Metal coordination complex catalyst for ion coordination polymerization, a method of ion coordination polymerization

 

(57) Abstract:

Use: catalyst for ion coordination polymerization, comprising a metal coordination complex. The inventive metal coordination complex of the General formula:

< / BR>
where Z = Si/CH3/2Si/CH3/2Si/CH3/2-, -CH2-CH2-, -CH2CH/CH3/ , M = titanium, zirconium or hafnium. The catalyst for ion coordination polymerization involving specified complex and socialization selected from the group consisting of methylalumoxane, Akilov aluminum and Lewis acids in a molar ratio of the complex : socialization equal to 1 : (1 - 1000). The method of ion coordination polymerization of a monomer selected from the group consisting of ethylene, propylene, butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, vinylcyclohexane, vinylbenzoate, in the presence of the specified catalyst at 80 - 160oC and a pressure of from atmospheric up to 3100 kPa. 3 N. p. F.-ly, 1 C. p. F.-ly.

The invention relates to metal coordination complexes with hard structure. The invention relates also to a number of new polymerization catalysts accession containing such m is olymerization accession, and to the resulting polymers.

Due to the unique location of the active metal center metal coordination complexes with hard structure, produced from these catalysts have unique properties. In some conditions, the catalysts of the invention allow to obtain new olefinic polymers with previously unknown characteristics because of their ability to polimerizuet alpha-olefins, diolefine, employed vinylidene aliphatic monomers, vinylidene aromatic monomers, and mixtures thereof.

Experts know a lot of metal coordination complexes, including complexes containing monosyllabically group and substituted monosyllabically group. Consider metal coordination complexes differ from those previously known fact that metal is associated with the replaced fragment with delocalized connection connection so that a tense structure around the metal. Preferably, the metal was associated with cyclopentadienyl, substituted cyclopentadienyl, or a similar group on both 5-ties, and bridge the communication included the rest of the ligands of the metal. anee were also known coordination complexes of transition metals, known as tucked complexes. Such complexes are described in Organometallics, 6, 232-241 (1987).

From U.S. patent N 4680353, 08 F 112/08, 1985 a method of obtaining a polymer including polystyrene, by polymerization in the presence of a metal catalyst complex, in particular titanium and aluminum-organic socializaton.

In the application of the U.S. N 8800, filed January 30, 1987 (published in equivalent form as EP 277004) revealed some bis(cyclopentadienyls) metal compounds obtained by the reaction of bis(cyclopentadienyl) metal complexes with salts of acids of Bronsted containing coordinarussia compatible anions. References disclose the fact that such complexes are successfully used as catalysts in the polymerization of olefins. The above catalysts are not considered particularly effective catalysts for the polymerization of olefins.

Past attempts to obtain copolymers vinylidene aromatic monomers with alpha-olefins, in particular copolymers of styrene and ethylene, have been unsuccessful either due to the inability of a significant inclusion vinylidene aromatic monomer, or because polymers with a low molecular weight. In Pol polymer was 8.3 x 10-4g of the polymer in micromoles used titanium.

It was found that previously known polymerization catalysts merger is not capable of high activity and polymerization of many monomers due to the fact that they have no tense structure.

One aspect of the invention relates to a metal coordination complex tense structures. More specifically relates to such coordination complexes, which are successfully used in combination with an activating socialisticheskie compounds or mixtures of compounds for the formation of a catalytic system that can be used in the polymerization of accession of the polymerized monomers, especially Ethylenediamine monomers.

In another aspect of the invention it relates to a method for producing polymers of accession, especially homopolymers and copolymers of olefins, diolefins, difficult aliphatic vinyl monomers and mixtures of the above monomers and the resulting polymers.

In accordance with the invention, proposed is a metal coordination complex corresponding to the formula

< / BR>
where R' in each case represents hydrogen or m

X represents in each case, chloride, methyl, benzyl or O-(N,N-dimethylamino)benzyl;

Y is-O-, -NR*- PR*-, where R* in each case represents hydrogen or 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 represents Si(CH3)2, -Si(CH3)2Si(CH3)2-, -CH2-CH2- or-CH2CH(CH3)-;

n represents the integer 1 or 2.

A catalyst suitable for ion coordination polymerization, containing the following components:

a) a metal coordination complex of the invention, preferably corresponding to the formula I and activating socialization selected from the group consisting of methylaluminoxane, Akilov aluminum and Lewis acids in a molar ratio of the complex socialization(1 1) (1 10000).

Further in accordance with the invention proposed a polymerization process comprising contacting one or more of the polymerized by the addition of monomers in the polymerization conditions of the merger with catalyst, including:

a) a metal coordination complex 160oC and a pressure of from atmospheric up to 3100 kPa.

Further in accordance with the proposed invention, the polymer containing polymerized form one or more of the polymerized by the addition of monomers obtained by contacting the polymerized by the addition of the monomer or mixture of monomers in the polymerization conditions of the merger with catalyst, containing:

a) a metal coordination complex, preferably corresponding to the formula I, and activating socializaton.

In the next version of the proposed EIPE polymers with high elasticity, interpolymer ethylene and one or more of the olefins other than ethylene.

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

The complexes of the invention is convenient to use as socialization for polymerization of accession for polymers that are suitable as molding, packaging films, foam cushioning materials, and for the modification of synthetic and natural resins. These complexes can so sah.

In Fig. 1 5 presents computer models of the complexes with the tense structure of the invention constructed on the basis of x-ray data of single crystals of Fig. 6 and 7, a computer model of metal complexes, calculated on the basis of x-ray analysis of single crystals, which are less stiff than the model of Fig. 1 5; Fig. 8 13 the calculated and the observed distribution of styrene, ethylene, back styrene segments in the copolymers of ethylene and styrene, corresponding pseudostatic inclusion in accordance with the invention; Fig. 14 the lack of correspondence between the calculated and observed distribution of styrene, ethylene and reverse styrene segments in the copolymers of ethylene and styrene, if fully complied with the rules of the statistical inclusion of Fig. 15 typical rheological curves EIPE resin according to the method of the invention. Presents the complex viscosity*and tan d as a function of shear rate for the resin, and Fig. 16 typical curve of modulus of elasticity from the melt index resin EIPE of the invention; Fig. 17 typical rheological curves of polyethylene resin, obtained in the usual way. Presents the complex viscosity*and tan d as a function of speed is whose of a single crystal shown in Fig. 1 7.

In Fig. 1 shows the structure /4 methylphenylamine/dimethyl/-tetramethyl-5-cyclopentadienyl/sentimentalised defined on the basis of the crystal x-ray crystallography crystal. The angle formed by the centroid cyclopentadienyls ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and the nitrogen atom N 14, is 105,7o.

In Fig. 2 shows the structure of (tert.-butylamide) dimethyl/tetramethyl-5-cyclopentadienyl/dilantinlevitra defined on the basis of x-ray crystallography single crystal. The angle formed by the centroid cyclopentadienyls ring (C2, C3, C3*, C5 and C5*), a zirconium atom (ZRI) and nitrogen atom (N 9), is 102,0o.

In Fig. 3 presents the structure (phenylamino/dimethyl/tetramethyl-5-cyclopentadienyl) sentimentalised defined on the basis of x-ray crystallography single crystal. The angle formed by the centroid cyclopentadienyls ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and nitrogen atom (N 14), is 106,1o.

In Fig. 4 shows the structure (tert.-butylamide/dimethyl- 5-cyclopentadienyl)silentservicecode defined on the basis of x-ray crystallographically. The angle formed by the centroid cellpenetrating ring (C2, C3, C5, and C6), the atom of zirconium (ZRI) and nitrogen atom (N 10), or the angle formed by the centroid cyclopentadienyls ring (C102 will turn on, S103, S, S and S), a zirconium atom (ZR101) and nitrogen atom (N 110), is 99.1o.

In Fig. 5 shows the structure of (tert.-butylamino) of dimethyl-/tetramethyl-5-cyclopentadienyl/silentservicecode. The angle formed by the centroid cyclopentadienyls rings (C1, C2, C3, C4, and C5), the atom of zirconium (ZR) and nitrogen atom (N), is 102,0o.

In Fig. 6 shows the structure of (tert.-butylamide/dimethyl/ tetramethyl-5-cyclopentadienyl)silentservicecode defined on the basis of single crystal x-ray crystallography. Relatively long disiplina linking group is an amide ligand allows the nitrogen atom to be less stressful. The angle formed by the centroid cyclopentadienyls ring (C2, C3, C5, C7 and C9), the atom of zirconium (ZRI) and nitrogen atom (N-17) is 118,0o.

The activity of this catalyst in the polymerization of olefins significantly lower compared to similar monosilane linking group (tert.-butylamide/dimethyl-5-cyclopentadienyl/ silenciador>-cyclopentadienyl/ dicyandiamide defined on the basis of x-ray crystallography single crystals. Relatively long disiplina linking group that connects cyclopentadienyls ring with the nitrogen atom of the amide ligand, provides less tension to the nitrogen atom. The angle formed by the centroid cyclopentadienyls ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and nitrogen atom (N 17), was 120.5o. Accordingly, the activity of this catalyst in the polymerization of olefins is significantly lower compared to similar monosilane bridge group, tert.-butylamide/dimethyl/ tetramethyl-5-cyclopentadienyl/sentimentalize.

The term "activating socialization", as used here, refers to the secondary component of the catalyst, which can increase the efficiency of metal complex as a catalyst for polymerization of accession or in another embodiment to balance the ionic charge of catalytically activated sample. Examples of the above-mentioned activating socialization for use in the invention include aluminum compounds, including Al-O bond, as alkylalkoxy, especially medialooks the applications of salt, non-competing oxidizing agents, such as salts of silver, iron ions, etc. as well as mixtures of the above compounds.

Additional suitable activating socializaton include compounds corresponding to the formula

< / BR>
where R means occurring every C1-10alkyl or aralkyl;

X is a halogen;

n is 1, 2 or 3.

The most preferred such socializaton as connection trialkylamine, in particular triethylamine.

The monomers of the polymerization of joining include, for example, Ethylenediamine monomers, acetylenic compounds, conjugated or unpaired diene, polyene, carbon monoxide, etc. Preferred monomers include C2-10alpha-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-penten and 1-octene. Other preferred monomers include styrene, halogen and alkyl-substituted styrene, vinyl chloride, Acrylonitrile, methyl acrylate, telecarrier, tetrafluoroethylene, Methacrylonitrile, vinylidenechloride, vinylbenzoate and 1,4-hexadiene.

The term "employed aliphatic vinylidene connection" means the polymerized attach vinylidene monomorium up to 20 carbon atoms;

G is independently in each case is hydrogen or stands;

G' in each case independently is hydrogen or stands, or other option;

G' and R" together form a cyclic system.

The term "steric bulk" understand that the monomer with the same Deputy who usually are not capable of participating in polymerization of accession with the usual polymerization catalysts of the Ziegler-Natta with a speed comparable to the polymerization of ethylene. Preferred sterically difficult aliphatic vinylidene compounds are monomers in which one of the carbon atoms containing the ethylene unsaturation, is three or chetyrehjadernym. Examples of such substituents include cyclic aliphatic groups as cyclohexane, cyclohexene, cyclooctene or cyclic alkyl or aryl-substituted derivatives thereof, tert.-butyl, norbornyl etc. Most preferred hampered aliphatic vinylidene compounds are the various isomeric vinyl-cyclically substituted derivatives of cyclohexene and substituted cyclohexene and 5-ethylidene-2-norbornene. The most suitable are 1-, 3 - and 4-vinylcyclohexane.

Under thermometry, corresponding to the formula:

CG2CG'R'",

where R'" is either R or aryl Deputy containing up to 20 carbon atoms;

G and G' have the previously indicated meanings.

For example, in addition to difficult aliphatic vinylidene compounds employed vinylidene compounds also include vinylidenefluoride monomers. The term "vinylidene aromatic monomers" means participating in polymerization attach the appropriate formula

CG C(G) Ph,

where G is independently in each case is hydrogen or stands;

Ph is phenyl, or halogen - or C1-4alkyl substituted phenyl group.

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

The term "alpha-olefin" refers to ethylene and C3-10olefins containing ethylene unsaturation in the alpha position. Preferred alpha-olefins are ethylene, propylene, butene, styrene, 4-methyl-1-penten, 1-hexene, 1-octene, vinylcyclohexane, vinyl is UP>5related groups that are cyclopentadienyls or substituted cyclopentadienyls groups that form a cyclic structure with atoms of metals. Preferred fragments with delocalized n-link group silapentane, indenyl and fertile, and their saturated derivatives, which form a cyclic structure with the metal atom. Each carbon atom in cyclopentadienyls radical may be substituted or unsubstituted, and the substituents may be the same or different and are selected from the group consisting of hydrocarbon radicals and substituted hydrocarbon radicals and substituted hydrocarbon radicals in which one or more of the hydrogen atoms substituted by a halogen atom, a hydrocarbon substituted metallogenic radicals, in which the metalloid selected from group 14 of the Periodic table of elements, and halogen radicals. In addition, two or more of these substituents may together form a condensed cyclic system. Suitable hydrocarbon and substituted hydrocarbon radicals which may be substituted, at least one hydrogen atom in cyclopentadienyls radical can contain 1 to 20 carbon atoms and include the major cyclic hydrocarbon radicals, aromatic radicals and alkyl substituted aromatic radicals. Suitable metalloorganic radicals include mono-, di - and tri-substituted metalloorganic radical elements in 14 groups, where each hydrocarbon group containing 1 to 20 carbon atoms. More specifically, suitable metalloorganic radicals include trimethylsilyl, pendimethalin, maildefinition, triphenylsilane, triphenylene, trimethylgermyl, etc.

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

The most preferred metal coordination complexes correspond to the formula

< / BR>
where R' in each case is hydrogen or stands, or a complex pair R'-group forms hydrocarbonyl ring, connecting in cyclopentadienyls part;

Y is-O-, -NR*-, -PR*-;

M represents titanium, zirconium or hafnium;

Z is Si(CH3)2, -Si(CH3)2Si(CH3)2-, -CH2-CH2- or-CH2CH(CH3)-; R* in each case is hydrogen or a fragment selected from the group consisting of alkyl, aryl, Silla, the halogenated alkyl, halogenated aryl and their S="ptx2">

It should be noted that because the formula I and the subsequent formulas indicate a cyclic structure for the catalyst, the relationship between M and Y is more correctly called a coordinate covalent bond. It should also be noted that the complex may exist as a dimer or higher oligomers.

Further, it is preferable that at least one of R', Z or R* was electron-donor fragment. So, particularly preferably, Y was nitrogen - or fosforsoderzhashchie group corresponding to the formula-N(R") -, or-P(R")-, where R" is C1-10the alkyl or aryl, that is, amido - or hospitaltype.

The most preferred complex compounds are aminosilane or aminoalkanoic-compounds corresponding to the formula

< / BR>
where M is titanium, zirconium or hafnium, bound-type5with cyclopentadienyls group;

R' each are hydrogen or stands, or adjacent pair of R' groups form a hydrocarbon ring condensed with cyclopentadienyls fragment;

E is silicon or carbon;

X takes on the values specified above;

m is 1 or 2;

n is 1 or 2 depending on the valency M

Examples vishey R' amide group is stands, the ethyl, propylene, bootrom, Pentium, hexyl (including isomers), norbornyl, benzyl, phenyl, etc. cyclopentadienyls, the group is cyclopentadienyl, indenolol, tetrahydroindene, florinela, octahydronaphthalene, etc. R' in the above cyclopentadienyls groups each time is hydrogen, stands, and X is chlorine, bromine, iodine, stands, ethyl, propylene, bootrom, Pentium, hexyl (including isomers), norbornyl, benzyl, phenyl, etc. Specific compounds are (tert. -butylamide//tetramethyl-5-cyclopentadienyl/-1,2-tenderloi-dichloride, (tert. -butylamide)(tetramethylcyclopentadienyl)-1,2-atavistically (methylamide)(tetramethyl-5-cyclopentadienyl/-1,2-candiicanedane (methylamide//tetramethyl-5-cyclopentadienyl/-1,2-atavistically (ethylamino//tetramethyl-5-cyclopentadienyl/-methylenedianiline, /tert.-butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/sentimentalised, (tert. -butylamino) (dimethyl/tetramethyl-5-cyclopentadienyl/chilanzarminibank (benzylamino/dimethyl-/tetramethyl-5-cyclopentadienyl/sentimentalised (phenylphosphino/dimethyl/ tetramethyl-5-cyclopentadienyl inventions get combining metal coordination compound and activating socialization in any order and in any suitable way. Preferably, the ratio of the coordination complex and socializaton was (1 1) (1 in 10,000) (per mol). Of course, I should note that the catalytic system can also be obtained in situ, if its components are added directly to the polymerization process and a suitable solvent or diluent, including condensed monomer, used in the specified polymerization process. Suitable solvents include toluene, ethyl benzene, alkanes, and mixtures thereof. In some cases, the catalysts can be distinguished from the solution and stored in an inert atmosphere prior to use. The components of the catalyst are very sensitive to moisture and oxygen, and to work with them and transfer them necessary in the inert atmosphere such as nitrogen, argon or helium, or vacuum.

Polymerization usually are well-known ways for types of polymerization Ziegler-Natta or Kaminsky-Sinn. That is, the monomer (monomers) and the catalyst is subjected to interaction at a temperature of 80 160oC from atmospheric pressure up to 3100 kPa. Polymerization lead in an inert atmosphere, which mold for control of molecular weight due to chain breakage, as known in the art. The catalyst can be used either as it is or on a suitable substrate, such as alumina, MgCl2or silicon dioxide, to obtain a heterogeneous deposited catalyst. At desire it is possible to use a solvent. Suitable solvents include toluene, ethyl benzene and excess vinylidene aromatic or olefinic monomer. The reaction may also be conducted in solution or in suspension, using perfluorinated hydrocarbons or similar liquid, in the gas phase, i.e. using a reactor with a fluidized bed, or in the solid phase polymerization in the powder). A catalytically effective amount of the examined catalyst and socializaton are any quantities that lead to successful receipt of the polymer. These amounts can easily be determined in the usual experiments known in the art. The preferred amount of catalyst and socializaton are sufficient to provide the equivalent relations of the polymerized attach the monomer catalyst from about 1 x 10101 1 to 100, preferably 1 x 1081) (500 1), more preferably (1 x 1061) (1000 1). Socialization usually used in Koli is 1).

Note that the metal complex can undergo various transformations or to form intermediate products before or during the polymerization process. Thus, it is possible to imagine other predecessors to achieve the same catalytic samples presented here, without leaving the scope of the invention.

The resulting polymer product produce by filtration or other known techniques. In the polymers of the invention can include additives and excipients to provide the desired characteristics. Suitable additives include pigments, UV stabilizers, antioxidants, foaming agents, lubricating agents, plasticizers, photosensitizers, and mixtures thereof.

Upon receipt of the copolymers containing vinylidene aromatic or employed aliphatic vinyl monomers, it is desirable to use comonomer, i.e. alpha-olefin, which is not partially sterically difficult. Without pretending to any particular theory, it can be assumed that this is due to the fact that the active site is blocked when switching difficulty vinyl compounds, which make it unlikely that inclusion in the polymerization of other difficult Finow, other than difficulty vinyl compounds, active site once again becomes available for inclusion difficulty of the vinyl monomer, but in limited quantities. Vinylidene aromatic monomer or sterically hindered vinyl monomer may be incorporated into the polymer chain in reverse order, i.e. in such a way that leads to the existence of two methylene groups between the substituted polymer fragments in the polymer chain.

Preferred such polymers, mol. M. which would have been more than 13,000, more preferably more than 20,000 and most preferably more than 30,000. Also preferably, such polymers have melt index I2ASTM D-1238 procedure a, condition E, less than 125, more preferably 0.01 to 100, and most preferably 0.1 to 10.

By using the previously mentioned catalytic systems containing a coordination complex with intense structure, it is possible to obtain copolymers that include a relatively large or monomers employed almost statistical manner at low concentrations, but at high concentrations in accordance with the logic of ordered inclusion. Copolymers of alpha-olefins, especially teleoperate hereinafter referred to as "pseudotachylites", that is, in the copolymers is not well-defined blocks of any monomer, however, the corresponding monomers are limited to some of the rules of procedure include.

These rules were derived from some experimental details the following from the analysis of polymers. These polymers was investigated using NMR13C spectroscopy at 130oC spectrometer Varian-VXR-300 when 75,4 MHz. The polymer samples 200 250 mg was dissolved in 15 ml of hot orthodichlorobenzene (1,1,2,2-tetrachlorethane-d2approximately 70/30 volume/volume, which amounted to approximately 0.05 M in chromium (III) Tris/acetylacetonate, and a portion of the resulting solution was injected in 10 mm vials NMR. The shooting conditions were as follows: spectral width 16500 Hz, accumulation time 0,090 C, pulse width 36othe delay of 1.0 s, and during this delay, decoupler disabled, the size of 32K FT, the number of scans over 30,000, the broadening of 3 Hz. As standard tetrachlorethane-d2(d/ 73,77 million dollars. in the TMS scale).

So, without contacting any particular theory, we can say that the results of the above procedure indicates that a particular hallmark of pseudostatic copolymers is the fact that all phenyl or volumetric strode, polymers containing monomers employed in the invention can be described by the following General formula (using as an illustration of the difficulty of monomer styrene):

< / BR>
where j, k and l1.

Explaining further, the above experimental and theoretical results and not binding to any specific theory, it can be assumed that in the polymerization process attach with the use of the catalyst, if hindered monomer include in the growing polymer chain, included the following monomer must be ethylene or difficult monomer, which is included in the reverse order or "tail to tail". This is illustrated next to difficult vinyl monomer, where M is the metal center of the catalyst, HG is hindered group, and R is a growing polymer chain:

< / BR>
During the polymerization reaction of ethylene can be enabled at any time. After turning difficult monomer "tail to tail", the following monomer must be ethylene, as the inclusion of another difficult monomer in this place will lead to the convergence difficult deputies closer than the minimum separation as described earlier.

Sledstvie ibud largely while a mixture of ethylene and styrene is rapidly polymerized and the styrene content may be high (up to 50 mol. styrene) copolymers.

As the following illustration, the description of a copolymer of alpha-olefin/hindered monomer of the invention used a computer model of the polymerization reaction for calculating the expected13From the NMR spectrum of the polymer product. The computer program used a random number generator to select on or alpha-olefin, or shortness of monomer into the growing polymer chain, and then counted the number of signals13For each type, resulting in such inclusion. The polymers was calculated by repeating this process for 10,000 or more Monomeric impurities, and calculated data for the13From the NMR spectrum was compared with the actual experimental13From the NMR spectrum for pseudotachylites copolymers, ethylene-styrene copolymer of the present invention.

Computer simulation of polymer and received 13With NMR spectra calculated pseudotachylites copolymers eTelestia was carried out using the assumption that if styrene monomer is included in the growing polymer chain, the following are included m the meaningful coincidence of the experimental and calculated spectra was observed for the case where he received approximately 15 styrene inclusions way "tail to tail". The observed and calculated spectra 13With NMR for such pseudotachylites copolymers, ethylene-styrene containing 1,4, 4,8, 9,0, 13, 37 and 47 mol. styrene is shown in Fig. 8 13. In each case observed in the calculated spectra are in good agreement.

Then carried out the computer simulation of the polymer and the corresponding spectrum13With NMR for fully random copolymers of alpha-olefin/hindered monomer without using assumptions about the inclusion of difficult monomer. In other words, poor monomer was incorporated into the growing polymer chain after the previous inclusion of difficult monomer, if the random number generator chose hindered monomer as the next monomer to be activated. The calculated spectra for these random copolymers are not consistent with the observed spectra 13With NMR, as seen in Fig. 14 to 37 mol. styrene in the copolymer of ethylene/styrene.

Before polymerization according to the method of the invention, the monomers and the solvent, if used, can be cleaned by vacuum distillation or by using molecular sieves, silica or OK is to connect trialkylamine, alkali metals, alloys of metals, especially of Na/K

Suitable vinylidene aromatic monomers that can be used in accordance with the method of the invention include styrene and alpha-methylsterol, C1-4alkyl, phenyl, substituted cyclic derivatives of styrene, such as ortho-, meta - and para-methylsterol or mixtures thereof, cyclic halogenated styrene, vinylbenzoate and divinylbenzene. Preferred vinylidene aromatic monomer is styrene.

When polymerization vinylidene aromatic monomers or obstructed aliphatic vinylidene compounds and olefin monomers are preferably combined in such proportions to achieve content vinylidene aromatic monomer (or difficult aliphatic vinylidene connection) 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 polymerization reactions are pressures from atmospheric to 1000 atmospheres. and temperature arow, may contain a small amount of homopolymer products resulting from free radical polymerization.

Some of the polymers obtained by the method of the invention, particularly copolymers of ethylene and alpha-olefins other than ethylene, characterized by unique rheological properties. In particular, it was found that the polymers (hereinafter called elastic polyethylene or EIPE) less newtonians than usual the linear polyethylene resin with the same content of the olefin. These polymers also have a higher elastic modulus, especially at high melt indexes in comparison with these values for conventional polymers. This property makes the resin is particularly useful in obtaining films of foamed materials and woven products, for example, obtained by the method of forming blown. The above phenomenon is more specifically defined with reference to Fig. 15, where the viscosity of the complex*measured in peasah at 190oC deferred as a function of shear rate, w is measured in radians on with typical EIPE copolymers of ethylene and 1-octene by the method of the invention. The slope of this curve indicates that the melt is highly Newtonian what such values of tan for the same EIPE polymer. This value is dimensionless and is calculated by dividing the modulus of viscosity on the modulus of elasticity. The real values of tan and w, used in the graph presented in table. 2.

For improved performance in applications for forming blown preferably, tan was from 0.1 to 3.0 for shear rates between 0.01 - 100 rad/s

The following property EIPE polymers is illustrated in Fig. 16: modulus of elasticity in Dyne/cm2, G, at 0.1 rad/s and 190oC for several ethylene/-1-octene EIPE resins constructed as a function of melt index. Used resins include resins of examples 11, 12, 14 16, 18 22, 24 - 26, 30 and 31.

Index values of the melt and the moduli of elasticity that was used to build the graph, see the following table. 3.

Typical characteristics*and for polyethylene resin obtained in the usual way, is shown for comparison in Fig. 17.

It is easy to see that EIPE resins have a higher elastic modulus in the melt. In particular, EIPE resins have a melt index (I2), ASTM D-1238 procedure a, condition E, of less than 200, preferably less than 125, and more preferably less than 50, and the elastic modulus of more than 1,000 Dyne/cm2more preferably more than 2000 Dyne/cm2. In the. ntroduction to Rheology, Elsevior publishing, Inc. 1989.

Density usually in the range of 0.85 to 0.97 g/ml, preferably of 0.89 to 0.97 g/ml Molecular weight distribution (MW/PM) is more than 2.0, preferably of 3.0 to 10.0. Usually the melting point in the range of 50 135oC.

Preferred polymers additionally demonstrate properties of homogeneous polymers as described in U.S. patent N 3645992, i.e. the ethylene copolymers have a substantially statistical distribution within a given molecule and substantially the same ratio of ethylene/copolymer between molecules. The polymers obtained at elevated temperatures, especially at temperatures exceeding 130oC, can give the curve a heterogeneous melt. Further, the polymers of the invention have better optical properties, especially low turbidity unlike conventional ethylene polymers, which makes them particularly adapted for the manufacture of films and articles by injection molding.

In addition, these polymers containing olefin and vinylidene aromatic monomers, especially ethylene and styrene, as was surprisingly found to have properties of elastomers. Thus, such polymers are surprisingly suitable for use as thermoplastics bitumen, adhesives, elastomeric products, etc.

The polymers of the invention can be modified in the usual grafting, crosslinking, hydrogenation, addition of functional groups or other reactions well known to the specialists. That specifically relates to polymers containing vinylidene aromatic compounds, vinylcyclohexane and/or 1,4-hexadiene functional groups, they can easily alfirevich or gloriavale to obtain functional derivatives, obtained by the standard technique. In addition, the polymers based on vinylcyclohexane easily stitched in the interaction of unsaturated functional groups of the loop.

The polymers of the invention, regardless of whether modified or not, can be mixed with synthetic or natural polymers to obtain mixtures having the desired properties. In particular, polyethylene, copolymers of ethylene/alpha-olefin, polypropylene, polystyrene, copolymers of styrene/Acrylonitrile (including resin modified their derivatives), syndiotactic polystyrene, polycarbonate, polyamide, aromatic complex polyester, polyisocyanate, polyurethane, polyacrylonitrile, silicone and polymers polyphenyleneoxides can be mixed with the polymer component is preferred variant of the invention the polymers, containing ethylene and styrene, are elastomeric in accordance with the definition of elastomeric substances in AST special technical Bulletin N 184, as a substance which can be at room temperature to stretch to twice the length and it will return to its original length upon release.

In addition to the modification of synthetic thermoplastics, these polymers can also be used as modifiers for the compositions of asphalt or bitumen. It is desirable to use polymers of styrene/ethylene.

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

1. The asphalt.

I. Petroleum asphalts.

A. Directly recovered asphalt.

pan.

C. Thermal asphalts, as a residue from the cracking of crude oil.

C. Oxidized asphalts.

1. Direct oxidation.

2. "Catalytic" oxidation.

2. Natural asphalts:

A. mineral content below 5

1. Asphaltite, such as Gilsonite, graphemic and clean asphalt.

2. Bermuda and other natural deposits.

C. mineral content higher than 5

1. Natural asphalts.

2. Trinidadian and other natural deposits.

II. Tar and derivatives.

1. Process residues from coal tar.

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

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

2. The remains of other pyrogenic distillates, such as wood, peat, bone, slate, resin and fatty acids of tar.

As easy to see specialists, srednevekovoi molecular weight of the various bitumens may vary in a wide range, for example 500 to 10000. In addition, the softening point of the different types of asphalt also vary 10 - 205oC.

From all ini thermal asphalts.

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

Describing the invention with the aid of the following examples, offer them as an additional illustration and should not be construed as limiting. If no contrary instructions, parts and percentages are given by weight.

Example 1. Receiving (tert-butylamide)dimethyl(tetramethyl-5-cyclo-pentadienyl)silentservicecode.

To 0,443 g (1,90 mmol) ZrCl4into the flask, add 8 ml of diethyl ether, and then 15 ml of tetrahydrofuran (THF). To the resulting suspension is added slowly a solution 0,500 g (1,90 mmol) delity(tert-butylamide)dimethyl(tetramethylcyclopentadienyl)silane in 15 ml of THF. The resulting yellow solution is stirred for several days. The solvent is removed, getting a sticky residue, which is extracted with a mixture of 5 1 (by volume) ethyl pentane and filtered from the white precipitate. The solvent is removed from the yellow filtrate receiving light yellow powder. Recrystallization from a mixture of ether pentane (5 1) gives the product (C5Me4(Me2Si-N-tert-Bu)ZrCl2in the form of almost white crystalline ve is.

A. Five ml with 1.009 M solution methylalumoxane (MAO) in toluene is added to the reactor containing 25 ml of 5-methyl-1-pentane. The catalytic solution was prepared by adding 500 ml 0,01172 M solution5Me4(Me2Si-N-tert-Bu)ZrCl2in toluene to 2 ml of toluene in the second reactor. Both reactor sealed and transferred from the camera with gloves in the autoclave of stainless steel. The autoclave pump and purge with argon.

A solution of 4-methyl-1-penten/toluene/MAO added to the autoclave and heated to 89oC at a pressure of ethylene of 620 kPa (6,88 kg/cm2and stirring. After adding the catalyst solution to the 4-methyl-1-penten/MAO/ethylene mixture pressure of ethylene is increased to 1240 1275 kPa (12,66 13,00 kg/cm2). After 2 h the solution is cooled to 30oC and open to the atmosphere. The polymer yield after drying under reduced pressure at 100oC over night get 10,0,

13With NMR analysis of the polymer shows that get a statistical copolymer of ethylene with 4-methyl-1-pentanol.

B. Polymerization.

Basically repeat the polymerization And except that instead of 4-methyl-1-pentene use 50 ml of 1-hexene, and the concentration of catalyst in toluene is 0,01012 M. Catalytic rest is bauleni catalytic solution, the temperature of the reaction mixture rises to 139oC. After 30 minutes the solution is cooled to 100oC. Heating and purging of ethylene was stopped and the solution is cooled and opened to the atmosphere. The polymer yield after drying under reduced pressure at 100oC during the night is to 36.8 g13With NMR analysis of the polymer shows that the product is a statistical copolymer of ethylene with 1-hexene (8 mol).

C. Polymerization.

Basically repeat the polymerization And except that they use 213 l catalyst solution (0,01172 M in toluene) and 143 mg of solid MAO. Olefin is added. Adding to the reactor a metal solution temperature rises to 109oC due to ekzotermicheskie the polymerization reaction. The reaction is stopped after one hour by cooling and opening the reactor to the atmosphere. The yield of polyethylene after drying under reduced pressure at 100oC over night get 11,0,

, 130 ml of toluene are placed in the autoclave used in the polymerization And then add 100 g of propylene. Add a solution of 0.828 g of MAO in toluene (8 ml), then 2130 m catalyst solution. The mixture reacts for 3.0 hours at the 8oC. the Reaction is quenched with acidified methanol and gain of 0.38 g of a white sticky substance.

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

To a solution of 21.5 g (167 mmol) clear in 150 ml of THF, cooled to -40oC, slowly add a solution of 8.00 g (55,6 mmol) 1,2,3,4-tetramethylcyclopentadiene of sodium in 80 ml of THF. The reaction mixture is allowed to warm to room temperature and stirred over night. The solvent is removed, the residue extracted with pentane and filtered. The pentane removed under reduced pressure, obtaining the product as a pale yellow oil.

The output of 10.50 g (88,0).

1H NMR (C6D6d 2,89 (s, 1H), 1.91 a (C, 6N), 1,71 (C, 6N), 0,14 (C, 6N).

13WITH NMR (C6D6d 137,8; 131,5; 56,6; 14,6; 11,4; 0,81.

(b) (Tert-butylamino)(dimethyl)tetramethylcyclopentadiene-2,4 - enyl)silane.

The solution 11,07 g (151 mmol) of tert-butylamine in 20 ml of THF added dropwise within 5 min to a solution 13,00 g (of 60.5 mmol) (chlorine) (dimethyl) (tetramethylcyclopentadienyl) silane in 300 ml of THF. The precipitate formed immediately. The suspension is stirred for 3 days, then remove the solvent, the residue is extracted with pentane and filtered. The pentane removed under reduced pressure, obtaining the product as a pale yellow oil.

13WITH NMR (C6D6d/ 135,4; 133,2; 57,0; 49,3; 33,8; 15,0; 11,2; 1,3.

(C) Delity(tert-butylamino)(dimethyl)-tetramethylcyclopentadienyl)silane.

To a solution of 3.00 g (11,98 mmol) (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 100 ml of ether is added slowly of 9.21 ml of 2.6 M (23,95 mmol) utility smesi C6aliphatic solvents. A white precipitate is formed and the reaction mixture was stirred overnight, then filtered. The solid residue is washed several times with ether, then dried under reduced pressure, obtaining the product as a white powder.

Output 3,134 g (99,8).

(g) (Tert-butylamino) (dimethyl) (tetramethyl-5-cyclopentadienyl)-sentimentalised.

0,721 g (of 3.80 mmol) of TiCl4add 30 ml frozen THF (-196oC). Mixture is allowed to warm to -78oC (bath of dry ice). To the resulting yellow solution slowly add a solution of 1.00 g (of 3.80 mmol) delity (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 30 ml of THF. The solution is allowed to warm to room temperature with stirring overnight. From the resulting very dark solution to remove the solvent. The residue is extracted with pentane and filtrauto yellow-green crystal. The solid is filtered and recrystallized from pentane, receiving olive-green product.

Output 0,143 g (10,2).

1H NMR (C6D6d a 2.00 (C, 6N), 1,99 (C, 6N), of 1.42 (s, N), 0,43 (C, 6N).

13WITH NMR (C6D6d 140,6, 137,9, 104,0, 62,1, 32,7, 16,1, 13,0, 5,4.

Getting 2.

Dry chamber with a syringe and injected into the flask to 100 ml of 4.00 ml of 2 M solution of isopropylacrylamide in diethyl ether. The ether is removed under reduced pressure leaving a colorless oil. Add 20 ml of a mixture of 4 1 (by volume) toluene THF, then 0.97 g (tert-butylamino)(dimethyl)(tetramethylcyclopentadienyl)silane. The solution is heated under reflux. After 8 to 10 h begins to form a white precipitate. After heating under reflux for 27 h, the solution is cooled and remove the volatiles under reduced pressure. The white solid residue is washed with pentane, filtered, obtaining a white powder (1.23 g, yield 62) Me4C5SiMeN-t-BuMg2Cl2(THF)2.

Dry chamber suspended 0.50 g TiCl3(THF)3in 10 ml of THF. Add 0,69 g hard Me4C5SiN-t-BuMg2Cl2(THF)2in the color varies from pale blue to dark purple. After 15 malaut under reduced pressure, getting yellow-green solid residue. Add toluene (20 ml), the solution is filtered and the toluene removed under reduced pressure, obtaining a yellow-green crystalline precipitate, 0.51 g (quantitative yield). Identify the product (tert-butylamino) (dimethyl)(tetramethyl-5-cyclopentadienyl)sentimentalised spectrum1H NMR (C6D6): d 1,992 (C) 1,986 (C) 1,414 (C), 0,414 ().

Getting 3.

TiCl40,72 g (of 3.80 mmol) are added to 35 ml of zamorozhennogo (-196oC) in the flask. The mixture is heated to -78oC. Slowly add a solution of 1.0 g (of 3.80 mmol) delity (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in THF. The resulting yellow solution is heated to room temperature and stirred over night. The solvent is removed, obtaining a dark residue, which was extracted with pentane and filtered. The product (C5Me4(Me2SiN-t-Bu) TiCl2) get in the form of dark green-yellow crystalline substance after double recrystallization from pentane at -35) (-40)oC. Identify the product by the spectra of13C and1H NMR.

Getting 4.

Dry chamber suspended TiCl3(THF)3(2.0 g, 5.40 mmol) in 40 ml THF. Then domovladelitsa darkens to dark blue. After 1 1/2 hours stirring AgCl (0.84 g, 5,86 mmol). Color immediately begins to lighten up red-orange. After 1 1/2 hours stirring THF is removed under reduced pressure. Add diethyl ether (50 ml), the solution is filtered and remove the volatiles under reduced pressure. The product yield (tert-butylamino) (dimethyl)(tetramethylcyclopentadienyl) sentimentalised 1,91,

1H NMR (C6D6d 1,992 (C) 1,987 (C) 1,415 (C), 0,415 ().

The polymerization.

The polymerization of mixtures of styrene/ethylene carry out the connection of 1.65 10 ml of a solution of MAO in toluene with a solution of 45 ml of toluene and 50 ml of styrene in the reactor of stainless steel. 250 ml 0,010 M solution of (tert-butylamide) dimethyl (tetramethyl-5-cyclopentadienyl) sentimentalised added to 2.5 ml of toluene in the second reactor. Both reactor block are transferred from the camera with gloves in a 600 ml autoclave made of stainless steel. The autoclave pump and purge with argon. A solution of styrene (toluene) MAO added to the autoclave and heated to 89oC at a pressure of ethylene of 620 kPa (6,33 kg/cm2and stirring. At the same time add a catalytic solution and increase the pressure up to 1275 kPa (13,00 kg/cm2), regulate pressure within 1240 ut 90oC and regulate within 90 92oC to the end of the reaction. After 1 h the supply of ethylene was stopped. The reaction mixture was open to the atmosphere and cooled to 30oC while adding methanol. The product is collected, washed with methanol and the remaining solvent is removed under reduced pressure at 120oC. the result of 9.02 g of substance.13With NMR analysis shows that the product is a statistical copolymer of styrene (15.2 by mol) and ethylene, the three peaks attributed to polystyrene.

Example 3 the polymerization of olefins).

Ethylene will polimerizuet by combining 5 ml of 1 M solution of triethylaluminum in a mixture of C6aliphatic solvents and 0.5 ml of 0.01 M solution of (tert-butylamide) dimethyl (tetramethyl-5- cyclopentadienyl) sentimentalised in toluene in a reactor made of stainless steel (NA). The solution of the titanium catalyst and triethylaluminium of socializaton add pressure in 3 l of NA autoclave containing 2 l of a mixture of aliphatic solvent (Isopar E, obtained from Exxon Chemicals, Inc. under the pressure of 3100 kPa (31,64 kg/cm), created by ethylene at a temperature of 150oC. the reaction Temperature support 150oC for 10 min. Pressure of ethylene also support postandpolmad obtained after drying under reduced pressure at 90oC during the night.

The output of 15.7 g

Example 4.

(Copolymerization of olefins).

In the camera with gloves in argon atmosphere merge of 5.0 ml of 1.0 M solution methylalumoxane (MAO) in toluene and 50 ml of 1-octene in a reactor made of stainless steel (NS), with the two sides of the float valve. In other NA reactor add 50 ml of 5.06 mmol) 0,0101 M solution of (tert-butylamide) dimethyl(tetramethyl-5- cyclopentadienyl)-silentservicecode in toluene to 2 ml of toluene. The reactor is hermetically sealed, transferring from the camera with gloves in 600 ml NS autoclave. The autoclave pump and purge with argon. A solution of 1-octene and MAO added to the autoclave. The solution is heated to 89oC at a pressure of ethylene of 620 kPa (6,33 kg/cm2and stirring. At the same time add a catalytic solution. The temperature of the exothermic reaction increases to 142oC. the Pressure of ethylene support between 1310 and 1345 kPa (made 13.36 13,71 kg/cm2).

After 0.5 h the supply of ethylene was stopped. The reactor is cooled to 30oC, open to the atmosphere and quenched the reaction with methanol. The product is collected on a porcelain filter and washed with methanol. The remaining solvent is removed under reduced pressure and 110oC, in the L. Differential scanning calorimetry (DSC) shows Tp100oC.

Density 0,895 g/ml, M. C. 44,000, M. C./M to 6.8 hours.

Example 5.

(Copolymerization of olefins).

Basically repeating the procedure of example 4, except that instead of 1-octene using 1-hexene. The temperature of the reaction support 133 - 140oC. the polymer Yield 37, the Incorporation of 1-hexene in the copolymer 8 mol. 21 wt.

Example 6.

(Homopolymerization a-olefin).

A. 4-methyl-1-penten (6,0 ml, 4.0 g) is added to 1.0 ml of 1.0 M solution of MAO in toluene 20 ml ampoule (crimp-top). There was added 100 ml of 0,01172 M toluene solution of a complex of zirconium catalyst of example 4. The vial sealed, shaken and left at room temperature (approximately 20 theoC) for 16 h, then heated to 48oC for another 24 h Viscous polymer solution is then precipitated by adding methanol. The polymer is collected, and the volatile components removed under reduced pressure and 100oC for 4 h, obtaining 3.8 g of pure polymer (exit 95).

13With NMR analysis shows that the polymer is atactic poly-4-methyl-1-pentanol.

B. basically repeat the procedure for the polymerization of A. 3.4 g of 1-Huck is a Vial sealed and heated at 50oC during the night. After quenching the reaction with acidified ethanol and drying obtain 3.0 g of poly(1-hexene).

Example 7.

(Homopolymerization ethylene).

The reactor stainless steel load 500 l (5,0 mole) 0,010 M solution of (tert-butylamide) dimethyl (tetramethyl-5-cyclopentadienyl)-sentimentalised in toluene and 2.5 ml of toluene in the camera with gloves filled with argon. In the second NA reactor to 92 ml of toluene, add 5.0 ml of 1.0 M solution of MAO in toluene. Both reactor sealed and transferred from the camera with gloves in a 600 ml autoclave. The autoclave pump, purge with argon and then filled with ethylene. The solution socializaton added to the autoclave and heated to 89oC at a pressure of ethylene of 620 kPa (6,33 kg/cm2). At this time in the reactor was added a solution of catalyst. The result is an exothermic reaction, the temperature rises to 109oC in a few seconds. The pressure of ethylene regulate between 1240 and 1275 kPa (12,66 13,00 kg/cm2). After 0.5 h, the temperature of the reactor was raised to 110oC and increase the flow of ethylene. An hour later, the supply of ethylene was stopped, the reactor open to the atmosphere and allow it to cool. The autoclave is opened, the reaction is quenched with methanol and separated polymer. After a mineralogicheskogo monomer.

4 vinylcyclohexane purified by vacuum distillation over Na/K alloy. Basically repeating the procedure of example 4, using 50 ml of 4-vinylcyclohexane and 5.0 ml of 1.0 M solution of MAO catalyst in toluene in a reactor of 500 ml 0,010 M solution of (tert.-butylamide) dimethyl(tetramethyl-5-cyclopentadienyl) silenzione-dichloride in toluene with 2 ml of toluene in a different reactor. The temperature rises to 114oC due to the exothermic reaction. The supply of ethylene was stopped after 1.0 h, cooled and opening the reactor to the atmosphere, quenched the reaction with acidified methanol. Gain of 12.6 g of substance.

13With NMR analysis shows that vinylcyclohexane forms a polymer in the amount of 1.5 mol.

Example 9. Copolymerization of ethylene/styrene.

Basically repeat the procedure described above polymerization except that the reaction temperature is 90oC. the Reactor was filled with 150 ml of a mixture of aliphatic solvents, 500 ml of styrene and 8 ml of 15 solution of MAO in toluene (1000 Al Ti). The reactor was filled with ethylene up to 1240 kPa (12,66 kg/cm2and to start polymerization add 20 Ámol [(C5Me4)SiMe2-N-phenyl)]TiCl2ethylene served until 1240 kPa (12,66 kg/cm2). After 60 min the solution drain out of the polymer of 26.6 g, the index of fusion (I2) 26,6.13With NMR analysis shows that the polymer contains 47 mol. styrene (76 wt.). 't see isotactic, atactic or syndiotactic sequence.

Example 10. Copolymerization of ethylene/styrene.

Basically repeat the reaction conditions of example 9 preparation of copolymers of styrene/ethylene different styrene content. The catalyst was (tert-butylamide) dimethyl (tetramethyl-5-cyclopentadienyl)sentimentalised instead of the above. Socialization MAO added in an amount to provide a ratio of Al 1000 M 1. Reaction conditions are given in table. 4.

Examples 11 32. In these examples, a chetyrehlitrovy autoclave load 2000 ml p astorias of a mixture of alkanes (Isopar-E) with different amounts of 1-octene. The catalyst is (tert. -butylamide) dimethyl/tetramethyl-5-cyclopentadienyl/sentimentalised dissolved in toluene. As socializaton use 10 solution of MAO in toluene. If desired, add hydrogen due to the expansion of 100 ml pressure vessel, above 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 and then add a solution of the catalyst. After 10 min the solution is drained from the reactor into a container, which contains a small amount of antioxidant (Iroanox 1010, supplied Ciba-Geigy). The polymer is dried in vacuum. The results are shown in table. 5.

Examples 33 to 42. Repeat the procedure of examples 11 to 32, except that the catalyst is (tert.-butylamide/dimethyl/tetramethyl - cyclopentadienyl/silencerqvigaob. The results are shown in table. 6.

Examples 43 to 57. Repeat the procedure of examples 11 to 32, except that they use a two-liter reactor, and the catalyst used (tert.-butylamide)dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised (2 ml of 0.005 M solution in toluene, 10 mmol). As socializaton use 15 MAO in toluene (2 ml, 500 Al, Ti).

The results are shown in table. 7.

Examples 58 77. Polymerization of olefins.

Ethylene and/or ethylene/1-octene will polimerizuet respectively as a homopolymer or copolymer, adding a solution of the appropriate catalyst in combination with MAO or acetalization triethylaluminium in three-liter SS autoclave containing a mixture of C6alkanes as a solvent (1-octene) (in different ratios) under snowy the flow meter controls the flow of ethylene. The polymer is then removed from the reactor and dried under reduced pressure at 90oC during the night. The results are shown in table. 8.

Example 78. Getting deposited on a substrate (tert.-butylamide/dimethyl/ tetramethyl-5-cyclopentadienyl/sentimentalised.

0,100 g dihydroxypropane silicon dioxide (HE concentration of about 1 mmol/g SiO2) are suspended in 20 ml solvent mixture of C6alkanes in the atmosphere of nitrogen in a dry box under stirring in a 50 ml Erlenmeyer flask. From this suspension of 1.0 ml selected syringe and connect with 1,10 ml 0,011 M solution in toluene (tert.-butylamide/dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised a 5 ml round bottom flask and stirred for 12 hours, After this period of time of 6.7 ml of 10 (wt./wt.) solution methylalumoxane (MAO) in toluene are added to a solution containing silicon dioxide.

The polymerization.

The polymerization are adding pressure above a suspension of titanium/silica/MAO in a three-liter autoclave containing 2 liters of a solvent mixture of alkanes, under pressure 3100 kPa (450 psi) of ethylene at 150oC for 10 min. Pressure of ethylene maintain a constant and RA and polyethylene emit after drying under reduced pressure at 90oC during the night. Output 30,0,

Example 79. Getting /2-methoxybenzylamine/dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised.

(a) ((Tetramethylcyclopentadienyl/dimethylallyl/2 - methoxyphenyl/Amin.

To 1.3 g (5.9 mmol) of ((tetramethylcyclopentadienyl/dimethylallyl/chloride in 50 ml of tetrahydrofuran (THF) is added 0,86 (5.9 mmol) of sodium-2-methoxyaniline. The resulting mixture is stirred over night. The solvent is removed under reduced pressure and the residue extracted with pentane. The pentane extracts are filtered, combined and concentrated to obtain a pale yellow liquid.

Yield 1.4 g (79).

1H NMR (benzene-d6d 6,91 (m, 2,2), 6,74 (m, 1,1), to 6.57 (d, 1,1 J 9), 4,25 (s, 1), 3,32 (3,7), of 1.93 (s, 6,7), 1,80 (6,8), 0,13 (6,3).

(b) Delity/tetramethylcyclopentadienyl/-dimethylallyl/- 2-methoxyphenyl/amide/

To 1.4 g (4.6 mmol) ((tetramethylcyclopentadienyl/dimethylallyl//2-methoxyphenyl/amine in diethyl ether is added dropwise to 3.9 ml of 2.5 M utility (9.8 mmol) in hexane. A white precipitate is formed. To this mixture pentane. The resulting suspension is filtered and the solid portion is washed with pentane.

(C) /2-methoxybenzylamine/dimethyl/tetramethyl-5- cyclopentadienyl/is and suspended in toluene, add 0,85 g TiCl4. The resulting mixture was stirred for three days and the solvent is removed in vacuum under reduced pressure. The residue is suspended in pentane and filtered to obtain a dark powder.

The output of 0.77 g (41).

1H NMR (benzene-d6d: 4,10 (s, 3), of 2.20 (s, 6.4), 1,99 (6,6), and 0.40 (s, 6,3).

Example 80. Receive (4 formanilide/dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised.

(a) ((Tetramethylcyclopentadienyl)dimethylsilane)(4-forfinal)- amine.

Equimolar amounts ((tetramethylcyclopentadienyl) dimethylsilane/chloride and lithium-4-fernilee combined in THF and the resulting mixture is stirred over night. The solvent is removed under reduced pressure.

1H NMR (benzene-d6d: 6,79 (m, 2.5), 6,33 (m, 2.4), 2,95 (s, 1), 2,90 (s, 1), of 1.87 (s, 6,9), to 1.79 (s, 6,9), 0,2 (5,8).

(b) Delity//tetramethylcyclopentadienyl/dimethylallyl/4 - forfinal/amide.

//Tetramethylcyclopentadienyl/dimethylallyl/-4-/4 - forfinally in solvent diethyl ether and utility 2.5 M in hexane are combined in equivalent quantities. A white precipitate is formed. To the suspension is added pentane. The precipitate is filtered, washed with pentane and SS) (4 formanilide/dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised

To 0,59 g (1.6 mmol) of TiCl3, ATHF in 50 ml of THF added 0.50 g (1.7 mmol) of delity//tetramethylcyclopentadienyl/ dimethylallyl/-4-forfinal/amide. After 0.5 h add 0.25 g (1.8 mmol) of AgCl. After two hours the solvent is removed under reduced pressure. The residue is extracted with diethyl ether. The ether extracts are filtered, combined and concentrated under reduced pressure to obtain a red glassy solid product. After dissolution in toluene and re-concentrating receive a waxy solid product. This solid product is extracted into pentane. The pentane extracts are filtered, combined and concentrated to obtain a waxy solid product. It is suspended in a small amount of pentane (2 ml) and filtered to obtain a powder of red. The output is 0.18 g (28).

1H NMR (benzene-d6d 7,10 (t) 6,80 (t) a 2.00 (C) of 1.97 (C) 0,35 ().

The polymerization.

Using the polymerization procedure of examples 11 to 32, using 1000 ml of a solvent mixture of alkanes, 200 ml of 1-octene and 5 ml of 15 MAO in toluene (1280 Al Ti), and the reaction temperature is 130oC. Hydrogen is supplied from 75 ml reservoir under pressure is added to to start the polymerization. The consumption of ethylene provide based 3100 kPa (psi). The polymer yield is 12.8 g, MV 103000, MV/PM 4,77, density 0,9387, the melt index 6,37.

Example 81.

Receiving /4 methoxybenzylamine/dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised.

To 0.73 g TiCl4, 2 in THF 30 ml of toluene added 0.7 g of delity/tetramethylcyclopentadienyl/dimethylallyl//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 is suspended in pentane and filtered to obtain a pellet of red powder. The output of 0.61 g (67).

1H NMR (benzene-d6d 7,28 (D. 2, J 8,8), 6,78 (2, J 8,9), with 3.27 (s, 2,8), was 2.05 (s, 5,6), a 2.01 (s, 5,6), 0,44 (4,8).

The polymerization.

By way of example 80, using 10 mmol of the above complex conduct polymerization. The polymer yield of 7.2 g MV 79,800, MV/PM 21,5. The melt index 2,90.

Example 82. Getting 1-/tert-butylamide/-2-/tetramethyl-5-cyclopentadienyl/- 1,1,2,2-tetramethylethylenediamine.

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

To a solution of 4,802 g (of 25.7 mmol) of 1,2-dichloro-1,1,2, is inciclopedia in 30 ml of dimethyl ether. The reaction mixture is stirred for several hours, then the solution is removed, the residue extracted with pentane and filtered. The pentane removed under reduced pressure to obtain the product as pale yellow oil.

Mass spectrum: m/e 272 (8).

1H NMR (C6D6d 2,70 (s, 1H) and 1.83 (s, 6N), 1.69 in (C, 6N), and 0.28 (s, 6N), 0,23 (C, 6N)

13WITH NMR (C6D6d 135,8, 134,0, 54,4, 14,6, 11,4, 3,2 2,4.

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

To a solution of 3.0 g (II mmol) 1-chloro-2-/tetramethylcyclopentadienyl/-1,1,2,2-tetramethyldisilane in 50 ml of ether is added 2,422 g (33,1 mmol) tert.-of butylamine. Quickly produces sludge. The resulting suspension is stirred for several days at room temperature, then gently heated to complete the reaction, amidohydrolase filtered and the pentane removed under reduced pressure to obtain the product as a yellow oil.

Output 3,150 (92,5).

Mass spectrum: m/e 309.

1H NMR (C6D6d to 2.75 (s, 1H), 1,95 (C, 6N), 1,82 (C, 6N), a 1.08 (s, N), of 0.51 (s, 1H), 0,24 (C, 6N), 0,16 (C, 6N)

13WITH NMR (C6D6d 135,2, 134,4, 55,2, 50,3, 34,1, 14,9, 1,7, 3,3 1,4.

(C) Delity-1-(tert. -butylamide/-2-/tetramethyl - cyclopentadienyl/-1,1,2,2-tetramethyldisilane in 100 ml of ether is added slowly of 7.70 ml, 2.60 M (a 20.2 mmol) utility in a solvent mixture of alkanes WITH6. The resulting suspension is stirred for several hours, then filtered and washed with ether, then dried under reduced pressure, resulting in a product in the form of a white powder. Output 2,918 g (93,4).

1H NMR (THF-d 8) d is 2.05 (s, 6N), at 1.91 (s, 6N), 0,87 (s, N), and 0.25 (s, 6N), 0,03 (C, 6N).

13With NMR (THF-d 8) d 117,3, 113,6, 53,5, 38,4, 34,1, 11,3, 8,4, 2,2.

(d) 1-/tert.-butylamide/-2-/tetramethyl-5-cyclopentadienyl/ -1,1,2,2-tetramethyldisiloxane

A suspension of 0.75 g (2,333 mmol) delity-1-(tert-butylamide-2- (tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane and 0,779 g (2,333 mmol) of TiCl4(THF)2and 50 ml of toluene is stirred for several days. Red-orange reaction mixture was filtered and the solvent is removed to obtain a sticky solid red. It is extracted with pentane and filtered. After concentration and cooling at -35oC in the freezer, collect microcrystalline product red on a Frit and washed with cold pentane to remove dark red oily material. Output 0,3643 g, 36

1H NMR (C6D6d of 2.20 (s, 6N), was 1.94 (s, 6N), to 1.48 (s, N), 0,44 (C, 6N), 0,43 (C, 6N).

13

Example 83.

Receiving /tert. -butylamide//dimethyl//tetramethyl-5- cyclopentadienyl/dilantinlevitra.

A solution of 0.5 g (1,215 mmol) (tert.-butylamide))(dimethyl)/ (tetramethylcyclopentadienyl/silentservicecode in 35 ml of ether cooled to -40oC. To this suspension is added to 1.41 ml metallyte (1,72 M, 2,43 mmol). The reaction mixture is left under stirring at room temperature for several hours. The solvent is removed and the residue extracted with pentane and filtered. The obtained filtrate is concentrated and cooled to -40oC. the Resulting colorless crystals emit decanter supernatant.

Output 0,2215 g, 49,2

1H NMR (C6D6d of 1.97 (s, 6N), at 1.91 (s, 6N), of 1.40 (s, N), and 0.46 (s, 6N), 0,00 (C, 6N).

13WITH NMR (C6D6d/ 130,2, 125,3, 95,7, 35,4, 34,0, 13,9, 10,9, 6,2.

Example 84. Receiving (tert. -butylamide/dimethyl/5-cyclopentadienyl/- silentservicecode.

To 0,6747 g (2,90 mmol) ZrCl4into the flask slowly add 4 ml of diethyl ether, and then 4 ml Thirty product combined with 0,6008 g (2,90 mmol) delity (tert.-butylamide//cyclopentadienyl//dimethyl/silane, obtained by the method of example 87 and 75 ml of toluene. The resulting suspension is stirred for several days, after which the colourless solution was filtered, the solvent is removed under reduced pressure and the residue suspended in pentane. This product is collected on a Frit and dried under reduced pressure.

Output 0,6186 g (60,0).

1H NMR (C6D6d to 6.43 (t, 2H), between 6.08 (t, 2H), 4,17 (Shir. C, 6N), 1.27mm (s, N), of 1.03 (Shir. C, 6N) and 0.22 (s, 6N).

13WITH NMR (C6D6d 122,0, 121,4, 109,5, 57,2, 32,8, 25,2, 0,7.

The structure was determined crystallographically by x-rays in the solid state the compound is a dimer (bridging chlorides).

Example 85. Receiving (anilide) (dimethyl) (tetramethyl-5- cyclopentadienyl/silentservicecode.

To 0,6905 g (2,963 mmol) ZrCl4into the flask slowly add 3 ml of diethyl ether, and then 4 ml of THF. The excess solvent is removed under reduced pressure to obtain a solid product, which is pounded into powder. The solid product combined with 0,8044 g (2,963 mmol) delity/anilino/dimethyl/- /tetramethylcyclopentadienyl/silane and 70 ml of toluene. Within a few minutes the suspension is painted in pale yellow-green color. A suspension of p is the pressure, and the residue is suspended in pentane. Very pale yellow product is collected on a Frit and dried under reduced pressure.

1H NMR (C6D6d 7,21 (t, 2H), and 7.1 (t, 1H), 6,97 (m, 2H), 2,50 (s, 3H), of 2.46 (s, 3H), of 1.87 (s, 3H), of 1.85 (s, 3H), of 0.53 (s, 3H), and 0.40 (s, 3H).

Example 86. Getting

(a) (Pair-toluidino) (dimethyl)tetramethyl-5- cyclopentadienyl/silencerqvigaob/pair-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 is added slowly 1,259 g (9,302 mmol) lithium-pair-of toluidine (0,3 ether adduct according to the1H NMR). The reaction mixture was stirred over night. The completion of the reaction is controlled according to gas chromatography. Add advanced lithium-para-toluidine in small portions (0,725 g, 14.7 mmol). The solvent is removed, the residue extracted with pentane and filtered. The pentane removed under reduced pressure to obtain product as a yellow oil. Output 2,456 g (92,5).

Mass spectrum m/e 285 (22).

1H NMR (C6D6d of 6.96 (d, 2H), to 6.57 (d, 2H), of 3.07 (s, 1H), 3,01 (s, 1H), 2,17 (s, 3H), 1.91 a (C, 6N), 1,80 (C, 6N), and 0.08 (s, 6N).

13WITH NMR (C6D6d 145,0, 136,2, 132,7, 130,2, 126x2">

To a solution of 2,233 g (7.82 mmol) of (pair-toluidino/(dimethyl/ tetramethylcyclopentadienyl/silane in 65 ml of ether is added slowly 6,17 ml of 2.60 M (16.0 mmol) of utility in a solvent mixture of C6alkanes. Not containing precipitate, the reaction mixture is stirred over night. The solvent is removed under reduced pressure. The obtained white solid product is suspended in pentane, collected on a Frit, washed with pentanol and dried under reduced pressure to obtain product as a white powder.

The output of 2.34 g (100% ).

1H NMR (THF-d-8) d 6.42 per (d, 2H), 6,18 (d, 2H), 2,09 (C, 6N), a 2.01 (s, 3H), of 1.94 (s, 6N), 0,36 (C, 6N).

13With 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) /pair-toluidino/dimethyl//tetramethyl-5- cyclopentadienyl/sentimentalised.

A suspension of 1.00 g (3,363 mmol) delity/paratoluidine/- (dimethyl) (tetramethyl-5-cyclopentadienyl/silane and 1,123 g (3,363 mmol) of TiCl4(THF)2in 70 ml of toluene. The reaction mixture is stirred for several days, then filtered and the solvent is removed. The obtained solid product is suspended in pentane and the resulting product is collected on a Frit and dried under reduced pressure. The product yield in the form of olive-brown powder is 5 (s, 6N).

13WITH NMR (C6D6d 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) (pair-toluidino) (dimethyl)(tetramethyl-5- cyclopentadienyl/silencerqvigaob.

To 0,7836 g (3,363 mmol) ZrCl4into the flask slowly add 3 ml of diethyl ether, and then 4 ml of THF. The excess solvent is removed under reduced pressure to obtain a solid product, which is pounded into powder. The hard part is combined with 1.0 g (3,363 mmol) delity/pair-toluidino) (dimethyl) (tetramethyl-5-cyclopentadienyl)silane in 70 ml of toluene. The resulting suspension is stirred for several days. The initial yellow color of the suspension turned brown. The yellow solution is filtered, the solvent is removed under reduced pressure and the solid product is suspended in pentane. Pale yellow product is collected on a Frit and dried under reduced pressure.

Output 0,8854 g (69,1).

1H NMR (C6D6d 7,06 (q, 2H), 6.87 in (q, 2H), 2,50 (c, 3H), 2,47 (c, 3H), 2,21 (c, 3H), 1,89 (c, 3H), 1,88 (c, 3H), 0,51 (c, 3H), 0,41 (c, 3H).

According to x-ray crystallography structure identified as ZiCl containing dimer with bridging chlorides.

Example 86a. Receiving (benzylamino/dimethyl/tetramethyl-

To a solution of 1.0 g (4,651 mmol) (chlorine) (dimethyl//tetramethylcyclopentadienyl/silane in 70 ml of ether is added slowly 0,526 g (4,651 mmol) liebenzeller. The reaction mixture was stirred overnight, then the solvent is removed, the residue extracted with pentane and filtered. The pentane removed under reduced pressure to obtain the product as a yellow oil.

Output 1,234 g (93,3).

Mass spectrum 285 (18).

1H NMR (C6D6d 7,0 from 7.24 (m, 5H), 3,71 (d, 2H), 2,73 (Shir. s, 1H), 1,88 (C, 6N), 1,76 (C, 6N), 0,43 (Shir. t, 1H), 0,07 (C, 6N).

13WITH NMR (C6D6d 144,3, 135,7, 132,0, 128,5, 127,3, 126,7, 56,7, 46,4, 14,6, 11,4 2,3.

(b) Delity/benzylamino/dimethyl/tetramethylcyclopentadienyl/- silane.

To a solution of 1,091 g (3,836 mmol) (benzylamino) (dimethyl) /tetramethylcyclopentadienyl/silane in 70 ml of ether is added slowly with 3.1 ml of 2.60 M (of 8.06 mmol) utility in a solvent mixture of C6alkanes. Simultaneously with the appearance of the precipitate appears pale pink color. The reaction mixture was stirred over night. The solvent is removed under reduced pressure. The obtained solid product spenderat in pentane, collected on a Frit, washed with pentane and dried under reduced pressure to obtain the product in view, N) 2,04 (C, 6N), 1,79 (C, 6N), and 0.15 (s, 6N).

13With 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) (benzylamino/dimethyl/tetramethyl-5-cyclopentadienyl/- sentimential.

Suspension 0,5052 g (1,699 mmol) delity(benzylamino/dimethyl//tetramethyl-5-cyclopentadienyl/silane and 0,5673 g (1,699 mmol) of TiCl4(THF)2in 40 ml of toluene is stirred for several days. Dark green-brown reaction mixture is filtered and the solvent is removed. The dark oily residue is suspended in pentane and the resulting product sobirajutsa the Frit and washed with cold pentane to remove dark oily material to obtain the product as a greenish-yellow powder.

Output 0,2742 g (40,1).

1H NMR (C6D6d 7,19 (m, 2H), 7,02 (m, 3H), lower than the 5.37 (s, 2H), 1,99 (C, 6N), to 1.98 (s, 6N), 0,03 (C, 6N).

13WITH NMR (C6D6d 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.

The polymerization.

The polymerization are by way of example 80, using 10 mcmole the above complex. The polymer yield of 14.4 g MV MV/Martyr of 5.0. The melt index 251, density 0,969.

Example 87. Receiving (benzylamino)dimethyl/tetramethyl-5- cyclopentadienyl/siland the IDO/dimethyl/tetramethyl-5cyclopentadienyl and 40 ml of toluene. Brownish-yellow suspension is stirred for several days, and then filtered and the solvent is removed under reduced pressure. Moist brownish-yellow residue is suspended in pentane and the resulting product is collected on a Frit and dried under reduced pressure.

Output yellowish-brownish product 0,2873 g (38,2).

1H NMR (C6D6d 7,51 (d, 2H), 7.23 percent (t, 2H), to 7.09 (t, 1H), 5,48 (d, 1H), 5,00 (d, 1H), 2,45 (C, 6N), was 2.05 (s, 3H), a 2.01 (s, 3H), a 2.01 (s, 3H), 0,34 (s, 3H), 0,20 (s, 3H).

13WITH NMR (C6D6d 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. Receiving (phenylphosphino)dimethyl/tetramethyl-5- cyclopentadienyl/sentimentalised.

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

To a solution of 1.5 g (6,983 mmol) (chlorine)) dimethyl//tetramethylcyclopentadienyl/silane in 55 ml of THF is added slowly 1,1248 g (7,665 mmol) of toluene in excess, since according to gas chromatography, the reaction 11 incomplete. Litefantastic (0,4 ether adduct according to the1H NMR spectroscopy). The reaction mixture is stirred for several days, then the solvent is removed, the residue extracted with pentane and the Phi is 1,985 g (98,5).

(b) Delity/phenylphosphino/dimethyl/tetramethylcyclopentadienyl/ silane.

To a solution of 1,858 g (6,451 mmol) (phenylphosphino//dimethyl/- /tetramethylcyclopentadienyl/silane in 65 ml of ether is added slowly to 5.21 ml of 2.60 M (13,55 mmol) utility in a solvent mixture of C6alkanes, forming a yellow precipitate. The reaction mixture was stirred over night. The product is collected on a Frit and washed with pentane, then dried under reduced pressure to obtain product as a white powder. Output (0,5 ether adduct according to the1H NMR) 2,0845 g (95,8).

(C) Phenylphosphino/dimethyl/tetramethyl-5-cyclopentadienyl/- sentimentalised.

In the flask combine 0.9 g (2,668 mmol) delity (phenylphosphino/dimethyl//tetramethyl-5-cyclopentadienyl/silane (0,5 ether adduct) and 0,8907 g (2,668 mmol) of TiCl4(THF)2in 75 ml of toluene. Coloration varies to dark green-black adding toluene. The reaction mixture is stirred for several days, then filtered and the solvent is removed. The dark residue is extracted with pentane and filtered until the remains of green-brown product on the Frit (0,2477 g) and black glassy product after removal of the pentane filtrate.

the EU. The polymer yield of 14.4, MV 27700, MV/PM 5,0, melt index 251, density 0,9690.

Example 89. Receiving (phenylphosphino/dimethyl/tetramethyl-5- cyclopentadienyl/silencerqvigaob.

To 0,6217 g (2,668 mmol) ZrCl4into the flask slowly add 3 ml of diethyl ether. The excess solvent is removed in vacuo to obtain a solid product, which is crushed into powder. The solid product combined with 0.9 g (2,668 mmol) delity/phenylphosphino/dimethyl/tetramethyl-5-cyclopentadienyl/ silane and 75 ml of toluene. The color changes to dark red-orange when adding toluene. The reaction mixture is stirred for several days, then the orange solution was filtered from a small amount of dark insoluble material and the solvent is removed. The residue is suspended with pentane and filtered. Brown solid product is collected on a Frit and dried under reduced pressure.

Example 90.

Receiving (tert.butylamide/dimethyl//indanyl/- sentimentalised.

a) (Tert.butylamide/dimethyl/indanyl/silane.

To a solution of 5,255 g (71,8 mmol) tert.of butylamine in 75 ml of ether is added 3.0 g (14.4 mmol) of 9-(chlorodimethylsilyl/-indene. The precipitate formed after a few minutes pageroot with pentane and filtered. The pentane removed under reduced pressure to obtain a pale yellow oily product as a mixture of two isomers. Output 3,313 g (93,9).

(b) Delity(tert.butylamide(dimethyl/indanyl/silane.

To a solution of 3.125 g (of 12.73 mmol) (tert. butylamino/dimethyl/ indanyl/silane in 75 ml of ether is added slowly 10,28 ml of 2.60 M (26,73 mmol) utility in a solvent mixture of C6alkanes. The colour of the solution without precipitate slightly darkens and becomes orange. The reaction mixture is stirred for several days, then the solvent is removed. Fluffy glassy material is stirred with pentane. Powder clumps together. Pentane decanted and the washing is repeated several times, then the hard part is dried under reduced pressure.

Output 2,42 g (73,9).

(C) (Tert.butylamide/dimethyl/indanyl/sentimentalised.

In the flask combine 1.0 g (3,887 mmol) delity/tert.butylamide//dimethyl/indanyl/silane and 1,298 g (3,887 mmol TiCl4. (THF)2with 70 ml of toluene. Instantly the color is red.

The reaction mixture is stirred for three days, then filtered and the solvent is removed. The residue is extracted with pentane and filtered to obtain the product in the form of red microcrystals method of example 80, using 10 mmol of the above complex. The polymer yield of 14.8 g

Example 91.

Receiving (tert.butylamide/dimethyl/ indenylzirconocenes.

To 0,9057 g (3,887 mmol) ZrCl4in the flask, slowly add 2 ml of THF. Excess THF removed in vacuo to obtain a solid product, which is crushed into powder. 1.0 g (3,887 mmol) delity/tert.butylamide/dimethyl/indanyl/silane added with 70 ml of toluene. The resulting suspension is stirred for several days, after which the solution is filtered, and the solvent is removed under reduced pressure. The residue is suspended in pentane, filtered and dried under reduced pressure.

Output brown-beige product 0,5668 g (36,0).

Example 92.

Getting 1-/tert.butylamide/-2-/tetramethyl-5- cyclopentadienyl/atavistically.

(a) Ethyl-2-/tetramethylcyclopentadienyl/acetate.

The solution 3,822 g (22,89 mmol) ethylbromoacetate in 25 ml of THF is cooled to -78oC and 3.00 g (20,80 g) nitrotyrosination in 50 ml of THF is added slowly to it. The resulting suspension allowed to warm to room temperature and stirred over night. The solvent is removed, the residue extraheras-spectrum m/e 208 (41).

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

16,35 ml of 2.00 M (to 32.7 mmol) of trimethylaluminum in toluene add 2,39 g (to 32.7 mmol) of tert.of butylamine in 50 ml of toluene. The solution is stirred for 45 min, then add 3,40 g ethyl-2-tetramethylcyclopentadienyl. The reaction mixture is stirred for several days with gentle heating. After aqueous processing of the obtained amide receive a mixture of three isomers in the form of an orange semi-crystalline paste.

Mass spectrum m/e 235 (21).

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

A mixture of amides dissolved in 120 ml of ether and 0,830 g (to 21.8 mmol) sociallyengaged add. The reaction mixture was stirred over night with gentle heating. Control by gas chromatography shows that the reaction is not completed. Ether substituted THF, add another sociallyengaged and the resulting solution is refluxed for several days. After water treatment receive three isomers 1-/tert.butylamino/-2- /tetramethylcyclopentadienyl/ethane.

The mass spectrum of the m-th 221 (11).

(d) Delity-1-/tert.butylamide/-2-/tetramethyl-5- cyclopentadienyl/ethane.

To a solution of 2.00 g (9,05 mmol) (tert.Buti-enyl/-ethane according to gas chromatography, of 1.34 g (the 6.06 mmol) in 50 ml of ether is added slowly 6,09 ml of 2.60 M (15.8 mmol) of utility in a solvent mixture of C6alkanes with the formation of a yellowish precipitate. The reaction mixture is stirred for three days, and then filtered. Pale yellow powder is washed several times with ether, then dried under reduced pressure.

Output 0,7908 g (55,9).

1H NMR (THF-d 8) d 2,43 (Shir. m, 4H), of 1.85 (s, 6N) and 1.83 (s, 6N), 1,0 (s, N).

13With 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. butylamide/-2-/tetramethyl-5-cyclopentadienyl/- atavistically

In the flask 0,3650 g (1,565 mmol) delity-1-/tert. butylamide/- 2-/tetramethylcyclopentadienyl/ethane and 0,5799 g (1,565 mmol) of TiCl3(THF)3combined with 60 ml of THF. The solution quickly becomes green. The reaction mixture was stirred over night, then add 1,121 g (7.82 mmol) AlCl. Within a few minutes the color begins to change to brown-orange. The suspension is stirred for two days and pay the solvent under reduced pressure. The residue is extracted with toluene, the solution is filtered and the solvent is removed. The residue is extracted with pentane, filtered, concentrated and cooled to -30oC. Bright orange product is collected on a Frit, p.

1H NMR (C6D6d to 4.01 (t, J 7,2, 2H), 2,58 (t, J 7,2, 2H), 2,02 (C, 6N), 1,89 (C, 6N), of 1.41 (s, N).

13WITH NMR (C6D6d 138,0, 129,3, 128,6, 69,1, 62,7, 28,6, 24,9, 13,0, 12,3

Polymerization of 1.

Conduct the polymerization according to the method of example 80, using 10 mcmole the above complex. The polymer yield and 64.3 g, the melt index is 3.21, density 0,9262.

Polymerization 2.

The above polymerization procedure, except that again, what 0.95 Ámol-1-/tert.butylamide/-2-/tetramethyl -5-cyclopentadienyl/atavistically added to start polymerization. The polymer yield 11.4 g, a melt index less than 0.1, the density 0,9119.

Polymerization of 3.

The above polymerization is repeated, except that 2.5 mcmole 1-/tert.butylamide/-2-tetramethyl-5- cyclopentadienyl/atavistically added to start polymerization. In addition, 300 ml of octene and 900 ml isopar use, but without hydrogen. The polymer yield of 36.2 g, a melt index of 0.21, density 0,9190.

Polymerization of 4.

Repeat the above conditions of polymerization 1, except that the temperature is 90oC.

The polymer yield of 66.7 g, index replevied.

In the flask 0,3862 g (1,657 mmol) ZrCl4and 0,3866 g (1,657 mmol) delity /-1-/tert. butylamino-2-/tetramethyl-5- cyclopentadienyl/ethane/combined with 50 ml of toluene. After stirring for several days, add 1 ml of THF, and the resulting suspension is stirred for several days, after which the solution is filtered and the solvent is removed under reduced pressure. The hard part is suspended in pentane, collected on a Frit and dried under reduced pressure. Output blignault product 0,6307 g (99.8 per cent).

1H NMR (C6D6d 2,75 (etc, 1H), of 2.38 (m, 2H), 2,11

(C, 6N), 2,03 (s, 3H), from 2.00 (s, 3H), 1,75 (etc, 1H),

a 1.08 (s,N)

13C NMR (C6D6d 131, 5mm, 128,7, to 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. Spent the polymerization of mixtures of ethylene, styrene or other polymerized monomer using (tert. butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/sentimentality complex and MAO socialization in an amount to provide an atomic ratio AI/Ti 1000:1. Reaction conditions and results are shown in table 9.

Example 95. The suspension polymerization. The following example illustrates the use of the catalyst infusion is shutting down, the reaction is carried out in the conditions where the polymer is insoluble in the reaction medium and precipitates from the reaction mixture as education. Temperature 70oC, 10 ml of octene, 1190 ml solvent mixture of alkanes, and 5 ml of 15 percent MAO in toluene (1280 AI:Ti) is used. After 20 minutes the reactor was released, gaining 4.6 g of polymer. In the reactor add additional solvent and heated to 170oC to remove the polymer, which forms long strands and curls around the agitator. The melt index of 0.28.

Example 96. Receiving /tert.butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/selandian (III) chloride. In the chamber with desiccant mix 0.24 g TiCl3(THF)3and 0.33 g IU4C5SiMe2N-tert.-BuMg2Cl2(THF)2. Add 15 ml of THF, get temoporary color. After 30 minutes, the volatile materials are removed under reduced pressure, leaving a dark solid product. Add 15 ml of toluene, the solution is filtered and the toluene removed under reduced pressure, leaving a purple-red powder, 0,22,

The polymerization. The polymerization are by way of example 80, using mokola the above complex. The polymer yield with 55.1 g, a melt index 1,71.

Example 97. Plaintively/sentimentalised. The polymer yield of 76.4 g MV Of 56,700, MV/MCH 4,5, density 0,8871, a melt index (I2) 10,13.

Example 98. Practically repeated polymerization method 97, except that the temperature is 80oC, the number of used catalyst 2.5 mcmole, use 250 ml of I-octene, and 950 ml of solvent mixture of alkanes. The reaction allowed to proceed for 1 hour. The polymer yield of 51.1, the melt Index of 0.11.

Example 99. Receiving (tert.butylamide/dimethyl/tetramethylcyclopentadienyl/-silencerriley.

In the chamber with desiccant 0.50 g HfCl4suspended in 10 ml of toluene. Add 10 ml of THF and the suspension is stirred for 5 minutes, and add 0,77 g Me4C5SiMe2N - tert.-BuMg2-Cl2-Cl2(THF)2. The solution is heated to boiling under reflux. After 30 minutes the solution is cooled and the volatile part is removed under reduced pressure. Add 20 ml of pentane, the solution is filtered and the pentane removed under reduced pressure to obtain a solid product is white. This solid product is washed with a small amount of pentane to obtain 0,077 g (10%) of a solid white product.

1H NMR (C6D6):d of 2.08 (6H), 1,30 (9H0, 0,44 (6H)

If almost by way povtoraut the polymerization method of example 97, but as the catalyst use pentamethylcyclopentadienyl-trichloride. The output of polymer 4,6,

Comparative example 2. By way of example 91 carry out the polymerization using as catalyst (tert.butylamide/pentamethyl-5-cyclopentadienylmanganese.

1H NMR (C6D6d 2,07 (c, 1H), 1,88 (c, 15H), 1,35 (c, 9H),

13C NMR (C6D6d 61,0, 31,3, 12,6

The polymer yield of 2.0 g

Comparative example 3. Repeat the polymerization process of example 97 except that the catalyst used bis-/tert.butylamide/dimethyltrimethylene. After 10 minutes of reaction the polymer was not observed.

Comparative example 4. Repeat the polymerization process of example 97 except that as the catalyst used dicyclopentadienyltitanium. The polymer yield 109,0 g, MV=16300,MV/PM 3,63, the melt index AS TM D-1238 procedure a, condition E, I2was above 1000, which indicates a very low molecular weight polymer.

Comparative example 5. By way of example 97 receive the polymer, except that as the catalyst use dicyclopentadienyltitanium. The polymer yield of 7.3 cue molecular weight of the polymer.

Example 100. A/ Obtaining /tert.butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/silane o-/N,N-dimethylamino/benzilidene, /formula /A //

< / BR>
In a dry box combined in a flask with a capacity of 100 ml of 4.45 mmole /tert.butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/silencecanbeheard (obtained in example 104) in 50 ml of tetrahydrofuran and 0.63 g (4,46 mmole) of o-LiCH2C6H4N(CH3)2. After 30 minutes, distilled volatile products under reduced pressure to obtain a red-brown solid product. Add 50 ml of pentane, dissolve filter and reduce the volume to 40 ml of This concentrated solution is cooled to -30oC. Filtered red crystals and dried under reduced pressure.

Receiving catalyst and polymerization. preparing a catalytic composition, combining a complex of the metal with triethylaluminium socialization in the polymerization reactor under stirring. Accordingly, in the reactor capacity 2 l with stirring download 740 g mixed alkangovolo solvent (Isopar Th TM), available from the company Exxon chemicals Inc.) and 118 g of 1-actinophage of co monomer. The reactor is heated to 120oC and saturated with ethylene at a pressure of 500 lb.inch2(3.5 MPa). Vodit 5(0.2 kPa). Mixed complex of the metal with socialization in a dry box by injecting syringe desired number 0,0050 M solution of the complex of the metal (in Isopar-ETMin the solution socializaton (also in Isopar-ETM). This solution is then transferred into the tank for the introduction of catalyst and injected into the reactor. Conduct polymerization for 15 minutes. then the solution is removed from the rector and quenched with isopropanol. Add antioxidant spatial hindered phenol and spend processing for removing the volatile components of copolymer ethylene/1-octene. the results are shown in table. 10.

Example 101. Essentially a repeat of the reaction usloviya of example 108, except that the complex is a (tert. butylamino)-dimethyl/tetramethyl-5-cyclopentadienyl/serendipidity (obtained by the reaction of two equivalents benzilate (tert.butylamino)dimethyl(tetramethyl-5-cyclopentadienyl)semanticannotation of example 2. In a reactor with a mixing capacity of 2 l load 700 g mixed alkangovolo solvent and 150 g of 1-actinophage of co monomer. The solution is heated to 90oC and saturated with ethylene at a pressure of 500 lb/in2(3.5 MPa). Hydrogen is injected through excessively the2(0,1 kPa). Complex metal and methylalumoxane socialization mixed in a dry box by mixing 1 ml 0,0050 M solution of the complex metal (Isopure-ETM) with 5 mmol of socializaton (10 ml Isopar-ETM) (Ti:AI 11:10000).This solution is then transferred into the additional capacity for catalyst and injected into the reactor. Polymerizatio hold for 10 minutes. Then the solution is removed from the reactor and quenched with isopropanol. Add antioxidant spatial hindered phenol and removed from the copolymer of ethylene/1-octene.

The yield of copolymer was 26.9,

1. A metal coordination complex of General formula

< / BR>
where R1in each case hydrogen or methyl, or an adjacent pair of R1group forms hydrocarbonyl ring, connecting in cyclopentadienyl part;

X is chloride, methyl, benzyl or O-(N,N-dimethylamino)benzyl;

Y is-O-, -NR - or-PR, where R in each case represents hydrogen or part selected from the group of alkyl, aryl or combinations thereof, containing up to 20 non-hydrogen atoms;

M is titanium, zirconium or hafnium;

Z Si(CH3)2, -Si(CH3)2Si(CH3)2, -CH2-CH2- or-CH2CH(CH3)-

n 1,2.

3. The catalyst for ion coordination polymerization, comprising a metal complex and socialization, characterized in that the metal complex, it contains a coordination complex under item 1, as socializaton a compound selected from the group consisting of methylalumoxane, Akilov aluminum and Lewis acids, in a molar ratio of the complex: socializaton 1 1 10.000.

4. The method of ion coordination polymerization by contacting one or more monomers with a catalyst, characterized in that as the monomer used as a compound selected from the group consisting of ethylene, propylene, butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, vinyl cyclohexane, vinylbenzoate, as the catalyst used

 

Same patents:

The invention relates to the field of polymer chemistry, namely the method for producing a heat-sensitive polymer hydrogels used as carriers of biologically active substances for controlled release of these substances into the environment

The invention relates to the field of polymer chemistry, namely the method for producing a heat-sensitive polymer hydrogels used as carriers of biologically active substances for controlled release of these substances into the environment

The invention relates to the petrochemical industry and can be used to obtain a butadiene-styrene rubber solution polymerization (DST, CWR)

The invention relates to the production of synthetic rubbers, in particular, to improve the stability of the rubber in terms of termostate

The invention relates to the production of synthetic rubbers, in particular, to improve the stability of the rubber in terms of termostate

The invention relates to the production of synthetic rubbers, in particular, to improve the stability of the rubber in terms of termostate

The invention relates to the production of synthetic rubbers, in particular, butyl rubber and can be used in the petrochemical industry

The invention relates to a technology for production of butadiene rubber stereospecific polymerization of butadiene and can be used in the synthetic rubber industry

The invention relates to a method for producing copolymers of tetrafluoroethylene (TPV) with perfluoroalkyl vinyl ethers (PTAVE), which differ in chemical resistance, heat stability, elasticity, strength, ability to processed high-performance methods (extrusion, extrusion and t

The invention relates to an improved electrochemical method for obtaining tetraethoxysilane, which finds application in the production of high-purity oxides and homogeneous compositions on their basis for optics, electronics, energy sources

The invention relates to a method of sililirovanie carbohydrates in liquid ammonia

The invention relates to new derivatives of pyridine and their salts, to a method for their herbicide composition containing a specified derivative as an effective ingredient, and to a method of controlling weeds

The invention relates to the field of production of organosilicon compounds containing organic radical at the silicon atom highly reactive vinyl groups: acrylic and methacryloyl

,

where R is H; CH3

The invention relates to improvements in the insulation of the water filling their water-gel compositions with subsequent transition in gels

FIELD: organic synthesis.

SUBSTANCE: invention relates to A-ring precursors of vitamin D having formula I:

in which A represents -CH2OH, -CH2-OCOR', -COR", or ethynyl; R represents hydrogen or C1-C6-alkyl; R1 hydrogen, C1-C6-alkyl, or (CH2)nOP; R2 hydrogen or -OP; R' is phenyl; R" hydrogen, hydroxyl, C1-C6-alkoxy; P hydrogen or group -Si(R3)3, wherein each R3 independently represents C1-C6-alkyl or phenyl; n = 0 or 1, provided that, when compound I has configuration 2S,3aS,4aS, A is formyl, hydroxymethyl, ethynyl, or methoxycarbonyl, and R and R2 are both hydrogen atoms, then R1 is not -OSi(R3)3.Preparation of compounds I comprises: (i) interaction of compounds having general formula 1:

,

in which A represents C1-C6-alkoxycarbonyl or C1-C3-alkylaminocarbonyl, with lipase in vinyl alkanoate or acid anhydride and (ii) conversion of resulting compound of formula 2: (2) or 2': (2'), where Z represents alkyl, preferably C1-C3-alkyl, into corresponding compound I via formation of a leaving group and cyclization caused by treatment with a base to form desired bicyclo[3.1.0]hexane, said conversion comprising: protection of hydroxy groups, hydrolysis of ester, inversion of 3- or 5-hydroxy group, and converting carboalkoxy or carbamoyl group into desired substituent A.

EFFECT: optimized synthesis conditions allowing more effective larger-scale preparation of precursors.

8 cl, 4 dwg, 45 ex

Up!