PL166689B1

Method of obtaining a coordination metal complex, catalyst for additive polymerization and method for obtaining such catalyst as well as additive polymerization process

Abstract

One or more addition polymerizable monomers are polymerized by catalysts comprising a metal monocyclopentadienyl coordination complex and an activating cocatalyst to form novel polymers, including atactic amorphous poly(alpha-olefins), elastic polyethylenes and pseudo-random copolymers.

PL166689B1, drawing sheet 1 — Sheet 1 of 29

Term

Term ended

Expired 30 August 2005, 21.1 years ago.

10 claims: 2 independent, 8 dependent

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Patent claims Zastrzeżenia patentowe 1. Addition polymerization catalyst characterized in that it consists of a) metal coordination complex of formula 2 in which R 'is in each case hydrogen or halogen or alkyl, aryl, silyl, germyl or cyano containing up to 20 atoms being hydrogen, or the adjacent pair of R 'groups forms, with the residue, a cyclopentadienyl group, an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group;X is in each case coordinated hydrogen or halogen or alkyl, silyl, germyl, aryl, aryloxy, alkoxy or siloxy or an amide residue containing up to 20 non-hydrogen atoms;Y is -O-, -S-, -NRX-, -PRX- or a neutral two-electron donor ligand selected from the group consisting of ORX, SRX, NRXg, or PRXg, M is a titanium, zirconium or hafnium atom, and Z is ^ 2, CRXa, SiRX2SiRXa, CRX2CRX2, CRX = CRX, CRX2SiRX2 and GeRX ^ BR BRX2, where RX is in each case hydrogen or alkyl, aryl, silyl, halogenated alkyl or halogenated aryl, containing up to 20 non-hydrogen atoms, and n is equal to 1 or 2 and b) an activating cocatalyst selected from the group consisting of aluminoxanes, aluminum alkyl compounds, aluminum halides, aluminum alkyl halides, Lewis acids and non-interfering oxidizing agents and mixtures thereof. 1. Katalizator do polimeryzacji addycyjnej, znamienny tym,, że składa się z a) kompleksu koordynacyjnego metalu o wzorze 2, w którym w każdym przypadku R' oznacza atom wodoru lub chlorowca lub alkil, aryl, silil, germyl lub resztę cyjanową, zawierające do 20 atomów nie będących atomami wodoru, albo sąsiadująca para grup R' tworzy z resztą cyklopentadienylową grupę indenylową, tetrahydroindenylową, fluorenylową lub oktahydrofluorenylową;X w każdym przypadku oznacza skoordynowany wodór lub chlorowiec lub alkil, silil, germyl, aryl, aryloksyl, alkoksyl lub siloksyl lub resztę amidową, zawierające do 20 atomów nie będących atomami wodoru;Y oznacza -O-, -S-, -NRX-, -PRX- lub obojętny dwuelektronowy ligand donorowy wybrany z grupy obejmującej ORX, SRX, NRXg, lub PRXg, M oznacza atom tytanu, cyrkonu lub hafnu, a Z oznacza ^2, CRXa, SiRX2SiRXa, CRX2CRX2, CRX = CRX, CRX2SiRX2, GeRX^ BRX oraz BRX2, gdzie RX w każdym przypadku oznacza wodór lub alkil, aryl, silil, chlorowcowany alkil lub chlorowcowany aryl, zawierające do 20 atomów nie będących atomami wodoru, a n jest równe 1 lub 2 i b) aktywującego kokatalizatora wybranego z grupy obejmującej aluminoksany, związki alkiloglinowe, halogenki glinu, alkilohalogenki glinu, kwasy Lewisa i niezakłócające działania środki utleniające i ich mieszaniny.
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A method for the preparation of an addition polymerization catalyst, characterized in that the metal coordination complex of formula 2 is contacted, wherein in each case R 'is hydrogen or halogen or alkyl, aryl, silyl, germyl or cyano containing up to 20 non-atoms hydrogen atoms or an adjacent pair of R 'groups forms a cyclopentadienyl group with an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group;X is in each case coordinated hydrogen or halogen, or alkyl, silyl, germyl, aryl, aryloxy, alkoxy or siloxy or an amide residue containing up to 20 non-hydrogen atoms, Y is -O-, -S-, -NR * -, -PR * - or a neutral two-electron donor ligand selected from the group consisting of OR *, SR *, NR * 2 or PR * 2, M is titanium, zirconium or hafnium, and Z is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2, GeR * 2, BR * and BR * 2, where R * is in each case hydrogen or alkyl, aryl, silyl, halogenated alkyl or halogenated aryl, containing up to 20 non-hydrogen atoms, and n is equal to 1 or 2, with an activating cocatalyst selected from the group consisting of aluminoxanes, alkylaluminum compounds, halides aluminum, aluminum alkyl halides, Lewis acids and non-interfering oxidizing agents and mixtures thereof. 10. Sposób wytwarzania katalizatora do polimeryzacji addycyjnej, znamienny tym, że kontaktuje się kompleks koordynacyjny metalu o wzorze 2, w którym w każdym przypadku R' oznacza atom wodoru lub chlorowca lub alkil, aryl, silil, germyl lub resztę cyjanową, zawierające do 20 atomów nie będących atomami wodoru, albo sąsiadująca para grup R' tworzy z resztą cyklopentadienylową grupę indenylową, tetrahydroindenylową, fluorenylową lub oktahydrofluorenylową;X w każdym przypadku oznacza skoordynowany wodór lub chlorowiec, lub alkil, silil, germyl, aryl, aryloksyl, alkoksyl lub siloksyl lub resztę amidową, zawierające do 20 atomów nie będących atomami wodoru, Y oznacza -O-, -S-, -NR*-, -PR*- lub obojętny dwuelektronowy ligand donorowy wybrany z grupy obejmującej OR*, SR*, NR*2 lub PR*2, M oznacza atom tytanu, cyrkonu lub hafnu, a Z oznacza SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, GeR*2, BR* oraz BR*2, gdzie R* w każdym przypadku oznacza wodór lub alkil, aryl, silil, chlorowcowany alkil lub chlorowcowany aryl, zawierające do 20 atomów nie będących atomami wodoru, a n jest równe 1 lub 2, z aktywującym kokatalizatorem wybranym z grupy obejmującej aluminoksany, związki alkiloglinowe, halogenki glinu, alkilohalogenki glinu, kwasy Lewisa i niezakłócające' działania środki utleniające i ich mieszaniny.

Independent claims2

615 paragraphs in 15 sections, as filed

The present invention relates to an addition polymerization catalyst and a method for the preparation of a catalyst. The new catalyst of the invention contains a metal coordination complex with voltage in the molecule.

Due to the unusual exposure of the active metal center in the metal coordination complexes with the voltage in the molecule, the catalysts obtained from them exhibit exceptional properties. Under certain conditions, the catalysts of the invention allow the production of new olefin polymers with properties not seen before, due to their exceptional ease of polymerization of α-olefins, diolefins, aliphatic sterically hindered vinylidene monomers, vinylidene aromatic monomers and mixtures thereof.

Numerous metal coordination complexes are known, including those containing monocyclopentadienyl and substituted monocyclopentadienyl groups. The metal coordination complexes contained in the catalyst according to the invention differ from the known complexes in that the metal is bonded to a delocalized, substituted π-linked moiety in a manner that causes tension around the metal atom. Preferably the metal is attached to a cyclopentadienyl group, a substituted cyclopentadienyl group or other similar group with a η bond5 and a bridge connection including other metal ligands. The complexes preferably contain metals having useful catalytic properties.

Transition metal coordination complexes, also known as corrugated complexes, are also known. Such complexes are described in Organometallics 6, 232-241 (1987).

In the patent application Ser. Amer. No. 8,800 of 30/01.87, corresponding to European Patent Publication No. 277 004, discloses certain bis (cyclopentadienyl) methyl compounds prepared by reacting a bis (cyclopentadienyl) metal complex with Bronsted acid salts containing a non-coordinating, compatible anion. The cited publications reveal that such complexes are successfully used as olefin polymerization catalysts.

However, these are not particularly effective olefin polymerization catalysts.

Previous attempts to produce copolymers of aromatic vinylidene compounds with α-olefins, in particular copolymers of styrene and ethylene, have not achieved significant incorporation of vinylidene aromatic monomer or have resulted in low molecular weight polymers. Polymer Bulletin, 20,237-241 (1988) describes a styrene ethylene random copolymer containing 1 mol% of embedded styrene. The yield of the polymer in question was 8.3 X 10_4g of polymer / mol of titanium used.

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It has now been found that known addition polymerization catalysts cannot exhibit high activity and are not able to polymerize many monomers due to the lack of voltage in the molecule.

The invention relates to a catalyst that contains a metal coordination complex with a voltage in the molecule in combination with activating cocatalysts or mixtures of such compounds. Such a catalyst can be successfully used in the polymerization of additionally polymerizable monomers, in particular ethylenically unsaturated monomers.

The invention also relates to a method for preparing such catalysts.

The catalyst according to the invention consists of a) metal coordination complex of formula 2, in which R 'is in each case hydrogen or halogen or alkyl, aryl, silyl, germyl or cyano, containing up to 20 non-hydrogen atoms, or an adjacent pair the R 'group forms a cyclopentadienyl group with an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group; X is in each case coordinated hydrogen or halogen or alkyl, silyl, germyl, aryl, aryloxy, alkoxy or siloxy or an amide residue containing up to 20 non-hydrogen atoms; Y is -O-, -S-, -NRX-, -PR * - or a neutral two-electron donor ligand selected from the group consisting of ORX, SRX, NR * 2 or PRX2, M is a titanium, zirconium or hafnium atom, and Z is SiRX2, CR * 2, SiR * 2SiR * 2, CRX2CRX2 , CRX = CRX, CRX2SiRX2, GeR * 2, BRX and BR * a, where Rx is in each case hydrogen or alkyl, aryl, silyl, halogenated alkyl or halogenated aryl, containing up to 20 non-hydrogen atoms, an is equal to 1 or 2 and b) an activating cocatalyst selected from the group consisting of aluminoxanes, aluminum alkyl compounds, aluminum halides, aluminum alkyl halides, Lewis acids and non-interfering oxidizing agents and mixtures thereof.

It should be noted that in Formula 2, which represents the cyclic structure of the complex, when Y is a two-electron donor ligand, then the bond between M and Y should be accurately defined as a coordination-covalent bond. It should also be noted that the complex may exist as a dimer or in the form of a higher oligomer.

Preferably, at least one of the R ', Z or RX groups is an electron-donating moiety. Thus, very preferably Y is a nitrogen or phosphorus containing group represented by the formula -N (R) -or -P (R) -, wherein R is C 1-10 alkyl or aryl, i.e. an amide or phosphide group.

Most preferably, the complex compounds are amidosilane or amidoalkanediyl compounds of the formula III in which M is a titanium, zirconium or hafnium atom bonded with an η5 with a cyclopentadienyl group, R 'is in each case a hydrogen atom or a silyl, alkyl or aryl group containing up to 10 carbon or silicon atoms; E is silicon or carbon; X is in each case coordinated hydrogen or halogen, alkyl, aryl, aryloxy or alkoxy containing up to 10 carbon atoms; m is 1 or 2 and n is 2.

Preferably, the catalyst contains a complex of formula 3 in which R 'is in each case hydrogen, C 1-6 alkyl, norbornyl, benzyl or phenyl or one or more R' attached to a cyclopentadienyl residue forms an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group with this residue , X is chlorine, bromine, iodine, C 1-6 alkyl, norbornyl, benzyl or phenyl and E, M, min are as defined above.

Particularly preferred are catalysts containing a coordination complex of formula 2 or 3 in which M is a titanium atom and the other substituents are as defined above.

Examples of the above-mentioned most preferred metal coordination compounds include those in which R 'on the amide group is methyl, ethyl, propyl, butyl, pentyl, hexyl (including its isomers), norbornyl, benzyl, phenyl R' on each cyclopentadienyl group means in each hydrogen, methyl, ethyl, propyla, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl and X is chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, pentyl, hexyl (including also isomers), norbornyl, benzyl, phenyl. Specific compounds include: (tert-butylamidoKtetramethyl-n-cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) -1,2-ethanediinediititane dichloride (methylamido) dichloromethyl5-cyclopentadienyl) -1,2-ethanediyl zirconium ((methylamidoXtetramethyl-n dichloride)5-cyclopentadienyl) -1,2-ethanediyl titanium, (ethylamido) dichloride (tetra166 689 methyl-n5-cyclopentadienyl) methylene titanium, (tert-butylamido X-dimethyl- / tetramethyl-n-dichloride5-cyclopentadienyl) silanitanium, (tert-butylamidimidomethylphthetramethyl-^ - cyclopentadienyl / silane) dibenzyl) zirconium, (benzylamido / dimethyl (tetramethyl-η) dichlorides-cyclopentadienyl) silicate, (phenylphospho / dimethyl) tetramethylene8-cyclopentanecarboxylic acid tert! opentadlenyloXsilano,/dibenzyl) zirconium.

The complexes can be prepared by contacting a metal reagent with a Group I metal derivative or a Grignard derivative of a cyclopentadienyl compound in a solvent and separating the by-product salt. Suitable solvents for making metal complexes are aliphatic or aromatic liquids such as cyclohexane, methylcyclohexane, pentane, hexane, heptane, tetrahydrofuran, diethyl ether, Ci-4monol or diethylene glycol alkyl ethers, C 1-4 alkyl mono- or dipropylene glycol ethers, benzene, toluene, xylene, ethylbenzene etc., and mixtures thereof.

According to a preferred method, the metal compound is a compound of formula MXn+ i in which M is at a lower oxidation state than in the corresponding compound MXn + 2 and than the oxidation state in the desired finished complex. A non-interfering oxidizing agent may then be used to increase the metal oxidation state. Oxidation is carried out simply by contacting the reagents with a solvent and under the same reaction conditions as in the production of the complex itself. The term "non-interfering agent" refers to a compound having an oxidizing potential sufficient to increase the metal oxidation rate without interfering with the formation of the desired complex or subsequent polymerization. AgCl is a particularly suitable non-interfering oxidizing agent.

In order to facilitate the handling of the metal compounds used according to the invention according to the formula MXn + 2, it may be advantageous to form their solid adduct first by using the appropriate coordination agent in accordance with known methods. Eg. since titanium tetrachloride is a fuming liquid that is difficult to manipulate, a TiCl adduct with ether, a tertiary amine, a tertiary phosphine or other basic nonproton compound can be prepared first. The resulting solids can be handled more easily. The preferred coordinating adduct is tetrahydrofuran.

The reactions used to form the metal complex can be carried out under heterophasic or homophasic conditions. This means that the various reactants or the resulting product need not be substantially soluble in the solvent mixture. Usually the reagents are contacted in an inert atmosphere for a few minutes to several days. If necessary, mixing can be used. The reaction temperature is generally from -90 to 150 ° C, preferably from -20 to 70 ° C.

The inventive catalysts are prepared by contacting a metal coordination complex of formula 2 as defined above with an activating cocatalyst compound selected from the group consisting of aluminoxanes, aluminum alkyl compounds, aluminum halides, aluminum alkyl halides, Lewis acids, and non-interfering oxidizing agents and mixtures thereof. in any order and in any appropriate way. Preferably, the molar ratio of the coordinating complex to the cocatalyst is from 1: 0.1 to 1:10,000. Of course, it should be understood that the catalyst system can also be generated in situ if its components are added directly to the polymerization system and the polymerization process is used a suitable solvent or diluent, including liquefied monomer. Suitable solvents include toluene, ethylbenzene, alkanes and mixtures thereof. In some cases, the catalysts can be separated from the solution and stored in an inert atmosphere before use. The components of the catalyst are sensitive to both moisture and oxygen, so that their handling and storage should take place in an inert atmosphere, e.g. in nitrogen, argon or helium, or under reduced pressure.

The catalysts of the invention are successfully used in addition polymerization to produce polymers useful as shaped articles, packaging films and upholstery foams, as well as in the modification of synthetic or natural resins.

Figures 1-5 show computer simulated models of complexes with voltage in a molecule based on the results of a single crystal X-ray analysis.

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Figures 6 and 7 show computer-simulated models of metal complexes, based on the results of single crystal X-ray analysis, showing less voltage than the models of Figures 1-5.

Fionn-u 8 - U iluetry of urnlicznin and zanhcprumuran scatter of styrene and ethylene units and reverse flow.

of other styrene units in ethylene / styrene copolymers, illustrating the principles of pseudostatic incorporation in accordance with the invention.

Figure 14 illustrates the disagreement between calculated and observed scatter of styrene, ethylene and inverse styrene units in ethylene / styrene copolymers, if the principles of completely accidental incorporation are adopted.

Figure 15 shows typical rheological curves for the E1PE resin of the invention. The curves of complex viscosity dependence, ηχ and tg δ as a function of shear rate, for resin.

Figure 16 shows a typical curve of the modulus of elasticity on the flow index for E1PE resins according to the invention.

Figure 17 shows typical rheological curves for polyethylene resin produced in the usual way. The curves of complex viscosity, η * and tg δ of resin versus shear rate are shown.

As used herein, the term "delocalized π-linked moiety refers to an unsaturated organic moiety, e.g., one that contains an ethylene or acetylene group in which the π electrons have been given to the metal to form a bond. For example, alkene, alkenyl, alkyne, alkynyl, allyl, polyene and polynyl moieties, as well as unsaturated cyclic systems.

The term "voltage in a molecule" means that there is a forced greater exposure of the active metal center in the metal atom as a result of the presence of one or more substituents on the delocalized, π-linked moiety. Preferably, the delocalized, π-linked moiety is a cyclopentadienyl group or a substituted cyclopentadienyl group forming part of the ring structure in which the metal is attached to the adjacent covalent moiety while being associated with the delocalized π-linked moiety through η bonds5. It is understood that the corresponding bonds between the metal atom and the atoms forming part of the delocalized π-linked moiety need not be equal. This means that the metal can be symmetrically or asymmetrically π-connected to the π-linked moiety.

The geometry of the active metal center can be more accurately determined as follows. The mass center of the π-linked moiety can be defined as the average of the corresponding coordinates X, Y and Z of the centers of the atoms forming the π-linked moiety. The angle przy formed at the center of the metal between the center of mass of the π-linked moiety and each of the other ligands of the metal complex can easily be calculated by known single crystal X-ray diffraction techniques. Each of these angles can increase or decrease, depending on the molecular structure of the metal complex with voltage. Those complexes in which one or more angles θ are smaller than in a similar, suitable complex, which differs only in that the voltage-causing substituent has been replaced by a hydrogen atom, show voltage in the sense of the invention. Preferably one or more of these angles θ is reduced by at least 5%, and more preferably by 7.5% compared to the comparison complex. It is very advantageous if the average size of all angles θ between the bonds is also smaller than in the comparative complex. Most preferably, the metal coordination complex with tension is in the form of a ring structure, which means that the voltage-causing substituent is part of the ring system that includes the metal atom.

Preferably the monocyclopentadienyl metal 4 or lanthanide coordination complexes according to the invention exhibit such a voltage that the smallest angle θ is smaller than 115 °, even more preferably smaller than 110 °, and most preferably smaller than 105 °.

Exemplary arrangement of atoms in complexes, determined on the basis of single crystal X-ray diffraction patterns, are presented in Figs. 1-7.

Figure 1 shows the structure, determined on the basis of X-ray crystallography of single crystal, (4-methylpenylamido / dimethyl) tetramethyl-n5-cyclopentadienyl / silanititane dichloride. The angle formed between the center of mass of the cyclopentacienyl ring (C2, C3, C5, C7 and C9), the titanium atom (Ti1) and the nitrogen atom (N14) is 105.7 °.

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Figure 2 shows the structure, determined on the basis of the x-ray of such single crystal crystallography, (tert-butylamίdo / dimethyl / tetΓa.m Ztyle-η5-cyclopentadienyl) si] - dimethyl zirconium poured. The angle formed between the center of the mass of the cyclopentinyl ring (C2, C3, C3X,

C5 and C5) with a zirconium atom (Zr1) and an 'amKi (N9) atom

WJJiAWSŁłM Λ. J «. V »* \ Evil * VŁŁł XJ Π J

X17MT «ZX« »and tolr TWrłF '» *** »/ *» »/ · ***** - jtm nj & uuvŁ, vuv

ΓΜ ΛΟΓ1r V4 <jV X- * ·

Figure 3 shows the structure determined from X-ray crystallography of monocrystalline ,. m-amylamido dichloride / dimetslo / that tramżtylo-ηs-cyclopeztadizzyl) silanefytano. Yalta was designatedat formed between the center of mass of the e ^ dpentadienyl ring (C2, C3, Cfrom, C7 and C9k, titanium atom (Ti1) and nitrogen atom (C14) is fromD6,1 °.

Figure 4 shows the structure denoted for the following three crystallographies of single crystal, dichloride (tert-butylamido / dimzty)ando / lj5~ cyclopenΐgdandZNria) silαnocyrkonz. From the structure it follows that this crysrineal molecule in the form of a dimer with two chloride formations. It has been determined that the angle formed between the center of mass of the cyaloptin ring (C2, C3, C4, C5 and C6), the zirconium atom (Zr1) and the nitrogen ztom (N10) and the angleand cyclopentz ring center of massatieny1owzgo (C102, C103, C104, C105 and C106), with a zirconium atom (Zofrom01) otm atnmzio ζτπΖζ (Ν110ζ is 9C10.

Figure 5 shows the structure, determined on the basis of X-ray crystallization of mozaccritical goldand D-phosphite (volert-butyl sizeanddownnπ: Imetylo / aetzrmetyandπ-n0πrklopżktadiżnylo} sandLazacfromrkozu. It was determined that the angle formed mlMedium required for mass cyclopropyl cyclismso (C1, C2, C3, C4 and C5), zirconium (Zr) and nitrogen atom (Nś 102.0 °).

Pictured: figure 6tavion sfromronthuja, determined on the basis of X-ray single crystal, dichloride (tert-butylamido / tetramethyl / tetramethyl-η5-cyclopentadienyl) disilanocyrkonu. Due to the relatively long disilyl group connecting the cyclopentadienyl ring to the nitrogen atom of the amide Ugand, the nitrogen atom is less stressed. It was determined that the angle formed between the center of mass of pieciez and ctklapentadandenylawega ΖΠ2, C3, C5, C7 and C9), Μπιζοι cyrican (Zr1) and nitrogen (N17) viso0 118.0 ° C. The activity of the kztzlCzztarz with respect to the polymerization of olefins is significantly reduced compared to the dichloride (tert-butyl conversido / dimethyl / tetramethyl-η5-cyclopżntadienyto) silane zirconium (Fig. 5) with analogous manosilane linker.

The structure shown in Figure 7 is based on X-ray crystallography of a crystaland dichloride (tert-butylπαmido / tetrαmżΐylo / tetramztylπ-η5-cyklπpżziαdiżzylπ) disilanotyizno- The relatively long disilyl group connecting the cyclpentadizinyl ring with the nitrogen atom of the amide ligand causes the nitrogen atom to be less strained. The angle formed between the center of mass of the cylindrical annular ozone ring (C2, C3, C5, C7 and C9), the density and nitrogen atom (N17) is 120.5 °. In this context, the type of catalyst in the olefin suitable for polymerization is significantly reduced compared to the analogue of dichloricism (tertbutylαmido / dimziyl / tetrαmzyl-η5-cyalnpzntadi6nyto OsMano ν! 8ηυ, containing a mannsilana linking group.

The term "activating cakatalinator" referred to herein refers to a secondary catalyst component that makes the mztal-containing complex become active as an addition polymerization catalyst, or alternatively balances the ionic charge of the catalytically activated fragment. Activating catalysts are aluminum compounds having an Al-O bond, such as alkylaluminoxanes, in particular methylaluminumand aluminum alkyl compounds, aluminum halides, alkyl alkylene halides, Lewis acids, interfering oxidizing agents, e.g. silver solz, ferrocarbons, etc., and mixtures of the above.

Specific methods for producing aluminoxane type compounds by contacting non-linear compounds with an inorganic room containing a cryptographic defectand disclosed in the initial description of Sranów Amzryki No. 4r42 Dl. According to a particular embodiment, the alkylaluminium compound is contacted with a regenerable water-containing substance such asandoz gunu, ^ ζοκιζ ^ or other subtransmitter- How to remove aluminumpzoksazu using takiah boringandsubstance abuse is disclosed in European Patent No. 338 04L

Other preferred activating cocatalysts include compounds having the formula AIR ^^, wherein R in each case ηΜα ^ α C1-10alkyl or α ^ ΐηα & ΐΐ, X is chloeowiεe, an is equal to p , 2 or °

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Most preferably such cocatalysts are trialkylaluminum compounds, especially triethylaluminum.

"Additive polymerizable monomers include, for example, ethylenically unsaturated monomers, acetylene compounds, conjugated and unconjugated dienes, polyenes, carbon monoxide, etc. Preferred monomers include C2-10 α-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Other preferred monomers include styrene, halogen and alky substituted styrenes, vinyl chloride, acrylonitrile, methyl aryl, methyl methacrylate, tetrafluoroethylene, methacrylonitrile, vinylidene chloride, vinylbenzocyclobutane and 1,4-hexadiene.

The term "sterically hindered aliphatic vinylidene compounds" refers to additionally polymerised vinylidene monomers defined by the formula CG2 = CG'R, in which R is a spherically expanded substituent containing up to 20 carbons, G is in each case hydrogen or methyl, and G 'independently in each case is hydrogen or methyl, or alternatively G' and R together form a ring system. The term "etherically expanded" means that the monomer containing such substituent is typically unable to addition polymerize by conventional Ziegler Natta polymerization catalysts at a rate comparable to that of ethylene polymerization. Preferred sterically hindered aliphatic vinylidene compounds include monomers in which one of the carbon atoms containing an ethylenically unsaturated substituent is tri- or tetra-substituted. Examples of such substituents include aliphatic groups such as cyclohexane, cyclohexene, cyclooctene, their ring-substituted alkyl or aryl derivatives, tert-butyl, norbornyl, etc. The most preferred sterically hindered aliphatic vinylidene compounds include various isomeric vinyl-substituted derivatives cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Particularly suitable are 1-, 3- and 4-vinylcyclohexene.

The term "sterically hindered vinylidene compound" refers to the addition polymerizable vinylidene monomers of formula CG2 = CGR 'wherein R' is R or an aryl substituent containing up to 20 carbons and G and G 'are as defined above. For example, sterically hindered vinylidene compounds in addition to sterically hindered aliphatic vinylidene compounds also include vinylidene aromatic monomers.

The term "vinylidene aromatic monomers" refers to additionally polymerizable compounds of the formula GC2 = C (G) -Ph, wherein G is in each case hydrogen or methyl, Ph is phenyl or halo or C1-alkyl substituted phenyl group . Preferred vinylidene aromatic monomers are monomers defined by the above formula, wherein G is in each case hydrogen. The most preferred vinylidene aromatic monomer is styrene.

The term "α-olefin refers to ethylene and C3-10 olefins with ethylenic unsaturation in position a. Preferred α-olefins include: ethylene, propylene, 1-butene, isobutylene, 4-methyl-1-pentene, 1-hexene and 1- octene and mixtures thereof.

The references to the periodic table of elements used in the description refer to the version of the system published in Handbook of Chemistry and Physics, CRC Press, 1987, in which the IUPAC system was used to determine groups.

Polymerization is usually carried out according to known Ziegler-Natta or Kaminsky-Sinn polymerization techniques. This means that the monomer (s) and catalyst are contacted at -30 to 250 ° C under reduced, elevated or atmospheric pressure. The polymerization is carried out in an inert atmosphere, which may be a shielding gas such as nitrogen, argon, hydrogen, ethylene, etc., or under reduced pressure. Hydrogen can additionally be used to regulate molecular weight causing chain termination in a known manner. The catalyst can be used as such or supported on a suitable support such as alumina, MgCl2 or silica, thus forming a heterophasic supported catalyst. If required, a solvent can be used. Suitable solvents include toluene, ethylbenzene, and excess vinylidene or olefinic aromatic monomer. The reaction may be carried out in solution or suspension, using a perfluorinated hydrocarbon or other similar liquid, in a gas phase, e.g. using a reactor with

166 689 fluidized bed, or as a solid phase polymerization, powder. The catalytic (effective) amount of the catalyst according to the invention and the cocatalyst is any amounts that ensure the formation of the polymer. Such amounts can easily be determined on the basis of routine experiments conducted by specialists. Preferred amounts of catalyst and cocatalyst are such as to provide an equivalent ratio of polymerizable monomer to catalyst of from 1X101O: 1 to 100: 1, preferably from IX 10®: 1 to 500: 1, and most preferably from · 1X 10e: 1 to 1000: 1. The cocatalyst is usually used in an amount to provide an equivalent cocatalyst to catalyst ratio of from 10,000: 1 to 0.1: 1, preferably from 1,000: 1 to 1: 1.

It is understood that the metal complex may undergo various transformations or form intermediate variants before or during polymerization. Accordingly, other precursors could probably be used to obtain the same catalytic forms as mentioned above, without departing from the scope of the invention.

The resulting polymer product is isolated by centrifugation or another suitable method. Additives and auxiliaries may be incorporated into the polymers of the invention to obtain the desired properties. Suitable additives include pigments, UV absorbers, anti-oxidants, blowing agents, lubricants, plasticizers, photosensitizers and mixtures thereof.

In the preparation of copolymers containing aromatic vinylidene monomers or aliphatic sterically hindered vinylidene monomers, it is desirable to simultaneously use a comonomer that is α-olefin without pronounced steroidal hindrance. Without being bound by any particular theory of action, it is believed that this is due to the fact that the active center is filled as a result of incorporation of a vinyl compound with spatial hindrance, so that it is impossible for another molecule of a vinyl compound with spatial hindrance to take part in the polymerization as the next monomer in sequence. After incorporation of one or more non-hindered vinyl olefins, the active center will again become available for hindered vinyl monomer. To a limited extent, however, the aromatic vinylidene monomer or sterically blocked vinylic monomer can be embedded in the polymer chain in an inverted position, so that 2 methylene groups are obtained between the substituted moieties in the polymer chain.

Preferably the molecular weight of such polymers, Mw is over 13,000, even more preferably over 20,000 and most preferably over 30,000. Equally preferably such polymers have a melt index (I2), ASTM D-1238, procedure A, conditions E, below 125, even more preferably from 0.01 to 100, and most preferably from 0.1 to 10.

By using the aforementioned catalyst system containing the voltage coordination complex, copolymers containing relatively large volumes or sterically hindered monomers can be produced in a substantially random manner, in small amounts and in larger amounts, according to the principle of ordered insertion. Copolymers of α-olefins, in particular ethylene with a sterically hindered aliphatic vinyl compound or with an aromatic vinylidene monomer, can more accurately be called "pseudostatic" copolymers. This means that the copolymers do not contain clear blocks of any of the monomers, although the insertion of individual monomers is limited according to certain rules.

These principles were deduced on the basis of some experimental details obtained from the analysis of polymers. The polymers were analyzed by spectroscopy 13C NMR at 130 ° C on a Varian VXR-300 at 75.4 MHz. Samples of 200-250 mg of polymer were dissolved in 15 ml of a hot mixture of o-dichlorobenzene-1,1,2,2-tetrachloroethane-d2 (about 70/30 by volume) containing about 0.05 molar chromium (III) tris (acetylacetonate). Part of the resulting solution was loaded onto a 10 mm NMR tube. - The parameters and measurement conditions were as follows: spectrum width 16 500 Hz; access time 0.090 s; pulse width of 36 °; 1.0 g delay with the decoupled masked during the delay; size FT 32 K; the number of sweeps - over 30,000; 3 Hz line extension. Spectra were recorded relative to tetrachloroethane-d2 (δ 73.77 ppm, TMS scale).

As a result, without being bound by any particular theory, the results of the above experiments indicate that the special feature of pseudostatic copolymers is that all phenyl groups or large volume groups that are spatial hindrances, constituting substituents on the polymer chain, are separated by two or more groups methylene. other

166 In other words, the polymers containing sterically hindered monomer according to the invention can be represented by the following general formula 4 (using, for example, styrene as hindered monomer), with j, k and 1> 1 in this formula.

More specifically explaining the experimental and theoretical results without binding to any particular theory, it can be concluded that during the addition polymerization reaction using the catalyst according to the invention, if the monomer with sterically hindered insertion occurs into the growing polymer chain, the next building up monomer must be ethylene or hindered monomer that builds up inversely, i.e. with a tail-to-tail connection. This is shown below in the diagram for spatial hindered vinyl monomer, where M is the center of the catalytic metal, HG is the hindered group, and P is the growing polymer chain.

During the polymerization reaction, ethylene insertion can occur at any time. After an inverted or tail-to-tail insertion of the hindered monomer, the next monomer must be ethylene, because the insertion of another hindered monomer at this point would have to cause the substituents constituting the hindrance to be located closer than the minimum distance mentioned above. The consequence of such polymerization principles is that the catalysts according to the invention do not significantly homopolymerize styrene, while a mixture of ethylene and styrene polymerizes very quickly, whereby copolymers with a high styrene content (up to 50 mole% styrene) can be obtained.

In order to more accurately illustrate the description of the olefin / spatial hindrance copolymer, according to the invention, a computerized polymerization reaction model was used to calculate the expected spectrum 13C NMR of the polymer produced. A computer program with a statistical number generator was used to select an α-olefin or sterically hindered monomer as a monomer to be incorporated into the growing polymer chain, after which the amount of each type of signal was calculated 13C NMR sent as a result of such insertion. Polymers were computer generated by repeating the above procedure for 10,000 or more insertions, followed by the calculated spectrum 13C NMR was compared with real experimental spectrum 13NMR of pseudostatic ethylene / styrene copolymers according to the invention.

Computer simulations of polymer and obtained spectrum 13The calculated NMR of the calculated pseudostatic ethylene / styrene copolymers was made on the assumption that if an insertion of styrene monomer into the growing polymer chain occurs, then the next incorporated monomer must be ethylene or styrene inversely incorporated, with a tail-to-tail connection. Optimal agreement between the experimental and calculated spectra was achieved when approximately 15% of the styrene insertion was tail-to-tail. Observed and computational spectra 13C NMR for such pseudostatic ethylene / styrene copolymers containing 1.4, 4.8, 9.0, 13.37 and 47 mole% styrene are shown in Figures 8-13. In all cases there is excellent agreement between observed and calculated spectrum.

Then computer simulation and its spectrum were performed 13C NMR in the case of a fully static α-oleffn <a / sterically hindered monomer, with no restrictions on insertion of sterically hindered monomer. In other words, spatial hindrance monomer insertion into the growing polymer chain was possible after spatial hindrance monomer insertion if the random number generator chose hindrance monomer as the next monomer to be incorporated. The calculated spectra of such completely statistical copolymers are not consistent with the observed spectra 13C NMR as shown in Figure 14 for an ethylene / styrene copolymer containing 37 mole% styrene.

Before polymerization, the monomers and optionally solvents can be purified by distillation under reduced pressure and / or contact with molecular sieves, silica or alumina to remove impurities. Additionally, reactive sheathing agents such as trialkylaluminum compounds, alkali metals and their alloys, in particular Na / K, can be used to remove impurities.

Suitable aromatic vinylidene monomers which may be used include styrene and also α-methylstyrene, styrene derivatives substituted with a C 1-4 alkyl or phenyl ring, such as o-, m- and p-methylstyrene, or mixtures thereof, ring halogenated styrenes, vinylbenzocyclobutanes and divinylbenzene. A preferred aromatic vinylidene monomer is styrene.

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When polymerizing aromatic vinylidene monomers or aliphatic sterically hindered vinylidene monomers with olefins, the monomers are preferably mixed in such a proportion that the obtained polymer has a content of aromatic vinylidene monomer (or aliphatic hindered vinylidene monomer) of at least 1.0 mol% more preferably from 1.5 to less than 50 mole%, very preferably from 5.0 to 48 mole%, and most preferably from 8.0 to 47 mole%. Preferred conditions for carrying out such polymerization reactions are atmospheric pressure to 10 MPa and temperature from 30 to 200 ° C. As a result of polymerization at temperatures above the autopolymerization temperature of the corresponding monomers, small amounts of homopolymerization polymerization products can be obtained as a result of free radical polymerization.

Certain polymers made using the catalyst of the invention, especially copolymers of ethylene and α-olefin other than ethylene, have unique rheological properties. In particular, the polymers (hereinafter referred to as flexible polyethylenes, E1PE) have been found to be less Newtonian than linear polyethylene resins with similar olefin content produced in the usual way. The polymers also have a higher modulus of elasticity, especially at higher flow rates, compared to conventional polymers. Due to this property, the resin is particularly useful for the production of films, foams and shaped products, e.g. by blow molding techniques. This phenomenon can be illustrated in detail with the help of Fig. 16, which shows the complex viscosity η *, measured in poise at 190 ° C as a function of shear rate, ω, measured in rad / s, for a typical ethylene 1-octene copolymer, type E1PE, according to the invention. The slope of this curve indicates that the alloy is highly non-Newtonian. The real values η * and ω used to construct the chart were as follows:

Figure 15 also shows tgó values for the same ELPE polymer. It is a dimensionless quantity calculated by dividing the viscosity modulus by the modulus of elasticity. The actual values tgó, and ω used to construct the chart were as follows:

Improved melt-blow processing characteristics provide a tg 0.1 to 3.0 size at shear rates from 0.01 to 10 rad / s.

Other properties of E1PE polymers are shown in Figure 16, a graph of the dependence of the modulus of elasticity G 'in dyne / cm2 at 0.1 rad / s, at 190 ° C, for a series of E1PE ethylene / octen-1 resins, as a function of the melt flow index. The resins obtained in Examples XI, XII, X1V-XVI, XVIII-XXH, XXIV-XXVI, XXX and XXXI were used.

The flow rate and modulus of elasticity values used to construct the chart were as follows:

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For comparative purposes, typical properties of η * and ω for a polyethylene resin obtained in the usual way are shown in Figure 17.

It can easily be said that E1PE resins have a higher elastic modulus in the alloy. In particular, E1PE resins have a melt index (I2), ASTM D-1238, procedure A, conditions E, below 200, preferably below 125, and most preferably below 50, and a modulus of elasticity over 100 Pa, and even more preferably over 200 Pa. All the above rheological measurements were carried out using standard techniques, such as those described in the work of HA Barnes et al., Introduction to Rheology, Elsevier Publishing, Inc., 1989. Densities are usually from 850 to 970 kg / m3, preferably 890-970 kg / m33. Molecular weight dispersions (Mw / Mn) are usually greater than 2.0, preferably 3.0-10.0. Typical melting points are from 50 to 13 ° C.

Preferred polymers additionally exhibit the properties of homogeneous polymers as defined in US Patent No. Amer. No. 3,645,992, i.e. copolymers of ethylene with substantially statistical comonomer distribution in a given molecule and with substantially the same ethylene / comonomer ratio in different molecules. Polymers produced at higher polymerization temperatures, especially at temperatures above 130 ° C, may exhibit a heterogeneous melt curve. The polymers of the invention are furthermore characterized by considerable transparency. In particular, polymers have better optical properties, especially less turbidity than typical ethylene polymers. That is why they are particularly well-suited for the production of films and injection products.

In addition, it has surprisingly been found that such olefin-containing polymers and an aromatic vinylidene polymer, especially ethylene and styrene, have elastomeric properties. Therefore, these polymers are uniquely suited for use in thermoplastic elastomer applications, such as impact strength modification of thermoplastic and thermoset polymers, including bitumens, adhesives, elastomeric moldings, etc.

Polymers prepared using the catalyst of the invention can be modified in a conventional manner by grafting, crosslinking, hydrogenation, introduction of functional groups or other reactions well known to those skilled in the art. Particularly with respect to polymers containing vinylidene, vinylcyclohexene or 1,4-hexadiene aromatic groups, sulfonation or chlorination can be easily carried out to obtain functional derivatives according to known techniques. Additional vinylcyclohexane based polymers can be easily crosslinked as a result of the unsaturated ring reaction.

These polymers, regardless of whether they have been further modified, can be mixed with synthetic or natural polymers to obtain blends with the desired properties. In particular, they can be mixed with polyethylene, ethylene / α-olefin copolymers, polypropylene, polystyrene, styrene / acrylonitrile copolymers (including their rubber-modified derivatives), syndiotactic polystyrene, polycarbonate, polyamide, aromatic polyester, polyisocyanate, polyurethane and polyoxyphenylene. The polymeric modifier is used in amounts of from 0.1 to 99.0, preferably 0.5-50% by weight.

Particularly preferred are polymers containing ethylene and styrene, which are elastomeric as defined in the definition of an elastomeric substance in ASTM Special Technical Bulletin No. 184 as a substance that can be stretched at room temperature to double its length, but will return to its original length after the release of voltage .

In addition to the use for the modification of synthetic thermoplastics, these polymers can also be successfully used as modifiers of asphalt or bituminous compositions. In this way, styrene-ethylene polymers are preferably used.

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The term "bitumen can generally be defined as a mixture of hydrocarbons of natural or pyrolysis origin, or combined, often with the addition of their non-metallic derivatives, which may be gaseous, liquid, semi-solid or solid, and which usually dissolve in carbon disulphide. From the point of view of the invention, liquid, semi-solid or solid bitumen can be used. From a technical point of view, bitumen is essentially limited to asphalt, tar and pitch. The list of various bituminous materials that can be used in accordance with the method of the invention is as follows:

I. Bitumen

1. Petroleum bitumens

A. Bitumens simply reduced

1. Atmospheric or reduced pressure reduction

2. Solvent precipitation, e.g. propane

B. Thermal bitumens and oil cracking residues.

C. Blown bitumens

1. Bitumen blown directly

2. Bitumen blown "catalytically

2. Natural bitumens

A. With a mineral content below 5%

1. Bitumens such as gilsonite, graphamite and clastic pitch

2. Bermudez and other natural deposits

B. With a mineral content of over 5%

1. Rock bitumens

2. Trinidad and other natural deposits

II. Tars and their derivatives

1. Residues of coal tar from coking plants

A. Coal pitches reduced to flowing species such as RT (road tar) used for road surfaces

B. Coal tar pitch reduced to softening grades

2. Residues from other pyrolysis distillates, such as water gas, wood, peat, bones, shales, rosin and tar with fatty acids.

It is understood by specialists that the molecular weights of various bitumens can vary in a very wide range, e.g. from 500 to 10,000. Softening temperatures of various types of asphalt, e.g. from 10 to 200 ° C, can also vary.

Of the many types of bitumens that can be used, natural and petroleum bitumens are desirable, with petroleum bitumens being preferred. Of the petroleum bitumens, thermal bitumens are preferred.

Bitumen is used in the compositions of the invention in amounts in the range of 65 to 99% by weight, preferably in amounts of 80-98% by weight.

After describing the invention, the following examples are given to illustrate it in more detail without limiting its substance. Unless otherwise stated, all parts and percentages are by weight.

Example 1. Preparation of dichloride (tert-butylamido / dimethyl / tetramethyl-n-cyclopentadienyl) -anyl zirconium.

To 0.443 g (1.90 mmol) of ZrCl4 in a flask were added 8 mL of diethyl ether followed by 15 mL of tetrahydrofuran (THF). A solution of 0.500 g (1.90 mmol) of dilitium salt (tert-butyioamido / dimethio / tetamethylcyclopentadienyl) sulfate in 15 ml THF was slowly added to the resulting suspension. The resulting yellow solution was stirred for several days. The solvent was removed to give a gummy residue, which was extracted with a 5/1 (v / v) diethyl ether / pentane mixture and the yellow precipitate was filtered off. The solvent was removed from the yellow filtrate to give a light yellow powder. Recrystallization from an ether / pentane mixture (5: 1) gave the product, (CsMe4) Me2-Si-N-tert-Bu (ZrCl2) as an off-white crystalline solid. 0.2207 product was obtained (28.2% yield). Identification was carried out by methods 13C and 11 H NMR.

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Polymerization

A. 5 ml of a 1 (00) M (molar) solution of methylaluminoxane (MAO) in toluene was added to a dosing container containing 25 ml of 4-methyl-1-pentene. The catalyst solution was prepared by adding 500 µl 0.01172 M CsMe solution4(Me 2 Si-N-t-Bu) ZrCl2 in toluene to 2 ml of toluene in a second dispensing tank. Both tanks were closed, removed from the handling chamber and connected to a 600 ml stainless steel pressure tank. Air was removed from the pressure vessel and the vessel was purged with nitrogen.

A 4-methyl-1-pentene (toluene) MAO solution was added to the pressure vessel and heated to 89 ° C under 620 kPa ethylene with stirring. After adding the catalyst solution to the 4-methyl-1-pentene (toluene) MAO mixture, the ethylene pressure was increased to 12-40-1275 kPa. After 2 hours, the solution was cooled to 30 ° C and deaerated. The yield of polymer obtained after drying under reduced pressure at 100 ° C overnight was 10.0 g. Analysis of the polymer by the method13C NMR showed that it is a statistical copolymer of ethylene with 4-methyl-1-pentene.

B. Polymerization procedure A essentially - repeated, 50 ml - hexene instead of 4-methyl-1-pentene, and the catalyst concentration in toluene was 0.01012 M. The catalyst solution was added to the 1-hexene (MAO) ethylene mixture, followed by ethylene pressure increased to 1240-1275 kPa. After adding the catalyst solution, the temperature of the reaction mixture increased to 139 ° C. After 30 minutes, the solution was cooled to 100 ° C. Heating and ethylene feed were discontinued, after which the reactor was cooled and vented. The yield of polymer obtained after drying under reduced pressure at 100 ° C overnight was 36.8 g. Analysis of the polymer by the method13C NMR showed that it is a statistical copolymer of ethylene with 1-hexene (8 mol%).

C. The polymerization procedure A was essentially repeated, except that 213 l catalyst solution (0.001172 M in toluene) and 143 mg solid MAO were used. No additional olefin was introduced. After adding the catalyst solution to the reactor, the temperature increased to 109 ° C due to the exothermic polymerization reaction. The reaction was stopped after 1 hour by cooling and venting the reactor. The yield of polyethylene obtained after drying under reduced pressure at 100 ° C overnight was 11.0 g.

D. 150 ml of toluene was added to the pressure tank used in polymerization A, followed by 100 g of propylene. A solution of 0.828 g MAO in 8 ml toluene was added, followed by a 2130 μΐ catalyst solution. The reaction mixture was kept at 8 ° C for 3 hours. The reaction was quenched with acidified methanol to give 0.38 g of a white viscous material. Polymer analysis by the methodnC NMR showed that it is atactic polypropylene.

Example. Preparation of (tert-butylamido) dimethyl (tetramethyl-n-dichloride5-cyklopentadienylz) ailαnotytanu.

Synthesis 1

a) (Chlzro) (dimethylene) (tetrαmethylcyclopentadl-2,4-ea, yl) silaa.

To a solution of 21.5 g (167 mmol) of dimethyldichloroalailine in 150 mL of THF cooled to -40 ° C, a solution of 8.00 g (55.6 mmol) 1,2,3,4-tetrameSylcyclopentadeneldodium in 80 mL THF was slowly added. The reaction mixture was allowed to warm to room temperature and then stirred overnight. The solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil. Yield 10.50 g (88.0%). H NMR (C6D6) δ 2.89 (s, 1H), 1.91 (s, 6H), 1.71 (s, 6H), 0.14 (s, 6H); ™ C NMR (CeDe) δ 137.88131.5, 56.61.6, 11.4, 0.81.

b) (Tert-buSylzαmiazX-dimethyl) (tetramethylcyclopentαdi-2,4-enylz) silane.

A solution of 11.07 g (151 mmol) ters-busylzαmin in 20 mL THF was added over a 5 minute period to a solution of 13.00 g (60.5 mmol) (chloro) (dimeSylz) (Setramethylcyclopenadienyl) silane in 300 mL THF. A precipitate formed immediately. The suspension was stirred for 3 days, after which the solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil. Yield 14.8 g (97.2%). MS (mass spectrum): 251; 'H NMR (C6D6) δ 2.76 (s, 1H), 2.01 (s, 6H), 1.84 (s, 6H), 1.09 (s, 9H), 0.10 (s, 6H ); 1 C NMR (C6D6) δ 135.4, 133.2, 57.0, 49.3, 33.8, 15.0, 11.2, 1.3.

c) Dilite salt (SerS-butylamido) (dimethyl) (teSramethylcyclopentadienyl) ailane.

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To a solution of 3.000 g (11.98 mmol) (tert-butylaminoX-dimethylXtetramiethylcyclopentadienyl) silane in 100 ml of ether was slowly added 9.21 ml 2.6 M butyllithium (23.95 mmol) in a mixed ce-alkane solvent. A white precipitate formed and the reaction mixture was stirred overnight, then filtered. The precipitate was washed several times with ether and then dried under reduced pressure to give the product as a white powder. Yield 3.134 g (99.8%).

d) (tert-butylamido / dimethyl / tetramethyl-n5-cyclopentadienyl) silanititane dichloride.

0.721 g (3.80 mmol) of TiCl was added to 30 mL of frozen (-196 ° C) THF. The mixture was allowed to warm to -78 ° C (dry ice bath). To the resulting yellow solution, a solution of 1,000 g (3.80 mmol) dilithium (tert-butylamido) (dimethylXtetramethylcyclopentadienyl) silane in 30 ml THF was slowly added. The solution was allowed to warm to room temperature and was stirred overnight. The solvent was removed from the resulting solution with a very dark color. The residue was extracted with pentane and filtered. Cooling in the cold trap caused the separation of a more soluble dark reddish brown material from a light yellow green crystalline solid. The solid was filtered off and recrystallized from pentane to give an olive-green product. Yield 0.143 g, 10.2%.11 H NMR (C.eD6) δ 2.00 (s, 6H), 1.99 (s, 6H), 1.42 (s, 9H), 0.43 (s, 6H); 13C NMR ^ D6) δ 140.6, 137.9, 104.0, 62.1, 32.7, 16.1.13.0, 5.4.

Synthesis 2

In a dry chamber, 4.0 mL of 2.0 M isopropyl magnesium chloride in diethyl ether was introduced into a 100 mL flask using a syringe. The ether was removed under reduced pressure to give a colorless oil. 20 ml of a 4: 1 (v / v) toluene / THF mixture was added, followed by 0.97 g (tert-butylamino / dimethyl / etetamelamelylcyclopen1 Udieenyl) silane. The solution was heated to boiling. After 8-10 hours, a white precipitate began to form. After heating for a total of 27 hours under reflux, the solution was cooled and the volatile materials were removed under reduced pressure. The solid white residue was suspended in pentane and filtered to give a white powder (1.23 g, 62% yield), MeaCsSiMezNtert-BzMgaClzfTHF ^.

In a dry chamber 0.50 g TiCl3 (THF) e was suspended in 10 ml THF. 0.69 g of solid Me ^sSiMeaN-tert-BuMgsCl3 THFjia was added, resulting in a color change from pale blue to purple. After 15 minutes, 0.35 g AgCl was added to the solution. The color began to immediately brighten to pale green-yellow. After 1.5 hours, THF 'was removed under reduced pressure to give a yellow-green solid. 200 ml of toluene was added, the solution was filtered, then toluene was removed under reduced pressure to give a yellow-green microcrystalline solid, 0.51 g (quantitative yield). The product was determined to be (tert-butylamido / dimethyl / tetramethyl-t-cyclopentadienyl) silanititane dichloride, based on 1H NMR (C6D6): δ 1.992 (s), 1.986 (s), 1.414 (s), 0.414 (s).

Synthesis 3

0.72 g (3.80 mmol) of TiCl was added to 35 mL of frozen THF (-196 ° C) in a flask. The mixture was warmed to -78 ° C. A solution of 1.0g (3.80 mmol) dilithium salt (tert-butylamido / dimethyl / tetramethylcyclopentadienyl) silane in THF was slowly added. The resulting yellow solution was warmed to room temperature and stirred overnight. The solvent was removed to give a dark colored residue, which was extracted with pentane and filtered. The product, CsMe ^ MeaSiN-tert-Bu) TiCl2, was obtained as a dark greenish yellow crystalline material after two recrystallization from pentane at -35 ° C to -40 ° C. The identification was made usingnC and 11 H NMR.

Synthesis 4

In a dry chamber, 2.0 g (5.40 mmol) of TiCl3 (THF) 3 was suspended in 40 ml of THF. Then the dilite salt (tert-amylamido / dimethyl / etetramelylcyclopentadienyl) silane was added to immediately darken the color, eventually turning dark blue. After stirring for 1.5 hours, 0.84 g (5.86 mmol) of AgCl was added. The solution immediately began to change to a lighter, red-orange color. After stirring for 1.5 hours, THF was removed under reduced pressure. 50 ml diethyl ether was added, the solution filtered and volatiles removed under reduced pressure. 1.91 g of product were obtained, (tert-butylamido / dimethyl / tetramethyl-t-cyclopentadienyl diisocyanate, dichloride.11 H NMR (C6D6): δ 1.992 (s), 1.987 (s), 1.415 (s), 0.415 (s).

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Polymerization

Polymerization of the styrene / ethylene mixture was carried out by combining a 1.65 ml 10% MAO solution in toluene with a solution of 45 ml toluene and 50 ml styrene in a stainless steel dosing tank. 250fA 0.010 M dichloride solution (tert-buylamido / dimeiyic / tetramethylG-j ^^ cycpenidienyloyl titanate) was added to 2.5 mL toluene in a second dispensing tank. Both tanks were closed, removed from the handling chamber and connected to a 600 mL stainless steel pressure tank. Air was removed from the pressure vessel and then purged with argon.

The styrene / toluene / MAO solution was added to the pressure vessel and heated to 89 ° C under 620 kPa ethylene pressure with stirring. At this point, the catalyst solution was added and the pressure was increased to 1275 kPa, then maintaining it in the range of 1240-1275 kPa. As a result of the exothermic reaction, the temperature increased to 95 ° C. The temperature was lowered to 90 ° C and then kept in the range of 90-92 ° C in the further reaction.

After 1.0 hour, the ethylene supply was stopped. The reactor was vented and cooled to 30 ° C while adding methanol. The product was collected, washed with methanol and the remaining solvents removed under reduced pressure at 120 ° C to give 9.02 g of material. Analysis14The C NMR of this material showed that it was a styrene (15.2 mol%) statistical copolymer with ethylene, not containing polystyrene bound peaks.

EXAMPLE III. Olefin polymerization. Ethylene was polymerized by combining 5 ml of a 1M solution of triethylaluminum in a mixed Ce-alkane solvent with 0.5 ml of a 0.01 M solution of dichloride (tert-butylamido / dimethyl / tetramethyl)5-cyclopeniadienyl) silanotitan in toluene in a stainless steel (SN) dosing tank. The titanium catalyst and triethylaluminum as cocatalyst in solution were then added under pressure to a 3 dm SN pressure tank3, containing 2 dm3 mixed alkane solvent (Isopar E available from Εχχοη Chemicals, Inc.) at 3100kPa ethylene pressure, at 150 ° C. The reaction temperature I50 ° C was maintained for -10 minutes. The ethylene pressure was kept constant. A mass flow meter showed that 15.7 g of ethylene had been absorbed. The polymer solution was removed from the pressure vessel. The polyethylene was isolated after drying overnight under reduced pressure at 90 ° C. Yield - 15.7 g.

Example IV - Polymerization of an olefin copolymer. In a handling chamber under an argon atmosphere, 5.0 ml of a 1.0 M solution of methylaluminoxane (MAO) in toluene was combined with 50 ml of 1-octene in a stainless steel (SN) dosing tank equipped with ball valves at both ends. In another metering tank with SN 500 // 1 (5.06 // mol) 0.0101 M dichloride solution (tert-butylamido / dimethyl / tetramethyl- / 75-cyclopentadienyl) silane zirconium in toluene was mixed with 2 ml toluene.

The dosing tanks were closed, removed from the handling chamber and connected to a 600 ml SN pressure tank. The pressure vessel was pumped out of air and then purged with argon. A 1-octene solution and MAO were introduced into the pressure vessel. The solution was heated to 89 ° C under 620 kPa ethylene pressure with stirring. At this point, the catalyst solution was added. As a result of the exothermic reaction, the temperature increased to 142 ° C. The ethylene pressure was kept within the range of 1310-1345 kPa.

After 0.5 hours, the ethylene supply was discontinued. The reactor was cooled to 30 ° C, vented to atmosphere, and then quenched with methanol. The rest of the solvent was removed under reduced pressure at 110 ° C to give 35 g of material. Analysisf3C NMR showed that the 1-octene content of the polymer was 7.8 mol%. Differential calorimetry (DSC) showed a melting point of 100 ° C. Density 895 kg / m3, Mw 44,000; Mw / Mn = 6.8.

Example V. Polymerization of olefin copolymer. The procedure of Example 4 was essentially repeated, except that 50 ml of 1-hexene was used instead of 1-octene. The reaction temperature was kept at 133-140 ° C. 37 g of polymer with 1-hexene content of 8 mol%, 21% by weight were obtained.

Example VI. Homopolymerization of α-olefin. A. 6.0ml (4.0g) 4-methyl-1-pentene was added to 1.0ml 1.0M MAO in toluene in a 20ml screw cap vial. Then 100/1 0.01172 M toluene solution of the zirconium catalyst complex from Example 4 was added.

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The vial was sealed, shaken and placed at room temperature (about 20 ° C) for 16 gπdrin, and then heated at 48 ° C for 24 hours. The viscous polymer solution was precipitated by the addition of methanol. The resulting polymer was collected, and then the components were removed with high pressure over 4 g pans of p mOC to obtain 3.8 g of a clear polymer (yield 95%). NMR analysis showed that the polymer was atactic for pπli-4-mettlπ-1-pentzn.

B. Procedure with polyurethane 3.0 ', -1οεΐΊ2ην, t, und 0οο1ροπρ MAO and 100 μΐ catalyst solution was added to a 20 ml vial with screw cap in a dry argon filled chamber. The vial was sealed and heated overnight at 50 ° C. After quenching the reaction with acidified ethanol and drying, 3.0 g pli (1-hr.

Example VII - Homopolymer of ethylene. The SN dosing tank was filled with 500μΐ (5.0 e / moles) of 0.010 M solution of dichloride (tertiary-buίytoamido / aimztyl / tetramethyl-η5-roar! Opzntαdiezyl) silanothane and 2.5 ml of toluene in an argon-filled handling chamber. 5.0 ml of 1.0 M 1.0 M Ma p tolueziz solution and 92 ml toluezo were added to the second SN test tank. Both dosing tanks were closed, removed from the handling chamber and connected to a 600 ml pressure tank from which air was previously removed, purged with argon and ethylene. The cocatalinαtorα solution was introduced into the pressure vessel and then heated to 89 ° C under 620 kPa ethyl pressure. The catalyst solution was then added to the reactor. As a result of the exothermic reaction, the temperature rose to 109 ° C in a few drawers. The ethyl pressure was regulated in the range of 1240-1275 kPa. After a drop of 0.5 hours, the reactor temperature was increased to 110 ° C, which caused ρτοϋ uptake of stile. After 1.0 hour, the ethylene feed was discontinued, the reactor vented to the atmosphere, and the coolant allowed to cool. The pressure vessel was opened, the reaction stopped with methanol, then the polymer π ^^ η ^ ιζο; 24 g of polyethylene were obtained after removal of the volatile components.

Example VIII - Polymerization of aliphasic acid in the Mazomzru region with spatial hindrance. 4-vinylcyclohekszz ο ^ ϋ ^ οζο by distillation pad under reduced pressure from the Na / K alloy. The procedure of Example 4 was followed in accordance with the procedure of 5.0 ml ^ ni ^; ^^ and ^^; ^ 1- ^ ohexesse and 5.0 ml of 1.0 M solution of mZtylalroinoxazu (MAO) p toluene in a eaten dosing tank and 500 0.010 M solution of dicyclic (tert-builyldido / aimethyl) / tz-trammitl-η5-cycloptazziezyl) tilazorrozole in toluzziz and 2 ml toluene in the second dosing tank.

As a result of the ergot temperature response, the temperature increased to 114 ° C. The ethylene feed was discontinued after 1 hour, after which the mixture was cooled and dehydrated and then the reaction was quenched with acidified mztazolzm.

12.6o product were obtained. NMR analysis showed that the polymer freezes pintlocyclohexesis in 1.5% mol.

Example IX. Ethylene oxide / thiocyanate copolimbrification - The above polymerization procedure was generally followed, except that the reaction temperature was 90 ° C. 150 ml of mixed alkane radical, 500 ml of styrene and 8 ml of 15% MAO in toluene (Al: Ti = 1000) were introduced into the reactor. The reactor was filled with utilization gas at a pressure of 1240 kPa, followed by the introduction of 20 / mole [(CtMz- (SiMe2) N-fIitloS] TiCl2 for polymerization) Free flow of ethylene under 1240 kPa pressure was ensured. After 60 minutes, the plaso solution from the reactor into a container containing a small amount of αztyu moisturizing. Pnlimzr was dried under reduced volume. 26.6 g of polymer with a melt index (I2) of 26.6 were obtained. Analysis≥ 5C NMR produced that the polymer contained 47 mole% (76 wt%) of styrene. Nin was observed in irotakitczych and zaktycznych or stzdiotzaitrzych sequences.

Example X. Copolymerization of starch / tertrez - The reaction under the conditions of Example 9 was replicated to obtain ethylene / styrene copolymers with a different styrene content. The catalyst used was the dichloride (ferro-butytharido / dimethythe / tetrαmztyl-.η5-rtktopεntαdizzylS) with the selected items. The MAO cocatalyst was used in an amount to provide the molar A1: M 1000: 1. The reaction conditions are given in Table 1.

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Table 1

<td>An attempt nay</td><td>mg (com- metacrylate)</td><td>T CC)</td><td>dissolved Thinner quantity (Ml)b</td><td>Ethylene pressure kPa</td><td>sty rhenium (Ml)</td><td>Time IN</td><td>productivity POWER to (G)</td><td>mol% styrene</td><td>mw</td><td>MW / Mn</td>

and the catalyst was dichloro (phenylamido / dimethyl / tetramethyl-i)5-cyclopentadienyl) silanititan b. T = toluene; I = mixed alkanes

Examples ΧΙ-ΧΧΧΪΙ. In these examples for an autoclave with a capacity of 4 dm3 2000 ml mixed alkane solvent (Isopar-E) was charged followed by various amounts of 1-octene. Dichloride (tert-butylamido / dimethyl / tetramethyl) was used as the catalyst5-cyclopentadiene) silanotitan dissolved in toluene. The cocatalyst was a 10% solution of MAO in toluene. If necessary, hydrogen was introduced by expansion from a 1 (M) ml tank at a pressure higher than the operating pressure of the reactor. The reactor was filled with solvent, 1 octene and MAO, heated to reaction temperature and compressed with ethylene at 3100 kPa to obtain a saturated solution. If necessary, hydrogen was expanded into the reactor, followed by the addition of a catalyst. After 10 minutes, the solution was withdrawn from the reactor into a container containing a small amount of antioxidant (Irganox 1010, available from Ciba-Geigy). The polymer was dried under reduced pressure. The results are summarized in Table 2.

Table 2

<td>At- Quad</td><td>The temperature rature reactor (° C)</td><td>octene (Ml)</td><td>h kPa °</td><td>catalytic holdup mmol</td><td>Al: Tib</td><td>Polymer yield (g)</td><td>mw</td><td>Mn</td><td>Mw / Mn</td><td>Melting point (° C)</td><td>Density kg / m3</td><td>Indicator flows- CiA®</td>

<td>XVIII</td><td> 160</td><td> 450</td><td> 345</td><td> 0,02</td><td> 500:1</td><td> 55</td><td> 42 500</td><td> 11 400</td><td> 3,73</td><td> 90“</td><td> 904,5</td><td> 31,20</td>

<td>nineteenth</td><td> 150</td><td> 150</td><td> 0</td><td> 0,02</td><td> 500:1</td><td> 75</td><td> 71 700</td><td> 16 500</td><td> 4,35</td><td> 108</td><td> 927,6</td><td> 2,46</td>

<td>XXIII</td><td> 150</td><td> 300</td><td> 345</td><td> 0,02</td><td> 500:1</td><td> 100</td><td> 51 000</td><td> 14 000</td><td> 3,64</td><td> 95“</td><td> 913,0</td><td> 13,62</td>

<td>XXVII</td><td> 130</td><td> 150</td><td> 345</td><td> 0,02</td><td> 250:1</td><td> 147</td><td> 136000</td><td> 29 400</td><td> 4,63</td><td> 110</td><td> 919,7</td><td> 0,15</td>

<td>XXVIII</td><td> 130</td><td> 150</td><td> 345</td><td> 0,02</td><td> 100:1</td><td> 83</td><td> 146 000</td><td> 26 300</td><td> 5,55</td><td> 105</td><td> 915,3</td><td> 0,15</td>

<td>XXXII</td><td> 110</td><td> 300</td><td> 345</td><td> 0,02</td><td> 250:1</td><td> 160</td><td> 141 000</td><td> 35 600</td><td> 3,96</td><td> 82</td><td> 900,0</td><td> 0,15</td>

and

£.

partial hydrogen pressure, tosunck equivalent, assuming the molecular weight of methylalumoxane (MAO) is 58 Iz, ASTM D-1238, procedure A, conditions E

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Example XXXIII-XLIL The procedure of Examples XIXXXII was essentially followed, with dichloride (tert-butylamido / dimethyl / tetramethyl) being used as the catalyst.5-cyclopentadienyl) silanocyrkonu. The results are summarized in Table 3.

Table 3

<td>Example</td><td>The temperature rature ° C</td><td>octene ml</td><td>ha kPa</td><td>Zr (Mmol)</td><td>Al: ZRA</td><td>Stacking performance. to Zr X10 '3B</td>

<td>XXXIII</td><td> 150</td><td> 300</td><td> 345</td><td> 0,02</td><td> 500</td><td> 50</td>

<td>XXXIV</td><td> 140</td><td> 300</td><td> 345</td><td> 0,01</td><td> 500</td><td> 122</td>

<td>XXXVI</td><td> 130</td><td> 450</td><td> 345</td><td> 0,005</td><td> 500</td><td> 302</td>

<td>XXXVII</td><td> 130</td><td> 150</td><td> 345</td><td> 0,005</td><td> 500</td><td> 230</td>

<td>XXXVIII</td><td> 130</td><td> 150</td><td> 345</td><td> 0,01</td><td> 250</td><td> 158</td>

<td>XXXIX</td><td> 130</td><td> 150</td><td> 345</td><td> 0,02</td><td> 100</td><td> 104</td>

a. Equivalent ratio when stacked, i.e. the MAO molecular weight is 58

b. Yield of kataiiMtorai g poiimer / g meode

Examples XLIII - LVII. The procedure of Examples XI-XXXII was generally followed, except that a 200 mL reactor was used. Dichloride (tert-butylamido / dimethyl / tetramethyl-n) was used as the catalyst5- cyclopentadienyl) silanititane (2 ml 0.005 M solution in toluene, 10 / mol). 15% MAO in toluene (2 ml, Al: Ti 500) was used as the cocatalyst. The results are summarized in Table 4.

Table 4

<td>Example</td><td>Temperature ° C</td><td>ΔΗ2 kPa</td><td>1-octene moths</td><td>Polymer g</td><td>Indicator melt ^</td><td>Density</td>

<td>XLIII</td><td> 100</td><td> 170</td><td> 1,59</td><td> 70,0</td><td> 0,1</td><td> 870,0</td>

<td>XLVII</td><td> 100</td><td> 345</td><td> 1,85</td><td> 131,9</td><td> 7,48</td><td> 855,2</td>

<td>XLVIII</td><td> 80</td><td> 170</td><td> 2,12</td><td> 139,3</td><td> 0,93</td><td> 852,8</td>

a. partial hydrogen pressure

b. ki ASTM D-1238i procedure Ai conditions E

Examples LVIII-LXXVII - Polymerization of olefins

Ethylene and / or ethylene / 1-octene polymerization was suitably polymerized as a homopolymer or copolymer by adding a solution of a suitable catalyst in combination with MAO or triethylaluminum as a cocatalyst to a 3 dm SN pressure vessel3 containing a mixture of Ce-alkane solvent with 1-octene (of various ratios) at 3100 kPa ethylene pressure at 150 ° C (or 5 ° C, if indicated) for 10 minutes. The ethylene pressure was kept constant at all times by determining the absorption of ethylene using a mass flow meter. The resulting polymer was removed from the pressure vessel and dried under reduced pressure at 90 ° C overnight. The results are summarized in Table 5.

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Table 5

<td>Example</td><td>catalytic holdup (A, b)</td><td>solvents Score / octene '</td><td>Polymer mass, (g)</td><td>Indicator melt flow (I2)</td><td>mw</td><td>Mn</td><td>Mw / Mn</td>

<td>LVIII</td><td>ti</td><td> 1/1</td><td> 61,1</td><td> 79,0</td><td> 45 600</td><td> 9 100</td><td> 5,01</td>

<td>LXVII</td><td>ti</td><td> 2/0</td><td> 15,6</td><td> 4,4</td><td> —</td><td> —</td><td> —</td>

<td>LXVIII</td><td>Zr</td><td> 2/0</td><td> 20,6</td><td> 2,8</td><td> 101000</td><td> 7 700</td><td> 13,10</td>

<td>LXXII</td><td>ti</td><td> 2/0,3</td><td> 74,5</td><td> 56,3</td><td> 44 400</td><td> 12 100</td><td> 3,67</td>

<td>LXXIII</td><td>ti</td><td> 2/0,3</td><td> 75,0</td><td> 56,9</td><td> 44 700</td><td> 9 800</td><td> 4,56</td>

<td>LXXIV</td><td>ti</td><td> 2/0</td><td> 15,6</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td>LXXVI</td><td>ti</td><td> 2/0,15</td><td> 34,5</td><td> 1,0</td><td> —</td><td> —</td><td> —-</td>

<td>LXXVII</td><td>Zr</td><td> 0/2</td><td> 88,3</td><td> 111,7</td><td> 35 100</td><td> 6 440</td><td> 5,45</td>

a) Ti = (tert-butylamido / dimethyl) tetraethyl-n-dichlorides-cyclopentadienyl / silanetitanium

Zr = (tert-butylamido / dimethyl) tetramethyl-η dichlorideβ-cyklopeπtadienylo / sllanocyrkonu

b) Metal / Al ratio = 1010Cp on the assumption of MYS 58

c) Guest of the widow3

d) Test at 175 ° C

e) Cocoa-Urr was used ^ i ^ e ^ y ^ l ^^ f ^ i ^; metal / Al ratio = 1: 1000

Example LXXVHI - Preparation of dichloromethane (tert-butylaamido (dimethyl) tetramethyl-η5cycapentadienyl) supported silanatitans.

0.100 g of dehydroxylated silica (concentration of OH groups about 1 mmol / g SiOa) was suspended in 20 ml of a mixed C6 alkane solvent under a nitrogen atmosphere in a dry chamber, with stirring, in a 50 ml Erlenmeyer flask. 1.0 ml of this suspension was withdrawn using a syringe and combined with 1.10 ml of 0.011 M toluene dichloride (tert-butylaamide (dimethyl) tetramethyl-η5-cyclopentadienyl) silanotitane solution in a 5 ml round flask, followed by stirring for 12 hours . After this period, 6.7 ml of a 10% by weight solution of methylaluminoxane (MAO) in toluene was added to the silica-containing solution.

Polymerization

Polymerization was carried out by adding the above titanium / silica / MAO suspension to a pressure vessel of 3 dm3 stainless steel (SN) containing 2dm3 of mixed alkane solvent under ethylene pressure of 3100 kPa at 150 ° C for 10 minutes. The ethylene pressure was kept constant and the mass flow meter showed absorption of 26.7 g of ethylene. The polymer solution was discharged from the pressure vessel, after which 30.0 g of polyethylene was recovered after drying under reduced pressure overnight at 90 ° C.

Example LXXIX - Preparation of dichlarCu (2-methoxyphenylamido (dlmethyl) tetramethyltin-5-cyclopentadienyl) silanatitane

a) (/ tetramethylcyclopentadienyl) / dimethylsilylX2-meioxyphenyene) amine.

To 1.3 g (5.9 mmol) of (tetramethylcyclopentadienyl) dimethylsilyl chloride in 50 ml of tetrahydrafnran (THF) was added 0.86 g (5.9 mmol) of 2-methoxyanilide sodium. The mixture was stirred overnight. The solvent was removed under reduced pressure and the residue was extracted with pentane. The pentane extracts were filtered, combined and concentrated to give a pale yellow liquid. Yield 1.4g (79%).1H NMR (benzene ^) 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, 3.7), 1.93 (s, 6.7), 1.80 (s, 6.8), 0.13 (6.3).

b) Dilithium salt ((tetramethylcyclopentadienyl) dimethylsilyl) (2-methoxyphenyl) amids.

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To 1.4 g (4.6 mmol) of ((SeSramethylcyclopensadlenyl) dimethylsillyl) (2-metz-cyfeayl) amine in diethyl ether was added 3.9 mL of 2.5 M butyllithium (9.8 mmol) in hexane as solvent. A white precipitate formed. Pentane was added to the mixture. The suspension was filtered and the solid washed with pentane.

c) Dichloride (2-Meΐox ^ phenylamido / dimeeyto / tetrαmethyl-δs-cyklzpentadίenylz) silanetitanium.

To 1.6 g of dilithium salt ((teSrαmet, ylcyclopropenyl) dlmethylsyl! X2-methoxypheayl) amide suspended in toluene, 0.85 g of TiClU was added. The mixture was stirred for 3 days, then filtered and the solvent removed under reduced pressure. The residue was suspended in pentane and filtered to give a dark powder. Yield 0.77 g (41%).1H-NMR (benzene-^) δ 4.10 (s, 3), 3.20 (s, 6.4), 1.99 (s, 6.6), 0.40 (s, 6.3) .

Example LXXX - Preparation of dichloride (4-fluorophenylamide (dlmeSylo) tetrαmethyl-ηscyclopentadienyl) silanetitanium

a) (/ tetramethylcyclopentadienyl / dimethytosilil) 4-fuorzfeaylz) ammα.

Equimolar amounts of chloride (teSramethylcyclopentadiene / dimeSylsillyl and l-fusophenyl phenyl) anilide were combined in THF and stirred overnight. The solvent was removed under reduced pressure. 1H NMR (benzene ^) δ 6.79 (m, 2.5), 6.33 (m, 2.4), 2.95 (s, 1), 2.90 (s, 1), 1.87 (s, 6.9), 1.79 (s, 6.9), 0.02 (s, 5.8).

b) Dilithium salt ((tetrarylethylcyclopeopeadiethyl) dimethylsillloX4-fl · urophenyl) amide.

((teSramethylcyclopentadienyl) dimethylsilzX4-fuorofeayl) aml in diethyl ether as solvent and 2.5 M butyllithium in hexane as solvent were combined in equimolar quantities. A white precipitate formed. Pentane was added to the suspension. The precipitate was filtered off, washed with pentane and dried.1H NMR (THF-d8) δ 7.28 (m, 2.0), 6.77 (m, 2), 3.27 (s, 2.7), 2.05 (s, 5.2), 2.01 (s, 5.2), 0.44 (s, 4.6).

c) Dichloride (4-fluoro-phenytoamide) / dlmethyl / Setramethylz-η5-cyklzpentadienylz) sllaaztytanu.

To 0.59 g (1.6 mmol) of TiCl3 · 3THF in 50 ml THF was added 0.50 g (1.7 mmol) of dilithium salt ((teSrαmethylcyclopentadienyl) dimethylaloyl-4-fuorophenyl) αmldu. After 0.5 hour, 0.25 g (1.8 mmol) AgCl was added. After 2 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 glassy red solid. Dissolved in toluene and re-concentrated to give a waxy solid which was extracted with pentane. The pentane extracts were filtered, combined and concentrated to give a waxy solid. It was suspended in a small amount of pentane (2 ml) and filtered to give a red powder. Yield 0.18 g (28 *%).1 H-NMR (benzene) δ 7.10 (t), 6.80 (t), 2.00 (s), 1.97 (s), 0.35 (s).

Polymerization

The polymerization procedure of Examples XI-XXXII was generally followed, using 1000 ml mixed alkane solvent, 200 ml 1-oxSeau and 5 ml 15% MAO in toluene (Al: Ti 1280) at a reaction temperature of 130 ° C. Hydrogen was fed from a 75 ml tank at a pressure of 3450 kPa to give a positive pressure of 345 kPa. 10e / moles of the above complex were added to initiate polymerization. A constant supply of ethylene at 3100 kPa was provided. 12.8 g of polymer were obtained, with Mw = 103,000, Mw / Mn = 4.77, density 938.7 and melt index = 6.37.

Example LXXXI - Preparation of dichloride ((2,6-di (1-methylzethyl) phenyl) amido) dimethylz (Setramesylz-η5-cyklopentadieaylz) amldztytanu.

Dilithium salt ((tetrαmethylcyclopopeatαdieaylo) dimethylzillyl) (2,6-di) 1-methylzetyl (phenyl) amide was obtained in an analogous manner to that described in Example LXXX.

To 1.5 g (4 mmol) of TiCl3 · 3THF in 25 ml THF was added 1.5 g (4 mmol) of dilite salt ((Setramethylcyclopenta-dienylz) dimethylzilyl) (2,6-di) 1-methylethyl (feaylz) amldu. After 0.5 hour, 0.63 g (4 mmol) of AgCl was added. After 1.5 hours, the solvent was removed under reduced pressure. The residue was extracted with pentane (3X8ml). The residue insoluble in pentane was extracted with diethyl ether. The ether extract was filtered and evaporated to dryness to give a crystalline yellow steel. 1H NMR (benzene-^) δ 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).

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Polymerization

Polymerization was carried out according to the procedure of the previous example, using 10 / moles of the above complex. 14.7 g of polymer were obtained.

Example LXXXII - Preparation of dichloride (4-methoxyphenylamido / 'dimethy' / tetramethylor / cyclopentadienyl) silanititane.

To 0.73 g of TiCl4 - 2THF in 30 ml of toluene, 0.7 g of dilithium salt ((tetramethylcyclopentadienyl) dimethylsilylX4-methoxyphenyl) amide (obtained in an analogous manner to that described in Example LXXXI9 was added.) The mixture was stirred for 2 days, filtered and concentrated under reduced pressure. The residue was suspended in pentane and filtered to give a brick powder, yield 0.61 g (67%). 1H NMR (benzene-d6) Ó 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 procedure of Example LXXX was followed, using 10 µm of the above complex. 7.2 g of polymer were obtained, with Mw = 79 800, Mw / Mn = 21.5, melt index = 2.90.

Example LXXXIII - Preparation of trichloride (tetramethyl-n5-cyclopentadienyl) dimethyl (I-methylethoxy) silanetitanium.

a) (Tetramethylcyclopentadienyl) dimethyl (1-methylethoxy) silane.

To 1.0g (4.8 mmol) of (tetramethylcyclopentadiene-limethylsilyl chloride in 10 mL of toluene was added 0.38 mL (5.0 mmol) of 2-propanol, followed by 0.66 mL (4.7 mmol) of triethylamine. and the residue was washed with mixed ce-alkane solvent. The wash liquid and filtrate were combined and concentrated under reduced pressure to give a pale yellow liquid. 1H NMR (benzene ^) δ 3.85 (heptet, 1, J = 6.0), 2.9 (s, 1.1), 2.03 (s, 5.7), 1.8 (s, 6.3), 1.10 (d, 6.3, J = 6.0), -0.02 (s, 5.0).

b) Potassium (dimethyl) 1-methylethoxy / silyl / -tetramethylcyclopentadione salt).

To 0.51 g (2.1 mmol) (tetramethylcyclopropenadienethimethite / 1-methylethoxy) sllane in toluene, 0.33 g (2.5 mmol) potassium benzide was added. The solution was filtered after 3 days and the solvent removed under reduced pressure to give an oil. The oil was washed with pentane. The rest of the pentane was removed under reduced pressure to give a vitreous, tan colored solid.1H NMR (THF-de) δ 3.89 (heptet, 1, J = 6.1), 2.00 (s, 6.1), 1.87 (s, 5.7), 1.05 (d , 5.1, J = 6.1), 0.22 (s, 4.4).

c) (Tetramethyl-η5-cyclopentadienyl) dimethyl (1-methyljoxy) silanititane trichloride.

To 0.42 g (1.1 mmol) T1Cl3-3tHf in 50ml THF, 0.83 mmol (dlmethyl) 1methylethyloxy (silyl) tetramylcyclopentadiene) potassium in 15 ml THF was added dropwise. 1 hour after the addition, 0.2 g (1.3 mmol) of AgCl was added. The resulting mixture was stirred for 18 hours. The solvent was removed under reduced pressure and the residue was extracted with pentane. The pentane extracts were filtered, combined and evaporated to give a red oil. The oil was dispersed in pentane and the mixture was filtered. The filtrate was stored at -30 ° C for 3 weeks. An orange precipitate formed, from which the solution was decanted.1H NMR (benzene ^) δ 3.8 (heptet, 1, J = 6.0), 2.35 (s, 6.9), 1.86 (s, 7.4), 1.04 (d, 7.1, J = 6.0), 0.45 (s, 6.7), 0.00 (s), 1.97 (s), 0.35 (s).

Example LXXXIV - Preparation of 1- (tert-butylamido) -2- (i.e., trimethyl-η5-cyclopentyl) -1,1,1,2,2-tetramethyldisylanotitane dichloride.

a) 1-chloro-2- (i.e., tetramethylcyclopuntenyl) -1,1,2,2-tetramethyl dlsllane.

To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 ml dimethyl ether, a solution of 2.285 g (12.8 mmol) 1,2,3,4-tetramethylcyclopentadieneld is slowly added dropwise. Sodium in 30 ml dimethyl ether. The reaction mixture was stirred for several hours, after which the solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil. Mass spectrum: m / e 272 (8%).1H NMR (C6D6) / 52.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H) ; 13C NMR ^ D6) δ 135.8, 134.0, 54.5, 14.6, 11.4, 3.2, -2.4.

b) 1- (i.e., tert-butylamino) -2- (i.e., tetroylcyclopentadinyl) -1,1,2,2-tetramyltilylate.

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To a solution of 3.000 g (11.0 mmol) 1-chloro-2- <tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane in 50 ml ether was added 2.422 g (33.1 mmol) tert-butylamine. A precipitate formed immediately. The suspension was stirred for several days at room temperature, then warmed gently to complete the reaction. The solvent was removed and the residue was extracted with pentane, the amine hydrochloride was filtered off, and the pentane was removed under reduced pressure to give the product as a yellow oil. Yield '3; 1' '50g (92.5%). Mass spectrum: M / e 309. Ή NMR ^ De) δ 2.75 (s, 1H), 1.95 (s, 6H), 1.82 (s, 6H), 1.08 (3.9H), 0.51 (s, 1H), 0.24 (s, 6H), 0.16 (s, 6H); 13C NMR (C6D6) $ 135.2, 134.4, 55.20.50, 3.3, 4.1, 144, 111, 6.3, -1.4.

c) 1- (tert-butylamido) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilene dilithium salt .

To a solution of 3.00 g (9.72 mmol) 1- (tert-butylamino) -2- (tetramethylcyclopentadienyl) 1,1,2,2-tetramethyldisilane in 100 ml ether was slowly added 7.70 ml 2.6 M butyllithium ( 20.2 mmol) in mixed C6 alkanes as a solvent. The resulting suspension was stirred for several hours, filtered and washed with ether, then dried under reduced pressure to give the product as a white powder. Yield 2.918 g (93.4%). Ή NMR (THF-da) δ 2.05 (s, 6H), 1.91 (s, 6H), 0.87 (s, 9H), 0.25 (s, 6H), -0.03 (s , 6H); 13C NMR (THF-da) δ 117.31 3.6, 53.5, 38.4, 34.1, 14.21.3, 8.4, 2.2.

d) 1- (tert-Butylamido) -2- (tetramethyl-n5-cyclopentadienyl} -1, 1, 2, 2-tetra-diisilanotitane dichloride.

Suspension 0.7500 g (2.333 mmol) of the dilithium salt of 1- (tert-butylamido) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane and 0.7790 g (2.333 mmol) TiCL (THF) 2 in 50 ml toluene was stirred for several days. The red-orange reaction mixture was filtered and the solvent removed to give a solid red (sticky) residue. Extracted with pentane and filtered. After concentration and cooling to -35 ° C in a cold trap, the shiny, microcrystalline red product was filtered off on a sintered glass filter, followed by washing with cold pentane to remove oily dark red material. Yield 0.3643 g 36.6%.1H NMR (C6D6) δ 2.20 (s, 6H), 1.94 (s, 6H), 1.48 (s, 9H), 0.44 (s, 6H), 0.43 (s, 6H) . 13C NMR (CeDe) δ 137.7, 135.5, 112.7, 65.9, 35.4, 16.6, 12.5, 2.8, -2.1.

Polymerization

The polymerization procedure of Example LXXX was followed, using 10 µm of the above complex. 12.1 g of polymer with Mw 62 400, Mw / Mn = 8.45, melt index 6.14 and density 944.1 were obtained.

Example LXXXV - Preparation of 1- (tert-butylamide) -2-tetramethyl-n5-cyclopentadienyl) -1,1,2,2-tetramethyldisilane zirconium dichloride.

A suspension of 0.7500 g (2.333 mmol) of the dilithium salt of 1- (tert-butylamido) -2- (tetramethylcyclopentadienyl) -1,1,2,2-tetramethyldisilane (obtained by the method of Example LXXXIV) and 0.5436 g (2.333 mmol) ZrCL in 75 ml toluene was stirred for several days. The pale yellow reaction mixture was filtered and the solvent was evaporated. The residue was extracted with pentane and filtered. After concentration and cooling to -35 ° C in a cold trap, the product in the form of colorless crystals was separated on a sintered glass filter. Yield 0.6720 g, 61.3%.1H NMR (CaDe) δ 2.14 (s, 6H), 1.94 (s, 6H), 1.49 (s, 9H), 0.36 (s, 6H), 0.34 (s, 6H) . 13C NMR (C.6De) δ 134.1, 131.0, 119.1, 58.4, 34.2, 15.1, 11.8, 4.7, -2.1.

Example LXXXVI - Preparation of (ter-butylamido) (dimethyl) (tetramethyl-n5-cyclopentadienyl) silane-dimethyl zirconium.

A solution of 0.5000 g (1.215 mmol) dichloride (tert-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silane zirconium in 35 ml ether was cooled to -40 ° C. 1.41 ml of methyl lithium solution (1.72 M, 2.43 mmol) was slowly added to it. The reaction mixture was then stirred for several hours at room temperature. The solvent was removed and the residue was extracted with pentane and filtered. The filtrate was concentrated and cooled to -40 ° C. The resulting colorless crystals were separated by decanting the liquid. Yield 0.2215 g, 49.2%. NMR (€ 606) δ 1.97 (s, 6H), 1.91 (s, 6H), 1.40 (s, 9H), 0.46 (s, 6H), 0.00 (s, 6H) . 13C NMR (CeDe) δ 130.2, 95.7,

54,7, 35,4, 34,0, 13,9,10,9, 6,2.

166 689

Example LXXXVII - Preparation of didhlide (t-t-butylamido (dimeyl S-η5cyclopeztadizzyl) thilazotitase.

a) (UhloroScycycloptataizzyl) (dimethylSilil.

A solution of 149 g (1.16 οοΐα) Mż2SiCl2 in 750 ml Oistyl ether was cooled to -78 ° C. Within

1.5 gotdrnz ιΙοΟΟζζ to the mottzZ ^ a and ^ óP 'γρΙά <± 30g 10.334 mol, ο / ί ^ οοεηΖΗΖίεηΐ <^ The pazostaniosis reaction mixture will warm to room temperature and then stir for 16 hours. The ether and a portion of Mż2SiCl2 were distilled off, after which distilled distillation under reduced pressure was carried out to remove the residue η ^ η, Mt2SiCl2 and the NaCl product formed during the reaction. After fractionation, the product was obtained in good yield in the form of a light yellow oil. Mass spectrum: m / e 158 (16%).

b) (T zzt-butylaamizoXryklopentadizzyzyχdimetρla) silane

To a solution of 3.69 g (50.4 mmol) of tert-butylmin n 45 ml of THF, 2.00 g (12.6 mmol) (chlaraXcyclapentadiezylS (dimethylstilazu) was added. A rapid precipitate formed. Suspension of οϊζϋαζο for several days, followed by the hydrochloride the amines were removed from the residue and the solvent removed under reduced pressure to give the product as a pale yellow oil, yielding 2.069 g, (84.2%). Mass spectrum: m / z 195 (6%). 1H and ^ NMR spectra show a range of isomers cρklopentadiezowych.

c) Dilithium salt (tert-boylamidoS (cyalopentαdiezylS (dimzilyl silane)

For a solution of 1.500 g (7.69 mmol) (tert-butylamino-cyclo-pentadiezyl) (dimzilyl-Stilazu in 60 ml ether, slowly add 6.21 ml of 1.72 M solution of mztllithium (10.68 mmol) in etzzzz, followed by 1.81 ml 2, 6 M butyllithium (4.706 mmol) n mixed alkanone solvent (15.39 mmol total alkyl lithium). The resulting mixture was stirred overnight, filtered and washed with pentane, then dried under reduced pressure to give the product as a white powder. Yield 1.359 g, ( 85.2%). 1 H NMR (THF-08) δ 5.96 (t, 2H), 5.87 (t, 2H), 1.10 (s, 9H), 0.05 (s, 6H). 13 C NMR (THF-de) δ 114.1 105.2, 103.5, 52, 38.3, 7.3.

d) Dichlozea (tzzt-builidimidimimeyl-S-η5-ryklopnztadiezylStila! eotρtazu

0.7000 g (3.38 mmol) dilithium salt (tzri-butylamidoXcyclopentadienyl Xdimethyl) and 1.128 g (3.38 mmol) TiCL · (THF) 2 were combined into a flask with 75 ml toluene. -bzonainz for several hours The reaction mixture was stirred for several days, after which the red solution was filtered, the solvent removed under reduced pressure. The resulting crystalline material was suspended in pentazis and filtered to remove red zorphous red impurities from the brown product. Yield 0.5369 g, (50.9%);1H NMR (CyDy) δ 6.60 (t, 2H), 6.07 (t, 2H), 1.38 (s, 9K), 0.18 (s, 6H). & Lt; 1 & gt; C NMR (U6DyS δ 126.3, 125.6, 110.0, 63.7, 32.2, -0.2.

Polymerization

Polymerization was carried out according to the procedure of Example LXXX, using 10e / nol of the above complex. 28.1 g of polymer with Mw 108,000, Mw / Mn 3.22, density 907.3 and melt index 2.92 were obtained.

Example LXXXVHI - Preparation of tetrafluxylamido (dimztyl) η5-cyclopropntntudic dichloride, lianocycloacetate.

To 0.6747 g (2.90 mmol) of ZrCL in kolbiz, 4 ml of diethylzol ether were slowly added, followed by 4 ml of THF. Excess rorrotrcralzików were removed under higher pressure to obtain a solid which was broken down in the fetus. The tzz powder was combined with 0.6008 g (2.90 mmol) of dilithium salt (iszt-boty5oαmido) (cyclorzztzdienylSaimztyl) silane (obtained according to the method of Example LXXXVII) in 75 ml of toluene. The resulting suspension was stirred for several hrs, after which the colorless solution was filtered, the solvent was removed under reduced pressure, and the suspension was suspended. The product was sintered through a sintered glass filter and dried under reduced pressure. Yield 0.6186 g, 60.0%. 1H NMR (CyDyS δ 6.43 (t, 2h), 6.08 (t, 2H), 4.17 (br2,6H), 1.27 (s ^ H), 1.03 ^, 6Η), 0.22 (^ 6Η). 13CNMR (CyDyS δ 122.0, 121.8, 109.5.78, 57.2, 32.8 '25.2, ¢, 7. ΚρδΖα ^ Γαίϊοζηζζηαιϊίζα zenOgenowska showed that zz.- in the state of stafyoe sZraktuza is dimzryczna (with chloride bridges).

166 689 25

Example LXXXIX - Preparation of (anilido) (dimethyl) (tetramethyl-n5-cyclopentadienyl) silanititane dichloride.

a) i ^ A ^ n ^ ilido) (dimethyl) (Teti ^ a ^ m ^ e ^ (^ s ^ l ^^ c ^ yklc ^ p ^ ^ ers di ^ enyl) silane

To a solution of 1.500 g (6.98 mmol) (chloro-dimethioXtetramety! Ooz! O-2-Baadienyl) sliasud in 50 ml THF slowly added 0.6911 (6.98 mmol) lithium anilide. Analysis of the reaction by gas chromatography (GC) showed that the reaction was not complete. A further 0.08 g (7.78 mmol) of lithium anilide was added. The reaction mixture was stirred overnight, after which the solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a pale yellow oil. Yield 1.875 g, (99.2%). Mass spectrum: m / e 271 (13%). Ή NMR (CeDe) 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). 13C NMR (C ^) δ 1475, 136 ,,, 132.6, 129.66 118.8 116.9, 55.0.14.3, 11.3, -2.2.

Dilithium (anilido) (dimethyl) (tetramethylcyclopentadienyl) silane salt.

To a solution of 1.875 g (6.91 mmol) (anilyl dimethyl tetramethylcyclopentadienyl)) butane in 50 ml ether was slowly added 5.31 ml 2.60 m butyllithium (13.8 mmol) in hexane as the solvent. A small amount of precipitate formed, which then dissolved. The reaction mixture was stirred overnight. The product was collected as a thick, viscous oil from the ether solution. The solvent was removed under reduced pressure to give a white solid which was suspended in pentane, filtered on sintered glass, washed with pentane and dried under reduced pressure to give the product as a white powder. Yield 1.943 g, 99.3%.

c) Dichlorotide (anilidoχdimethylχte'tramethyl-n5_cyclopentadienyl)) ilanitan

A suspension of 0.8025 g (2.333 mmol) dilithium salt (anilidoXdimethylXtetramethylcyclopentadienyloylane and 0.9871 g (2.333 mmol) TiCLfTHF) in 70 ml toluene was stirred for several days. The red-brown reaction mixture was filtered and the solvent removed. The solid residue was triturated with pentane, after which the product was filtered off on sintered glass and washed with cold pentane to remove the dark red oily material to give the product as a yellow-beige powder. Yield 0.6400 g, 55.8%.1H NMR (CeDe) 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); 13C NMR (CeDe) δ 152.4, 141.19 129.3, 124.4, 119.6, 105.3, 16.1, 13.0, 2.7.

Polymerization 1

The polymerization procedure of Example LXXX was used using 10 / m of the above complex. 12.8 g of polymer with Mw 103,000, Mw / Mn 4.77, density 938.7 and melt index 6.37 were obtained.

Polymerization 2 - Ethylene / styrene copolymerization

Polymerization was carried out essentially according to the above procedure, except 900 ml mixed alkane solvent, 184 ml styrene, hydrogen at 345 kPa overpressure and 20 / m [(C5Me4) SiMe2 (tert-butyl)] TiCl2 was used. The reaction was carried out at 120 ° C reactor temperature. After 10 minutes, the contents were removed from the reactor. 62.3 g of polymer with a melting index of 3.68 were obtained.

Example XC. - Preparation of (anilido) (dimethyl) (tetramethyl-n5-cyclopentadienyl) siliconium zirconium dichloride

To 0.6905 g (2.963 mmol) of ZrCL in the flask was slowly added 3 ml of diethyl ether followed by 4 ml of THF. Excess solvents were removed under reduced pressure to give a solid which was broken down into powder. This powder was combined with 0.8044 g (2.963 mmol) dilite salt (anilidoX-dimethyltetamethyl-n5-cyclopentadienyl)) ilane in 70 ml toluene. Within a few minutes, the suspension turned pale yellow-green. The suspension was stirred for several days, then the solution was filtered, the solvent was removed under reduced pressure, and the residue was dispersed in pentane. The product with very pale yellow color was separated on sintered glass and then dried under reduced pressure. Ή NMR (CeDe) δ 7.21 (t, 2H), 7.1 (t, 1H), 6.97 (m, 2H), 2.50 (s, 3H), 2.46 (s, 3H) , 1.87 (s, 3H), 1.85 (s, 3H), 0.53 (s, 3H), 0.40 3H).

166 689

Example XCI - Preparation (p-Schluidino) (dimethyl) (SeSrameSylz-ηδ-cyklopenSadlenylo) aϋiaaocyrkonu.

a) (p-SzluldynoXdlmetylzXSeSrameSylzycyclopent, adieaylz) ailaa

To a solution of 2.000 g (9.302 mimol) (ch] ίoroXdiίyesyloX2,3,4,5-ίetfaryesylcyclopentadlenyl) silane in 70 ml THF slowly added 1.259 g · (9.302 mmol) p-lithium Szluldide (0.3 ether adduct based on 1H NMR) . The reaction mixture was stirred overnight. Analysis by GC showed that the reaction was not complete. An additional amount of 0.725 g lithium p-toluidide (total 14.7 mmol) was introduced in small portions. The solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a yellow oil. Yield 2.456g, 92.5%. Mass spectrum: m / e 285 (22%).1H NMR (C6D6) δ 6.96 (d, 2H), 6.57 (d, 2H), 3.07 (s, 1H), 3.01 (s, 1H), 2.17 (s, 3H) , 1.91 (s, 6H), 1.80 (s, 6H), 0.08 (s, 6H). "C NMR ^ D6) δ 145.0,136,2,132,7,1302,126,9,116,9,55,2,20.5, 143,01,3, -2-2

b) Dilite salt (p-SoluidyaoXdimeSyloχseSrameSylzycycopeaSadleaylo) allan

To a solution of 2.233 g (7.82 mmol) (p-Soluidya) (dlmethylχteSr · amylSylcyclopenta-dienyl) silane in 65 mL of ether was slowly added with 6.17 mL of 2.6 M butyllithium (16.0 mmol) in a mixture of C6 alkanes as solvent. The reaction mixture without solid was stirred overnight, after which the solvent was removed under reduced pressure. The white solid residue was dispersed in pentane, filtered on porous glass, washed with pentane and dried under reduced pressure to give the product as a white powder. Yield 2.34 g, (100%). Ή NMR (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).INC NMR (THF d-8) δ 103.88 121.13 115.19, 115.2, 112.2 106.2, 20.8.14.7, -11.7, 5.2.

c) (p-toluidino) (dimethyl) (Setramethyl-η) dichloride^-cyklopentadleaylo) aiłaaotySanu

A suspension of 1,000 g (3.363 mmol) of dilithium salt (p-Soluldyao-dimethylXteSrameSylz-η-cil!ABOUTpεntadlenyl) silane and 1.123 g (3.363 mmol) TiCl (THF) 2 in 70 ml toluene. The reaction mixture was stirred for several days, then filtered and the solvent removed. The resulting solid was suspended in pentane and the product was separated on a porous glass and then dried under reduced pressure. An olive-brown powder of 0.7172 g, 53.0% was obtained. Ή NMR (C6D6) 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). "C -NMR (C6D6) δ 150.3, 141.7, 137.5, 130.0, 129.7, 117.6,

21,0,20,6,16,4,16,0, 13,3, 2,8, 2,6.

d) Dichloride (p-toluidino) (dimeSyloXtetrαmethylz-η5-cykίopeaSadlenylo) aliαaocyrkonu

To 0.7836 g (3.363 mmol) of ZrCl in a flask was slowly added 3 mL diethyl ether followed by 4 mL THF. Excess solvents were removed under reduced pressure and the solid residue was broken up into powder. This powder 'was combined with 1,000g (3.363 mmol) of dilite salt (p-toluidino) (dimethyl) (teSramethyl-η5-cykiopentadienyl) silα in 70 ml toluene. The suspension was stirred for several days. The initial yellowish color changed to brownish. The yellow solution was filtered, the solvent removed under reduced pressure, and the solid residue suspended in pentane. The pale yellow product was separated on sintered glass and dried under reduced pressure. Yield 0.8854 g, (59.1%). , H NMR (CeDe) δ 7.06 (d, 2H), 6.87 (d, 2H), 2.50 (s, 3H), 2.47 (s, 3H), 2.21 (s, 3H ), 1.89 (s, 3H), 1.88 (s, 3H), 0.51 (s, 3H), 0.41 (s, 3H). X-ray crystallographic analysis showed that the structure is a dimer containing LiCl, with chloride bridges.

Example XCII - Preparation of dichloride (benrylamido) (dimethylXSetrameSylo-η5-cyklzpentαdienylz) and! lαnzSyίanu

a) (Benzyloamίno) dimethyl (tetracyclopentadlenylz) silaa

To a solution of 1,000 g (4.651 mmol) (Chloro-dimethyl) (tetramethylcyclopenadienylz) silane in 70 ml ether was slowly added 0.526 g (4.651 mmol) lithium benzylamide. The reaction mixture was stirred overnight, after which the solvent was evaporated and the residue extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product in

166 689 pale yellow oil forms. Yield 1.234 g, (93.3%). Mass spectrum: m / e 285 (18%). 1H NMR (C6D6) δ 7.07-7.24 (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).13C NMR (Ο ^) δ 141.5, 135.7, 132.0, 128.5, 127.73 126.7, 56.46.4, 14.6, 11.4, -2.3.

b) Dilithium salt (benzylamido-dimethyltetramethyl-cyclopentadienyl) silane To a solution of 1.091 g (3.836 mmol) (benzylamino-dimethyl-tetramyl-cyclopentadienyl) silane in 70 ml ether was slowly added 3.1 ml 2.60 M butyllithium (8.06 mmol alkanol) in a mixture of solvents. A pale pink color appeared and a precipitate began to form. The reaction mixture was stirred overnight after which the solvent was removed under reduced pressure. The solid residue was suspended in pentane, filtered on porous glass, washed with pentane and dried under reduced pressure to obtain a very pale pink powder. Yield 1.105 g, 96.9%.1H NMR (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). 13C NMR (THF d-8) δ 152.11, 128.81, 127.7, 125.0, 115.8,

111,9,108,3, 54,0,15,0,11,2, 4,6.

c) Benzyl amido (dimethyl) tetramethyl-η5-cyclopentadlenyl) sianitanium dichloride Slurry 0.5052 g (1.699 mmol) of dilitium salt (benzylamido) (dimethyl) (i.e. tramethyl-η5 cyclopentadienyl) butane and 0.5673 g (1.699 mmol) ) 2 in 40 ml toluene was stirred for several days The dark green-brown reaction mixture was filtered and the solvent removed. The dark oily residue was suspended in pentane, then the product was separated on a porous glass and washed with cold pentane to remove the dark oily material to give the product as a grayish-yellow powder. Yield 0.2742 g, 40.1%.1H NMR (CeDe) 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). 13C NMR (CeDe) δ

141,4,1409,135,8, 128,8,126,9,126,3, 111,6, 103,6, 59,3,15,6, 1,7.

Polymerization

The procedure of Example LXXX was followed, using 10 / mol of the above complex. 14.4 g of polymer with Mw / Mn 5.0, melt index 251 and density 969.0 were obtained.

Example XCIII - Preparation of (benz; ^] ^^^] ^^ (to) (dimethyl) tetramethyl-n5-cyclo-pentadienyl) -sian zirconium, dichloride.

0.3930 g (1.687 mmol) of ZrCl4, 0.5015 g (1.687 mmol) of dilitium (benzylamido) (dimethylXtetramethyl-n5-cyclopentadienyl) silane and 40 ml of toluene were combined in the flask. The brownish-yellow suspension was stirred for several days, then filtered and the solvent removed under reduced pressure. The wet beige residue was dispersed in pentane, then the product was separated on a porous glass and dried under reduced pressure. Yield of off-brown product 0.2873 g, (38.2%). , H NMR (CeDe) δ 7.51 (d,

2H), 7.23 (t, 2H), 7.09 (t, 1H), 5.48 (d, 1H), 5.00 (d, 1H), 2.45 (s, 6H), 2, 05 (s, 3H), 2.01 (s, 3H), 0.34 (s, 3H), 0.20 (s, 3H). 13CNMR (CEDe) δ 145.2135,1,132,2,131,8,1294,129,0,128,9, 1288,8,127.0,

126,6, 1 26,6, 1 06,6, 17,2, 1 6,0, 1 5,6, 1 2,5, 1 1,1, 2,6.

Example XLIV - Preparation of dichloride (phenylphosphine / di-methyl / tetramethyl-η5-cyclopentadienyl) -anitanitane.

a) (phenylphosphine methylmethyltrimethylcycloprenentadienyl) sllane.

To a solution of 1.500 g (6.983 mmol) (chloro dimethyl ^ C-tetramethyl-cyclopentadienyl) -anate in 55 mL THF was slowly added 1.11248 g (7.665 mmol) excess, because GC showed that at a 1: 1 ratio the reaction was not complete (lithium phenylphosphide / adduct 0.4-ether based on spectroscopy 11 H NMR). After stirring for several days, the solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a yellow oil. Yield 1.985 g, 98.5%.

b) Dilite salt (phenylphosphido / dlmethyl / tetramethylcyclopentadjenyl) sllane

To a solution of 1.858 g (6.451 mmol) (phenylphospho-methylmethyltetramethylcyclopentadlenyl) silane in 65 ml ether was slowly added 5.21 ml 2.60 M (13.55 mmol) butyllithium in a mixture of alkanes as a solvent, with an immediate yellowish precipitate. The reaction mixture was stirred overnight. The product was separated on a porous glass, washed with pentane and dried under reduced pressure to give the product as a white powder. Yield (G ^ ether adduct based on spectroscopy 11 H NMR) 2.0845 g (95.8%).

166 689

c) Dichloride (phenylphosphine (dimethyl) tetramethyl-n'5-Cyklopentadienylo) siianotytanu

0.900 g (2.688 mmol) of dilite salt (phenylphosphido) (dimethyl) (tetramethyl n) was combined in the flask.s-cyclopentadienyl) silane (0.5-ether adduct) and 0.8907 g (2.668 mmol) of TiCLi (THF) 2 in 75 ml of toluene. After the addition of toluene, there was an immediate dark green-black color change. The reaction mixture was stirred for several days, then filtered and the solvent removed. The dark residue was extracted with pentane and filtered to give 0.2477 green-brown product on a sintered glass filter as well as a glassy product that was colored after removing the pentane from the filtrate.

Polymerization

The polymerization procedure of Example LXXX was followed using 10 / mol of the above complex. 14.4 g of polymer with Mw 27 700, Mw / Mn 5.0, melt index 251 and density 969.0 were obtained.

Example XCV - Preparation of (phenylphosphido (dimethyl) tetramethyl-n dichloride5-cykiopentadienylo) silanocyrkonu.

To 0.6217 g (2.688 mmol) of ZrCl in a flask was slowly added 3 mL of diethyl ether. Excess solvent was removed under reduced pressure to give a solid which was broken down into powder. This powder was combined with 0.9000 g (2.668 mmol) of dilite salt (phenylphosphido X-dimethyl) tetramethyl-ns-cyclopentadienyl) silane in 75 ml toluene. There was a dark red-orange color after toluene was added. The reaction mixture was stirred for several days, after which the orange solution was filtered off from a large amount of dark, insoluble material. After removal of the solvent, the residue was suspended in pentane and filtered. The brown solid was separated on the porous glass and dried under reduced pressure.

Example XCVI - Preparation of (tert-butylamido (dimethyl) indenyl) silanititane dichloride.

a) (Tert -butylamino (dimethyl) indenyl) sulfate

To a solution of 5.255 g (71.8 mmol) of tert-butylamine in 75 ml of ether was added 3.000 g (14.4 mmol) of 9- (chlorodimethylsilyl) indene. Within a few minutes of starting the addition, a precipitate formed. The suspension was stirred overnight, after which the solvent was removed and the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil, a mixture of 2 isomers. Yield 3.313 g (93.9%).

b) Dilite salt (tert-butylamido (dimethyl) indenyl) silane

To a solution of 3.125 g (12.73 mmol) (tert-butylamido (dimethyl) indenyl) silane in 75 mL of ether was slowly added 10.28 mL 2.60 M (26.73 mmol) of butyllithium in a mixture of Cs alkanes as solvent. The color of the solution without any precipitate changed slightly to darker, beige and orange. The reaction mixture was stirred for several days after which the solvent was removed. Fluffy, glassy material was dispersed in pentane. The powder got stuck together. The pentane was decanted, and the washing was repeated several times. The solid was dried under reduced pressure. Yield 2.421 g, 73.9%.

c) (tert-butylamido (dimethyl) indenyl) silanititane dichloride

1,000 g (3.887 mmol) of dilithium salt (tert-butylamido X-dimethyl) (indenyl) silane and 1.298 g (3.887 mmol) of TiCl (THF) 2 in 70 ml of toluene were combined in the flask. A dark red color appeared immediately. The reaction mixture was stirred for 3 days, then filtered and the solvent removed. The residue was extracted with pentane and filtered to give the product as a red microcrystalline material. Yield 0.4917 g, 34.9%.

Polymerization

The polymerization procedure of Example LXXX was followed, using 10 µm of the above complex. 14.8 g of polymer were obtained.

Example XCVII - Preparation of (tert-butylamidoXdimethyl) indenyl) silan zirconium dichloride.

To 0.9057 g (3.887 mmol) of ZrCl in a flask was slowly added 2 mL of THF. Excess THF was removed under reduced pressure to give a solid which was broken down into powder. Added 1,000g (3.887 mmol) dilithium salt (tert-butylamido (dimethyl) indenyl) silane and 70ml

166 689 toluene. The resulting suspension was stirred for several days, after which the solution was filtered, from the solvent removed under reduced pressure. The residue was pentane, filtered and in vacuo under reduced pressure. The product has a bzunatnr - beige color in the amount of Π 6AA2 and AG ^ A "w, yWjW ZV / ·

Example XCVIII - Preparation of ΟκΗο ^ mztyIoamίdo (dimziyl) tztramztyl-η5-ryalorzztαaiznyl) silazoiytαnu.

a) (MethylamisimidylStztrαmztylo-η5-cyclopzntα0iznyl) silase

To a solution of 1.900 g (8.845 mmol) of ŚlozoχOimztyloXtztramztylocalpzntadiskiylstilan n 75 ml THF was quickly added 0.33272g (8.846 mmol) of lithium copperdiazidium. The clear solution was stirred overnight, after which 0.008 more lithium tetraflamide (9,062 mmol total) was added, as the lawn chromatography showed that the reaction was not complete and the solution was stirred overnight again. The solvent was removed and the residue was extracted with liquid and filtered, then the liquid was removed under reduced pressure and the product was obtained in the form of a very pale yellow oil. Patents and, 669 g, 9917%. Mass Spectrum: Oz 2 (^ S ^, (13%).1H NMR śDyDy) δ 2.82 (s, 1Η), 2.33 (Ο, J = 6.6 ^, 3H), 1.95ΜΗ), 1.83 (s, 6H), -0.04 (s , 6H). 13 C NMR (CyDyS δ 135.14, 132.7, 56.1, 27.8, 19.0, 11.0, -3.5.

b) Dilithium salt (mztylamido (dimztρlo) tetramztylcyclopzztaaiznylΌ) tilane

To the production of 1.563 g (7.463 mmol) of methylaminoχ -imztylXttramztylcyclopenzidil) silane with 65 ml of ztzzzzzzzz (1: 1) mixture, 6.03 ml of 2.60 M (15.7 mmol) butyllithium in a mixture of alkanes as solvent was slowly added. The solution changed into a thick syrup, which then formed a slurry. The reaction mixture was stirred overnight then filtered. The precipitate was washed several times with ztrzm, followed by pentane, after which it was dried under reduced pressure to give the product as a white powder. Yield 1.883 g in the form of a 0.25 ztzzonzgo adduct, as determined by spectroscopy11 H NMR. 1H NMR (THF d-8) δ 3.41 (q, 1 = 7.0¾ 1H), 2.45 (s, 3H), 2.01 (s, 6H), 1.93 (s, 6H), 1.11 (t, J = 7.01.5H), 0.01-0.14 (bz, 6H).

c) Dirhlorzk (mztylamido (dimziρlo) tetzαmztyl-η5-rρalopzntαaiznylSilanititan

To a solution of 0.6708 g (2.597 mmol) of anilithium salt (mztρloamiao (dimziylStztramztyl-η5 cyclorzntadisylSilazu in 80 ml THF) was added in one portion 0.9623 g (2.597 mmol) TiCl2 (THF) 3. The solution changed the color immediately and intensively - The reaction mixture was stirred for 4 days, after which 1.861 g (12.98 mmol) of AgCl was added The suspension was stirred for several days, after which the reaction mixture was filtered, the solvents removed under reduced pressure. The residue was extracted with toluzzism, after which the dark brown-orange-colored solution was filtered and the solvent removed. After extraction with pentane and filtration, the filtrate was concentrated to give a light brownish-wο ^ ηο ^, dark mesonized suspension. After cooling to -30 ° C, the light-yellow basvian product was separated from the porous glass, washed with pentane and dried under reduced pressure. Yield 0.3168 g, 31.4%. Ή NMR (CyDyS: δ 3.64 (s, 3H), 1.97 (s, 6H), 1.95 (s, 6H), 0.21 (s, 6H). ^ C NMR śYyDyS: δ 143, 5, 135.5, 103.0, 41.8, 15.5, 12.3, 0.6.

Polymerization

The polymerization procedure of Example LXXX was followed, using 10 e / mole of the above complex. 30.2 g of polymer were obtained.

Example XCIX - Wytnαrrαniz airhloride (mztρloamido (dimztyl-Strzmizyl-η5-cyclopropta -tazyl))

0.5705 g (2.448 mmol) of ZrCh and 0.6318 g (2.446 mmol) of salt of Smttydiozmido (dimztylSiztramzt-rl-η5-ropo-tztadizizyl-Stilaz with 75 ml of toluene) were combined in the flask, and the suspension was obtained with a few days of filtrate, for a few days, and the solvent was evaporated under pressure. The pressure was distributed in pentane, dissolved on porous glass, washed with liquid and dried under medium pressure. The product was obtained as a powder with a very pale blue color in the amount of 0.6162 g, 68.2%. 1H NMR (CDe) δ 3.50 (s, 3H), 2.49 (s, 3H), 2.36 (s, 3H), 2.14 (s, 3H), 2.10 (s, 3H) , 0.46 (s, 3H), 0.43 (s, 3H).

166 689

PrzykiadC. - Preparation of 1- (tert-butyioamido) -2- (tetrametio-η dichloride5-cyclopentadienyl) etanodiylotytanu.

a) ethyl 2- (tetramethylcyclopentadiene) ethyl acetate

A solution of 3.822 g (22.89 mmol) of ethyl bromoacetate in 25 mL of THF was cooled to -78 ° C, followed by the slow addition of 3,000 g (20.80 mmol) of sodium tetramethylcyclopentadione in 50 mL of THF. The resulting suspension was allowed to warm to room temperature and then stirred overnight. The solvent was removed and the residue was extracted with pentane and filtered. Pentane was removed to give a mixture of isomers. Yield 3.733 g (86.3%). Mass spectrum: m / e 208 (41%).

b) 2- (tetramethylcyclopentadienyl) -tert-butylacetamide

16.35 mL 2.00 M triethylaluminum (32.7 mmol) in toluene was added to 2.39 g (32.7 mmol) tert-butylamine in 50 mL toluene. The solution was stirred for 45 minutes, after which 3.40 g of ethyl 2-tetramethylcyclopentadienyl ethyl acetate were added. The reaction mixture was stirred for several days with gentle heating. After treatment with water, the amide was obtained as a semi-crystalline orange paste, as a mixture of three isomers. Mass spectrum: m / e 235 (21%).

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

The amide mixture was dissolved in 120 ml of ether, then 0.830 g (21.8 mmol) of lithium aluminum hydride was added thereto. The reaction mixture was stirred overnight with moderate heating. Analysis by GC showed that the reaction was not complete. The ether was replaced with THF, more lithium aluminum hydride was added and the solution was refluxed for several days. After treatment with water, 3 isomers of 1- (tert-butylamino) -2- (tetramethylcyclopentadienyl) ethane were obtained. Mass spectrum: m / e 221 (11%).

d) Dilite salt 1- (tert-butylamido) -2- (tetramethylene-η5-cykiopentadienyio) ethane

To a solution of 2.00 g (9.0 mmol) of isomers (tert-butylamino ^^ tetramethylcyclopentadienyl) ethane (67% 1- (tert-butylamino-2- (2,3,4,5-tetramethylcyclopentadio-2,4-enyl ) ethane, based on GC, 1.34 g (6.06 mmol) in 50 mL of ether, 6.09 mL 2.60 M (15.8 mmol) of butyllithium slowly added in a mixture of Ce alkanes as solvent, with immediate precipitation. The reaction mixture was stirred for several days and then filtered. Light yellow powder - washed several times with ether and then dried under reduced pressure. Yield 0.7908.g, 55.1H NMR (THF d-8) δ 2.43 (br m, 4H), 1.85 (s, 6H), 1.83 (s, 6H), 1.00 (s, 9H). 13 C NMR (THF d-8) δ 109.5.107.7 106.3.50.5.45.29.28.28.2 202.2 10.9.10.8.

e) Dichloride -1 - (tert-butyioamido) -2- (tetrametyio-η5-cykiopentadienyio) etanodiyiotytanu

0.3650 g (1.565 mmol) dilithium salt of 1- (tert-butylamido) -2- (tetramethylcyclopentadienyl) ethane and 0.5799 g (1.565 mmol) TiCl3 (THF) 3 in 60 ml THF were combined in the flask. The solution quickly turned green. The reaction mixture was stirred overnight, after which 1.121 g (7.82 mmol) AgCl was added. Within minutes, the color began to change to brown-orange. The suspension was stirred for 2 days after which the solvents were removed under reduced pressure. The residue was extracted with toluene, the resulting solution was filtered and the solvent was evaporated. The residue was extracted with pentane, filtered, concentrated and cooled to -30 ° C. The light orange product was filtered on porous glass, washed with a small amount of cold pentane and dried under reduced pressure. Yield 0.1904 g, 36.0%.1H NMR (C6D6) δ 4.01 (t, J = 7.2.2H), 2.58 (t, J = 7.2.2H), 2.02 (s, 6H), 1.89 (s , 6H), 1.41 (s, 9H). & Lt; 1 & gt; C NMR (CeDe) δ 138.0, 129.33 128.6, 69.1, 28.6, 24.9, 13.0, 12.3.

Polymerization 1

The procedure of Example LXXX was followed, using 1 Osmoli of the above complex. 64.8 g of polymer were obtained, with a melting index of 3.21 and a density of 926.2.

Polymerization 2

The above procedure was followed, except that 0.95 moles of dichloride (1- (tert-butylamido) -2- (tetramethyl-n) was added to initiate polymerization.5-cykiopentadienylo) ethanediyl. 11.4 g of polymer were obtained with a melt flow index below 0.1 and a density of 911.9.

Polymerization 3

The above polymerization procedure was followed, except that 2.5 ^ moles of 1- (tert-butyioamido) ~ 2- (ΐ-tetramethyl-η was added to initiate polymerization)5- cyclopentadienyl) ethanediyl titanium, dichloride. In addition, 300 ml of octene and 9-00 ml of Isopar solvent were introduced, but no hydrogen was used. 36.2 g of polymer were obtained with a melt index of 0.21 and a density of 919.0.

166 689

Polymerization 4

Polymerization 1 was repeated except that the temperature was 90 ° C. 66.7 g of polymer with a melt index of 0.16 was obtained.

-5 »Λ ^» Λ »ΜΑ / ΙΐΑ ^ 1 / \« · ί «ι 1 Ζ + Λ« · α Κ «» ^ »1λλ« »« ζΪλ \ / * Α ^ · ηΜ * Λ4 ^> τ «k® «» 1 »1 α« »α · .4α in jiwcia4: xiaaav ua ^ auma ^ aa Ae.i ^ Ai ^ uuiyjiucuiiiKAM / Ttf / ^ iCHUiaiiiitijrAU -, /" VjAJLVpvuu & 'iij mau dienyl) ethanediyl zirconium.

0.33862 g (1.657 mmol) of ZrCL and 0.3866 g (1.657 mmol) of 1- (tert-butylamido) -2- (tetramethyl-n5.-cyclopentadienyl) ethane dilite in 50 mL of toluene were combined in the flask. After stirring for several days, 1 ml THF was added and the suspension was stirred for a further 1 day, after which the solution was filtered and the solvent removed under reduced pressure. The solid residue was dispersed in pentane, filtered on porous glass and dried under reduced pressure. A pale yellow product was obtained in an amount of 0.6307 g, 99.8%. NMR (CeDe) δ 2.75 (t doublets, 1H), 2.38 (m, 2H), 2.11 (s, 6H), 2.03 (s, 3H), 2.00 (s, 3H) , 1.75 (t doublets, 1H), 1.08 (s, 9H). and3C NMR (CeDe) δ 131.5, 128.87, 126.8, 126.2, 26.9, 50.2, 79.23, 1.1, ^ A, 13.2, .

Example CII - Terpolymerization

Mixtures of ethylene, styrene and other additive polymerizable monomer were polymerized using a complex, dichloride (tert-butylamido (dimethyl) tetramethyl ^ -cyclopentadienyl diisocyanate and MAO as a cocatalyst, in an amount ensuring the atomic ratio Al: Ti 1000: 1. The reaction conditions and results are summarized table 6.

Table 6

In each case, methylaluminoxane was used as the cocatalyst, and the metal complex was (tert-butylamido (dimethyl) tetramethyl-n-dichloridee-cyclopentadienyl) titanium

<td>Attempt</td><td>Complex (Mg)</td><td>T (° C)</td><td>dissolved Thinner (Ml)and</td><td>Ethylene kPa</td><td>styrene (Ml)</td><td>olefin (G)</td><td>Time (H)</td><td>productivity POWER to (G)</td><td>Styrene mol%</td><td>Olefine mole%</td><td>mw</td><td>Mw / Mn</td>

<td> 1</td><td> 1,8</td><td> 90</td><td>I (670)</td><td> 1515</td><td> 38</td><td>butene (19)</td><td> 0,5</td><td> 51</td><td> 2,3</td><td> 6,6</td><td> 141000</td><td> 2,9</td>

<td> 2</td><td> 1,9</td><td> 90</td><td>I (630)</td><td> 1515</td><td> 76</td><td>butene (9)</td><td> 0,5</td><td> 45</td><td> 3,4</td><td> 4,5</td><td> 155 000</td><td> 2,4</td>

<td> 3</td><td> 1,9</td><td> 90</td><td>I (455)</td><td> 1515</td><td> 250</td><td>butene (5)</td><td> 0,5</td><td> 70</td><td> 7,2</td><td> 3,2</td><td> 153000</td><td> 2,4</td>

<td> 4</td><td> 2,2</td><td> 90</td><td>T (40)</td><td> 1240</td><td> 133</td><td>vinyl-BCB</td><td> 2,0</td><td> 37</td><td> 22,4</td><td> 1</td><td> 39 000</td><td> 1,7</td>

(1,5)b

a. I = have a dispersion; an alkane solvent; T = tohien

b. vinyl-BCB = vinylbenzocyclobutane

Example CIII - Suspension polymerization.

This example demonstrates the use of the catalyst of the invention under suspension polymerization conditions. The procedure of Examples XI-XXXII was followed, except that the reaction was carried out in such conditions that the polymer did not dissolve in the reaction mixture and precipitated from the reaction medium upon formation. The reaction was carried out at 70 ° C using 10 ml of octene, 1190 ml of mixed alkanes as the solvent and 5 ml of 15% MAO in toluene (Al: Ti = 1280). After 20 minutes, the reactor was evacuated to give 4.6 g of polymer. Additional solvent was added to the reactor and heated to 170 ° C to remove the polymer that had precipitated as long fibers that had wrapped around the stirrer. The melt flow index was 0.28.

Example CIV - Preparation of (tett-butylamido (dimethyl) tetramethyl-n5-cyclopentadienyl) silanititan (III).

0.24 g of TiCl3 (THF) 3 and 0.33 g of Me4 are mixed in a dry chamber5SiMe2N-tertBuMg2Cl2 (THF) 2. 15 ml THF was added to give a dark red color. After 30 minutes, the volatile components were removed under reduced pressure to give a dark colored precipitate. 15 ml toluene was added, the solution filtered and toluene removed under reduced pressure to give 0.22 g of purple powder.

Polymerization

Polymerization was carried out according to the procedure of Example LXXX, using 10 / moles of the above complex. 55.1 g of polymer with a melting index of 1.71 was obtained.

166 689

Example of a CV. Polymerization was carried out according to the procedure of Example LXXX, using W / rmon dichloride (tert-butylaamido (dimethyl) tetramethyl-η5-cyclopentadienyl) silanatitane. 76.4 g of polymer with Mw 56 700, Mw ^ Mn 4.5, density 887.1 and melt index (I2) 10,13.

CVI example. Polymerization was carried out essentially according to the procedure of Example CV, except that the temperature was 80 ° C, 2.5 / mole catalyst, 250 ml 1-octene and 950 ml mixed alkanes were used as the solvent. The reaction was carried out for 1 hour. 51.1 g of polymer with a melt index of 0.11 was obtained.

Example CVIL - Preparation of (tert-butylaamido (dimethyl) tetra-ethylcyclopentadienyl) silanehafnium dichloride.

In a dry chamber 0.50 g of HfCU was suspended in 10 ml of toluene. 10 ml THF was added, the suspension was mixed for 5 minutes, then 0.77 g Me4C5SiMe2N-tert-BuMg2Cl2 (THF) 2 was added. The solution was heated to boiling. After 30 minutes, the solution was cooled and the volatile components were removed under reduced pressure. 20 ml of pentane was added, the solution was filtered and the pentane was removed under reduced pressure to give a white solid residue. It was washed with a small amount of pentane to obtain 0.077 g (10%) of a white substance. 1H NMR (C6D6) δ 2.08 (6H), 1.30 (9H), 0.44 (6H).

Polymerization of ethylene in a manner essentially the same as in Example 7, a small amount of polyethylene is obtained.

Example CVIII (comparative). The polymerization procedure of Example CV was followed, except that pentamethylcyclopentadiethyltitanium trichloride was used as the catalyst. 4.6 g of polymer were obtained.

CIX example (comparative). The polymerization procedure of Example XCVII was followed, except that (tert-butylamido) pentamethylene dichloride was used as the catalyst75-cyklapentadienylatytanu, 1H NMR (C6D6): δ 2.07 (s, 1H), 1.88 (s, 15H), 1.35 (s, 9H). inc NMR (C6D6): δ 61.0, 31.3, 12.6. 2.0 g of polymer was obtained.

Example CX (comparative). The polymerization procedure of Example CV was followed, except that bis (tert-bstylaamido) dimethylsilanatitane dichloride was used as the catalyst. After 10 minutes of reaction, no polymer was observed.

Example CXI (comparative). The polymerization procedure of Example CV was followed, except that dicyclopentadienylcirconium dichloride was used as the catalyst. 109.0 g of polymer with Mw 16 300, Mw / Mn 3.63 and melt index, ASTM D-1238, procedure A, conditions E, over 1000 were obtained, which indicates very low molecular weight of the polymer.

Example CXII (comparative). The polymerization procedure of Example CV was followed, except that dicyclopentadienyltheryl dichloride was used as the catalyst. 7.3 g of polymer with flow index was obtained, ASTM D-1238, procedure A, conditions E, I2 over 1000, which indicates a very low molecular weight of the polymer.

Example CXIII. A catalyst mixture was prepared by combining a 2ml 0.005M toluene solution (tert-butylaamide (dimethyl) tetramethyl-η5-cyclopentadienyl) silane (dibenyyl) titanium and 2 ml 0.005M toluene solution of tris (perfluarophenyl) ram. The mixture was stirred for about 1 minute and then charged to a reactor containing 715 g of a mixture of alkanes as a solvent (Isopar E ™ from Exxon Chemicals Inc.), 170g of 1 octene, hydrogen (75 ml X 0.3 MPa) and ethylene (3, 2 MPa) at 130 ° C. Ethylene rapidly absorbed and the reactor temperature increased by 18.5 ° C. After 10 minutes of reaction, the contents of the reactor were discharged, the volatiles removed, and 110 g of ethylene / 1-octene copolymer with a melt index (MI) of 170 was obtained.

Example CXIV. To 25 ml of deaerated purified toluene was added 25 / mole (tert-butylamido (dimethyl) tetramethyl-η5-cyclapentadienyl (silano) dibenzyl) cyanate and 25 / mole tetracis (pentafluorafenyl) borate ferrate. The mixture was stirred for about 1 minute until the blue color of the solid salt of salt disappeared. 21 mixtures of alkanes as solvent (Isopar E ™) and 300 ml of 1-octene were introduced into the reactor, heated to 150 ° C and ethylene was introduced at a pressure of 3.1 MPa. All components were previously deaerated and purified. 20 ml of catalyst solution was added, resulting in immediate

166 689 rapid ethylene uptake and large reactor temperature rise (approximately 50 g ethylene per minute and 26 ° C temperature rise). After 10 minutes, the reactor contents were discharged, and volatiles removed to give 78 g of ethylene / 1-octene copolymer. The content of 1-octene in the polymer, determined by rAumo method »nfogi woe nnmAiitlo 7 ^ fó,

AVnilVTTU ^ I iilMłJy TT j AIK / UIAU> / rj uassass tt jr wu ·

CXV example. The catalyst solution was prepared by combining 1 ml of 0.005 M toluene Lewis acid solution, tris (pentafluorophenyl) borate, with 1 ml of 0.005 M toluene solution of [(tert-butylamido (dimethyl) tetramethyl-n5-cyclopentadienyl) silane) dibenzyl) titanium [^ Me ^ SiMe, ^^^^^,] (prepared by the reaction of dichloride (tert-butylamido (dimethyl) tetramethyl ^ -cyclopentadienyl diisocyanate and benzyl lithium. In turn, dichloride was prepared by reacting lithium 1,2,3,4-tetramethylcyclopentadiene with (Nt-butyldimethyl) silane chloride, followed by conversion of the dilite salt, reaction with TiCl to form a closed ring structure of (Nt-butylamido (dimethyl) tetramethyl-n5 chloride -cyclopentadienyl) titanium and central metal oxidation with methylene chloride to give (Nt-butylamido (dimethyl) tetramethyl-n5-cyclopentadienyl) titanium dichloride). The mixture was shaken for 10 seconds at 25 ° C to give a catalyst solution clearly darker than the initial red-orange solution containing titanium.

The catalyst solution was combined with a mixture of Isopar E ™ solvent, 0.211-octene and ethylene (3.1 MPa) in the 21 reactor. The reactants were previously deaerated and purified and the reactor contents heated to 130 ° C. The temperature in the reactor immediately increased by 7 ° C. Ethylene was supplied as needed to maintain a pressure of 3.1 MPa. After 10 minutes, the reactor contents were discharged, the volatiles removed, and 80.0 kg of ethylene / octene copolymer with a flow rate of 0.104 was obtained.

CXVI example. A catalyst solution was prepared by combining 1 ml of a 0.005 M toluene Lewis acid solution, tris (p-fluorophenyl) borate with 1 ml of a 0.005 M toluene solution of (tert-butylamldo (dichloromethyl) tetramethyl-η5-cyclopentadienyl) silane) dljzyl Zirconium [Si] Bu)] ZrBz5] (produced by the same technique as in the example CXV). The mixture was shaken for 10 seconds at 25 ° C to give a catalyst solution slightly darker than the light yellow stock solution containing zirconium.

A solution of 10 / mole catalyst in 2 ml of Isopar E ™ solvent was combined with a mixture of 0.81 Isopar E ™ solvent and 0.41 propylene in the 21 reactor. The reactor contents were heated to 50 ° C. After 45 minutes, the reactor contents were discharged, the volatiles removed, and 30.1 g of polypropylene with a 24.3 melt index and a syndiotacticity index of 83.5 (measured with respect to racemic triads) was obtained.

Example CXVII. Polymerization was carried out as in Example CXVI, using 1.25 / m (tert-butylamldo (dlmethyl) tetamethyl-η5-cyclopentadienyl) sllane (dibjzyl) titanium, [(C6Mj4) SiMe2N (t-Bu)] TlBz2, and 1.25 / / m Lewis acid, 13 (061,) 3, mixed black in 2 ml Isopar E. The reaction temperature was 160cC. 10g propylene was added and hydrogen was introduced, increasing the pressure by 0.7 MPa. The ethylene pressure was 3.3 MPa. Polymerization was carried out for 15 minutes. 22.9 ethylene / propylene copolymer was isolated.

Example CXVIII. Polymerization was carried out as in Example CXVII, using 1.00 / m (tert-butylamldo (dimethyl) i.e.tramethyl-η5-cyclopentadenyl) dimethylsilane (dlmethyl) titanium, [(CeMj4) SlMe2N (t-Bu)] TlMj2, and 1.00 / m Lewis acid, B ^ F,)), mixed in 2 ml of Isopar E solvent. The reaction temperature was 90 ° C. 1000 ml of Isopar E and 200 ml of 1-octene were charged to the reactor without adding hydrogen. The ethylene pressure was 3.55 MPa. The polymerization lasted 15 minutes. 85.9 g ethylene / octene copolymer with an approximate density of 0.87 g / ml and a melt index (I2) of 0.3 were obtained.

CXIX example. Polymerization using a dimethyl derivative (tert-butylamido (dimethyl) tetrahydrofluoreno) silanotitane.

Preparation of tetrahydrofluoren g (90.2 mmol) of fluene was dissolved in 200 ml of tetrahydrofuran (THF) and ethylenediamine solution in a 1: 1 ratio. The solution was cooled in an ice bath and 3.13 g of lithium (451.2 mmol) was added in small portions while stirring. After all the lithium was added, the solution was stirred for 2 hours, resulting in a dissolution of lithium metal. The resulting solution was poured into an HCl / ice mixture. The solution was then extracted with diethyl ether. The organic washes were combined, washed with water and dried over MgSO4. The solution was filtered and the solvent removed

166 689 on a rotary evaporator. The crude material was purified by dissolving in hexane and passing through a silica gel column. 11.4 g (75% yield) of product were obtained after removal of the solvent.

Preparation of tesrahydrffϊzrenyl /,fox g tetrahydrofluoren (59 mmol) was dissolved in 75 ml of pentane. 21 ml (2.65 M) n-butyl are added dropwise to the resulting solution over 20 minutes. The solution was stirred overnight, then the precipitate collected was collected by filtration, washed with pentane and dried under reduced pressure. 7.14 g (70% yield) of product were obtained.

Preparation of (N-terS-butylαminz (dimethylz) teSrahydrofluorenyl) sllaau.

5.78 g (34.9 mmol) of ClSiMe2NHCMe3 (prepared by the method described in J. Prakt. Chem., 24 (3-4), 226-30 (1964)) was added to 100 mL of tHf. To the resulting solution, 6.15 g (34.9 mmol) of lithium teSrαhydrofluzreak were added. The solution was then refluxed for 10 minutes and cooled to room temperature. Gas chromatography (GC) showed that the reaction was complete. The solvent was removed under reduced pressure and the residue was extracted with pentane, filtered and the solvent removed again under reduced pressure. 9.80 g of product were obtained (94% yield).

Preparation of (N-teΓt-buSylamldo-dimimeSylzXSeSrαhydrofluorenyl) allnodllite.

9.80 g (32.8 mmol) (N-terS-butylaminz) (dimethyl) (tetrahydrofluorophenyl) silane were dissolved in 100 g of diethyl ether. 26.6 ml (70.6 mmol) nBuLi (2.65 M) was added dropwise to the resulting solution. After the addition was complete, the solution was stirred for 2 hours, then the solvent was removed under reduced pressure to give an orange oily residue which solidified on trituration with pentane to give 11.86 g (98%) of a yellow solid which was identified by NMR as an adduct (Nt -butylαmino) (dimethyl) (Setrahydrzfluorenyl) ailaaedilite with ether (3/4 Et2O per molecule).

Preparation of [(Nt-butyl-methyl-dimethyl-tetrarahydrofluorenyl) sila-o]-titanium dichloride.

([(Tetrahydrofluorenylo) SiMe2N (t-Bu)] TiCl 2).

6g (16.1 mmol) TiCl3 (THF) 3 was dissolved in 75 ml tetrahydrofuran. To the resulting solution, 5.92 g (16.1 mmol) of solid ether adduct (N-t-butylamido-dimethyl-zetrahydrofluzyl) silanedilite (3/4 Et2O) was added while stirring. The solution was stirred for 45 minutes, then 2.25 g (8.1 mmol) PbCl was added, and the solution was stirred for 45 minutes. Tetrahydrofuran was removed under reduced pressure. The residue was triturated with pentane and the solution was cooled to -20 ° C over 3 hours. The red precipitate was collected by filtration, washed with cold pentane and dried in vacuo. 5.00g (75% yield) of product were obtained.

Preparation of [(Nt-butylamido) (dimeSylzχsetrahydrofluzrenyl) silano] dlmeίyl titanium ([(teSrahydrffluorenyto) SiMe2N (- Bu)] Ti (CH3) 2)

5.0 g of a suspension of [(Nt-butylamidimethyl dimethylXteSrahydrzfluorenyl) ailanz] titanium dichloride (12 mmol) in 100 ml Et, O. was suspended. 8.40 ml of methylmagnesium iodide (MeMgJ) (3.0M solution in diethyl ether, Et2O) were added to the suspension over 20 minutes with stirring. After the addition, the solution was stirred for 40 minutes. Then Et0O was removed under reduced pressure and the residue was extracted with pentane. The solution was filtered and the filtrate evaporated to dryness under reduced pressure to obtain 3.48 g (77% yield) of the product.

Polymerization

Polymerization was carried out according to Example CXVII using 2.00 moles [(t2trahydrofUto2enyto) SiMe2N (t-Bu)] Ti (CH3) 2 and 2imols of Lewis acid, B ^ Fs ^, mixed in 2 ml of Isopar E. The reaction temperature was 130 ° C . 808 g of Isopar E and 100 g of 1-octene were charged into the reactor. No hydrogen added. The ethylene pressure was 3.55 MPa. The polymerization lasted 15 minutes. 41.1 g of ethylene / octene copolymer was isolated.

Example CXX.

Polymerization using a dimethyl derivative (tert-butylamido (dimethyl) 1,3-dimethylSylz-5,6,7,8-tetrahydiadenyl) silanththane,

Preparation of 4,5,6,7 - eerahydro-1-meSyl-inda-3-Zn

27.3 g (0.30 mo3 a) of cyclohexene, 2n, 7 2 {0.30 mm crotonic acid and 30 ml of diphosphoric acid were stirred mechanically under nitrogen at 60 ° C for 30 minutes. The suspension

166 689 was poured into water and the aqueous solution was extracted with diethyl ether. The extract was washed successively with 10% NaHCOa solution and saturated NaCl solution. The organic extract was then dried over anhydrous MgSO4. The solution was filtered and the solvent was evaporated under reduced pressure, after which the crude product was purified by vacuum distillation (bp 87-92 ° C at 6.66 X 2 Pa) to obtain 32.6 g (66%) of the purified product.

Production of 7,9-dimethylbicyclic> [4.3.0] -ηοηΗ-1 (6), 7-diene

To a solution of 17.7 g (0.118 mol) 4,5,6,7-tetrαhydro --- methyl-indαπ-3-one in 50 ml diethyl ether was added dropwise under argon 96 ml (1.5 M) methyllithium. the reaction mixture was heated to reflux for 18 hours. The mixture was then hydrolysed and extracted with diethyl ether. The ether extracts were dried over anhydrous MgSO 4 and filtered. 0.5 ml of 6M HCl was added to the ethereal solution, and the solution was stirred for 1 hour. The ether solution was then washed with water, dried over anhydrous MgSO 4, filtered and concentrated. After distillation under reduced pressure, 8.0 g (45%) of product was obtained.

Preparation of 1,3-dimethyl-5,6,7,8-errahydroindenyllithium

To 100 ml of pentane (5.0 g, 33.5 mmol) was added 7,9-dimethylbicyclic [4.3.0) -nona-1 (6), 7-dirne. 13 ml (2.7 M) of n-BuLi in pentane solution was added dropwise to the resulting solution, and the mixture was stirred for 12 hours. The resulting white precipitate was collected by filtration, washed with pentane and dried under reduced pressure. 5.02g (97%) of product were obtained.

Preparation of (Nt-butylaminoXdSmethyl) (1,3-dimethyl-5,6,7,8-etrahydroindrinyl) silane

0.77 g (4.67 mmol) ClSiMeaNHCMea was added to 50 mL THF. 0.75g (4.67 mmol) 1,3-dimethyl-5.6 was added to the resulting solution)7.8 - etrraiydroindenylolitu. The solution was then heated to reflux for 10 minutes and then cooled to room temperature. Gas chromatography (GC) showed that the reaction was completed. The solvent was removed under reduced pressure, the residue was extracted with pentane, filtered and the solvent removed again under reduced pressure. 1.21 g of product were obtained (94% yield).

Preparation of (N-butylamido X-dimethyl), 3-dimethyl-5,6,7,8-etrahydroindrinyl) silanedilite

1.21 g (4.36 mmol) (Nt-butylamino) (dimethyl-1,3-dimethyl-5,6,7,8-t-tetrahydroindrinyl) silane were dissolved in 100 ml of diethyl ether. 5.72 ml (9.15 mmol) nBuLi (1.6 M solution in pentane) was added dropwise to the resulting solution. After the addition was complete, the solution was stirred for 2 hours before the solvent was removed under reduced pressure to give an oily yellow residue which solidified on trituration with pentane. 1.00 g (79% yield) of a brown solid were obtained.

Preparation of [(Nt-butylamidoX-dimethyl-1,3-dimethyl-5,6,7,8-ethahydroindenyl) silane] titanium dichloride [[1,3-dimethyl tetrahydroindenyl) SiMe2N (t-Bu)] TiCl2)

0.64 g (1.72 mmol) TiCl2 (THF) 3 was dissolved in 75 mL THF. To the resulting solution, 0.50 g (1.72 mmol) of (Nt-butylamido-dimethylX 1,3-dimethyl-5,6,7,8-tetrahydroindenyl) silanolite was added as a solid while stirring. The solution was stirred for 45 minutes then PbCl2 (0.239 g, 0.86 mmol) was added and stirred for 45 minutes. THF was then removed under reduced pressure and the residue was extracted with toluene. The solution was filtered and toluene removed under reduced pressure. The residue was then triturated with pentane and cooled to -20 ° C for 3 hours. The product was collected by filtration and washed with cold pentane and dried in vacuo. 0.32 g of product was obtained (47% yield).

Preparation of [(Nt-butylamidoX-dimethyl-1,3-dimethyl-5,6,7, -tetrahydroindrinyl) silano] (dimethyl) titanium ([(1,3-dimethyl-tetrαhydromdenite) SiMe2N (t-Bu)] Ti (C ^ 3 ) 2)

0.32 g (0.81 mmol) of dichloride (Nt-butylαmSdoXdSmethylX1,3-dimethyl-5,6,7,8-etrahydroindrinyl) siianitanium was suspended in 40 ml Et2O. 0.56 ml MeMgJ (3.0 M solution in diethyl ether) was added dropwise to the resulting suspension with stirring for 20 minutes. After the addition was complete, the solution was stirred for 40 minutes, after which the Et 2 O was removed under reduced pressure and the residue was extracted with pentane, the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 0.21 g (73% yield) of the product.

166 689

Polymerization

The process according to example CIII was carried out, with the difference that 0.50 pm [(1,3-dimethyl-tetrahydroindenyl) SiMe2N (t-Bu)] Ti (CH3) 2 and 0.5 μΰι acid was used for the preparation of the mixture of catalyst and cocatalyst Lewis B ^ Fs) », mixed in 2 ml of Isopar E solvent. The reaction temperature was 120 ° C. 797 g of Isopar E solvent and 61 g of 1-octene were charged to the reactor and hydrogen was added to a pressure increase of 0.14 Pa. The ethylene pressure was 3.55 MPa and the polymerization time was 10 minutes. 29.2 g ethylene / octene copolymer was isolated. The micro flow indicator (I2) was 0.975.

Example CXXI.

The process of Example CXX was carried out with the difference that 0.10pm [(1,3-dimethyl-tetrahydroindenyl) SiMe2N (t-Bu)] Ti (CH3) 2 and 0.10pm Lewis acid, B (C6F5) 3, mixed in 2 ml of Isopar E solvent. The reaction temperature was 90 ° C. -715g of Isopar E and 143 g of 1-octene were charged to the reactor and hydrogen was added to a pressure increase of 0.07 MPa. The ethylene pressure was 3.45 MPa. The polymerization lasted 10 minutes. 64.5 g of ethylene / octene copolymer and a rate of (I2) 0.346 were isolated.

Example CXXII.

The process of Example CXXI was carried out with the difference that 2.00μτα [(tetrahydrofluorenyl} -SiMe2N (t-Bu)] Ti (Bz) 2 (prepared by reaction of [(N- * t-butylamidoXdimethylXtetrahydrofluorenyl) silane]] was used to prepare the catalyst. titanium with benzyl magnesium chloride) and 2.0 pm Lewis acid B ^ Fs ^, mixed in 2 ml Isopar E. The reaction temperature was 150 ° C. 822 g of Isopar E and 36 g of 1-octene were charged to the reactor and hydrogen was added to increase the pressure by 0.07 MPa. The ethylene pressure was 3.55 MPa. The polymerization lasted 15 minutes. 20.1 g ethylene / octene copolymer was isolated, with a melting index of I2, 0.327.

Example CXXIII.

Polymerization using (t-butylamido (dimethyl) t-butyl-n5-cyclopentadienyl) silano (dimethyl) titanium t-butylcyclopentadienyl lithium

To a solution of 4.18 g (39.4 mmol) of 6,6-dimethylfulvene in 80 mL diethyl ether at 0 ° C was added 22.9 mL of 1.72 M (39.4 mmol) solution of methyllithium in ether. The resulting suspension was stirred for several days, then filtered, washed with pentane and dried in vacuo.

and N-t-butylamino) (dimetyloχt-butyiocyklopentadienylo) siian

To a solution of 3.35 g (20.2 mmol) (Nt-butylamiexchloro) dimethylsilyl in 75 mL THF was added 3.58 g (17.7 mmol) of tert-butylcyclopentadienyl lithium ether. The reaction mixture was stirred for several hours. The solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed in vacuo to give 2.87 g of product as a pale yellow oil in 64.6% yield.

[(Nt-butyloamidoχdimetyloχt-butyiocyklopentadienylo)] silanodiiit

To a solution of 2.87 g (11.4 mmol) (N-t-butylamieldimethyl-t-butyl-cyclopentadienyl) silane in 70 mL ether was added 15.8 mL of 1.48 M (23.4 mmol) solution in hexane. The resulting clear solution was stirred overnight, after which the solvent was removed under reduced pressure. 107% of the impure product was obtained.

Dichloride [(t-butylamidoX-dimethylXt-butyl-n5-cyclopentadienyl) silane] titanium and [(t-butyio-C5H3) SiMe2N (t-Bu)] TiCl 2)

0.60 g (2.27 mmol) of solid [(Nt-butylamidoXdimethylXt-butylcyclopentadienyl] silanedilite and 0.84 g (2.27 mmol) of solid TiCl3 (THF3) were combined in the flask. 40 ml of THF were added. The resulting dark purple solution was stirred for 10 minutes then 0.35 g (1.25 mmol) PbCl2 was added The reaction mixture was stirred for less than an hour, after which the intense orange-brown color reaction mixture was filtered and the solvent removed under reduced pressure. The residue was extracted with pentane, and the solution was filtered and concentrated until a solid started to form. The suspension was cooled in the refrigerator overnight, filtered through a glass frit and the yellow product collected, which was washed with pentane and dried under reduced pressure. 0.58 g of product was obtained (with 69.6% yield).

[(Butyloamidoχdimetyloχt t-butyl-η5-cyclopentadieeio) silano] dimethyl titan and [it-butyl-C5H3) SiMe2N (t-Bu)] Ti (CH3) 2)

166 689 37

0.80 mL of 2.78 M (2.22 mmol) of a solution of methylmagney iodide in 15 mL of ether were slowly added over 20 minutes to 0.41 g (1.11 mmol) of dichloride [(t-butylamldo) (dimethyl) (t- butyl-η5..cycapentadienyl) silane] titanium in 15 ml ether. The solution was stirred for 20 minutes after which the solvent was removed. The residue was extracted with pentane and the resulting solution was filtered and sought for the formation of an oil which crystallized on standing. 0.34 g of product was obtained (with a yield of 94.6%).

Polymerization

Polymerization was carried out according to example CXXIII using 0.25 / m [(t-butyl-C5H3) SiMe2N (t-Bu)] Ti (CH ^ 3) 2 and 0.25 / m Lewis acid, B (C6F5) 3, mixed in 2 ml of E-copar. The reaction temperature was 80 ° C. 1000 ml of Isopar E, 100 g of propylene were introduced into the reactor and hydrogen was added to a pressure of 0.34 MPa. The ethylene pressure was 3.38 MPa and the polymerization time was 10 minutes. 6.3 g of ethylene / propylene copolymer was isolated with a melting index of I2 1.291 and a density of 0.8868 g / ml.

Example CXXIV. Ethylene / norbornene copolymer

Polymerization was carried out according to example CXVIII using 1.25 / m [(C5Me4) SiMe2N (t-Bu)] Ti (CH3) 2 and 1.87 / m Lewis acid, B (C6Fs) 3 mixed in 2 ml to produce the catalyst Isoparu E. The reaction temperature was 140 ° C, 808 g Isoparu E was added,

19.5 g norbornene and hydrogen for an increase of 0.17 MPa. The ethylene pressure was 3.55 MPa and the polymerization time was 10 minutes. 41.3 g of an e-tylene / norbornene random copolymer with a melt index (I2) of 0.587 was isolated. The polymer contained 2.38 wt. norbornene, as determined by the method13C NMR.

Example CXXV.

Polymerization using phenyl bis (perflsorophenyl) borate as Lewis acid

Production B ^ Fs ^^^)

250 the ml flask was evacuated, cooled to -78 ° C and charged with 120 ml hexanes as solvent. The flask was filled with argon to a pressure of 0.11 MPa and 10.00 g (40.5 mmol) of bromacentafluarobenzene (from which oxygen was removed by purging with nitrogen) were added using a syringe. Mixing of the mixture was started with a magnetic stirrer and a transparent colorless solution was obtained, to which was added by means of a syringe 16.2 ml of a 2.5 M solution of n-buytilite (40.5 mmol) in hexane. When n-bntioliolite was added, a transparent colorless precipitate separated from the mixture. The suspension was stirred at -78 ° C for 70 minutes, then 3.22 g (20.3 mmol, 0.50 equiv) dichlorophenylboron were added from the syringe. After stirring for a further 30 min at -78 ° C, no change was observed and the mixture was allowed to warm to ambient temperature. When the mixture warmed up, a thick white precipitate formed. After stirring at 22 ° C for 15 minutes, the flask was connected to vacuum and the volume of the mixture was reduced to 50 ml. The mixture was filtered, the precipitate extracted with three 20 mL portions of mixed hexane solvent, and the volume of filtrate was reduced to 20 mL under reduced pressure. The resulting solution was cooled to -78 ° C and a very thick colorless suspension of crystallization of the solid was obtained. The suspension was diluted with 20 ml hexane. The solid was collected by filtration and dried under reduced pressure. 4.86 g of product are obtained in 57% yield.

Polymerization

Polymerization was carried out according to Example CXVII except that 850 ml of Isopar E was added to the reactor followed by 20 g of propylene. Then hydrogen was added to a pressure increase of 0.17 KPa and the solution was heated to 130 ° C, after which it was saturated with ethylene to a pressure of 3.55 MPa. 10 / m metal complex, [(C5Me4) SiMe2N (t-Bu)] TiMe2, and 10 / m Lewis acid, B (CeF5) 2 ^ CeH5) were mixed in 2 ml of Isopar E and the resulting solution was transferred to the reactor to start polymerization . The reaction ran for 15 minutes with ethylene feed such that the pressure was 3.55 MPa. 2.8 g of ethylene / propylene copolymer with a melting index of 1.2.52 were obtained.

Example CXXVI. Ethylene / ethylidenenarbornene copolymer

The process according to example CXXIV was carried out by introducing in two successive portions the catalyst solution prepared by mixing 50 / m [(C5Me4) SiMe2N (t-Bu)] Ti (CH ^) 2 and 5.0 / m Lewis acid, B (C6F5) 3, in 2 ml Isopar E. The reaction temperature was 130 ° C. A solution of 1200 ml containing 50 ml of 5-ethylidene-2-norbarnene in Isopar E i was added

166 689 hydrogen for a pressure increase of 0.34 MPa. Ethylene pressure was 3.38 MPa. Polymerization time was 20 minutes. 59.9 o. Aorolimzz ztyleiz / 5-ntylidene-2-norbornnes with a melt index, I2, 1.55 were isolated. The polymer contained 9.06% by mass. 5-ethyldene-2-norboznznUi as determined by 13 C NMR.

smrcja mosmms with zaKMMia pmstrs & m hresser egandsegon types. *>

Gfowa Insignia for general and dazwdon

Scheme

FIG.2

FIG.3

FIG.4

ΛΜβ

FIG.5

6 discloses

F8G.7

FI6.8

aoaasfasijesasaaaiOEitswijssMwsijtsaisjsijgajJsassJsaiJa

ABOUT

166 689

FI6.9

49 48 47 46 45 44 43 42 4140 39 38 37 36 35 34 33 32 31 39 29 20 27 23 2S 24 23 22 21 20

FIG.1O

FIG.II

SS S4 8838 81S9® 23 89 S3S30 233881 ^

FIG.I2

S04 »48 47 464S 44 43 42 4l 49 39 38 37 M3SM39 33 31 38 2S2Q37tt2S34S922 2e28

FIG.I3

S3 «S4347 <SeS <44341 41« 9 »£ 83;! 3 & 29»)! 9ΒΙ £ 3232327232524291211

FIG.I4

166 689

FIG.I6

1400

100 AT..... .1

001 about

U ...... ........ 1

100 1400

166 689

UP Department of Publications. NaWai 90 copies Price PLN 1.00

Contents15

638 members in 39 offices

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Document	Office	Kind	Date
40134489	United States of America	A	1989-08-31
40134489	United States of America	A	1989-08-31
40134589	United States of America	A	1989-08-31
40134589	United States of America	A	1989-08-31
42808289	United States of America	A	1989-10-27
42808289	United States of America	A	1989-10-27
42827689	United States of America	A	1989-10-27
42827689	United States of America	A	1989-10-27
42828389	United States of America	A	1989-10-27
42828389	United States of America	A	1989-10-27
43652489	United States of America	A	1989-11-14
43652489	United States of America	A	1989-11-14
54540390	United States of America	A	1990-07-03
54540390	United States of America	A	1990-07-03
90545403	–	–	–
US19890401344	–	–	–
US19890401345	–	–	–
US19890428082	–	–	–
US19890428276	–	–	–
US19890428283	–	–	–
US19890436524	–	–	–
US19900545403	–	–	–

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JPS63141702A	Japan	A	1988-06-14
DE3741002A1	Germany	A1	1988-07-14
JPS63221010A	Japan	A	1988-09-14
NO903797D0	Norway	D0	1990-08-30
JPH0248404B2	Japan	B2	1990-10-25
CA2024333A1	Canada	A1	1991-03-01
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NO954469L	Norway	L	1991-03-01
AU6203990A	Australia	A	1991-03-07
CN1049849A	China	A	1991-03-13
EP0416815A2	European Patent Office (EPO)	A2	1991-03-13
HU905704D0	Hungary	D0	1991-03-28
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IL95542D0	Israel	D0	1991-06-30
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BR9004460A	Brazil	A	1991-09-10
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ZA906969B	South Africa	B	1992-05-27
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Showing 100 of 638

Method of obtaining a coordination metal complex, catalyst for additive polymerization and method for obtaining such catalyst as well as additive polymerization process

Abstract

Term

FIG.2

FIG.3

FIG.4

FIG.5

F8G.7

FI6.8

ABOUT

FI6.9

FIG.1O

FIG.II

FIG.I2

FIG.I3

FIG.I4

FIG.I6

U ...... ........ 1

Priority claims22

Members638

Events

Numbers

Titles

Classification