CZ9004259A3 - Metallic coordination complex, catalytic composition in which the complex is comprised and addition polymerization process - Google Patents

Abstract

A metal coordination complex comprises a metal of gp. 3 (other than scandium), 4-10 or the lanthamide series and a delocalised pi-bonded moiety (I) substd. with a constrain-inducing moiety (II). The complex has a constrained geometry about the metal atom such that the angle at the metal between the centroid of (I) and the centre of at least one remaining substit. is less than such an angle in a comparative complex which differs only in that (II) is replaced by hydrogen, and providing that for complexes comprising more than one (I), only one (I) for each metal atom of the complex is a cyclic. The metal coordination complex is used, along with an activating cocatalyst, as a catalyst in addn. polymerisation. Also claimed are the prepn. of the coordination complex, prepn. of the catalyst, an addn. polymerisation process using the complex, and the polymers formed by this process including pseudo random polymers.

Description

Technical field

The invention relates to metal coordination complexes. In addition, the invention also relates to a catalyst composition suitable for addition polymerization comprising the metal coordination complex and to a process for addition polymerization of polymerizable monomers, particularly suitable for preparing copolymers of aliphatic vinylidene monomers.

Since the active metal position of the metal coordination complex catalyst of the invention is exposed to the surrounding reaction medium, the resulting catalyst has unique properties. Under certain reaction conditions, novel olefin polymers of previously unknown properties can be prepared when applying the catalysts of the invention due to their extraordinary ability to polymerize alpha-olefins, diolefins, sterically hindered vinylidene aliphatic monomers, vinylidene aromatic monomers, and mixtures thereof.

BACKGROUND OF THE INVENTION

Numerous metal coordination complexes are known in the art, including metal coordination complexes containing monocyclopentadienyl groups and substituted monocyclopentadienyl groups. The metal coordination complexes of the invention differ from these known metal coordination complexes in that the metal is bonded to a cyclopentadienyl or substituted cycloperrtadienyl or the like via a t-bond and a bridged linkage, as well as other ligands thereof.

In addition, coordination complexes containing a transition metal atom as the central atom are also known from the prior art, which are referred to as tucked complexes. These complexes are described in Organometallics 6, 232-241 (1987).

In U.S. patent application Ser 8 _m 800, filed January 30, 1987 (published in an equivalent form to EP0277004) discloses certain bis (cyclopentadienyl) metal compounds prepared by reaction of a bis (cyclopentadienyl) metal complex with Bronsted acid salts containing a non-coordinating compatible anion. It is also mentioned in this patent that such complexes are useful as catalysts in the polymerization of olefins. The foregoing known catalysts are not considered to be particularly effective catalysts in the polymerization of olefins.

Previous attempts to prepare copolymers of vinylidene aromatic monomers and alpha-olefins, in particular copolymers of styrene and ethylene, have either failed to fail to achieve significant incorporation of vinylidene aromatic monomer into the resulting copolymer, or in other words, only low molecular weight polymers have been obtained in these experiments. . Polymer Bulletin, 20, 237-241 (1988) describes a styrene-ethylene random copolymer containing 1 mole percent of styrene incorporated. The polymer yield is 8.3 x 10 < 6 > grams of polymer per micromole of titanium used.

In an article on the name of the Chiraler Organotitanium (IV) Verbindung fiir Enantioselective Synthesen, published in August 1983 in the Fachbereich Chemie der Phílipps-University of Marburg, Thomas Kíikenhóhner describes l-oxy-3-cyclopentadienylpropane-1,3-di-1,3-propyl complexes in which the propanediyl moiety is optionally substituted with an alkyl group. Examples of such complexes include 1-oxy-1-tert-butyl-3-dimethyl-3-cyclopentadienyl-propane-1,3-diyl-titanium dihalide, dimethyl and halomethyl complexes. However, no specific use of these complexes is disclosed.

J. Okuda (Chem. Ber. 123 (1990) 1649-1651, published August 1990) discloses (tert-butylamido) • (dimethyl) (3-tert-butyl-cyclopentadienyl) silanetitanium dichloride complexes. does not disclose any specific use of these complexes.

EP-A-0420436 describes, inter alia, metal coordination complexes of the general formula A:

in which :

M means titanium, zirconium or hafnium, being in their highest formal oxidation state (+4, άθ complex), (C ₅ H _{5 y y x x} R _x ) means:

(i) a cyclopentadienyl ring which is substituted by zero to five substituent groups R, x is 0, 1, 2, 3, 4 or 5 indicating the degree of substitution, and each substituent group R, independently of one another, represents a hydrocarbyl group containing 1 to 20 carbon atoms, a substituted hydrocarbyl group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by a halogen atom, a metalloid group substituted by a hydrocarbyl group containing 1 to 20 carbon atoms, wherein said metalZoid is from group 14 of the periodic system or (ii) a cyclopentadienyl ring in which two adjacent R-groups are joined to form a ring containing 4 to 20 carbon atoms to form a saturated or unsaturated polycyclic cyclopentadienyl ligand, (JR ' _of -P-y) means a heteroatom ligand in which J is an element with a coordination number three of group 15 not or an element having a coordination number two of group 16 of the Periodic Table of the Elements, and each R ', independently of one another, means a hydrocarbon group having 1 to 20 carbon atoms or a substituted hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms is replaced by a halogen atom, az means the coordination number of element J,

Q at each occurrence is independently a monovalent anionic ligand, with the proviso that if Q is a hydrocarbyl group, then this Q substituent is different from (C 1 H 4, Y 3 R 3), or both substituents Q together represent a divalent anionic chelating agent,

B is a covalent bridging group comprising an element of group 14 or 15 of the Periodic Table of the Elements,

L means:

(i) a Lewis base, or (ii) a second transition metal compound of the same type, such that the two metal centers M and M 'are bridged by Q and Q', where M 'has the same meaning as M and Q' has the same meaning as Q, w is a number from 0 to 1, and y is 0 or 1 if w is greater than 0, and y is 1 if w is 0.

These metal coordination complexes according to this European patent EP-A-0420436 are used simultaneously with aluminoxane as catalysts in the olefin polymerization process.

European Patent EP-A-0418044 (published March 20, 1991) discloses, inter alia, catalysts corresponding to formula B:

CpMX _n ⁺ A '(B) in which:

Cp represents one? -Cyclopentadienyl or η? -Substituted cyclopentadienyl group which is optionally covalently bonded to M via a substituent,

M is hafnium, titanium or zirconium, attached by the type of bond rjp to the cyclopentadienyl or substituted cyclopentadienyl group,

X is independently a hydride group or a group selected from halogen, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof containing up to 20 non-hydrogen atoms, and neutral Lewis base ligands containing up to 20 non-hydrogen atoms or optionally one substituent X together with Cp form a metalocycle with M containing up to 20 non-hydrogen atoms,

R is an alkyl or aryl group of up to 10 carbon atoms, n is 1 or 2, depending on the valence of M, and

A 'means a non-coordinating, compatible anion from a salt of Bronsted acid.

SUMMARY OF THE INVENTION

The present invention provides a metal coordination complex of formula I:

in which :

M means titanium, zirconium or hafnium,

R 'is independently selected at each occurrence from the group consisting of hydrogen or a group selected from silyl, alkyl, aryl and combinations thereof containing up to 10 carbon atoms,

Z stands for SiR’2 »

Y stands for -NR’-,

X is a halide, alkyl, aryl or alkoxy group containing up to 10 carbon atoms at each occurrence,

Ride or 2.

Preferably, in the metal coordination complex of formula M, it is titanium.

Also preferred according to the invention is a metal coordination complex of the above formula wherein X is a halide.

Also preferred is a metal coordination complex according to the invention of the above formula wherein Y is a t-butylamide group.

Most preferably, according to the invention, the metal coordination complexes of the above general formula are selected from the group consisting of:

(t-butylamido) (tetramethyl-4-cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (t-butylamido) (tetramethyl-4-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamido) (tetramethyl-7H-cyclopentadienyl) - 1,2-ethanediyl zirconium mercury dichloride, (methylamido) (tetramethyl-4-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamido) (tetramethyl-7H-cyclopentadienyl) -methylenititanium pichloride, (tert-butylamido) dimethyl (tetramethyl) -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanzirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride, and (phenylphosphonamide) tetramethyl) silanzirkoniumdibenzyl.

The present invention also relates to a catalyst composition suitable for addition polymerization comprising:

(a) any metal coordination complex of formula I as defined above, and (b) an activating cocatalyst.

The present invention also relates to an addition polymerization process for preparing a polymer by contacting one or more addition polymerizable monomers with a catalyst under addition polymerization conditions comprising the use of a catalyst composition as defined above.

Preferably, the alpha-olefin is copolymerized with vinylidene aromatic monomer, most preferably ethylene copolymerized with styrene.

The metal coordination complexes according to the invention belong to a more general group of complexes which can be characterized by the general formula Ia:

She-R in which:

M represents a titanium bonded by a type of bond to a cyclopentadienyl group,

R 'at each location is a hydrogen atom or a group selected from the group consisting of a silyl group, an alkyl group, an aryl group, and combinations thereof containing up to 10 carbon or silicon atoms,

E is silicon,

X represents at each occurrence a haloalkyl, aryl or alkoxy group containing up to 10 carbon atoms, m is 1 or 2, and n is 1 or 2, depending on the valency of M.

In this context, it should be noted that said complexes may exist as dimers or as higher oligomers.

The following metal coordination complexes of formula I or Ia can be prepared by contacting a metal compound of formula:

or a coordinated adduct of this compound with a dianionic salt of the following formula II or III (L ^{+ x} ) _y (Cp * - (ER ' ₂ ) _m -NR') - ² ((LX ') ^{+ X} ) _y (Cp * - ( ER ' ₂ ) _m -NR') ' ² (II) (III) in which:

L stands for Group 1 or Group 2 metal

Cp * represents a cyclopentadienyl or substituted cyclopentadienyl group C 1-4 R 4 of formula I or Ia,

X 'means fluorine, chlorine, iodine or bromine, in

X and γ are either 1 or 2, wherein the sum of x and y is 2, and η, Ε, M, m, R a and X have the same meaning as above, the reaction being carried out in an inert solvent.

The metal coordination complex of formula I or Ia may also be prepared by a process comprising the following steps:

(A) contacting a metal compound of the general formula:

or a coordinated adduct thereof with a dianionic salt of the above formula II or III in an inert solvent; and (B) oxidizing the metal to a higher oxidation state by contacting the reaction product of step (A) with a non-interfering oxidizing agent.

The metal coordination complexes of the present invention are used together with activating cocatalysts as catalysts to carry out addition polymerizations.

Using these catalysts, E1PE polymers can be prepared which are highly elastic interpolymers of ethylene and one or more olefins other than ethylene.

In addition, pseudo-statistical alpha-olefin interpolymers, especially ethylene and vinylidene aromatic monomer, sterically hindered aliphatic vinylidene monomer, or mixtures thereof, can also be prepared using the catalysts of the present invention.

The complexes of the present invention are preferably used as catalysts for carrying out addition polymerization reactions to produce polymers suitable for preparing molded articles, films used for packaging a variety of products, and for preparing foamed materials used as padding, further using these substances in the modification of synthetic and naturally occurring resins. These complexes can also be used as catalysts for hydrogenation processes, catalytic cracking processes and other industrial applications.

Description of the picture

By way of illustration, the atomic arrangements of the complexes of the present invention, as determined from single crystal X-ray diffraction values, are shown in the accompanying Figures 1 to 13.

Figure 1 shows the structure of (4-methylphenylamido) dimethyl (tetramethyl-4-cyclopentadienyl) -4-silanetitanium dichloride, as determined by single crystal X-ray crystallographic analysis. The angle formed by the center of gravity of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), the titanium atom (Til) and the nitrogen atom (N14) is 105.7 ”. This center of gravity of the cyclopentadienyl ring represents the intersection of the corresponding coordinates of the X, Y and Z atomic centers forming the ring.

Figure 2 shows the structure of (phenylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride, as determined by single crystal X-ray crystallographic analysis. The angle formed by the center of gravity of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and the nitrogen atom (N14) is 106.1 °.

tc / c.

Figure 3 shows the structure of (t-butylamido) tetramethyl (tetramethyl-4-cyclopentadienyl) disilanetitanium dichloride, as determined by single crystal X-ray crystallographic analysis. The relatively long disilyl linking group that binds the cyclopentadienyl ring to the nitrogen atom of the amide ligand allows less restriction on the nitrogen atom. The angle formed by the center of gravity of the cyclopentadienyl ring (C2, C3, C5, C7 and C9), the titanium atom (T11) and the nitrogen atom (N17) is 120.5 °. Accordingly, the activity of this catalyst in olefin polymerization is considerably lower than that of a similar complex with the monosilane linking group in (t-butylamido) dimethyl (tetramethyl-β-cyclopentadienyl) silanetitanium dichloride.

Figures 4 to 9 show experimentally determined C-values of the nuclear magnetic resonance spectrum of pseudo-statistical ethylene-styrene copolymers containing 1.4 (Figure 4), 4.8 (Figure 5), 9.0 (Figure 4). 6), 13 (FIG. 7), 37 (FIG. 8) and 47 (FIG. 9) mole percent of styrene.

E.

Figure 10 shows the nuclear magnetic resonance spectrum of a random copolymer of ethylene and styrene.

Fig. 11 shows graphically the dependence of the complex viscosity eta at 190 ° C on the shear rate (omega) for a typical E1PE copolymer (elastic polyethylene), in particular a copolymer of ethylene and 1-octene.

Fig. 12 shows other properties of ElPE polymers, namely copolymers of ethylene and 1-octene, namely the modulus of elasticity measured in dynes / cm at 0.1 radian per second and a temperature of 190 ° C.

Figure 13 shows the values of complex viscosity (eta) and tangent δ as a function of shear rate for polyethylene polymers prepared in the conventional manner for comparison.

By activating cocatalyst is meant a second catalyst component which is capable of further enhancing the efficiency of the metal-containing complex of the invention when used as an addition polymerization catalyst or alternatively balances the ionic charge of the catalytically activated species. Examples of activating cocatalysts suitable for use in the present invention include aluminum compounds containing an Al-O bond, such as alkylaluminoxanes, in particular methylaluminoxane, alkyl aluminum compounds, aluminum halides, aluminum alkyl halides, Lewis acids, ammonium salts, non-interfering oxidizing agents, e.g. means, for example, silver salts and ferrocenium ions, mixtures of said compounds.

A particular method of preparing an aluminoxane type compound by contacting an alkyl aluminum compound with an inorganic salt containing crystalline water is described in U.S. Patent 4,542,119. In a particularly preferred embodiment, the alkyl aluminum compound is contacted with a recoverable water-containing substance. such as hydrated alumina, silica, or other substance. A process for the preparation of an aluminoxane using this regenerable material is described in EP 338-444.

Other suitable activating cocatalysts include compounds of the following formula:

^A1R n ^X ”3-n in which:

R at each occurrence is an alkyl or aralkyl group containing 1 to 10 carbon atoms,

X 'is a halogen atom, and n is 1, 2, or 3.

The most preferred cocatalysts of this type are

4Γ

- C12c trialkyl aluminum compounds, in particular triethyl aluminum.

Additionally polymerizable monomers include, for example, ethylenically unsaturated monomers, acetylenic compounds, conjugated or unconjugated stem and polyenes, such as those containing 2 to 20 carbon atoms. Preferred monomers include α-olefins containing 2 to 10 carbon atoms, in particular ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Other preferred monomers include styrene, halogen or alkyl substituted styrene, vinyl chloride, acrylonitrile, methyl acrylate, methyl methacrylate, tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinylbenzocyclobutane and 1,4-hexadiene.

The term sterically hindered aliphatic vinylidene compounds in the present description refers to the addition polymerizable vinylidene monomers of the following general formula:

CG ₂ = CG'R '' in which:

R '' means a sterically large aliphatic substituent containing up to 20 carbon atoms,

G independently of its location is hydrogen or methyl, and

G *, independently of its location, represents a hydrogen atom or a methyl group, or alternatively G 'and R' together form a ring system.

4G

Sterically dimensional here is understood to mean that the monomer carrying this substituent is normally incapable of addition polymerization using a standard Ziegler-Natta polymerization catalyst at a rate comparable to that of ethylene polymerization. Preferred sterically hindered aliphatic vinylidene compounds are monomers in which at least one of the carbon atoms attached to the ethylenic unsaturation is tertiary or quaternary substituted. Examples of such substituents include cyclic aliphatic groups such as cyclohexene or cyclooctene or ring-substituted derivatives thereof with an alkyl or aryl group, or a tert-butyl group, a norbornyl group, etc. The most preferred sterically hindered aliphatic vinylidene compounds are various isomeric cyclohexene derivatives substituted on the ring with vinyl and substituted cyclohexenes as well as 5-ethylidene-2-norbornene. Particularly preferred are

1-vinylcyclohexene, 3-vinylcyclohexene and 4-vinylcyclohexene.

Sterically hindered vinylidene compounds are addition polymerizable vinylidene monomers of the following general formula:

CG ₂ = CG'R ”'in which:

R '' means a substituent R 'or an aryl group of up to 20 carbon atoms, and

G and G 'have the same meaning as above. In addition to sterically hindered aliphatic vinylidene compounds, vinylidene aromatic monomers may also be included in the group of sterically hindered vinylidene compounds.

Vinylidene aromatic monomers are addition polymerizable compounds of the following formula:

CG ₂ = C (G) -Ph in which:

G independently of its location is hydrogen or methyl, and

Ph represents a phenyl group or a phenyl group substituted by halogen or an alkyl group having 1 to 4 carbon atoms.

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

The term alpha-olefin refers to ethylene and olefins containing from 3 to 10 carbon atoms having an ethylenic unsaturated group in the alpha position. Preferred alpha-olefins are ethylene, propylene,

1-butene, isoburylene, 4-methyl-1-pentene, 1-hexene and 1-octene, as well as mixtures thereof.

As mentioned above, the metal coordination complexes of the invention preferably comprise structures having altered or improved catalytic activity at the metal site when combined with a cocatalyst. In this regard, it has been found that the catalytic efficiency of said complexes is improved by electron donating substituents.

Examples of the most preferred metal coordination complexes of the above formula are compounds wherein:

R 'on an amide group means a methyl group, tf

- ethyl, propyl, butyl, pentyl, hexyl (including isomers thereof), norbornyl, benzyl or phenyl,

R 'on a cyclopentadienyl group at each location is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group (including isomers thereof), a norbornyl group, a benzyl group or a phenyl group;

X represents a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group (including isomers thereof), a norbornyl group, a benzyl group or a phenyl group.

Specific examples of the metal coordination complexes include:

(t-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride, and (benzylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Said coordination complexes can be prepared by a method of contacting a metal reactant with a metal-cyclopentadienyl derivative of the compound (I). or with a Grignard derivative of a cyclopentadienyl compound in a solvent, followed by separation of the byproduct salt. Suitable solvents used in the preparation of the metal coordination complexes include aliphatic and aromatic solvents such as cyclohexane, methylcyclohexane, pentane, hexane, heptane, tetrahydrofuran, iP diethyl ether, alkyl ethers having 1 to 4 carbon atoms in the mono-derived alkyl group or diethylene glycol, alkyl ethers having 1 to 4 carbon atoms in the alkyl group derived from mono- or dipropylene glycol, benzene, toluene, xylene, ethylbenzene or mixtures thereof.

In a preferred embodiment of the process, the metal compound is a compound of the formula wherein:

M has a lower oxidation state than in the corresponding compound of the formula and than the oxidation state M in the desired final complex. A non-interfering oxidizing agent may be used to increase the oxidation state of the metal M. This oxidation is accomplished by simply contacting the reactants using the solvents and reaction conditions used to prepare the metal coordination complex itself. As used herein, the term "non-interfering oxidizing agent" (or oxidizing agent not adversely affecting the reaction) means a compound having sufficient oxidation potential to increase the oxidation state of said metal without interfering with the formation of the desired final metal coordination complex or subsequent polymerization process. A particularly suitable non-interfering oxidizing agent is silver chloride.

To facilitate handling of used metal h

yt with compounds corresponding to the above general formula MX _{n +} 2, it is in some cases advantageous to first prepare their solid adduct using a suitable coordinating agent using methods known in the art. For example, while titanium tetrachloride is a fuming liquid that is very difficult to handle, titanium tetrachloride adduct with ether, tertiary amine, tertiary phosphine or other basic non-protic compound can be prepared instead. The resulting solid adducts are then easier to handle. A preferred coordination adduct is tetrahydrofuran.

The reactions used in the preparation of the metal coordination complexes can be carried out either heterogeneously or homogeneously. This means that the individual reactants or the resulting product may not be substantially soluble in the solvent mixture used. Generally, the reactants are contacted under an inert atmosphere for a period of from a few minutes to several days. The reaction mixture may be stirred if necessary. The reaction temperature is generally in the range of -90 to 150 ° C, preferably -20 to 70 ° C.

Suitable catalysts for use herein are prepared by mixing the metal coordination complex with the activating cocatalyst in any order and by any suitable process. Preferably, the molar ratio of the metal coordination complex to the cocatalyst is in the range of 1: 0.1 to 1: 10,000. However, it should also be noted that the catalyst system can also be prepared in situ by adding its components directly into the polymerization process in the case of this

Suitable solvents or diluents, including the condensed monomer, will be used in the polymerization process. Suitable solvents include toluene, ethylbenzene, alkanes, and mixtures thereof. In some cases, the catalysts may be isolated from solution and kept under inert atmosphere prior to use. Because the components of the catalyst are sensitive to both moisture and oxygen, they should be handled under an inert atmosphere such as nitrogen, argon or helium, or be handled under vacuum.

These polymerization processes are usually carried out by the conventional polymerization methods of the Ziegler-Natta or Kaminsky-Sinn type. That is, the monomer or monomers and the catalyst are contacted at a temperature of from -30 ° C to 250 ° C under reduced, elevated or atmospheric pressure. The polymerization is carried out under an inert atmosphere, which may consist of an inert gas such as nitrogen, argon, hydrogen or ethylene, or under vacuum. In addition, hydrogen can also be used as a molecular weight regulating agent, since the hydrogen has a chain terminating capability as is known in the art. The catalyst may be used as such or on a suitable support, such as alumina, magnesium chloride or silica, to yield a heterogeneous supported catalyst. If desired, a solvent may be used. Suitable solvents for this include toluene, ethylbenzene and an excess of vinylidene aromatic or olefin monomer. The polymerization reaction may also be carried out under solution or suspension polymerization conditions using a perfluorocarbon or similar liquid in suspension polymerization, and a gas phase polymerization process, i.e. a fluidized bed reactor, may also be used. or a solid phase polymerization process under powder polymerization conditions. Catalytically effective amounts of the catalyst and cocatalyst of the present invention are any amount whose use determines the acceptable formation of the desired final polymer. These amounts can be readily determined by routine experiments that can be performed by any person skilled in the art. These preferred amounts of catalyst and cocatalyst are those sufficient to provide an equivalent polymerizable monomer / catalyst ratio of 1 x 100: 1 to 100: 1, preferably from x 10 ® to 500: 1 and most preferably Preferably, the cocatalyst is used in an amount such that the equivalent cocatalyst / catalyst ratio is 10,000: 1 to 0.1: 1, preferably 1000: 1 to 1: 1.

It is understood that the metal coordination complex may undergo various transformations before or during the polymerization or may form intermediate compounds. Accordingly, it is within the scope of the present invention to include other precursors by which the same catalyst substances as described above can be formed without departing from the present invention.

The resulting polymer product is isolated by filtration or other suitable separation technique. Adjuvants and additives may be incorporated into these polymers to achieve the desired properties of the final polymers. Suitable additives are, in particular, pigments, UV stabilizers, airtioxidants, blowing agents, lubricants, plasticizers, photosensitizers and mixtures thereof.

In the preparation of copolymers containing vinylidene aromatic or sterically hindered aliphatic vinyl monomers, it is desirable to also use a comonomer such as an alpha-olefin, which is not particularly sterically hindered. Without wishing to be bound by any theoretical justification for the polymerization process, it is believed that the active sites of the catalyst become by incorporation of a sterically hindered vinyl compound crowded and unwilling to accept another sterically hindered vinyl compound and thus enter this additional hindered vinyl compound into the polymerization process as another unit of the polymer chain. Only after incorporation of one or more olefins other than said sterically hindered vinyl compound will the active site of the catalyst become available again for inclusion of a sterically hindered vinyl monomer. However, to a limited extent, the vinylidene aromatic monomer or sterically hindered vinylidene monomer may enter the polymerization chain in reverse order, i.e. two methyl groups are each between the longer polymer chains formed by said substituted polymer components.

Preferably, such polymers also have a molecular weight Mw of greater than 13,000, more preferably greater than 20,000 and most preferably greater than 30,000. Preferably, the polymers also have a melt flow index (I ₂ ) as defined by ASTM D-1238 (process). A, condition E) less than 125, more preferably in the range of 0.01 to 100 and most preferably in the range of 0.1 to 10.

Due to the use of the above-described catalyst system comprising a metal coordination complex according to the invention, copolymers can be prepared in which relatively large or sterically hindered monomers are incorporated, these large or sterically hindered monomers being incorporated in the copolymers in a low concentration in a substantially random manner and at a higher concentration in a manner having a certain logic of the arrangement. These copolymers of alpha-olefins, in particular ethylene and a sterically hindered aliphatic vinylidene compound or vinylidene aromatic monomer, may therefore be referred to hereinafter as pseudo-statistical copolymers. This is because these copolymers lack well-defined blocks of one of the monomers, although the incorporation of these monomers into the polymer chain does still follow certain rules.

These incorporation rules were derived from some experimental details obtained from the analysis of the resulting polymers. These polymers were analyzed by C-nuclear magnetic resonance spectroscopy at 130 ° C using a VXR-300 spectrometer operating at 75.4 MHz. According to these analyzes, samples containing 200-250 milligrams of polymer are dissolved in 15 milliliters of hot o-dichlorobenzene / 1,1,2,2-tetrachloroethane-d2 (each component is present in approximately 70:30 by volume) to form 0%. A 0.5 M solution in chromium tris (acetylacetonate) is then transferred to a 10 mm nuclear magnetic resonance spectroscopy cuvette. The following parameters and conditions were used in this spectroscopy: spectral width

500 Hz, acquisition time 0.090 seconds, pulse width 36 °, dwell time 1.0 second with decoupler disconnected during dwell time, FT value 32K, scan counts greater than 30,000, line spacing

Hz. The spectra obtained are relative to carbon tetrachloride (δ 73.77 ppm, TMS scale).

Without being bound by theory, the results of the experiments described above suggest that the distinguishing feature of the pseudo-statistical copolymers is that all phenyl or bulky sterically hindered groups present as substituents on the polymer chain are always separated. two or more methylene units. In other words, the polymers containing the sterically hindered monomer of the invention can be described by the following general formula (styrene is used as a hindered monomer here to illustrate):

wherein j, m and sl are greater than or equal to one.

However, while further clarifying the experimental and theoretical results obtained without, however, limiting the following considerations to any theoretical justification, it may be noted that if the sterically hindered monomer was incorporated last into the growing polymer chain during addition polymerization, then the additional monomer incorporated must be ethylene. or a sterically hindered monomer which, however, is incorporated in the polymer chain upside down, i.e., in the heel-like manner. This situation is illustrated in the following reaction scheme in which

M stands for catalytic metal center,

HG means a sterically hindered group,

P stands for the growing polymer chain:

HG

M-P + incorporation of hindered monomer

HG

incorporation of ethylene HG

HG

HG

heel-to-heel installation

KG

HG unrealizable incorporation head-heel KG HG li

During the polymerization reaction, ethylene can be incorporated into the growing polymer chain at any point in time. After the sterically hindered monomer has been incorporated into the growing polymer chain, i.e., the heel-like manner, the additional hindered monomer has to be already added, since inserting another hindered monomer at this point would mean placing the next hindered substituent more closely than it would corresponds to the minimum separation of these substituents, as discussed above. As a result of these polymerization rules, the catalyst of the invention does not substantially homopolymerize styrene, while the styrene / ethylene mixture is rapidly polymerized, and a high styrene content (up to 50 mole percent styrene) of styrene in the resulting styrene / ethylene copolymers can be achieved.

As another attempt to illustrate the description of the alpha-olefin copolymer and the sterically hindered monomer of the invention 1, a computerized polymerization reaction model was used to calculate the expected ^J C nuclear magnetic resonance spectrum of the polymer product. Computer program using a random number generator to determine when to be built into the growing polymer chain alpha-olefin, and when it is incorporated into the hindered monomer and then calculate the number of * 1 of each type ^J C-NMR signals corresponding to each given type of installation. The polymers were computer generated until at least 10,000 of the monomer incorporations were achieved, and the thus determined C-nuclear magnetic resonance spectrum of the computer model was compared to the actual experimentally determined nuclear magnetic resonance spectrum of the pseudo-statistical ethylene-styrene copolymer of the invention.

Computer Simulations of Polymer and Resultant 1 3

The C-nuclear magnetic resonance spectrum of the calculated pseudo-statistical ethylene-styrene copolymer was based on the principle that if the last incorporated monomer in the growing polymer chain is styrene monomer, then the other incorporated monomer must be ethylene or styrene reversed, i.e. heel. Optimum consistency between the experimentally determined and calculated results was achieved when the heel-foot method incorporated approximately 15 percent styrene into the polymer chain. Experimentally calculated and calculated C-nuclear magnetic resonance spectra of such pseudo-statistic copolymers of ethylene and styrene containing 1.4; 4.8; 9.0; 13, 37 and 47 mole percent of styrene are shown in the accompanying Figures 4 to 9. In all cases, the experimentally obtained results and the calculated results are excellent;

Computer simulations of polymer and resulting η a

The C-nuclear magnetic resonance spectra of the complete random copolymer of alpha-olefin and sterically hindered monomer were performed without any restriction on the insertion of sterically hindered monomers. In other words, if the last monomer incorporated in the growing polymer chain was a sterically hindered monomer, then the other molecule of the sterically hindered monomer is not prevented from being incorporated as an additional monomer unit into the polymer chain if the statistical number generator has determined that the hindered monomer is to be included as another monomer. In this case, the calculated spectrum for these completely random copolymers does not match the corresponding experimentally determined C-nuclean magnetic resonance spectrum, as is apparent from the attached Figure 10, which shows the spectrum for an ethylene-styrene copolymer containing 37 mole percent of styrene.

Prior to the actual polymerization process of the present invention, the monomers and any solvents used may be vacuum distilled and / or purified by contact with molecular sieves, silica or alumina to remove contaminants. In addition, reactive purifying agents such as trialkylaluminum compounds, alkali metals and metal alloys, especially sodium-potassium alloys, can be used to remove impurities.

Suitable vinylidene aromatic monomers which may be used in the present invention include styrene, as well as alpha-methylstyrene, styrene derivatives substituted on the ring with a C 1 -C 4 alkyl group or a phenyl group such as ortho, meta and para-methylstyrene or mixtures thereof, halogen-substituted styrenes or halogens, vinylbenzocyclobutanes and divinylbenzene. The preferred vinylidene aromatic monomer is styrene.

In the polymerization of vinylidene aromatic monomers or sterically hindered aliphatic vinylidene compounds and olefins, said monomers are preferably combined in an amount such that the resulting polymer contains at least 1.0 mole percent, more preferably 1.5 to less than 50 mole percent, even more preferably 5.0 up to 48 mole percent, and most preferably 8.0 to 47 mole percent vinylidene

- Λ ⁷ aromatic monomer (or sterically hindered aliphatic vinylidene compound). The polymerization is preferably carried out at a pressure in the range of atmospheric pressure (0.1 MPa) to 100 MPa and at a temperature in the range of 30 to 200 ° C. When polymerized at a temperature that is higher than the autopolymerization temperature of the individual monomers, the resulting polymer may contain small amounts of homopolymer polymerization products formed by free-radical free-radical polymerization.

Some polymers prepared by the process of the invention, in particular copolymers of ethylene and an alpha-olefin other than ethylene, have unique theological properties. In particular, it has been found that polymers of this type (hereinafter referred to as Elastic Polyethylenes - E1PE) are less Newtonian than linear polyethylene polymers prepared by conventional olefin-like processes. These polymers have higher modulus values, especially at higher melt index values, compared to similar commonly produced polymers. These properties make these polymers particularly suitable for the production of films, films, foamed products and molded products, such as blow molded products.

The above is defined in more detail by reference to Figure 11, in which the complex viscosity eta (T} *), measured in Pois (1 Poise = 0.1 Pa.s) at 190 ° C, is plotted against the omega shear rate. (to), measured in radians per second, for a typical E1-ethylene-1-octene copolymer of the invention. The slope of this curve indicates that the melt is highly Newtonian. The following complex viscosity and shear rate values are used in the graph below:

&

- -

Complex viscosity (^ *) Shear speed (u>) 1,962 x 10 ⁵ 0.01000 1,511 x 10 ⁵ 0.01585 1,115 x 10 ⁵ 0.02512 8,292 x 10 ⁴ 0,03981 6,322 x 10 ⁴ 0,06310 4,920 x 10 ⁴ 0,10000 3,956 x 10 ⁴ 0.15850 3,230 x 10 ⁴ 0.2512 2,713 x 10 ⁴ 0.3981 2,293 x 10 ⁴ 0.6310 1,966 x 10 ⁴ 1.0000 1,701 x 10 ⁴ 1.5850 1,464 x 10 ⁴ 2.5120 1,265 x 10 ⁴ 3.9810 1,088 x 10 ⁴ 6,310 9,336 x 10 ³ 10,000 7,964 x 10 ³ 15,850 6,752 x 10 ³ 25,120 5,677 x 10 ³ 39,810 4,721 x 10 ³ 63,100 3,854 x 10 ³ 100,000

The graph of Figure 11 also shows the tangent δ values of the same E1PE polymer. This tangent value δ is a dimensionless value and is calculated by dividing the viscosity module by the modulus of elasticity. The following tangent δ and shear rate values are used in the graph shown:

Tangent δ Shearing speed (tu) 0.5526 0.01000 0.5231 0.5771 0.6597 0.01585 0.02512 0,03981 0.7971 0,06310 0.9243 0,10000 1,080 0.15850 1,243 0.2512 1,381 0.3981 1,543 0.6310 1,615 1.0000 1,690 1.5850 1,729 2.5120 1,737 3.9810 1,718 6,310 1,677 10,000 1,620 15,850 1,552 25,120 1,475 39,810 1,398 63,100 1,315 100,000

In view of improving performance characteristics in melt blown applications, it is preferred that the tangent value is in the range of 0.1 to 3.0 for shear rates of between 0.01 and 100 radians per second.

Another property of ElPE polymers is illustrated by reference

3Ί in Figure 12, in which the elastic modulus values, measured in dyn / cm (G ') at 0.1 radian per second and 190 ° C, are plotted for some ethylene-1-octene ElPE copolymers depending on the flow index melt. The copolymers obtained in Examples 6 below were used.

7, 9-11, 13-17, 19-21, 25 and 26.

The following melt index and elastic modulus values are used in the graph used:

Melt flow index Modulus of elasticity 0.10 98760 0.15 35220 0.18 35920 0.22 14270 0.45 11140 1.72 3003 2.46 10620 3.34 4381 5.34 5858 6.38 10480 10.12 5276 10.66 6222 16.28 2697 16.32 6612 18.42 9669 31.2 4516 31.53 5012 31.69 3238 41.02 2972

yr

For comparison, typical complex viscosity values 7f * (eta) and tangent S as a function of the shear rate for polyethylene polymers prepared by a conventional process are shown in the graph in Figure 13.

It is apparent from the foregoing results that said ElPE polymers are characterized by a high melt modulus. These E1PE resins have a melt index ((I2), ASTM-1238, Method A, Condition E) of less than 200, preferably less than 125, and most preferably less than 50, and the modulus of elasticity of these ElPE polymers is greater than 1000 dynes / cm, more preferably greater than 2000 dynes / cm. All of the above rheological measurements were performed using standard techniques described by H. A. Barnes et al. in Introduction to Rheology, Elsevier Publishng et al., 1989. The densities of said polymers normally range from 0.85 to 0.97 g / ml, preferably from 0.89 to 0.97 g / ml. Their molecular weight distributions (Mw / Mn) are greater than 2 and preferably lie in the range of 3.0 to 10.0. The polymers have typical melting points in the range of 50-135 ° C.

In addition, preferred polymers demonstrate the properties of homogeneous polymers as defined in U.S. Pat. No. 3,645,499, i. ethylene copolymers having a substantially statistical distribution of individual comonomers in a given molecule and substantially the same ethylene / comonomer ratio in all molecules. Polymers prepared at elevated polymerization temperatures, particularly at temperatures above 130 ° C, may exhibit a heterogeneous melting curve. The polymers of the invention are further characterized by high purity and clarity. These polymers have better optical properties, in particular a lower degree of haze than conventional ethylene polymers, which make the polymers according to the invention suitable materials for film production and injection molding.

Moreover, it has been surprisingly found that these polymers containing olefin and vinylidene aromatic monomer, in particular ethylene and styrene, have elastomeric properties. Such polymers are particularly suitable for use in combination with thermoplastic elastomers, and in particular for modifying the impact strength of thermoplastic and thermosetting polymers, including bitumens, adhesives and elastomeric melts.

The polymers of the invention may be modified by conventional methods known per se, in particular by grafting, crosslinking, hydrogenation and functional group alterations or other reactions known to those skilled in the art. In particular, in the case of polymers containing a vinylidene aromatic, vinylcyclohexene or 1,4-hexadiene functional group, these polymers can be easily sulfonated or chlorinated to give the corresponding functional derivatives. In addition, vinylcyclohexene-based polymers are readily crosslinkable by reaction with an unsaturated ring functional group.

The polymers of the invention, both in modified or unmodified form, can be blended with synthetic or natural polymers to obtain blends with desirable properties. In particular, polyethylene, ethylene-alpha-olefin copolymers, polypropylene, polystyrene, styrene copolymers can be blended in particular with the polymers of the present invention.

and acrylonitrile (including their rubber-modified derivatives), syndiotactic polystyrene, polycarbonate, polyamide, aromatic polyester, polyisocyanate, polyurethane, polyacrylonitrile, silicone, and polyphenylene oxide polymers. The polymeric modifying agent may be used in an amount of from 0.1 to 99.0% by weight, preferably in an amount of from 0.5 to 50% by weight.

In a particularly preferred embodiment of the invention said polymers comprising ethylene and styrene are elastomeric materials as defined in ASTM Special Technical Bulletin No. 184; such a substance can be expanded at twice its length at room temperature and, after releasing the tension it expands, it will be reduced to its original length.

While the polymers of the invention may be used to modify synthetic thermoplastic materials, these polymers may also be used to modify asphalt or bitumen mixtures. Styrene and ethylene polymers are particularly suitable for this purpose.

The term bitumen ”may generally be defined as a mixture of hydrocarbons of natural or pyrogenic origin, or a combination of both, often accompanied by non-metallic derivatives thereof, which may be gaseous, liquid, semi-solid or solid and which are usually soluble in carbon disulphide. Bitumen of liquid, semi-solid or solid consistency may be used in the present invention. From a commercial point of view, bitumen is generally limited to asphalts and tars and pitch. The following is a list of bitumen materials that may be used in the present invention.

(I) Asphalts (1) Petroleum asphalts (A) Directly reduced asphalts (1) Reduction at atmospheric or reduced pressure (2) Precipitated by a solvent such as propane (B) Thermal asphalts as residues from cracking operations on oil platforms (C) Air blown asphalts (1) direct blown (2) catalytic blown (2) natural asphalts (A) with a mineral content of less than 5 percent (1) asphaltites such as gilsonite, graphamite and black asphalt varieties (2) asphalts of Bermuda and other natural origin (B) ) with a mineral content of more than 5% (1) rock asphalts (2) asphalts of Trinidad and other natural origin (II) pitch and derivatives (1) pitch residues from coke ovens (A) coal pitch reduced to free-flowing RT-quality materials for road and road superstructure (B) coal tar pitch reduced to softening temperature (2) residues from other pyrogenic distillates such as water gas, wood, peat on, bones, rosin, tar acids derived from fatty acids.

tf

It is well known to those skilled in the art that the weight average molecular weight of different bitumens can vary over a very wide range, for example from 500 to 10,000. In addition, the softening temperature of different types of bitumen varies, for example, from 10 to 10,000. to 200 ° C.

Of all the possible types of asphalt used, petroleum and natural asphalts are preferably used in the present invention, with petroleum asphalts being particularly preferred asphalts. Of these petroleum bitumen, said thermal asphalts are preferably used.

The amount of bitumen used in the compositions of the invention is preferably 65 to 99 parts by weight, preferably 80 to 98 parts by weight.

Examples

The metal coordination complexes, the catalysts suitable for the addition polymerization, the processes for the preparation of the metal coordination complex, as well as the process for the preparation of said catalysts and the actual addition polymerization and the copolymer preparation will be explained in more detail below. they do not limit the scope of the present invention.

kO

- Example 1

Preparation of (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Preparation 1

Stage (a):

(Chloro) (dimethyl) (tetramethylcyclopentadi-2,4-enyl) silane.

To a solution containing 21.5 grams (167 millimoles) of dimethyldichlorosilane in 150 milliliters of tetrahydrofuran cooled to -40 ° C was slowly added a solution containing 8.00 grams (55.6 millimoles) of 1,2,3 sodium salt. 1,4-tetramethylcyclopentadiene: 14 U in 80 mL of tetrahydrofuran. The reaction mixture was allowed to warm to room temperature and stirred overnight. Then the solvent was removed and the residue was extracted with pentane and filtered. The pentane was then removed from the extract under reduced pressure to give the above product as a pale yellow oil.

Yield of product: 10.50 g (88.0%).

@ 1 H NMR (CDCl3) .delta.: 2.89 (s, 1H), 1.91 (s, 6H), 1.71 (s, 6H), 0.14 (s, 6H);

1 C-nuclear magnetic resonance spectrum (CgDg) δ 137.8, 131.5, 56.5, 14.6, 11.4, 0.81.

Stage (b):

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

To a solution containing 13.00 grams (60.5 millimoles) of (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 300 ml of tetrahydrofuran was added a solution containing 11.07 grams (151 millimoles) over 5 minutes. tert-butylamine in 20 ml of tetrahydrofuran. A precipitate formed immediately from this solution. The slurry was stirred for 3 days, the solvent was removed and the residue was extracted with pentane and filtered. The filtered extract was then stripped of pentane under reduced pressure to give the above product as a pale yellow oil.

Yield: 14.8 g (97.2%).

1 H-NMR Spectrum (CgDg) δ:

2.76 (s, 1H), 2.01 (s, 6H), 1.84 (s, 6H), 1.09 (s, 9H),

0.10 (s. 6H);

@ 1 H-NMR spectrum (CDCl3) .delta .:

135.4, 133.2, 57.0, 49.3, 33.8, 15.0, 11.1,

1.3.

Stage (c):

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

To this solution, a solution of 3.000 grams ([11.198 millimoles) of (tert-butylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 100 milliliters of ether was slowly added with 9.21 milliliters of a 2.6 M solution (23, 95 millimol) butyllithium in a mixed C8-alkane solvent. A white precipitate would be formed, the reaction mixture was stirred overnight and filtered. The solid was washed several times with ether and dried under reduced pressure to give the above product as a white powder.

Yield: 3.134 g (99.8%).

Step (d) (tert-Butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

To the frozen (to -196 ° C) tetrahydrofuran was added 0.721 grams (3.8 millimoles) of titanium tetrachloride. The reaction hy so obtained was allowed to warm to -78 ° C (dry ice bath).

To the resulting yellow solution was slowly added a solution containing 1,000 grams (3.80 millimoles) of dilithium (tert-butylamido) -dimethyl (tetramethylcyclopentadienyl) silane in 30 ml of tetrahydrofuran. The solution was allowed to warm to room temperature and stirred overnight. Solvent was then removed from the resulting very dark solution. The residue obtained was extracted with pentane and filtered. Cooling in the freezer resulted in the separation of the highly soluble dark red-brown material from the light yellow-green crystalline solid. The solid was filtered and recrystallized from pentane to give an olive green product.

Yield: 0.143 g (10.2%).

NMR Spectrum (CgDg) δ:

2.00 (s, 6H), 1.99 (s, 6H), 1.42 (s, 9H), 0.43 (s, 6H);

• 1 H NMR spectrum (CgDg) δ:

140.6, 137.9, 104.0, 62.1, 32.7, 16.1, 13.0

5.4.

Preparation 2

4.0 mL of 2.0 M isopropylmagnesium chloride in diethyl ether was added to a 100 mL flask in a drying box. The ether was then removed under reduced pressure leaving a colorless oil in the flask. To this oil was added 20 mL of toluene / tetrahydrofuran (4: 1 by volume) followed by 0.97 g of (tert-butylamino) dimethyl (tetramethylcyclopentadienyl) silane. The solution was heated to reflux. After 8 to 10 hours a white precipitate began to form. After refluxing for a total of 27 hours, the solution was cooled and the volatiles were removed under reduced pressure. The white solid residue was then triturated and suspended in pentane and then filtered. A white powder of the product consisting of Me ₄ C ₅ SiMe ₂ N 4 -BuMg ₂ Cl ₂ (THF) _{2 was obtained} .

Yield of product: 1.23 g (62%).

Then 0.50 g of TiCl 2 (THF) was suspended in 10 ml of tetrahydrofuran in an oven. 0.69 g of solid Me ₂ Cl ₂ SiMe 4 -Z-BuMg ₂ Cl ₂ (THF) ₂ was then added to the suspension resulting in a color change from pale blue to dark purple. After 15 minutes, 0.35 g of silver chloride was added to this solution. The color of the solution immediately began to light up to a light yellow-green color. After one hour and 30 minutes, tetrahydrofuran was removed in vacuo

Ml

reduced pressure to give a yellow-green solid. 20 ml of toluene were added, the mixture was filtered and the filtrate was removed under reduced pressure to give a yellow-green microcrystalline product.

Product yield: 0.51 g (quantitative yield).

The identity of the product thus obtained was shown by 1 H-nuclear magnetic resonance spectrum, which indicates that it is (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride. 1 H-NMR Spectrum (CgDg) δ:

1.992 (s), 1.986 (s), 1.414 (s), 0.414 (s).

Preparation 3

To a flask containing 35 mL of frozen (to -196 ° C) tetrahydrofuran was added 0.72 g (3.80 mmol) of titanium tetrachloride. The mixture was allowed to warm to -78 ° C (dry ice bath). To this mixture was slowly added a solution containing 1.0 grams (3.80 millimoles) of dilithium (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silane in tetrahydrofuran. The yellow solution was allowed to warm to room temperature and stirred overnight. The solvent was removed to give a dark colored residue, which was then extracted with pentane and filtered. After recrystallization twice from pentane at -35 to -40 ° C, the product (C (-Me ^-N-t-Bu) TiCl ₂ ) was obtained as a dark greenish-yellow crystalline material.

3

The identification of this product was confirmed by the Ca @ 1 H-NMR spectrum.

Preparation 4

2.0 grams of TiCl 3 / THF (5.40 millimoles) was used and suspended in 40 ml of tetrahydrofuran in a drying box. 1.42 grams (5.39 millimoles) of dilithium (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silane was then added to the suspension resulting in an immediate darkening of the reaction mixture until a dark blue color. After stirring for 90 minutes, 0.84 g (5.86 millimoles) of silver chloride was added. The reaction mixture thus prepared began to light immediately until a red-orange color was obtained. After stirring for 90 minutes, tetrahydrofuran was removed under reduced pressure. 50 ml of diethyl ether were added to the residue, the solution was filtered and the filtrate was removed under reduced pressure. In this way, (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride was obtained.

Yield: 1.91 g.

1 H-NMR Spectrum (CgDg) δ:

1.992 (s), 1.987 (s), 1.415 (s), 0.415 (s).

Polymerization

The polymerization of the styrene / ethylene mixture was carried out by mixing 1.65 ml of a 10% methylaluminoxane solution in toluene with a solution containing 45 ml of toluene and 50 ml of styrene in a syringe box. The tank was made of stainless steel. In a second injection tank, 250 µL of a 0.010 M solution of (t-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride was added to 2.5 ml of toluene. The two injection tanks were then sealed, removed from the handling box and connected to a 600 mL stainless steel pressure vessel. The pressure vessel was then evacuated and purged with argon.

The pressure vessel was then charged with a solution containing styrene, toluene and methylaluminoxane (MAO), which was heated in the vessel at 89 ° C and at an ethylene pressure of 620 kPa. Heating was performed with stirring. The catalyst solution was then added to the pressure vessel, and the ethylene pressure was raised to 1275 kPa and the pressure was controlled between 1240 and 1275 kPa. As a result of the ongoing exoteric reaction, the temperature in the reactor was increased to 95 ° C. The temperature was then lowered to 90 ° C and maintained between 90 and 92 ° C for the remainder of the polymerization reaction.

After one hour, the ethylene feed was cut off. The reactor was vented to atmospheric pressure and cooled to 30 ° C and methanol was added. The product was isolated, washed with methanol, and the remaining solvents were removed under reduced pressure at 120 ° C to give the final copolymer.

Copolymer yield: 9.02 g.

The C-NMR spectrum of this product proved to be a random copolymer of styrene (15.2 mole percent) and ethylene. The spectrum does not show peaks corresponding to polystyrene.

Example 2

Polymerization of olefin

5 ml of a 1 M solution of triethyl aluminum in a mixture of up to 6 carbon alkane solvents and 0.5 ml of a 0.01 M solution of (t-butylamido) dimethyl (tetramethyl-β-cyclopentadienyl) were mixed in a stainless steel dosing tank. of silane titanium dichloride in toluene. The titanium catalyst and the triethyl aluminum cocatalyst solution were then pressurized to a 3 liter pressure vessel containing 2 liters of mixed alkane solvent (Isopar E, a commercially available product from Exxon Chemicals, Inc.) under a pressure of 3100 kPa ethylene at 150 ° C. . The reaction temperature was then maintained at 150 ° C for 10 minutes. The ethylene pressure was then kept constant, with a flow meter measuring ethylene consumption of 15.7 grams. The polymer solution was then removed from the pressure vessel and the desired polymer was obtained after drying overnight under reduced pressure at 90 ° C.

Polymer yield: 15.7 g.

Example 3

Ethylene homopolymerization

A glove box was used in which a 0.010 M solution of (tert-butlamido) dimethyl (tetramethyl-cyclopentadienyl) silanetitanium dichloride in 2.5 ml of toluene was added to a stainless steel injection tank under argon atmosphere. In a second injection tank, 5.0 ml of a 1.0 M solution of methylaluminoxane (MAO) in toluene was added to 92 ml of toluene. The two tanks were then sealed, removed from the handling box, and attached to a 600 mL pressure vessel. The pressure vessel was evacuated and purged with argon and then ethylene. A cocatalyst solution was added to the purged pressure vessel and the contents of the pressure vessel were heated to 89 ° C at an ethylene pressure of 620 kPa. A catalyst solution was then added to the reactor. Due to the ongoing exothermic reaction, the temperature of the reaction mixture rose to 109 ° C in a few seconds. The ethylene pressure was then maintained in the pressure range from 1240 to 1275 kPa. After 30 minutes, the temperature in the reactor was raised to about 110 ° C, after which ethylene consumption increased. After one hour, the ethylene feed was interrupted, the reactor was vented to atmospheric pressure and allowed to cool. The container was opened, its contents rapidly quenched with methanol, and the polymer was isolated. After removal of the volatiles, final polyethylene was obtained.

Yield: 24 g.

Example 4

Copolymerization of ethylene and styrene.

A glove box with argon atmosphere was used in this space and mixed in a syringe tank equipped with a stainless steel ball valve at both ends with 8.0 milliliters of methylaluminoxane (MAO) solution (15- solution in toluene with 150 ml of a mixture of alkane solvents, and 500 ml of styrene were added. In another injection tank, 20 pmoles of anilidodimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride in toluene were added to 2 milliliters of toluene.

The two injection tanks were then sealed, removed from the handling box and connected to a 600 mL stainless steel pressure vessel. This pressure vessel was evacuated and purged with argon. The contents of the first injection tank were then introduced into the pressure vessel, the contents were heated to 90 ° C with stirring, and ethylene saturation at 1240 kPa was performed. The catalyst solution from the second injection tank was then added to the pressure vessel. Ethylene was then fed as needed at a pressure of 1240 kPa. After 60 minutes the ethylene feed was interrupted. The contents of the reactor were cooled to> 40 ° C, the reactor was vented to atmospheric pressure, and the reaction mixture was treated with acidified methanol. The solution was then removed from the reactor to a vessel containing a small amount of antioxidant. The polymer was dried under reduced pressure. Yield of polymer: 26.6 grams.

Melt flow index (I2) ^: 26.6.

-i α

C-NMR showed that the final polymer contained 47 mole percent (76 weight percent) styrene.

Isotactic, atactic or syndiotactic sequences were not observed in the polymer.

Example 5

Copolymerization of ethylene and styrene

Styrene-ethylene copolymers with different styrene contents were prepared using essentially the same procedure as in Example 4.

In cases where no other catalyst was specifically mentioned, the catalyst used was (tert-butylamido) dimethyl (tetramethyl-β-cyclopentadienyl) silanetitanium dichloride. The methylaluminoxane cocatalyst (MAO) was used in an amount necessary to achieve an Al: M atomic ratio of 1000: 1. The reaction conditions are shown in Table I below.

TABLE I

Try Complex (mg) Temperature t CC) Solvent ^, amount (ml) Pressure ethylene (kPa) 1 0.92 90 T, 50 1240 2 2.50 90 T, 138 1240 3 2.20 90 T, 160 1240 4 2.20 90 T, 204 1240 5 3.70 90 I, 350 1515 6 3.70 90 I, 525 1515 7 3.70 90 I, 600 1515 8 3.70 90 I. 440 1515 9 1.90 90 I, 650 1515 10 1.90 90 I, 650 1515 11 2.20 90 T, 180 1240 12 ^a 2.30 90 T, 180 1240

TABLE I (continued)

Try Styren (ml) Time (throw.) Yield (grams) Mol. % styrene Mw Mw / Mn 1 50 1.0 9 15.2 147000 2.5 2 138 2,0 29 18.4 65100 2.7 3 80 2,0 27 Mar: 11.7 70100 2.6 4 36 2,0 30 8.1 72300 2.5 5 350 1.0 57 10.3 121000 2.8 6 175 0.75 70 6.8 304000 2.6 7 100 ALIGN! 0.33 46 4.8 180000 2.6 8 260 0.33 43 9.0 172000 2.5 9 50 0.5 12 2.5 113000 3.2 10 50 0.5 40 2.8 154000 2.6 11 60 2,0 30 13.3 78600 3.1 12 60 2,0 11 37.0 - -

Notes:

^{and the} catalyst used was (phenylamido) dimethyl (tetramethyl- -fy5_ yklopentadienyl _C) silanetitanium b T = toluene

I = alkane mixture

Examples 6 to 27

In these examples, 2000 milliliters of solvent, which was a mixture of alkanes (Isopar-E) and then 1-octene in different amounts, was charged into a 4 liter autoclave. The catalyst used was (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride dissolved in toluene. A 10% solution of methylaluminoxane (MAO) in toluene was used as the cocatalyst. If necessary, hydrogen was added under pressure from a 100 milliliter vessel to achieve a pressure equivalent to the reactor operating pressure. The reactor was charged with solvent, 1-octene, and methylaluminoxane (MAO), the contents of the reactor were heated to the reaction temperature, and the reactor was then pressurized to a pressure of 3100 kPa with ethylene until saturation of the solution was achieved. Subsequently, hydrogen was optionally fed under pressure and the catalyst solution was added. After 10 minutes, the reactor solution was transferred to a vessel containing a small amount of an antioxidant (Irganox 1010, commercially available from Ciba-Geigy). The polymer was then dried under reduced pressure. The results obtained are shown in Table II below.

TABLE

II

Example Temperature Okten 2η ₂ Kataly- Al: Ti b Yield in reaction- (ml) (kPa) ^a zátor polymer toru (mmoly) (G) CC) 6 140 300 0 0.02 500: 1 182 Ί 160 300 0 0.02 500: 1 61 8 140 300 690 0.02 500: 1 157 9 160 300 690 0.02 500: 1 58 10 140 150 345 0.02 500: 1 128 11 160 150 345 0.02 500: 1 90 12 140 450 345 0.02 500: 1 148 13 160 450 345 0.02 500: 1 55 14 150 150 0 0.02 500: 1 75 15 Dec 150 150 690 0.02 500: 1 85 16 150 450 0 0.02 500: 1 107 17 150 450 690 0.02 500: 1 85 18 150 300 345 0.02 500: 1 100 ALIGN! 19 Dec 150 300 345 0.02 500: 1 93 20 May 150 300 690 0.02 500: 1 115 21 130 150 345 0.02 500: 1 166 22nd 130 150 345 0.02 250: 1 147 23 130 150 345 0.02 100: 1 83 24 110 150 345 0.01 250: 1 98 25 120 300 345 0.02 250: 1 123 26 110 450 345 0.02 250: 1 145 27 Mar: 110 300 345 0.02 250: 1 160

TABLE

II (continued)

Example Mw Mn Mw / Mn Temperature thaw ('C) Density (g / ml) Melt flow index ^c 6 - 91 0.9063 1.72 7 50900 12800 3.98 95 ^d 0.9177 16.28 8 57500 14900 3.86 96 0.9175 7.91 9 38500 10700 3.60 100 ^d 0.9230 31.69 10 66500 17400 3.82 105 0.9174 3.34 11 53000 13400 3.96 106 ^d 0.9317 10.66 12 71700 17100 4.19 86 0.9010 3.84 13 42500 11400 3.73 90 ^d 0.9045 34.20 14 71700 16500 4.35 108 0.9276 2.46 15 Dec 44900 13400 3.35 108 0.9261 18.42 16 62500 14800 4.22 92 ^d 0.9090 5.34 17 58200 12900 4.51 124 0.9516 6.38 18 51000 14000 3.64 95 ^d 0.9130 13.62 19 Dec 53700 14700 3.65 96 ^d 0.9121 10.12 20 May 43000 14200 3.03 95 ^d 0.9118 31.53 21 105000 23200 4.53 109 0.9198 0.18 22nd 136000 29400 4.63 110 0.9197 0.15 23 146000 26300 5.55 105 0.9153 0.15 24 161000 42000 3.83 106 0.9140 0.15 25 112000 28,500 3.93 89 0.9016 0.45 26 130000 37400 3.48 76 ^ 0.9000 0.22 27 Mar: 141000 35600 3.96 82 = £ 0.9000 0.15

(ρ

- & Notes:

^and the hydrogen partial pressure b at the equivalent ratio of the molecular weight of MAO 58 ^C I2 ASTM D-1238, Procedure A, Condition E.

Examples 28 to 42

In these examples, essentially the procedure of Examples 11 to 32 was repeated except that a 2000 ml reactor was used. The catalyst used was (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride (2 ml of a 0.005 M solution in toluene, 10 pmoles).

Al: Ti = 500). The results obtained are shown in Table III below.

TABLE III

Example Heat- Δη ₂ ^(kPa) l-octene (moles) Polymer (grams) Index flow melt ^ Density the (° C) 28 100 ALIGN! 170 1.59 70.0 <0.1 0.8700 29 80 170 1.59 67.0 <0.1 0.8672 30 90 170 1.85 98.2 0.8582 31 100 ALIGN! 170 2.12 118.3 0.96 0.8575 32 100 ALIGN! 345 1.85 131.9 7.48 0.8552 33 80 170 2.12 139.3 0.93 0.8528 34 90 0 1.59 104.4 0.25 0.8594 35 90 345 2.12 133.1 0.8556 36 90 170 1.85 130.2 0.8550 37 100 ALIGN! 0 1.85 110.0 0.66 0.8570 38 90 170 1.85 141.0 0.8545 39 80 345 1.85 161.2 5.44 0.8525 40 80 0 1.85 118.1 0.48 0.8536 41 90 0 2.12 150.8 3.12 0.8516 42 90 345 1.59 136.7 3.43 0.8578

^{and the} partial pressure of hydrogen b12, ASTM D-1238, Procedure A, Condition Ef &

Process of olefin polymerization

According to these examples, ethylene and / or ethylene / 1-octene were polymerized as a homopolymer or copolymer by adding a solution of the appropriate catalyst in combination with methylaluminoxane (MAO) or triethyl aluminum (methylaluminoxane or triethyl aluminum is used herein as a cocatalyst) to a three liter stainless steel pressure vessel containing solvent. , a mixture of 6-carbon / 1-octene alkanes (in different proportions). The polymerization was then carried out at an ethylene pressure of 3100 kPa at 150 ° C (or at 175 ^and C where specifically indicated) for 10 minutes. The ethylene pressure was kept constant and the flow meter measured ethylene consumption. The resulting polymer was then removed from the pressure vessel and dried under vacuum overnight at 90 ° C. The results obtained are shown in Table IV below.

5Q

- & TABLE IV

Example Catalyst ^3- ' Solvent / octene ^c Mass polymer (g) 43 Ti 1/1 61.1 44 Ti 2 / 0.3 48.7 45 Ti 1/1 41.5 46 Ti 2/0 15.6 47 Ti 1/1 47.5 48 Ti 2 / 0.3 75.0 49 Ti 2 / 0.3 75.0 50 Ti i / o 15.6 51 Ti 2 / 0.15 19.9 52 Ti 2 / 0.15 34.5

Example Melt flow index (I ₂ ) Mw Mn Mw / Mn 43 79.0 45600 9100 5.01 44 1.7 88300 101000 8.74 45 137.6 36300 9950 3.68 46 4.4 47 25.8 54000 108000 5.00 48 56.3 44400 12100 3.67 49 56.9 44700 9800 4,56 50 51 52 1.0

¢ 0

- Note:

^a Ti = (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride b Metal / Al ratio 1/1000 at molecular weight of methylaluminoxane (MAO) 58 ^c Liters of each of these substances d Triethyl aluminum was used as cocatalyst; metal / Al ratio = 1: 1000

Example 53

Preparation of (tert-butylamido) dimethyl (tetramethyl-tert-cyclopentadienyl) silanetitanium dichloride.

0.100 grams of dehydroxylated silica (OH concentration of about 1 millimol / gram SiO ₂ ) was suspended in a 50 ml Erlenmayer flask in 20 milliliters of a 6-alkane solvent solvent in a drying box under a nitrogen atmosphere. carbon. 1.0 ml was withdrawn from this suspension by syringe and combined in a 5 ml round bottom flask with 1.10 ml of a 0.011 M toluene solution of (t-butylamido) dimethyl (tetramethyl 1 - [(5-cyclopentadienyl) silanetitanium dichloride). The reaction mixture was stirred for 12 hours. Then 6.7 ml of a 10% by weight solution of methylaluminoxane in toluene was added to the silica-containing solution.

Polymerization

The polymerization was then carried out into a 3 liter stainless steel pressure vessel ¢ 4

- Λ * containing 2 liters of mixed alkane solvent added under pressure the above slurry containing titanium, silica and methylaluminoxane. The polymerization was carried out at an ethylene pressure of 3100 kPa at 150 ° C for 10 minutes. The ethylene pressure was kept constant while ethylene consumption was measured by a mass flow meter. The ethylene consumption was 26.7 grams. The polymer solution was then removed from the pressure vessel and the polyethylene was isolated after drying overnight under reduced pressure at 90 ° C. Polymer yield: 30 grams.

Example 54

Preparation of (2-methoxyfenylamido) dimethyl (tetramethyl yklopentadienyl _C) silanetitanium.

Stage (a)

Preparation of ((tetramethylcyclopentadienyl) dimethylsilyl) (2-methoxyphenyl) amine.

0.86 g (5.9 mmol) of sodium 2-methoxyanilide was added to 1.3 g (5.9 mmol) of ((tetramethylcyclopentadienyl) dimethylsilyl) chloride in 50 ml of tetrahydrofuran. The reaction mixture was stirred overnight. The solvent was then removed under reduced pressure and the residue was extracted with pentane. The pentane extracts were combined and the combined extracts were filtered and concentrated to give a pale yellow liquid. Yield of product: 1.4 g (79%). ^* -ΝΜΡ spectrum (benzene-dg) δ:

6.91 (m, 2.2), 6.74 (m, 1.1), 6.57 (d, 1.1, J = 9),

4.25 (s, 1), 3.32 (s, 6.7), 1.93 (s, 6.7),

1.80 (s, 6.8), 0.13 (s, 6.3)

Stage (b)

Preparation of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) - (2-methoxyphenyl) amide.

To 1.4 g (4.6 millimoles) of ((tetramethylcyclopentadienyl) dimethylsilyl) (2-methoxyphenyl) amine in diethyl ether was added dropwise 3.9 mL of a 2.5 M solution of butyllithium (9.8 millimoles) in hexane. solvent. A white precipitate was formed in this way.

Pentane was added to the reaction mixture. The resulting suspension was filtered and the solids were washed with pentane.

Stage (c)

Preparation of (2-methoxyphenylamido) dimethyl (tetramethylphenyl ₎ cyclopentadienyl) silanetitanium dichloride.

To this, 1.6 g of rithium tetrachloride was added to 1.6 g of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (2-methoxyphenyl) arnica suspended in toluene. The mixture was stirred for three days, filtered, and the solvent was removed under reduced pressure. The residue was slurried in pentane and the suspension was filtered and dried to give the desired product as a dark powder. Yield: 0.77 g (41%).

1 H-NMR spectrum (benzene-dg) δ:

4.10 (s, 3), 2.20 (s, 6.4), 1.99 (s, 6.6), 0.40 (s, 6.3).

Example 55

Preparation of (4-fluorophenylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Stage (a)

Preparation of ((tetramethylcyclopentadienyl) dimethylsilyl) (4-fluorophenyl) amine.

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

· * · Η-ΝΜΡ spectrum (benzene-d 6> ^5: 6.79 (m, 2.5), 6.33 (m, 2,4), 2.95 (s, 1), 2.90 (s, 1), 1.87 (s, 6,9), 1.79 (s, 6.9) 1.79 (s, 6.9), 0.02 (s, 5,8).

Stage (b)

Preparation of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (4-fluorophenyl) amide

An equivalent amount of ((tetramethylcyclopentadienyl) dimethylsilyl) (4-fluorophenyl) amine in diethyl ether and a 2.5 M solution of butyllithium in hexane was combined. A white precipitate was formed. Pentane was added to the reaction mixture. The precipitate was then filtered off, washed with pentane and dried.

@ 1 H-NMR Spectrum (tetrahydrofuran-dg) .delta .:

7.28 (m, 2.0), 6.77 (m, 2), 3.27 (s, 2.7),

2.05 (s, 5.2), 2.01 (s, 5.2), 0.44 (s, 4.6).

Stage (c)

Preparation of (4-fluorophenylamido) dimethyl (tetramethylrf-cyclopentadienyl) silanetitanium dichloride.

To 0.59 g (1.6 mmol) of TiCl3.3 THF in 50 mL of tetrahydrofuran was added 0.50 g (1.7 mmol) of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (4-fluorophenyl) amide. After 30 minutes, 0.25 g (1.8 mmol) of silver chloride was added. After another two hours, the solvent was removed under reduced pressure. The residue was extracted with diethyl ether. The ether extracts were filtered, combined and concentrated under reduced pressure to give a red glass. Dissolve this product in toluene and re-concentrate to obtain a waxy consistency product. The product was extracted with pentane. The pentane extracts were filtered, combined and concentrated to give a waxy product. This waxy product was triturated with a small amount of pentane (2 mL) and filtered to give a red powdered product. Yield: 0.18 g (28%). @ 1 H-NMR spectrum (benzene-d6) .delta .:

7.10 (t), 6.80 (t), 2.00 (s), 1.97 (s), 0.35 (s).

Polymerization

This polymerization was carried out in substantially the same manner as the polymerization process of Examples 6 to 27, (ΰΡ

-Λ ¹ while using 1000 ml of mixed alkane solvent, 200 ml of L-octene and 5 mL of 15% ^ - whom you methylalumoxane (MAO) in toluene (ratio Al: Ti = 1280). The reaction temperature in this case was 130 ° C. Hydrogen was fed from a 75 milliliter stock tank, which was pressurized to 3450 kPa to achieve a hydrogen partial pressure of 345 kPa. 10 micromoles of the above complex were added to initiate polymerization. Ethylene was fed as necessary at a pressure of 3100 kPa.

Polymer yield: 12.8 g;

Mw = 103,000;

M w / M n = 4.77;

density = 0.9387;

melt index = 6.37.

Example 56

Preparation of ((2,6-di (1-methylethyl) phenyl) amido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (2,6-di (1-methylethyl) phenyl) amide was prepared in a manner analogous to that described in Example 55.

In a further procedure, to 1.5 grams (4 millimoles)

TiCl3.3 THF in 25 mL of tetrahydrofuran was added 1.5 grams (4 millimoles) of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (2,6-di (1-methylethyl) phenyl) amide. After 30 minutes, 0.63 g (4 millimoles) of silver chloride was added. After 90 minutes, the solvent was removed under reduced pressure. The residue was extracted

Qb

- with pentane (three portions of 8 ml each). The pentane insoluble residue was extracted with diethyl ether. The ether extract was filtered and evaporated to dryness to give a yellow crystalline product.

1 H-NMR spectrum (benzene-dg) d:

3.04 (heptet, 2, J = 6.7); 2.18 (s, 5.8); 1.98 (s, 5.8);

1.49 (d, 5.8, J = 6.5), 1.12 (d, 6.2, J = 6.8),

0.48 (s, 5.2).

Polymerization

The polymerization process was carried out essentially in the same manner as the polymerization process described above using 10 micromoles of the above complex. The polymer yield was 14.7 grams.

Example 57

Preparation of (4-methoxyphenylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

To 0.73 grams of TiCl4.2 THF in 30 mL of toluene was added 0.7 grams of dilithium ((tetramethylcyclopentadienyl) dimethylsilyl) (4-methoxyphenyl) amide (prepared analogously to Example 56). The reaction mixture was stirred for two days, then filtered and concentrated under reduced pressure. The obtained residue was suspended in pentane and filtered to give a brick red powder product.

Yield: 0.61 g (67%).

1 H-NMR spectrum (benzene-dg) δ:

7.28 (d, 2, J = 8.8); 6.78 (d, 2, J = 8.9); 3.27 (s, 2.8);

2.05 (s, 5.6); 2.01 (s, 5.6); 0.44 (s, 4.8).

Polymerization

The polymerization process was performed essentially in the same manner as the polymerization process of Example 55 except that 10 micromoles of the above complex were used.

Polymer yield: 7.2 grams;

Mw = 79,800;

Mw / Mn = 21.5;

Melt Flow Index = 2.90.

Example 58

Preparation of 1- (tert-butylamido) -2- (tetramethyl-4-cyclopentadienyl) -1,1,2,2-tetramethyldisilanetitanium dichloride.

Stage (a)

Preparation of 1-chloro-2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane.

According to this embodiment, the solution was

4.802 grams (25.7 millimoles) of 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 milliliters of dimethyl ether slowly added a solution containing 2.285 grams (12.8 millimoles)

Sodium 1,2,3,4-tetramethylcyclopentadiene in 30 ml of dimethyl ether. The reaction mixture was stirred for several hours, the solvent was removed under reduced pressure, and the residue was extracted with pentane and filtered. The pentane was then removed under reduced pressure to give a pale yellow product in (t> 8)

- in the form of oil.

Mass spectrum: m / e 272 (80%).

1 H-NMR Spectrum (CgDg) δ:

2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H),

0.28 (s, 6H); 0.23 (s, 6H);

1 C-NMR (CgDg) δ:

135.8, 134.0, 54.4, 14.6, 11.4, 3.2, -2.4.

Stage (b)

Preparation of 1- (tert-butylamino) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane.

To a solution containing 3,000 grams (11.0 millimoles) of 1-chloro-2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane in 50 milliliters of ether was added 2.422 grams (33.1 millimoles) of tert-butylamine. . In this way, a precipitate precipitated almost immediately. The suspension was stirred for several days at room temperature and warmed slightly to complete the reaction. The solvent was then removed and the residue was extracted with pentane; The resulting amine hydrochloride was filtered off and the pentane was removed under reduced pressure to give a yellow product as an oil.

Yield of product: 3.150 g (92.5%);

Mass Spectrum: m / e 309.

¹ H-NMR (C ₆ D ₆ ) δ:

2.75 (s, 1H), 1.95 (s, 6H), 1.82 (s, 6H), 1.08 (s, 9H)

0.51 (s, 1 H), 0.24 (s, 6 H), 0.16 (s, 6 H);

1 C-NMR (CgDg) δ:

135.2, 134.4, 55.2, 50.3,

34.1

14.9, 11.6, (Λ - (fa 3.3, -1.4.

Stage (c)

Preparation of Dithithium 1- (tert-butylamido) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane.

To a solution containing 3.00 grams (corresponding to 9.72 millimoles) of 1- (tert-butylamino) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane in 100 mL of ether, was slowly added 7 70 ml of a 2.60 M solution (20.2 mmol) of butyllithium in a mixed N-alkane solvent. The suspension was stirred for several hours, then filtered and washed with ether. After drying under reduced pressure, a white powder product was obtained.

Yield: 2.918 g (93.4%).

@ 1 H-NMR spectrum (THF d-.delta.) Δ:

2.05 (s, 6H), 1.91 (s, 6H), 0.87 (s, 9H), 0.25 (s, 6H),

-0.03 (s, 6H);

1 H-NMR spectrum (THF d-8) δ:

117.3, 113.6, 53.5, 38.4, 34.1, 14.2, 11.3, 8.4,

2.2.

Stage (d)

Preparation of 1- (tert-butylamido) -2- (tetramethyl-N-cyclopentadienyl)

-1,1,2,2-tetramethyldisilanetitanium dichloride.

A suspension containing 0.7500 grams (2,333 millimoles) of dilithium-1- (t-butylamido) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane and 0.7790 grams (which is 2.333 mmol of TiCl4 / THF in 50 ml of toluene was stirred for several days. The red-orange reaction mixture was filtered and the solvent was removed from the filtrate to give a sticky red product. This product was then extracted with pentane and filtered. Concentration and cooling to -35 ° C in the freezer gave a shiny microcrystalline red product, which was isolated on a frit, which was also washed with cold pentane to remove the dark red oily material.

Yield: 0.3643 g (36.6%).

1 H-NMR Spectrum (CgDg) δ:

2.20 (s, 6H), 1.94 (s, 6H), 1.48 (s, 9H), 0.44 (s, 6H)

0.43 (s, 6 H).

¹³ C-NMR (CGD ₆ (δ:

137.7, 125.5, 112.7, 65.9, 35.4, 16.6, 12.5,

2.8, -2.1.

Polymerization

This polymerization process was carried out in the same manner as the polymerization process described in Example 55 except that 10 micromoles of the above complex were used. The polymer yield in this case was 12.1 g. Mw = 62,400;

Mw / Mn = 8.45;

Melt Flow Index = 6.14;

Density = 0.9441.

Example 59

Preparation procedure (butylamido) Alimethyl / (η ³ -cyclopentaΜ)

67 dienyl) silanetitanium dichloride.

Stage (a)

Preparation of (chloro) (cyclopentadienyl) (dimethyl) silane.

A solution containing 149 grams (1.16 mole) of Me 2 SiCl 2 in 750 ml of diethyl ether was used and the solution was cooled to -78 ° C. Using a powder addition funnel, solid sodium cyclopentadiene (30 grams, 0.341 mol) was then added to the solution over 90 minutes. The reaction mixture was allowed to warm to room temperature and stirred for 16 hours. The ether and a portion of M 2 SiCl 2 were then distilled off and the remaining ether was distilled off under vacuum.

Me 2 SiCl 2 and the product from sodium chloride formed during the reaction. Fractionation gave the product in good yield as a pale yellow oil.

Mass spectrum: m / e 158 (16%).

Stage (b)

Preparation of (tert-butylamino) (cyclopentadienyl) (dimethyl) silane.

A solution containing 3.69 grams (50.4 millimoles) of t-butylamine in 45 milliliters of tetrahydrofuran was added to which was added 2.00 grams (12.6 millimoles) of (chloro) (cyclopentadienyl) (dimethyl) silane . Almost immediately after this addition a precipitate formed. The suspension was stirred for several days, then the amine hydrochloride was filtered off and the solvent was removed under reduced pressure to give a solid.

4b

- Not required product in the form of a pale yellow oil.

Product yield: 2.069 grams (4.2%)

Mass spectrum: m / e 195 (6%).

Both the Η- and C-NMR spectra indicate the presence of several cyclopentadiene isomers.

Stage (c)

Preparation of dilithium (tert-butylamido) (cyclopentadienyl) (dimethyl) silane.

A solution containing 1.500 grams (7.69 millimoles) (tert-butylamido) (cyclopentadienyl) (dimethyl) silane in 60 milliliters of ether was added to which was then slowly added 6.21 milliliters of a 1.72 M solution ( of methyllithium ether solution and then 1.81 ml of a 2.6 M solution (4.706 mmol) of butyllithium in a mixed alkane solvent (total 15.39 mmol of alkyllithium compounds). The suspension was stirred overnight, filtered and washed with pentane. After drying under reduced pressure, the product was obtained as a white powder.

Yield: 1.359 g (85.2%).

¹ H-NMR spectrum (THF d-8) δ:

5.96 (ΐ, 2H), 5.87 (ΐ, 2H), 1.10 (s, 9H), 0.05 (s, 6H) ¹³ C-NMR (THF d-8) d:

114, 105.2, 103.5, 52, 38.3, 7.3.

Stage (d)

Preparation of (tert-butylamido) dimethyl (4-cyclopentadienyl) silanetitanium dichloride.

69 Into a flask containing 75 ml toluene was added 0.7000 g (3.38 mmol) dilithium (tert-butylamido) (cyclopentadienyl) (dimethyl) silane and 1.128 g (3.38 mmol) TiCl4. The resulting yellow suspension turned reddish brown within a few hours. The reaction mixture was stirred for several days, then the red solution was filtered off under reduced pressure. The separated crystalline product was then suspended in pentane and filtered to separate the brown product from the soluble red impurity.

Yield: 0.5369 g (50.9%).

@ 1 H-NMR spectrum (C, D6) .delta .:

6.60 (t, 2H), 6.07 (t, 2H), 1.38 (s, 9H), 0.18 (s, 6H).

1 C-NMR (C 8 D 6) δ:

126.3, 125.6, 110.0, 63.7, 32.2, -0.2.

Polymerization

The polymerization procedure was carried out in the same manner as in Example 55, using 10 micromoles of the above complex.

Polymer yield: 28.1 g;

Mw = 108,000;

Mw / Mn = 3.22;

Density = 0.9073;

Melt Flow Index = 2.92.

Example 60

Preparation of (anilido) (dimethyl) (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Stage (a)

Preparation of (anilido) (dimethyl) (tetramethylcyclopentadienyl) silane.

A solution containing 1500 grams (6.98 millimoles) of (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 50 milliliters of tetrahydrofuran was added to which 0.6911 grams (6.98 millimoles) was slowly added. lithium anilide. Monitoring by gas chromatography showed that the reaction was not complete. Therefore, an additional amount of lithium anilide (0.08 grams, 7.78 millimoles overall) was added. The solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the desired product as a pale yellow oil. Yield: 1.875 g (99.2%).

Mass spectrum: m / e 271 (13%).

1 H-NMR Spectrum (CgDg (δ:

7.14 (m, 2H), 6.76 (t, 1H), 6.60 (d, 2H), 3.08 (s, 1H), 3.04 (s, 1H), 1.89 (s, 6H), 1.79 (s, 6H), 0.07 (s, 6H) ¹³ C-NMR spectrum (C ⁸ D 8) δ:

147.5, 136.3, 132.6, 129.6, 118.2, 116.9, 55.0,

14.3, 11.3, -2.3.

Stage (b)

Preparation of dilithium (anilido) (dimethyl) (tetramethylcyclopentadienyl) silane.

A solution containing 1.875 grams (6.91 millimoles) of (anilido) (dimethyl) (tetramethylcyclopentadienyl) silane in 50 milliliters of ether was added to which was then slowly added 5.31 milliliters of a 2.60 M solution (i.e. 13.8 millimoles) of butyllithium in hexane solvent. A small amount of precipitate was formed but dissolved. The reaction mixture was stirred overnight. The product was then isolated as a thick viscous oil in an ether solution. The solvent was then removed under reduced pressure. A white solid was obtained, which was slurried in pentane, isolated on a frit, washed with pentane and dried under reduced pressure to give the desired product as a white powder.

Product yield: 1.943 (99.3%).

Stage (c)

Preparation of (anilido) (dimethyl) (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

A suspension containing 0.8025 grams (2.333 mmol) of dilithium (anilido) (dimethyl) (tetramethylcyclopentadienyl) silane and 0.9871 grams (2.333 mmol) of TiCl4 (THF) 2 in 70 ml of toluene was used. this suspension was stirred for several days. The red-brown reaction mixture was then filtered and the solvent was removed under reduced pressure. The solid was then triturated in pentane and the product collected on a frit and washed with cold pentane to remove the dark red oily material to give the desired product as a yellow-beige powder.

Yield: 0.6400 g (55.8%).

1 H-NMR Spectrum (CgDg) δ:

7.32 (d, 2H), 7.18 (m, 2H), 6.85 (t, 1H), 2.02 (s, 6H)

1.99 (s, 6H); 0.42 (s, 6H).

1 C-NMR (CgDg) δ:

152.4, 141.9, 137.8, 129.3, 124.4, 119.6, 105.3,

16.1, 13.0, 2.7.

Polymerization 1

This polymerization was carried out in the same manner as the polymerization procedure described in Example 55, using 10 micromoles of the above complex.

Polymer yield: 12.8 g;

Mw = 103,000;

M w / M n = 4.77;

Density = 0.9387;

Melt Flow Index = 6.37.

Polymerization 2

Copolymerization of ethylene and styrene

The polymerization process was essentially performed in the same manner as the polymerization process except that 900 ml of mixed alkane solvent, 184 ml of styrene, 345 kPa (partial pressure of hydrogen) and 20 micromoles [(CgMe ^ JSiMe2) (t-butyl) were used. The temperature of the reactor content was 120 [deg.] C. After 10 minux, the reactor content was removed from the reactor and 62.3 grams of polymer was recovered, and the polymer melt index was 3.68.

Example 61

Preparation of (p-toluidino) (dimethyl) (tetramethyl-cyclopentadienyl) silanetitanium dichloride.

Stage (a)

Preparations of (p-toluidino) (dimethyl) (tetramethylcyclopentadienyl) silane.

A solution containing 2.000 grams (9.302 millimoles) of (chloro) (dimethyl) (2,3,4,5-tetramethylcyclopentadienyl) silane in 70 mL of tetrahydrofuran was slowly added to which 1.259 grams ( Lithium p-toluide (9.302 millimoles) (found to be 0.3-ether adduct by 1 H-NMR spectroscopy). The reaction mixture was stirred overnight. Monitoring by gas chromatography revealed that the reaction was not complete. An additional portion of lithium p-toluidine (0.725 grams, 14.7 millimoles total) was added in small amounts. The solvent was then removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the desired product as a yellow oil.

Yield: 2.456 g (92.5%).

Mass spectrum: m / e 285 (22%).

1 H-NMR Spectrum (CgDg) δ:

6.96 (d, 2H); 6.57 (d, 2H); 3.07 (s, 1H); 3.01 (s, 1H); 2.17 (s, 3H); 1.91 (s, 1H); 6H), 1.80 (s, 6H), 0.08 (s, 6H) 1 H-NMR spectrum (C 8 D 8) δ:

145.0, 136.2, 132.7, 130.2,

20.5, 14.3, 11.3, -2.2.

126.9, 116.9, 55.2,

Stage (b)

Preparation of dilithium (p-toluidino) (dimethyl) (tetramethylcyclopentadienyl) silane.

A solution containing 2.233 grams (7.82 millimoles) of (p-toluidino) (dimethyl) (tetramethylcyclopentadienyl) silane in 65 milliliters of ether was slowly added to a solution of 6.17 milliliters of a 2.60 M solution. (16.0 millimoles) butyllithium in a mixed C8-alkane solvent. The precipitate-free reaction mixture thus prepared was stirred overnight. The solvent was then removed under reduced pressure. The resulting white solid was suspended in pentane, isolated on a frit, washed with pentane, and dried under reduced pressure to give the desired product as a white powder.

Yield of the product: 2.34 g (100%).

¹ H-NMR spectrum (THF d-8) δ:

6.42 (d, 2H), 6.18 (d, 2H), 2.09 (s, 6H), 2.01 (s, 3H),

1.94 (s, 6H); 0.36 (s, 6H).

¹³ C-NMR (THF d-8) δ:

160.8, 129.1, 121.3, 115.9, 115.2, 112.2, 106.2,

20.8, 14.7, 11.7, 5.2.

Stage (c)

Preparation of (p-toluidino) (dimethyl) (tetramethyl- ^3- cyclopentadienyl) silanetitanium dichloride.

According to this procedure was combined 1.000 g (3.363 millimoles a) dilithium (p-toluidino) (dimethyl) (tetramethyl-7) ³ _cyklopentadienyl) silane and 1.123 g (3.363 mmoles) of TiCl ₄ (THF) ₂ in 70 ml of

Ψ?

toluene. The resulting suspension was stirred for several days, filtered and the solvent was removed. The resulting solid was slurried in pentane and the product collected on a frit and dried under reduced pressure. In this way, the desired product was produced in the form of an olive-brown powder.

Yield: 0.7172 g (53%).

¹ H-NMR Spectrum (CgDg) δ:

7.26 (d, 2H), 7.01 (d, 2H), 2.08 (s, 3H), 2.04 (s, 6H)

2.00 (s, 6H); 0.45 (s, 6H).

¹³ C-NMR spectrum (CgDg) δ:

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.

Example 62

Preparation of (benzylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Stage (a)

Preparation of (benzylamino) dimethyl (tetramethylcyclopentadienyl) silane.

A solution containing 1.000 g (4.651 mmol) of (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 70 ml of ether was slowly added to 0.526 g (4.651 mmol) of lithium benzylamide. The reaction mixture was stirred overnight, the solvent was removed under reduced pressure, and the residue was extracted with pentane and filtered. The pentane was then removed under reduced pressure to give the product as a pale yellow oil.

Yield: 1.234 g (93.3%).

Mass spectrum: m / e 285 (18%).

1 H-NMR Spectrum (CgDg) δ:

7.0-7.24 (m, 5H), 3.71 (d, 2H), 2.73 (br s, 1H),

1.88 (s, 6H), 1.76 (s, 6H), 0.43 (br t, 1H),

-0.07 (s, 6H).

¹³ C-NMR spectrum (CgDg) δ:

144.5, 135.7, 132.0, 128.5, 127.3, 126.7, 56.7,

46.4, 14.6, 11.4, -2.3.

Stage (b)

Preparation of dilithium (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane

A solution containing 1.091 g (3.836 millimoles) of (benzylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 70 ml of ether was slowly added, followed by the slow addition of 3.1 ml of a 2.60 M solution (i.e. 8.06 millimoles of butyllithium in a mixed C8-alkane solvent. This reaction mixture turned pink at the same time as a precipitate formed. The reaction mixture was stirred overnight. The solvent was then removed under reduced pressure. The solid was slurried in pentane, collected on a frit, washed with pentane and dried under reduced pressure to give the desired product as a very light pink powder.

Yield: 1.105 g (96.9%).

* 1

- χ 1 H-NMR spectrum (THF d-8) δ:

7.15 (m, 4H), 7.00 (t, 1H), 4.02 (s, 2H), 2.04 (s, 6H),

1.79 (s, 6H), -0.15 (s, 6H).

¹³ C-NMR (THF d-8) δ:

152.1, 128.1, 127.9, 125.0, 115.8, 111.9, 108.3

54.0, 15.0, 11.2, 4.6

Stage (c)

Preparation of (benzylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

A suspension containing 0.5052 grams (1.699 millimoles) of dilithium (benzylamido) (dimethyl) (tetramethyl-4-cyclopentadienyl) silane and 0.5673 grams (1.699 millimoles) of TiCl 4 XTHF 4 in 40 milliliters was used. toluene, and the suspension was stirred for several days. The dark green-brown reaction mixture was filtered and the solvent was removed. The dark oily residue was slurried in pentane and the product collected on a frit and washed with cold pentane to remove the dark oily material to give the product as a greenish yellow powder.

Yield: 0.2742 g (40.1%).

1 H-NMR Spectrum (CgDg) δ:

7.19 (m, 2H), 7.02 (m, 3H), 5.37 (s, 2H), 1.99 (s, 6H),

1.98 (s, 6H), 0.03 (s, 6H).

1 C-NMR (CgDg) δ:

141.4, 140.9, 135.8, 129.0, 128.8, 126.9, 126.6,

126.3, 111.6, 103.6, 59.3, 15.6, 12.4, 1.7.

Polymerization

The polymerization was carried out using the same polymerization procedure as in Example 55, using 10 micromoles of the above complex.

Polymer yield: 14.4 g;

Mw = Mw / Mn = 5.0;

Melt Flow Index = 251;

Density = 0.9690.

Example 63

Preparation of (methylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

Stage (a)

Preparation of (methylamino) dimethyl (tetramethyl-4-cyclopentadienyl) silane

A solution containing 1.900 grams (8.845 millimoles) of (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 75 milliliters of tetrahydrofuran was added rapidly to 0.3272 grams (8.846 millimoles) of lithium methylamide. . The clear solution was stirred overnight and an additional portion of lithium methylamide (0.008 g,

9.062 millimoles in total), and it was found by gas chromatography that the reaction was not complete. The solution was stirred again overnight. The solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give very a

- (γ) a slightly yellow oily product.

Yield: 1.698 g (91.7%).

Mass spectrum: m / e 209 (13 percent).

1 H-NMR Spectrum (CgDg) δ:

2.82 (s, 1H), 2.33 (d, J = 6.6Hz, 3H), 1.95 (s, 6H),

1.83 (s, 6H); -0.04 (s, 6H).

¹³ C-NMR spectrum (CgDg (δ:

135.4, 132.7, 56.1, 27.8, 14.0, 11.0, -3.5.

Stage (b)

Preparation of dilithium (methylamido) dimethyl (tetramethylcyclopentadienyl) silane.

A solution containing 1.563 grams (7.463 millimoles) of (methylamino) (dimethyl) (tetramethylcyclopentadienyl) silane in 65 mL of a 1: 1 mixture of ether and pentane was slowly added to the solution. 03 ml of a 2.60 M solution (representing 15.7 mmol) of butyllithium in a mixed C8-alkane solvent. The solution was then turned into a thick syrup which was then slurried. The reaction mixture was stirred overnight and filtered. The solid product was washed several times with ether and then with pentane and dried under reduced pressure to give the product as a white powder.

Product yield: 1.883 grams of @ 1 H-NMR showed to be a 0.25-ether adduct.

ή

2.01 (s, 6H), ¹ H-NMR spectrum (THF d-8) δ:

3.41 (q, J = 7.0 Hz, 1H); 2.45 (s, 3H);

1.93 (s, 6H), 1.11 (t, J = 7.01, 5H),

0.01 - 0.14 (br, 6H).

Stage (c)

Preparation of (methylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

A solution containing 0.6708 grams (2.597 millimoles) of dilithium (methylamido) dimethyl (tetramethyl-1-η 5 -cyclopentadienyl) silane in 80 ml of tetrahydrofuran was added, and 0.9623 grams (2.597 grams) was added in one portion. milimol) TiCl 2 (THF). The solution was immediately turned brown-orange. This coloring was very intense. The reaction mixture was stirred for four days, and 1.861 g (12.98 mmol) of silver chloride was added thereto. The suspension was stirred for several days, then the reaction mixture was filtered and the solvent was removed under reduced pressure. The residue was then extracted with toluene and the dark orange-brown solution obtained was filtered and the solvent was removed from the filtrate. After extraction with pentane and filtration, the filtrate was concentrated to give a light brown suspension, the liquid portion of which was dark red in color. After cooling to -30 ° C, the bright pale yellow product was isolated on a frit, washed with pentane, and dried under reduced pressure.

Yield: 0.3168 g (37.4%).

1 H-NMR Spectrum (CgDg) δ:

3.64 (s, 3H), 1.97 (s, 6H), 1.95 (s, 6H), 0.21 (s, 6H). @ 1 H-NMR spectrum (CDCl3) .delta .:

140.5, 135.5, 103.0, 41.8, 15.5, 12.3, 0.6.

Polymerization

The polymerization was carried out in the same manner as in Example 55 using 10 micromoles of the above complex.

Polymer yield: 30.2 g.

Example 64

Polymerization of terpolymer.

Mixtures of ethylene, styrene and other other polymerizable monomers were polymerized using (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride complex and methylaluminoxane (MAO) cocatalyst in an Al / Ti atomic ratio of 1000: 1. the reaction conditions and the results obtained are summarized in the following Table V.

fy

- TABLE V (in all cases was employed as the cocatalyst is methylaluminoxane and the metal complex was (t-butylamide) X-dimethyl (tetramethyl-T) ⁵ -cyclopentadienyl) titaniumdichlor id) ^first

Method Complex (mg) Temperature (° C) Solvent ^3- (ml) Ethylene (kPa) Styren (ml) Olefin (G) 1 1.8 90 I (670) 1515 68 butene (19) 2 1.9 90 I (630) 1515 76 butene Italy (9) 3 1.9 90 I (456) 1515 250 butene (5) 4 2.2 90 T (40) 1240 133 vinyl-BCB (1,5) ^b

η- Ž3

TABLE V (continued)

Method Time (clock) Yield (grams) Styrene (mol%) Olefin (mol%) Mw Mw / Mn 1 0.5 51 2.3 6.6 141000 2.9 2 0.5 45 3.4 4,5 155000 2.4 3 0.5 70 7.2 3.2 153000 2.4 4 2,0 37 22.4 <1 39000 1.7

Notes:

^and I = mixed alkane solvent, T = toluene

Vinyl-BCB = vinylbenzocyclobutane

-% 4 Example 65

Suspension polymerization

This example demonstrates the possibility of using the catalyst of the invention for suspension polymerization processes. The procedures of Examples 9 to 27 were substantially repeated except that the reaction was carried out under conditions in which the polymer was insoluble in the reaction medium and separated from the reaction medium at the time of its formation. A temperature of 70 ° C, milliliters of octene, 1190 milliliters of mixed alkane solvent and 5 milliliters of 15% methylaluminoxane (MAO) in toluene (Al: Ti = 1280) was used. After 20 minutes, the reactor was drained to give 4.6 grams of polymer. Additional solvent was then introduced into the polymerization reactor, and the temperature in the reactor was raised to 170 ° C to remove the polymer that had formed long fibers that wound around the stirrer.

Melt Flow Index = 0.28.

Example 66

Preparation of (tert-butylamido) dimethyl (tetramethyl-4-cyclopentadienyl) silanetitanium dichloride.

0.24 grams of TiCl-i (THF) -j and 0.33 grams were mixed in a drying box

Me ₄ C ₂ SiMe ₂ Nt-BuMg ₂ Cl ₂ (THF) ₂ 15 ml of tetrahydrofuran were then added and the mixture turned dark red. After 30 minutes the volatiles were removed under reduced pressure to give a dark solid. To this residue was added 15 ml of toluene, the solution was filtered and the toluene used ii

Pi was removed under reduced pressure to give a red-purple powder.

Yield: 0.22 g.

Polymerization

This polymerization was carried out under the conditions of Example 55 using 10 micromoles of the above complex.

Yield of polymer: 55.1 g;

Melt Flow Index = 1.71.

Example 67

The polymerization process was repeated under the conditions of Example 55, using 10 micromoles of (tert-butylamido) dimethyl (tetramethyl) -3-cyclopentadienyl) silanetitanium dichloride.

Polymer yield: 76.4 g;

Mw = 56.700;

Mw / Mn = 4.5;

Density = 0.8871;

Melt flow index (I2) = 10.13.

Example 68

The polymerization process was repeated under the conditions of Example 67 except that the temperature was 80 ° C, the amount of catalyst was 2.5 micromoles, the amount of 1-octene was 250 milliliters, and the amount of mixed alkane solvent was 950 milliliters. The reaction time was 1 hour.

Polymer yield: 51.1 g;

Melt Flow Index = 0.11.

Comparative Example 1

The polymerization procedure of Example 67 was repeated except that pentamethylcyclopentadienyltitanium trichloride was used as the catalyst. Polymer yield: 4.6 g.

Comparative Example 2

Example 67 was repeated except that pentamethyl-N-cyclopentadienyltitanium-tert-butylaminodichloride having the 1 H-NMR spectrum (CgDg) was used as the catalyst.

2.07 (s, 1 H); 1.88 (s, 15H); 1.35 (s, 9H);

and 1 C-NMR spectrum (CgDg)

61.0, 31.3, 12.6).

Polymer yield: 2.0 g.

Comparative Example 3

The polymerization procedure of Example 67 was repeated except that bis (tert-butylamido) dimethylsilanetitanium dichloride was used as the catalyst. No polymer formation was observed after 10 minutes of reaction.

Comparative Example 4

The polymerization procedure of Example 67 was repeated except that dicyclopentadienylzirconium dichloride was used as the catalyst.

Polymer yield: 109.0 g;

=ν = 16300

Mw / Mn = 3.63;

Melt Flow Index (ASTM D-1238, Method A, Condition E):

I 2 is greater than 1000, indicating a very low molecular weight of the polymer obtained.

Comparative example 5

The polymerization procedure of Example 67 was repeated except that dicyclopentadienyl titanium dichloride was used as the catalyst.

Polymer yield: 7.3 grams;

Melt Flow Index (ASTM D-1238, Method A, Condition E):

I 2 was greater than 1000, indicating a very low molecular weight of the polymer obtained.

Claims (9)

PATENT CLAIMS 1. A metal coordination complex of formula I: R ’ R ’ Ύ R 'R' (X) n in which: M means titanium, zirconium or hafnium, R 'is independently selected at each occurrence from the group consisting of hydrogen or a group selected from silyl, alkyl, aryl and combinations thereof containing up to 10 carbon atoms, Z stands for Sulfur2 » Y stands for -NR’-, X represents at each occurrence a halide, alkyl, aryl or alkoxy group containing up to 10 carbon atoms, n being 1 or 2. The metal coordination complex of claim 1, wherein M is titanium. The metal coordination complex according to any one of the preceding claims, wherein X is a halide. 4. A metal coordination complex according to any of the above -tt-rc. of the preceding claims, wherein Y is a t-butylamide group. A metal coordination complex according to any preceding claim selected from the group consisting of: (tert-butylamido) (tetramethyl-z; ^3- cyclopentadienyl) 1,2-ethanediyl zirconium dichloride, (tert-butlamido) (tetramethyl-t-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamido) (tetramethyl-1,2-cyclopentadienyl) 1,2-ethanediomethylsulfonamide; (methylamido) (tetramethyl-β-cyclopentadienyl) 1,2-ethanediyltitanium dichloride, (ethylamido) (tetramethyl-β-cyclopentadienyl) methylenetitanium iichloride, (tert-butylamido) dimethyl (tetramethyl-η-cyclopentadienyl) silanetitanium dichloride (tetramethyl-β-cyclopentadienyl) silanetitanium dichloride) (cyclopentadienyl) silanzirconium dibenzyl, (benzylamido) dimethyl (tetramethyl- [ ^beta] -cyclopentadienyl) silanetitanium dichloride, and (phenylphosphino) dimethyl (tetramethyl-4-cyclopentadienyl) silanzirconium dibenzyl. 6. A catalyst composition suitable for addition polymerization comprising: (a) a metal coordination complex according to any one of the preceding claims, and (b) an activating cocatalyst. 7. The addition polymerization process for preparing a polymer by contacting one or more addition polymerizable monomers with a catalyst under addition polymerization conditions, S> 0, characterized in that the catalyst composition according to claim 6 is used. A process according to claim 7, wherein the alpha-olefin is copolymerized with a vinylidene aromatic monomer. 9. The process of claim 8 wherein the ethylene is copolymerized with styrene. Zastú