduced pressure, leaving a dark solid. 15 ml of toluene are added, the solution is filtered and the toluene is removed under reduced pressure, leaving a purple-red powder, 0.22 g.

 Polymerization. The polymerization is carried out according to the method of example 80, using 10 μmol of the above complex. The polymer yield of 55.1 g, the melt index of 1.71.

Example 97. The polymerization is carried out according to the method of example 80, using 10 μmol (tert.butylamido / dimethyl / tetramethyl-η ^5- cyclopentadienyl / silantitane dichloride. The polymer yield is 76.4 g of MW 56700, MW / MW 4.5, density 0.8871, melt index (I ₂ ) 10.13.

Example 98. The polymerization in accordance with method 97 was practically repeated, except that the temperature was 80 ^° C., the amount of catalyst used was 2.5 μmol, 250 ml of I-octene were used, and 950 ml of a solvent mixture of alkanes. Reactions allow 1 hour to flow. The polymer yield is 51.1 g. The melt index is 0.11.

 Example 99. Obtaining (tert.butylamido / dimethyl / tetramethylcyclopentadienyl / -silangafnium dichloryl.

In a chamber with a desiccant, 0.50 g of HfCl _{4 is} suspended in 10 ml of toluene. Add 10 ml of THF, the suspension is stirred for 5 minutes, and 0.77 g of Me ₄ C ₅ SiMe ₂ N - tert.-BuMg ₂ -Cl ₂ -Cl ₂ (THF) _{2 is} added. The solution was heated to boiling under reflux. After 30 minutes, the solution was cooled, and the volatile portion was removed under reduced pressure. 20 ml of pentane was added, the solution was filtered, and pentane was removed under reduced pressure to obtain a white solid. This solid was washed with a small amount of pentane to give 0.077 g (10%) of a white solid.

1 H NMR (C ₆ D ₆ ): d 2.08 (6H), 1.30 (9H0, 0.44 (6H)
If, practically by the method of Example 7, ethylene is polymerized, a small amount of polyethylene is obtained.

 Comparative Example 1. The polymerization method of Example 97 was repeated, but pentamethylcyclopentadienyl titanium trichloride was used as a catalyst. Polymer yield 4.6 g.

Comparative example 2. According to the method of example 91, polymerization is carried out using (tert.butylamido / pentamethyl-η ⁵ -cyclopentadienyl titanedichloride as a catalyst.

1 H NMR (C ₆ D ₆ ) d 2.07 (s, 1H), 1.88 (s, 15H), 1.35 (s, 9H),
13C NMR (C ₆ D ₆ ) d 61.0, 31.3, 12.6
The polymer yield of 2.0 g.

 Comparative Example 3. The polymerization process of Example 97 was repeated, except that bis / tert.butylamido / dimethylsilantitane dichloride was used as the catalyst. After 10 minutes, no polymer reaction was observed.

Comparative Example 4. The polymerization process of Example 97 was repeated, except that dicyclopentadienyl zirconium dichloride was used as a catalyst. The polymer yield is 109.0 g, MW = 16300, MW / MW 3.63, melt index according to AS TM D-1238 procedure A, conditions E, I ₂ turned out to be higher than 1000, which indicates a very low molecular weight of the polymer.

Comparative Example 5. By the method of Example 97, a polymer was prepared, except that dicyclopentadienyl titanedichloride was used as a catalyst. The polymer yield is 7.3 g, the melt index by ASTM D-1238, procedure A, conditions A, I ₂ turned out to be higher than 1000, which indicates a low molecular weight of the polymer.

В сухом боксе объединяют в колбе емкостью 100 мл 4,45 ммоля /трет.бутиламидо/диметил/тетраммметил-η⁵-циклопентадиенил/силантитанийхлорида (полученного по примеру 104) в 50 мл тетрагидрофурана и 0,63 г (4,46 ммоля) о-LiCH₂C₆H₄N(CH₃)₂. Через 30 минут отгоняют летучие продукты при пониженном давлении, чтобы получить красно-коричневый твердый продукт. Прибавляют 50 мл пентана, раство фильтруют и уменьшают объем до 40 мл. Этот концентрированный раствор охлаждают до -30^oC. Отфильтровывают красные кристаллы и сушат при пониженном давлении.Example 100. A / Preparation of / tert.butylamido / dimethyl / tetramethyl-η ^5- cyclopentadienyl / silane o- / N, N-dimethylamino / benzyl titania, / formula / A //

In a dry box, combine in a flask with a capacity of 100 ml 4.45 mmol / tert.butylamido / dimethyl / tetrammethyl-η ^5- cyclopentadienyl / silantitanium chloride (obtained in Example 104) in 50 ml of tetrahydrofuran and 0.63 g (4.46 mmol) o -LiCH ₂ C ₆ H ₄ N (CH ₃ ) ₂ . After 30 minutes, the volatiles were distilled off under reduced pressure to obtain a red-brown solid. Add 50 ml of pentane, filter the solution and reduce the volume to 40 ml. This concentrated solution was cooled to -30 ^° C. Red crystals were filtered off and dried under reduced pressure.

Catalyst preparation and polymerization. Catalytic compositions are prepared by combining a metal complex with a triethyl aluminum cocatalyst in a polymerization reactor with stirring. Accordingly, 740 g of a mixed alkane solvent (Isopar-E tm, available from Exxon Chemicals Inc.) and 118 g of a 1-octene comonomer are loaded into a 2 L tank with stirring. The reactor is heated to 120 ^° C. and saturated with ethylene at a pressure of 500 psi ² (3.5 MPa). Hydrogen is introduced due to excess expansion pressure from an additional container of about 75 ml in volume to provide η ⁵ (0.2 kPa). The metal complex is mixed with the cocatalyst in a dry box by injecting with the syringe the desired amount of a 0.0050 M metal complex solution (in Isopar-E ^TM ) into the cocatalyst solution (also in Isopar-E ^TM ). This solution is then transferred to a container for introducing a catalyst and introduced into the reactor. Polymerization is carried out for 15 minutes. then the solution is removed from the rector and quenched with isopropanol. Spatially hindered phenol is added to the antioxidant and the ethylene / 1-octene copolymer is removed from the copolymer. the results are shown in table. 10.

Example 101. In essence, the reaction conditions of Example 108 are repeated with the exception that the complex is (tert. Butylamido) dimethyl / tetramethyl-η ⁵ -cyclopentadienyl / silandibenzyltitanium (obtained by reacting two equivalents of benzyl lithium with (tert.butylamido) dimethyl (tetramethyl -η ⁵ -cyclopentadienyl) silanthanitanium dichloride of Example 2. 700 g of a mixed alkane solvent and 150 g of 1-octene comonomer are charged into a 2-liter stirred reactor, the solution is heated to 90 ^° C. and saturated with ethylene at a pressure of 500 psi ² (3.5 MPa). Hydrogen is introduced due to excess pressure expansion from the additional tank volume of about 75 ml to ensure ΔH ₂ 10 lb / in ² (0.1 kPa). The metal complex and cocatalyst mmetilalyumoksanovy mixed in a drybox by mixing 1 ml of a 0.0050 M metal complex solution (in Isopar-E ^TM ) with 5 mmol of cocatalyst (in 10 ml of Isopar-E ^TM ) (Ti: AI 11: 10000). This solution is then transferred to an additional catalyst container and introduced into reactor. Polymerization is carried out for 10 minutes. Then the solution is removed from the reactor and quenched with isopropanol. Spatially hindered phenol is added to the antioxidant and ethylene / 1-octene is removed from the copolymer.

 The copolymer yield is 26.9 g.

Claims (4)

1. The metal coordination complex of the General formula

where R ¹ in each case is hydrogen or methyl, or an adjacent pair of R ¹ groups forms a hydrocarbonyl ring joined to the cyclopentedienyl moiety;
X chloride, methyl, benzyl or O- (N, N-dimethylamino) benzyl;
Y —O—, —NR— or —PR—, where R in each case is hydrogen or a part selected from the group of alkyl, aryl or combinations thereof containing up to 20 non-hydrogen atoms;
M titanium, zirconium or hafnium;
Z Si (CH ₃ ) ₂ , -Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ , -CH ₂ -CH ₂ - or -CH ₂ CH (CH ₃ ) -
n 1,2. 2. The complex according to claim 1, which is (tert-butylamido) dimethyl (tetramethyl-η ^5- cyclopentadienyl) -silantitane dichloride, (tert-butylamido) dimethyl (tetramethyl-η ^5- cyclopentadienyl) - silanzirconium dichloride, (tert-butylamido) dimethyl ( tetramethyl-η ⁵ -cyclopentadienyl) -silanedimethyltitanium, (2-methoxyphenylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silantitane-dichloride, (4-fluorophenylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silantithiodichi (1-methylethyl) phenyl) amido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silantitandihlorid (4-methoxy phenylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) - silanetitanium dichloride, (1-tert-butylamido) -2- (tetramethyl-η ⁵ -cyclopentadienyl) -1,1,2,2- tetrametildisilantitandihlorid, (tert-butylamido) dimethyl ( tetramethyl-η ⁵ -cyclopentadienyl) -silanedimethylzirconium, (tert-butylamido) dimethyl (η ⁵ -cyclopentadienyl) -silanzirconium dichloride, (n-toluidino) (dimethyl) (tetramethyl-η ⁵ cyclopentadienyl) -silanzylmethyl (dimethyl) dimethyl η ⁵ -cyclopentadienyl) - silantitane chloride, (benzylamido) dimethyl (tetramethyl- _η 5 -cyclopentadienyl) -silanzirconium horide, (phenylphosphino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silantitane dichloride, (tert-butylamido) dimethyl (indenyl) -silantitane dichloride, (tert-butylamide) dimethyl (indenyl) -silanzirconium dichloride, (methylamide ⁵ -dimethyl) -cyclopentadienyl) - silantitanedithichloride, 1- (tert-butylamido) -2- (tetramethyl-η ⁵ -cyclopentadienyl) ethylenitanedichloride, 1- (tert-butylamido) -2- (tetramethyl-η ⁵ -cyclopentadienyl) ethylene zirconium dichloride, (tert -butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) - silantitane (III) chloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silangafnium dichloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) -silanedibenzyl titanium.  3. The catalyst for ion-coordination polymerization, comprising a metal complex and cocatalyst, characterized in that as a metal complex it contains a coordination complex according to claim 1, as a cocatalyst, a compound selected from the group consisting of methylaluminoxane, aluminum alkyls and Lewis acids , with a molar ratio of complex: cocatalyst 1 1 10,000. 4. The method of ion-coordination polymerization by contacting one or more monomers with a catalyst, characterized in that the monomer is a compound selected from the group consisting of ethylene, propylene, butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, vinyl-cyclohexane, vinylbenzocyclobutane, the catalyst according to claim 3 is used as a catalyst, the polymerization process is carried out at 80-160 ^o C and pressure from atmospheric to 3100 kPa.

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