A ligand for a metallocene catalyst used to prepare propylene based polymers, and its preparation method

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DESCRIPTION

Ligand for a metallocene catalyst to make polymers based on propylene and method of obtaining the same.

The present invention relates to ligands useful as intermediates for the synthesis of a class of metal complexes used in a high throughput process to produce propylene-based, substantially amorphous polymers having high molecular weights.

Metallocene compounds are well known in the state of the art as catalyst components in olefin polymerization reactions, in association with appropriate cocatalysts, such as alumoxanes or aluminum derivatives. For example, European patent EP 0 129 368 describes a catalyst system for the polymerization of olefins, consisting of a bis-cyclopentadienyl coordination complex with a transition metal, in which the two cyclopentadienyl groups can be linked by a divalent bridging group, for example an ethylene or dimethylsilanediyl group.

Another class of polymerization catalysts known in the state of the art are cyclopentadienyl amido bridged catalysts, which usually include monocyclopentadienyl titanium compounds, activated by an alumoxane or other appropriate co-catalysts (see, for example, EP 0 416 815 and EP 0 420 436).

In the international patent application WO 98/22486, in the name of the same applicant, bridged and unbridged metallocenes are described, which comprise at least one coordinating group, which contains a central residue of six π electrons, which directly coordinates an atom of transition metal, to which one or more radicals containing at least one non-carbon atom are attached, selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te. Such metallocenes are useful as catalyst components for the production of polyethylene and propylene.

International patent application WO 98/37106 describes a polymerization catalyst system consisting of a catalytic complex formed by activation of a transition metal compound, consisting of a group 13, 15 or 16 heterocyclic fused cyclopentadienido ligand and by a metal chosen from the group consisting of metals in groups 3-9 and 10; said heterocyclic fused cyclopentadienido ligand preferably contains, as endocyclic heteroatoms, one or more atoms of B, N, P, O or S.

In the international patent application WO 99/24446, in the name of the same applicant, bridged and non-bridged metallocenes are described, comprising at least one heterocyclic cyclopentadienyl group of one of the following formulas:

<img file="ES2326537T3_D0001.tif" />

wherein one of X or Y is a single bond, the other is O, S, NR, or PR; R is hydrogen or a hydrocarbon group; R², R³ and R⁴ are hydrogen, halogen, -R, -OR, -OCOR, -SR, -NR₂ or -PR₂; a is a number from 0 to 4. These metallocenes can be used as catalyst components in olefin polymerization, especially for the production of ethylene homo- and copolymers.

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International applications WO 98/06727 and WO 98/06728 describe metal complexes containing cyclopentadienyl substituted with a heteroatom in position 3 and in position 2, respectively, which are useful as catalysts for olefin polymerization; more specifically, these complexes contain a heteroatom-Cp bond at position 3 and position 2 of Cp, respectively, and are used for the manufacture of ethylene / 1-octene copolymers.

Applicant has now found, unexpectedly, ligands useful as intermediates for the synthesis of a class of metallocene compounds useful as catalyst components for the polymerization of propylene, capable of producing substantially amorphous, high-grade propylene (co) polymers. molecular weight, in high yields.

The present invention relates to a ligand of formula (II)

<img file="ES2326537T3_D0002.tif" />

<img file="ES2326537T3_D0003.tif" />

in which:

X is a nitrogen or phosphorous atom;

Z is a C, Si or Ge atom; Y² is chosen from the group formed by CR⁸ and Y¹; and m is the number 0 or 1; when group Y² is a CR group⁸, m is number 1 and the 6 membered ring formed is an aromatic benzene ring; when and² is different from CR⁸, m is the number 0 and the carbon atom that joins the group R⁴ is directly attached to the cyclopentadienyl ring and the ring formed is a 5-membered ring; the R groups¹, equal to or different from each other, are chosen from the group consisting of hydrogen, a C1-C20 linear or branched, saturated or unsaturated alkyl radical, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 arylalkyl that optionally contain Si or heteroatoms belonging to groups 13 or 15-17 of the Periodic Table of the Elements or two R groups¹ together they form a C4-C ring_7;

Y¹ is an atom selected from the group consisting of NR⁷, oxygen (O), PR⁷ or sulfur (S), in which the R group⁷ is selected from the group consisting of a C alkyl moiety₁-C₂₀ linear or branched, saturated or unsaturated, aryl C₆-C₂₀and arylalkyl C₇-C₂₀;

the R groups² and R³ are the same or different from each other and are selected from the group consisting of hydrogen, halogen, -R, -OR, -OCOR, -OSO2CF3, -SR, -NR2 and -PR2, in which R is a C1 -C20 alkyl moiety straight or branched, saturated or unsaturated, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl; two R's can also form a saturated or unsaturated C4-C7 ring, R is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, pn-butyl-phenyl or benzyl residue or R² and R³ form a C4 -C aromatic or aliphatic ring₇ condensate, which may be substituted by one or more R groups⁹, in which R⁹ is selected from the group consisting of halogen, -R, -OR, -OCOR, -OSO₂CF₃, -SR, -NR₂ and -PR₂, in which R has the meaning indicated above, or two R groups⁹ neighbors together form a fused C4-C7 aliphatic or aromatic ring;

the R groups⁸, R⁴ and R⁵ are the same or different from each other and are selected from the group consisting of hydrogen, halogen, -R, -OR, -OCOR, -OSO2CF3, -SR, -NR2 and -PR2, where R has the meaning defined above, or R⁸ and R⁴, R⁴ and R⁵ or R⁵ and R⁸ together they form a C ring₄-C₇ condensed, which may be optionally substituted by one or two R groups;

ES 2 326 537 T3 group R⁶ is selected from the group consisting of a Ci -C alkyl moiety₂₀ linear or branched, saturated or unsaturated, aryl C₆-C₂₀ and arylalkyl C₇-C₂₀, optionally containing heteroatoms belonging to groups 13 or 15-17 of the Periodic Table of the Elements; these ligands are especially useful as intermediates for obtaining the titanium complexes described in (patent application) EP-1 159 310.

The titanium complexes of the formula (I) can conveniently be used in the form of complexes, for example in the presence of coordination molecules of the Lewis base type.

The preferred complexes of the formula (I) are those belonging to the three classes (1), (2) and (3), having the formulas (III), (IV) and (V), respectively.

Class (1)

Titanium complexes belonging to class (1) have the following formula (III):

<img file="ES2326537T3_D0004.tif" />

where X, Z, Y¹, L, R¹, R², R³, R⁴, R⁵, R⁶ and R⁸ have the meanings defined above, provided that R² and R³ do not form an aromatic or aliphatic C ring₄ C₇ condensed.

Preferably, in the titanium complexes of formula (III):

X is a nitrogen atom; the divalent bridge> ZR¹₂ is preferably selected from the group consisting of dimethylsilyl, diphenylsilyl, diethylsilyl, di-n-propylsilyl, di-isopropylsilyl, di-n-butylsilyl, di-tert-butylsilyl, di-n-hexylsilyl, ethylmethylsilyl, n -hexylmethylsilyl, cyclopentamethylenosilyl, cyclotetramethylenosilyl, cyclotrimethylenosilyl, methylene, dimethylmethylene and diethylmethylene; and, more preferably, it is dimethylsilyl, diphenylsilyl or dimethylmethylene;

Y¹ is N-methyl, N-ethyl or N-phenyl;

R² and R³, equal to or different from each other, they are selected from the group consisting of hydrogen, halogen, -R, -OR, -OCOR, -OSO2CF3, -SR, -NR2 and -PR2; more preferably, R² is hydrogen, methyl, ethyl, propyl, or phenyl; and R³ is hydrogen, methyl or phenyl; even more preferably, R² is hydrogen or methyl;

R⁴ and R⁸ they are hydrogen or methyl;

R⁵ is hydrogen, methoxy or tert-butyl;

R⁶ selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, pn-butylphenyl, benzyl, cyclohexyl, or cyclododecyl; more preferably, R⁶ is tert-butyl;

the substituents L, the same or different from each other are preferably halogen atoms, C7C alkylaryl groups₂₀ linear or branched, saturated or unsaturated, C alkyl groups₁ -C₆, or OR, where R has the meaning described above; more preferably the L substituents are Cl, CH₂C₆H₅, OCH₃ or CH₃.

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Examples of complexes of formula (III) are:

<img file="ES2326537T3_D0005.tif" />

and the corresponding complexes of titanium dichloride or dimethoxide.

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Titanium complexes belonging to class (1) can be obtained from the ligands of formula (IIIa)

<img file="ES2326537T3_D0006.tif" />

i⁶ (girl) in which X, Z, Y¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁸ and R⁹ have the meaning defined above.

Class (2)

Titanium complexes of class (2) have the following formula (IV)

<img file="ES2326537T3_D0007.tif" />

(IV) in which X, Z, Y¹, L, R¹, R⁴, R⁵, R⁶ and R⁸ have the meaning defined above and k is a number between 0 and 4.

Preferably, in the titanium complexes of formula (IV):

X is a nitrogen atom; the divalent bridge> ZR¹₂ is preferably selected from the group consisting of dimethylsilyl, diphenylsilyl, diethylsilyl, di-n-propylsilyl, di-isopropylsilyl, di-n-butylsilyl, di-tert-butylsilyl, di-n-hexylsilyl, ethylmethylsilyl, n -hexylmethylsilyl, cyclopentamethylenosilyl, cyclotetramethylenosilyl, cyclotrimethylenosilyl, methylene, dimethylmethylene and diethylmethylene; and, still more preferably, it is dimethylsilyl, diphenylsilyl or dimethylmethylene;

Y¹ is N-methyl, N-ethyl or N-phenyl;

k is the number 0 or 1 and R⁹ is methyl, 2-isopropyl or tert-butyl;

R⁶ selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, pn-butylphenyl, benzyl, cyclohexyl, and cyclododecyl; more preferably, R⁶ is tert-butyl;

R⁴, R⁵ and R⁶ they are hydrogen atoms;

the substituents L, the same or different from each other, are halogen atoms, C-alkyl groups₁ -C₆ linear or branched, saturated or unsaturated, C alkylaryl groups₇-C₂₀ or OR, where R has the meaning described above, more preferably the L substituents are Cl, CH3, OCH3 or CH2C6H5.

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Examples of titanium complexes of formula (IV) are as follows:

<img file="ES2326537T3_D0008.tif" />

and the corresponding titanium dichloride or dimethoxy complexes.

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Titanium complexes belonging to class (2) can be obtained from the ligand of formula (IVa):

<img file="ES2326537T3_D0009.tif" />

where X, Z, Y¹, R¹, R⁴, R⁵, R⁶, R⁸, R⁹ and k have the meaning defined above.

Class (3)

Titanium complexes belonging to class (3) have the following formula (V):

<img file="ES2326537T3_D0010.tif" />

where X, Z, L, Y¹, L¹, R¹, R², R³, R⁴, R⁵ and R⁶ have the meaning defined above.

Preferably, in the titanium complexes of formula (V):

X is a nitrogen atom; the divalent bridge> ZR¹₂ is preferably selected from the group consisting of dimethylsilyl, diphenylsilyl, diethylsilyl, di-n-propylsilyl, di-isopropylsilyl, di-n-butylsilyl, di-tert-butylsilyl, di-n-hexylsilyl, ethylmethylsilyl, n -hexylmethylsilyl, cyclopentamethylenosilyl, cyclotetramethylenosilyl, cyclotrimethylenosilyl, methylene, dimethylmethylene and diethylmethylene; and, more preferably, it is dimethylsilyl, diphenylsilyl or dimethylmethylene;

two and¹ are the same group, more preferably they are NR⁷ or S;

R² is hydrogen, methyl, ethyl, propyl, or phenyl; and R³ is hydrogen or R² and R³ they form a fused benzene ring, which can be substituted by one or more R groups;

R⁴ is hydrogen and R⁵ is hydrogen, methyl, ethyl, propyl or phenyl or R⁴ and R⁶ they form a fused benzene ring, which can be substituted by one or more R groups;

R⁶is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, pn-butylphenyl, benzyl, cyclohexyl, and cyclododecyl; more preferably, R⁶ is tert-butyl;

ES 2 326 537 T3 the substituents L, the same or different from each other, are preferably halogen atoms, C alkylaryl groups₇-C₂or, Ci-C alkyl groups₆, linear or branched, saturated or unsaturated, or OR; more preferably the L substituents are Cl, CH₂C₆H₅, OCH₃ or CH₃.

Examples of complexes of formula (V) are:

<img file="ES2326537T3_D0011.tif" />

<img file="ES2326537T3_D0012.tif" />

<img file="ES2326537T3_D0013.tif" />

<img file="ES2326537T3_D0014.tif" />

and the corresponding titanium dichloride or dimethoxy complexes.

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Titanium complexes belonging to class (3) can be obtained from the ligand of formula (Va)

<img file="ES2326537T3_D0015.tif" />

where X, Z, Y¹, R¹, R², R³, R⁴, R⁵ and R⁶ have the meaning defined above.

The ligands of the formula (II) can be obtained by a process consisting of the following steps: i) a compound of the formula (VI) is reacted:

<img file="ES2326537T3_D0016.tif" />

in which Y¹, m, Y², R², R³, R⁴, R⁵ and R⁸ have the meaning defined above, with at least one equivalent of a base, such as hydroxides and hydrides of alkali metals or of alkaline earth metals, metal compounds of sodium and potassium or of organolithium, such as butyllithium, methyl lithium and thereafter the compound obtained is contacted with a compound of the formula R¹₂ZY³ Y⁴, in which R¹ and Z have the meanings defined above, Y³ is a halogen atom, preferably chlorine, and Y⁴ is a halogen atom, preferably chlorine, or an R group⁶XH, in which R⁶ and X have the meaning defined above and H is hydrogen;

ii) if Y⁴ is a halogen atom, the product obtained is reacted with a compound of the formula R⁶XH₂, in which R⁶ and X have the meaning defined above and H is hydrogen and the product is recovered.

The compounds of formula VI can be obtained according to the general procedures already known from the state of the art, starting from commercial products or derivatives that can be obtained by known procedures. The synthesis of the compounds of the formula (VI) can be found, for example, in documents WO 99/24 446, EP 99 2204566, EP 99 204565 and WO 01/47939.

The ligand can finally be purified by general processes known in the art, such as crystallization or chromatography. All steps are carried out in an aprotic solvent, which can be a polar or apolar solvent. Examples of polar aprotic solvents that can be used in the above procedure are tetrahydrofuran, dimethoxyethane, diethyl ether, and dichloromethane. Examples of apolar solvents suitable for the above procedure are toluene, pentane, hexane, and benzene. The temperature of the various passages is preferably kept between -180 ° C and 80 ° C, and more preferably between -20 ° C and 40 ° C.

The titanium complexes of the formula (I) can be prepared by first reacting a ligand of the formula (II), obtained in the manner described above, with a compound capable of forming a delocalized dianion, such as alkali metal hydroxides and hydrides or of alkaline earth metals, metal compounds of sodium and potassium or of organolithium, such as butyllithium, methyl lithium, in the cyclopentadienyl ring and in the group X and then, with a compound of the formula TiL '₄, where the substituents L 'are halogen or -OR, where R has the meaning defined above. Examples of compounds of the formula TiL '₄ they are titanium tetrachloride and titanium tetramethoxide.

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According to a preferred method, a ligand (II) is dissolved in a polar aprotic solvent and at least two equivalents of an organic lithium compound are added to it. The anionic compound thus obtained is added to the solution of the compound TiL '₄ in an aprotic solvent. At the end of the reaction, the solid product obtained is separated from the reaction mixture by techniques usually used in the state of the art. Examples of aprotic polar solvents suitable for the aforementioned processes are tetrahydrofuran, dimethoxyethane, diethyl ether and dichloromethane. Examples of nonpolar solvents suitable for the aforementioned process are pentane, hexane and toluene. During the entire process, the temperature is preferably kept between -180 ° C and 80 ° C, and more preferably between -20 ° C and 40 ° C.

All the above processes are carried out in an inert atmosphere, for example nitrogen.

The titanium compounds of the formula (I), in which at least one substituent L is different from halogen, can be obtained in a convenient way by methods already known from the state of the art, for example, such compounds can be obtained by reacting a metallocene dihalogenated with alkylmagnesium halides (Grignard reagents) or with alkyl lithium compounds.

When one or both of the L substituents are alkyl, the above titanium complexes (I) can be obtained, in a convenient way, by reacting a ligand of the formula (II) with at least one molar equivalent of a compound of the formula TiCl₄, in the presence of at least 3 molar equivalents of an appropriate alkylating agent; said alkylating agent can be an alkali or alkaline earth metal, such as a dialkyl lithium, dialkyl magnesium or a Grignard reagent, as described in WO 99/36427 and WO 00/75151.

An alternative procedure for obtaining the titanium complex of formula (I), in which both L substituents are OR groups, consists of obtaining the titanium complex of formula (I), in which two L groups are R and then contacting the complex obtained with oxygen. The resulting derivative having, as L substituents, two OR groups, shows a greater solubility than that of the corresponding R-substituted complex and therefore can be stored for a long time, without losing activity.

Suitable activating cocatalysts according to the process of the invention are alumoxanes or compounds capable of forming an alkylmetallocene cation.

Useful alumoxanes as catalysts (B) can be linear alumoxanes of formula (VII):

<img file="ES2326537T3_D0017.tif" />

in which R¹⁰ is selected from the group consisting of halogen, Ci-C alkyl moieties₂₀, linear or branched, saturated or unsaturated, cycloalkyl C₃-C₂₀, aryl C₆-C₂₀, alkylaryl C₇-C₂₀ and arylalkyl C₇-C₂₀, and "y" is a number between 0 and 40;

or cyclic alumoxanes of the formula (VIII):

<img file="ES2326537T3_D0018.tif" />

in which R¹⁰ has the meaning described above and "y" is an integer between 0 and 40.

The above alumoxanes can be obtained according to procedures known in the state of the art, by reacting water with an organo-aluminum compound of the formula AlR¹⁰3 or Al2R¹⁰6, provided that at least one R¹⁰ not halogen. In this case, the molar ratios between Al and water, in the reaction, are between 1: 1 and 100: 1. Particularly suitable are the organometallic aluminum compounds of the formula (II), described in EP 0 575 875 and those of the formula (II), described in WO 96/02 580. Also suitable cocatalysts are those described in WO 99 / 21899 and in WO 01/21674.

The molar ratio of aluminum to titanium metal complex is approximately between 10: 1 and 5000: 1, and preferably between 100: 1 and 4000: 1.

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Examples of suitable alumoxanes as activation cocatalysts for the process of the invention are methylalumoxane (MAO), tetra-isobutyl-alumoxane (TIBAO), tetra-2,4,4-trimethylpentyl-alumoxane (TIOAO) and tetra-2-methyl-pentylalumoxane. Mixtures of different alumoxanes can also be used.

Non-limiting examples of aluminum compounds of the formula AlR¹⁰3 or Al2R¹⁰6 are as follows:

tris (methyl) aluminum, tris (isobutyl) aluminum, tris (isooctyl-aluminum), bis (isobutyl) hydride, methylbis- (isobutyl) -aluminum, dimethyl (isobutyl) aluminum, tris (isohexyl) aluminum, tris (benzyl) aluminum, tris (tolyl) aluminum), tris (2,4,4-trimethylphenyl) aluminum, bis (2,4,4-trimethyl-pentyl) -aluminum hydride, isobutyl-bis (2-phenyl-propyl) aluminum, diiso-butyl (2-phenylpropyl) aluminum, isobutyl-bis (2,4,4-trimethyl-pentyl) aluminum, diisobutyl- (2,4,4-trimethyl-pentyl) -aluminum, tris (2,3-dimethyl-hexyl) aluminum, tris (2,3,3-trimethyl-butyl) aluminum, tris (2,3-dimethyl-butyl) aluminum, tris (2,3-dimethyl-pentyl) aluminum, tris (2-methyl-3-ethyl-pentyl) -aluminum, tris (2-ethyl-3-methyl-butyl) aluminum, tris (2-ethyl-3-methyl-pentyl) aluminum, tris (2-isopropyl-3 -methyl-butyl) aluminum and tris (2,4-dimethyl-heptyl) aluminum.

Particularly preferred aluminum compounds are trimethylaluminum (TMA), tris (2,4,4-trimethylpentyl) -aluminum (TIOA), triisobutylaluminum (TIBA), tris (2,3,3-trimethyl-butyl) aluminum and tris (2 , 3-dimethyl-butyl) aluminum.

Mixtures of different organometallic aluminum compounds and / or alumoxanes can also be used.

In the catalyst system used in the process of the invention, both said titanium complex and said alumoxane can be made to pre-react with an aluminum organometallic compound of the formula AlR¹⁰3 or Al2R¹⁰6, in which R¹⁰ has the meaning defined above. The pre-reaction time can vary between 20 seconds and 1 hour, preferably between 1 minute and 20 minutes.

Other suitable activating cocatalysts as component (B) of the catalysts of the invention are compounds capable of forming an alkylmetallocene cation; preferably, said catalysts have the formula Q 'W, in which Q⁺ is a Br0nsted acid, capable of donating a proton and reacting irreversibly with a substituent L of the compound of formula (I) and W^- it is a non-coordinating compatible anion, capable of stabilizing the active catalytic species, which result from the reaction of the two compounds and which is labile enough to be displaced by an olefinic substrate. Preferably, the anion W^- contains one or more boron atoms. More preferably, the anion W is an anion of the formula BrAr₄^(-), in which the Ar substituents, equal to or different from each other, are aryl moieties, such as phenyl, pentafluorophenyl, bis (trifluoromethyl) phenyl. Tetrakis-pentafluorophenyl borate is particularly preferred. Furthermore, compounds of the formula BAr3 can be conveniently used.

The catalyst system of the present invention can also be supported on an inert vehicle (support), for this the titanium complex (A) or the reaction product of the titanium complex (A) with the cocatalyst (B) or the cocatalyst (B) and successively the titanium complex (A), on the inert support, such as silica, alumina, magnesium halides, olefin polymers or prepolymers (for example, polyethylenes, polypropylenes or styrene-divinylbenzene copolymers). The supported catalyst system thus obtained, optionally in the presence of alkylaluminum compounds, either untreated or pre-reacted with water, can be used in a useful way in gas phase polymerization processes. The solid compound thus obtained, in combination with an additional alkyl aluminum compound, as is or pre-reacted with water, is used in a useful way for gas phase polymerization.

The polymerization yield depends on the purity of the metallocenes in the catalyst; The metallocene according to the present invention can be used as it is or it can be previously subjected to purification treatments.

In an appropriate way, components (A) and (B) of the catalyst can be contacted with each other before polymerization. The contact time can be between 1 and 60 minutes, preferably between 5 and 20 minutes. The pre-contact concentrations of the titanium complex (A) are between 0.1 and 10^-8 moles / l, while, for the cocatalyst (B), they are between 2 and 10 ⁸ moles / l. The pre-contact is generally carried out in the presence of a hydrocarbon solvent and optionally small amounts of monomer.

The catalysts of the present invention are particularly advantageous in the polymerization of propylene, where they provide substantially amorphous propylene polymers with high activities. When, in the compounds of formula (I), Y¹ is NR⁷ and, preferably, the compounds of formula (I) belong to class (1) or (2), the propylene polymers obtained by the process of the invention have a predominantly syndiotactic structure. The syndiotacticity of a polyolefin can be conveniently defined by the content of the rr triads, as described in L. Resconi et al., Chemical Reviews 100, 1253, 2000. When in the compounds of formula (I), Y¹ is NR⁷ and, preferably, the compound of formula (I) belongs to classes (1) or (2), the propylene polymers obtained with the process of the present invention typically have triad contents between 60-80%, most preferably 65-75%. Its syndiotacticity is not high enough to produce substantial crystallinity (measured by DSC), but it is high enough to build resilience in polypropylene.

Being substantially void of crystallinity, its enthalpy of fusion (AH_F) is preferably less than about 20 J / g and still more preferably less than 10 J / g.

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An also interesting use of these catalysts is focused on obtaining propylene-based copolymers, in which the appropriate comonomers are ethylene, alpha-olefins of the formula CH2 = CHR ', in which R' is a C-alkyl₂-C₁₀ linear or branched, for example 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, unconjugated diolefins, containing up to 20 carbon atoms, for example said diolefins can conform to the formula CH2 = CH (CR "₂)_h-CR "₂= CR ", where R" is hydrogen or a C alkyl₁-C₁₀ linear or branched and h is a number from 1 to 15, for example 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 7-methyl-1,6-octadiene, 1,7 -octadiene and the like, or said olefins can be norbornene or its derivatives, for example 5-ethylidene-2-norbornene.

The preferred ranges for the composition depend on the type of polymer desired and the type of polymerization process employed. For example, in the case of amorphous copolymers of propylene with ethylene, for example those described in EP 729984, the ethylene content is between 1 and 35 mol%, preferably between 5 and 20 mol%. In the case of ethylene / propylene elastomers, the ethylene content is between 20 and 80% by weight, preferably between 70 and 30% by weight, while, in the ethylene / propylene / diene elastomers, the diene content, which is preferably ethylidenenonorbornene or 1,4-hexadiene, is between 0.5 and 5% by weight.

Furthermore, the molecular weight of the polymers can be varied by changing the polymerization temperature or the type or concentration of the catalyst components or by using molecular weight regulators, for example hydrogen, already known in the state of the art. Furthermore, the molecular weight of propylene-based polymers can be easily controlled by copolymerizing small amounts of ethylene.

The polymerization process according to the present invention can be carried out in the gas phase or in the liquid phase, optionally in the presence of an inert solvent of the hydrocarbon type, either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane or cyclohexane).

The polymerization temperature is between 0 ° C and 180 ° C, preferably between 40 ° C and 120 ° C, more preferably between 60 ° C and 90 ° C.

The molecular weight distribution can be varied by using mixtures of different metallocenes or by carrying out the polymerization in several stages, which differ in the polymerization temperature and / or in the concentration of the monomers to be polymerized.

The following examples are provided for illustrative purposes.

General procedures and characterizations

All operations are carried out under a nitrogen atmosphere, using conventional Schlenk on-line techniques. Solvents are purified by degassing with N₂ and making them pass over Al₂OR₃ activated (for 8 hours, purge with N₂, at 300 ° C) and are stored under a nitrogen atmosphere. The cocatalyst is a commercial MAO from Witco AG (10% by weight solution in toluene). The Me₂Yes (Me₄Cp) (NtBu) TiCl₂ to Witco AG.

NMR-H¹

The proton spectrum of the ligands and metallocenes is obtained using a Bruker DPX 200 spectrometer, operating in the Fourier transform mode at room temperature, at a frequency of 200.13 MHz. The samples are dissolved in CDCl₃, CD₂Cl₂, C₆D₆ or C₆D₅CD₃. As a reference, the residual peak of CHCl is used.₃, CHDCl₂, C₂D₅H or C₆D₃CD₃, in the H spectrum¹ (7.25 ppm, 5.35 ppm, 7.15 and 2.10 ppm, respectively). Proton spectra are obtained with a pulse of 15 ° and a delay of 2 seconds between pulses; 32 transients are stored for each spectrum. All NMR solvents are dried over activated molecular sieves and kept under a nitrogen atmosphere. Sample preparation is carried out under a nitrogen atmosphere, using standard inert atmosphere techniques.

C-NMR¹³

Carbon spectra are obtained using a Bruker DPX 400 spectrometer, operating in the Fourier transform mode, at 120 ° C and a frequency of 100.61 MHz. The samples are dissolved in C₂D₂Cl₄. The peak of the pentad mmmm of the C spectrum¹³ (21.8 ppm) is used as a reference. Carbon spectra are obtained with a 90 ° pulse and a 12 second delay between pulses; approximately 3000 transients are stored for each spectrum. The ethylene content is determined according to M. Kagugo, Y. Naito, K. Mizunuma, T. Miyatake, Macromolecules 15, 1150, 1982. The content of 1-butene is determined from the dyad distribution of the S carbons. . „,, as described by JC Randall, Macromolecules 11, 592, 1978.

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CG-EM

GC-MS analyzes are carried out on a gas chromatograph of the type HP 5890-series 2 and a quadrupole mass spectrometer, of the type HP 5989B.

Viscosity measurements

The intrinsic viscosity (IV) is measured in tetrahydronaphthalene (THN) at 135 ° C.

The molecular weights of the polymers are determined from the viscosity values.

DSC analysis

Melting point and heat of fusion measurements are made on a Perkin Elmer DSC-7 instrument, heating the sample from 25 ° C to 200 ° C, at a rate of 10 ° C / minute, maintaining 200 ° for 2 minutes. C, cooling from 200 ° C to 25 ° C, at a rate of 10 ° C / minute, maintaining 25 ° C for 2 minutes, heating from 25 ° C to 200 ° C, at a rate of 10 ° C / minute. Recorded values ​​are those determined in the second warm-up scan.

The values ​​of T_g are determined on a Mettler DSC30 instrument, equipped with a cooling device, heating the sample from 25 ° C to 200 ° C, at a rate of 20 ° C / minute, maintaining 200 ° C for 10 minutes, cooling from 200 ° C at -140 ° C, maintaining -140 ° C for 2 minutes, heating from -140 ° C to 200 ° C, at a rate of 20 ° C / minute. Recorded values ​​are those determined in the second warm-up scan.

Example 1

Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyltitanium (B-1)

N

First synthetic route (a) Synthesis of 2-methyl -5,6-dihydroindeno [2,1-b] indole

All operations are carried out in air, with solvents and reagents packed in bottles: isopropanol, RPE Carlo Erba (99%); 2-indanone, Chemische Fabrik Berg (99%); p-tolylhydrazine hydrochloride, Aldrich (98%).

In a glass reactor (Büchi) of 11 capacity, jacketed, with a three-fin stirrer, magnetically actuated, connected to a thermostat for temperature control, 85.0 g of 2-indanone (PM = 132, 16.0.63 moles), 102.0 g of p-MeC₆H₄NHNH₂-HCl (MW = 158.63, 0.63 mole) and 0.5 L of i-PrOH. The viscous suspension is heated with stirring at 80 ° C for about 30 minutes and the suspension turns dark brown. The mixture is heated at 80 ° C for 1 hour and then cooled to room temperature in about 30 minutes.

By siphoning the suspension is poured over 1.2 l of water, which contains 1.5 equivalents of NaOHCO₃, forming a fine dispersion of a dark green product (no heat evolution is observed). The suspension is filtered through a G3 frit, washed with water, dried in air with a moderate vacuum and then on a rotary evaporator at 80 ° C and finally, with a high vacuum (mechanical pump).

121.2 g of the desired product are obtained, in a yield of 87.3% (purity 99.6%, according to GC).

NMR-H¹ (CDCh, δ, ppm): 2.52 (s, 3H, CH3); 3.70 (s, 2H, CH2); 7.01-7.66 (m, 7H, Ar); 8.13 (broad s, 1H, NH).

ES 2 326 537 T3 (b) Synthesis of N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indole

10.2 g of 2-methyl-5,6-dihydroindeno [2,1-b] indole (MW = 219.28, purity = 99.6%, 46.33 mmol), obtained in the manner just described, in 100 ml of 1,3-dioxolane (Aldrich). Then 5.42 g of tert-BuOK (Fluka, 97%, MW = 112.22, 46.85 mmol) are added; the solution turns one color from green to dark brown and is stirred at room temperature for 10 minutes; 2.90 ml of MeI are then added (MW = 141.94, d = 2.280, 46.58 mmol). After 15 minutes of stirring a solid begins to form. Stirring was continued for 1 hour and then the reaction mixture was poured into water containing 4 g of NH₄Cl. The solid formed is isolated by filtration and dried under vacuum, obtaining 9.5 g of the desired product, in the form of a brown microcrystalline solid, in pure state, in a yield of 86.3% (purity 98.2% , according to CG).

NMR-H¹ (CDCl3, δ, ppm): 2.52 (s, 3H, CH3); 3.68 (s, 2H, CH2); 3.78 (s, 3H, N-CH3); 7.02-7.64 (m, 7H, Ar).

(c) Synthesis of chlorodimethyl (N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indol-6-yl) silane

9.5 ml of a 2.5 M solution of n-BuLi in hexane (23.75 mmol) are added dropwise to a solution of 5.1 g of N-methyl-2-methyl-5,6-dihydroindole [ 2,1-b] -indole, obtained as just described (purity 98.2%, MW = 233.32, 21.46 mmol; indenoindole: n-BuLi = 1: 1.1) in 70 ml of THF, previously cooled to -78 ° C. At the end of the addition, the brown solution is allowed to warm to room temperature and stir for 6 hours. It is then cooled again to -78 ° C and added dropwise to a solution of dichlorodimethylsilane (MW = 129.06, d = 1.064, 2.6 ml, 21.43 mmol; indenoindole: Me₂SiCl₂ = 1: 1) in 20 ml of THF, previously cooled to -78 ° C. At the end of the addition, the brown solution is allowed to warm to room temperature and stir overnight. The solvents are evaporated under reduced pressure, obtaining a sticky brown solid, which according to H-NMR analysis¹, turns out to be the desired product, with few by-products. The product is used for the next step without further purification.

NMR-H¹ (CDCl₃, δ, ppm): -0.13 (s, 3H, Si-CH3); 0.48 (s, 3H, Si-CH3); 2.53 (s, 3H, CH3); 3.44 (s, 1H, CH); 3.88 (s, 3H, N-CH3); 6.90-7.71 (m, 7H, Ar).

(d) Synthesis of 6- [dimethylsilyl (tert-butylamino)] N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indole

3.96 g of dichlorodimethyl (N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indol-6-yl) silane (MW = 325.92.12.15 mmol), obtained according to described above, in 50 ml of toluene and added at -78 ° C to a solution of tertBuNH₂ (3.0 ml, MW = 73.14, d = 0.696, 28.55 mmol) in 20 ml of toluene. At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirred for 2 days, obtaining a black suspension, which was filtered to remove the ammonium salt formed. The filtrate is concentrated in vacuo, obtaining 3.49 g of the desired product, as a black sticky solid (crude yield = 79.2%).

NMR-H¹ (CDCl3, δ, ppm): 0.15 (s, 3H, Si-CH3); 0.04 (s, 3H, Si-CH3); 1.23 (s, 9H, tert-Bu); 2.52 (s, 3H, CH3);

3.44 (s, 1H, CH); 3.86 (s, 3H, N-CH3); 6.90-7.71 (m, 7H, Ar).

(e) Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyl-titanium

25.3 ml of a 1.6 M solution of MeLi in diethyl ether (40.48 mmol) are added dropwise at room temperature to a solution of 3.49 g of 6- [dimethylsilyl (tert-butylamino)] N-methyl-2-methyl-5,6-dihydro-indeno [2,1-b] indole (MW = 362.69, 9.62 mmol), obtained as just described, in 45 ml of Et2O. The reaction mixture was stirred overnight: an increasing turbidity formed, at the end the suspension had a black hue. Then 1.05 ml of TiCl are slowly added at room temperature.₄ (MW = 189.71, d = 1.730, 9.62 mmol) in 40 ml of pentane and the resulting mixture was stirred overnight. The solvent is removed under reduced pressure, obtaining a sticky black solid, which is extracted with 50 ml of toluene. The extract is concentrated, yielding 3.02 g of the desired compound as a black powder (crude yield = 71.6%).

NMR-H¹ (C6D6, δ, ppm): -0.02 (s, 3H, Ti-CH); 0.07 (s, 3H, Ti-CH3); 0.56 (s, 3H, Si-CH3); 0.74 (s, 3H, Si-CH3); 1.41 (s, 9H, tert-Bu); 2.45 (s, 3H, CH3); 3.12 (s, 3H, N-CH3); 6.90-7.94 (m, 7H, Ar).

Second synthetic route

a) Synthesis of N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indole

22.37 g of 2-methyl-5,6-dihydroindeno [2,1-b] indole (99.6% according to GC, MW = 219.28, 101.6 mmol) are dissolved in 220 ml 1,3-dioxolane (Aldrich) and 11.46 g of tert-BuOK (Aldrich, MW = 112.22, 101.6 mmol) are added. The solution turns from green to dark brown and is stirred at room temperature for 10 minutes; 6.33 ml of MeI (Across, MW = 141.94, d = 2.280, 101.6 mmol) are then added. After 15 minutes of stirring, a solid begins to form. Stirring is continued for 1 hour and poured into water,

ES 2 326 537 T3 containing 8 g of NH₄Cl (Carlo Erba RPE, purity: 99.5%). After 2 hours of stirring, the solid formed is isolated by filtration and dried under vacuum, obtaining 23.2 g of brown powder, which was analyzed by NMR and GC-MS spectroscopy. GC-MS analysis indicates a purity in the desired product of 91.5% (yield = 89.5%). The 2-methyl-5,6-dihydroindeno [2,1-b] indole and N-methyl-2,6-dimethyl-5,6-dihydro-indeno [2,1-b] indole are also obtained, in about percentages of 2.6% and 3.7%, respectively.

An aliquot of the product (9.98 g) is suspended in 150 ml of MeOH (Carlo Erba RPE, purity: 99%), bp. = 64.6 ° C). After stirring for 30 minutes at room temperature, a dark brown microcrystalline powder (9.18) is isolated by filtration. GC-MS analysis indicates high purity (99.0%) in the desired product.

NMR-H¹ (CDCl3, δ, ppm): 2.53 (s, 3H, CH3); 3.65 (s, 2H, CH2); 3.76 (s, 3H, N-CH3); 7.00 7.60 (m, 7H, Ar).

C-NMR¹³ (CDl3, δ, ppm): 21.52 (CH₃); 29.98 (CH₂); 31.08 (N-CH₃); 109.38; 118.11; 119.13; 121.83; 122.14; 122.26; 124.62; 126.95; 129.11 (2C); 139.59; 140.50; 124.14; 148.87.

m / z (%): 233 (100) [M⁺]; 218 (35).

(b) Synthesis of (tert-butylamino) dimethylchlorosilane

15.7 ml of M are added dropwise at 0 ° C₂SiCl₂ (MW = 129.06, d = 1.07, 130.21 mmol) in 20 ml of Et₂Or to a solution of 20.0 g of tert-BuNH₂ (MW = 73.14, d = 0.696, 273.44 mmol, tert-BuNH₂: Me2SiCl₂ = 2.1: 1) in 40 ml of Et₂O. The resulting solution is allowed to warm to room temperature and stir for 1.5 hours. A color change is observed, turning from yellow to light yellow, with a final formation of a white, milky suspension. The latter is filtered and the filtrate is concentrated in vacuo, obtaining 18.93 g of a light yellow oil, which according to H-NMR analysis¹ appears to be the main desired product, along with a by-product, identified as di (tert-butylamino) dimethylsilane. Silylamine is used for the next step, without any further purification. Yield = 65.8% (purity according to H-NMR¹ = 75.0 mol%).

NMR-H¹ (CD2Cl2, δ, ppm): 0.48 (s, 6H, Si-CYL); 1.26 (s, 9H, tert-Bu); 1.42 (broad s, 1H, NH).

(c) Synthesis of 6- [dimethylsilyl (tert-butylamino)] N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indole

At 0 ° C, 6.66 ml of 2.5 M n-BuLi in hexane (16.65 mmol) are added dropwise to a solution of 3.53 g of N-methyl-2-methyl-5,6-dihydroindene [2,1-b] indole (MW = 233.32, purity = 99.0%, 15.21 mmol) in Et₂O. At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirred for two hours. 3.34 g of (tert-butylamino) dimethylchlorosilane (MW = 165.74, purity = 75.0 mol%, d = 0.887, 20.17 mmol) are then added to the suspension of the Li salt and the resulting mixture is allowed to warm to room temperature. After stirring for three hours, the solvents are evaporated under reduced pressure and the residue is dissolved in 50 ml of toluene, obtaining a dark brown suspension, which is filtered. The filtrate is concentrated under reduced pressure to dryness, obtaining 5.86 g of a dark brown oil, which turns out to be 86.5% pure by weight (calculated by H-NMR¹). Yield = 92.4%.

NMR-H¹ (C6D6, δ, ppm): -0.14 (s, 3H, Si-CH3); -0.13 (s, 3H, Si-CH3); 0.99 (s, 9H, tert-Bu); 2.54 (s, 3H, CH3); 3.27 (s, 3H, N-CH3); 3.40 (s, 1H, CH); 7.10-7.90 (m, 7H, Ar).

m / z (%) = 362 (39) [M⁺]; 232 (16); 130 (100); 74 (18).

(d) Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyl-titanium

19.4 ml of a 1.6 M solution of MeLi in diethyl ether (30.63 mmol) are added dropwise at 0 ° C to a solution of 2.76 g of 6- [dimethylsilyl (tert-butylamino)] N-methyl-2-methyl-5,6-dihydroindeno [2,1-b] indole (MW = 362.69, 7.62 mmol), obtained as just described, in 40 ml of Et₂O. The resulting light brown solution is allowed to warm to room temperature and stir for 1.5 hours. Then 0.84 ml of TiCl are slowly added at room temperature.₄ (MW = 189.61, d = 1.730, 7.63 mmol) in 4 ml of pentane and the resulting black mixture was stirred for 1.5 hours. The solvents are removed under reduced pressure and the residue is extracted with 50 ml of toluene. 70 ml of pentane are added to the extract (3.07 g), the resulting black suspension is stirred at room temperature for 30 minutes and filtered, yielding a dark brown powder as a residue, which is dried and analyzed by H-NMR.¹. H-NMR analysis¹ indicates a purity of 97.0%, on the desired catalyst, together with 3% by weight of the starting ligand. Yield = 64.4% (2.22 g).

NMR-H¹ (C6D6, δ, ppm): -0.02 (q, 3H, Ti-CYL, J = 0.36 Hz); 0.07 (q, 3H, Ti-CH3, J = 0.36 Hz); 0.55 (s, 3H, SiCH₃); 0.74 (s, 3H, Si-CH₃); 1.39 (s, 9H, tert-Bu); 2.43 (s, 3H, CH₃); 3.10 (s, 3H, N-CH₃); 6.91 (d, 1H, J = 8.31 Hz); 7.02 (ddd, 1H, J = 8.61, 6.87, 1.17 Hz); 7.13 (dq, 1H, J = 8.31, 1.57, 0.59 Hz); 7.31 (ddd, 1H, J = 8.26, 6.87, 0.96 Hz); 7.80 (dt, 1H, J = 8.61, 0.96 Hz); 7.77-7.79 (m, 1H, Ar); 7.92 (dt, 1H, J = 8.26, 1.17 Hz).

ES 2 326 537 T3

C-NMR¹³ (C6D6, δ, ppm): 6.91 (C-Si); 7.37 (C-Si); 21.66 (CH₃); 33.01 (N-CH₂); 34.62 (tert-Bu), 55.56 (C-Ti); 57.24 (C-Ti); 68.74 (C-tert-Bu); 109.43 (CH); 120.76 (CH), 124.17 (CH); 124.27 (CH); 125.22 (CH); 125.76 (CH);

128.44 (CH).

m / z (%) by “direct insertion probe” technique: 439 (32) [M⁺+1]; 422 (100); 407 (26).

Example 2

Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyltitanium (B-2)

<img file="ES2326537T3_D0019.tif" />

(a) Synthesis of 2-methoxy-5,6-dihydroindeno [2,1-b] indole

In a 250 ml flask, fitted with a magnetic stirrer, charge 8.21 g of 2-indanone (Aldrich, 98%, MW = 132.16, 60.88 mmol), 40 ml of isopropanol, 10, 84 g of p-methoxyphenylhydrazine hydrochloride (Aldrich, 98%, MW = 174.63, 60.83 mmol). The suspension is heated to reflux (82 ° C) (a black suspension forms) and is refluxed for 1 hour. The dark brown viscous suspension is cooled to room temperature, 200 ml of water saturated with NaHCO3 (final pH approx. 7.5-8) are introduced into the reactor, the resulting mixture is filtered and the residue is washed with plenty of water. . The dark green solid is dried under vacuum at 70 ° C on the filter for 4 hours (14 g, purity = 98.9% according to GC, yield of pure product = 96.7%).

NMR-H¹ (CDCl3, δ, ppm): 3.69 (s, 2H, CH2); 3.93 (s, 3H, O-CH3); 6.83-7.64 (m, 7H, Ar); 8.14 (broad s, 1H, NH).

(b) Synthesis of N-methyl-2-methoxy-5,6-dihydroindeno- [2,1-b] indole

7.53 g of 2-methoxy-5,6-dihydroindeno [2,1-b] indole (MW = 235.29, purity: 98.9%, 31.65 mmol), obtained in the manner just described, in 60 ml of 1,3-dioxolane (Aldrich). 3.6 g of tert-BuOK (Fluka, MW = 112.22, 31.90 mmol) are added; The solution turns from green to dark brown and is stirred at room temperature for 10 minutes. Then 1.96 ml of MeI (MW = 141.94, d = 2.280, 31.50 mmol) are added. After 10 minutes of stirring, a solid begins to form. Stirring was continued for 1 hour and the reaction mixture was poured into water containing 5 g of NH4Cl. The solid formed is isolated by filtration and the brown residue is dried in vacuo, yielding 7.85 g of a brown microcrystalline solid. Purity according to GC = 85.8%, yield of the pure product = 85.2%.

NMR-H¹ (CDCl3, δ, ppm): 3.65 (s, 2H, CH2); 3.75 (s, 3H, N-CH3); 3.93 (s, 3H, O-CH3); 6.85-7.61 (m, 7H, Ar).

(c) Synthesis of chlorodimethyl (N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indol-6-yl) silane

3.4 ml of a 2.5 M solution of n-BuLi in hexane (8.50 mmol) are added dropwise to a solution of 2.22 g of N-methyl-2-methoxy-5,6-dihydroindole [ 2,1-b] -indole, obtained as just described (MW = 249.32, purity: 85.8%, 7.64 mmol; indenoindole: n-BuLi = 1: 1.1) in 50 ml of THF , previously cooled to -78 ° C. At the end of the addition, the brown solution is allowed to warm to room temperature and is stirred for 5 hours. Cool again to -78 ° C and pour over a solution of dichlorodimethylsilane (MW = 129.06, d = 1.064, 0.92 ml, 7.64 mmol; indenoindole: Me2SiCl₂ = 1: 1) in 20 ml of THF, previously cooled to -78 ° C. At the end of the addition, the brown solution is allowed to warm to room temperature and is stirred overnight. The solvents are evaporated under reduced pressure, obtaining the desired product, which contains a small amount of by-products, in the form of a sticky solid; this product is used in the subsequent step, without further purification.

ES 2 326 537 T3 (d) Synthesis of 6- [dimethylsilyl (tert-butylamino)] N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indole

3.25 g of chlorodimethyl (N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indol-6-yl) silane (MW = 341.91, 9.50 mmol) are dissolved, obtained as just described, in 50 ml of toluene and pour at -78 ° C on a solution of tertBuNH₂ (2.3 ml, MW = 73.14, d = 0.696, 21.89 mmol) in 20 ml of toluene. At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirred overnight, obtaining a brown suspension, which was filtered to remove the ammonium salt formed. The filtrate is concentrated in vacuo, yielding 2.18 g of the desired product, as a brown sticky solid (crude yield = 60.6%). This product is used for the next step without further purification.

NMR-H¹ (CDCls, δ, ppm): -0.14 (s, 3H, Si-CH₃); -0.02 (s, 3H, Si-CH₃); 1.23 (s, 9H, tert-Bu); 3.86 (s, 3H, N-CH₃); 3.926 (s, 1H, CH); 3.934 (s, 3H, O-CH3); 6.80-7.70 (m, 7H, Ar).

The toluene-insoluble fraction is extracted with 30 ml of CH2Cl2 and 0.58 g of the by-product bis (n-methyl) -2-methoxy-5,6-dihydroindeno [2,1-b] indol-6-yl are isolated ) dimethylsilane, formed in the previous step, in the form of a light brown powder (yield: 13.7% with respect to the starting N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indole).

NMR-H¹ (CDCl₃, δ, ppm): -0.23 (s, 3H, Si-CH₃); 3.35 (s, 6H, N-CH₃); 3.91 (s, 6H, O-CH₃); 3.93 (s, 2H, CH); 6.82-7.63 (m, 14H, Ar).

(e) Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methoxy-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyl-titanium

15.6 ml of a 1.6 M solution of MeLi in diethyl ether (24.96 mmol) are added dropwise to a solution of 2.18 g of 6- [dimethylsilyl (tert-butylamino)] N -methyl-2-methoxy-5,6-dihydro-indeno [2,1-b] indole (MW = 378.58, 5.76 mmol), obtained as just described, in 45 ml of Et2O. The reaction mixture was stirred at room temperature for 5 hours, forming a dark brown suspension. 0.65 ml of TiCl are slowly added at room temperature₄ (MW = 189.71, d = 1.730, 5.93 mmol) in 20 ml of pentane and the resulting mixture was stirred overnight. The solvents are removed under reduced pressure, obtaining a black solid, which is extracted with 35 ml of toluene. The extract is concentrated, obtaining 1.16 g of the desired compound as a brown powder (crude yield = 44.3%).

NMR-H¹ (C₆D₆, δ, ppm): -0.01 (s, 3H, Ti-CH₃); 0.04 (s, 3H, Ti-CH₃); 0.55 (s, 3H, Si-CH₃); 0.74 (s, 3H, Si-CH₃); 1.40 (s, 9H, tert-Bu); 3.09 (s, 3H, N-CH3); 3.55 (s, 3H, O-CH3); 6.82-7.92 (m, 7H, Ar).

Example 3

Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl-1,8-dihydroindeno [2,1-b] pyrrol-6-yl) titanium (B-3)

<img file="ES2326537T3_D0020.tif" />

(a) N-methyl-2-methyl-1,8-dihydroindeno [2,1-b] pyrrole is obtained by the method described in patent application WO 99/24446 (b) Synthesis of 8- [dimethylsilyl ( tert-butylamino)] N-methyl-2-methyl-1,8-dihydroindeno [2,1-b] pyrrole

18 ml of a 1.6 M solution of BuLi (28 mmol) in hexane are added dropwise at -30 ° C to a solution of 3.5 g of N-Me-2-Me-indenopyrrole (19 mmol) in 60 ml of ether. At the end of the addition, the solution is allowed to warm to room temperature and stir for 4 hours. It is then heated again to -30 ° C and treated with 5 ml of Me₂SiCl₂ (42 mmol) in 5 ml of ether. The mixture is allowed to warm to room temperature and is stirred overnight.

ES 2 326 537 T3

The resulting suspension is filtered and the solvent is evaporated in vacuo. The crude product is dissolved in 50 ml of ether and treated dropwise at -20 ° C with 17.5 ml (167 mmol) of tert-butylamine. The resulting mixture is allowed to warm to room temperature and stir overnight. The solution is isolated by filtration and the solvent is evaporated, obtaining the silylamine as a reddish-brown oil. Yield: 4.67 g (83%).

NMR-H¹ (toluene-d⁸): 7.48 (d, 1H); 7.44 (d, 1H); 7.23 (t, 1H); 7.05 (t, 1H); 6.18 (1H); 3.12 (s, 3H); 2.15 (s, 3H); 1.02 (s, 9H); -0.11 (s, 3H); -0.12 (s, 3H).

(c) Synthesis of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl-1,8-dihydroindeno- [2,1-b] pyrrol-6-yl) dimethyl-titanium

49 ml of a 1.33 M solution of MeLi in diethyl ether (65.2 mmol) are added dropwise at -20 ° C to a solution of 8- [dimethylsilyl (tert-butylamino)] - N-methyl -2-methyl-indenopyrrole (14 mmol) in 60 ml of ether. The reaction mixture was stirred overnight, then cooled to -30 ° C and treated with 1.54 ml of TiCl₄ in 60 ml of hexane. The resulting black mixture is stirred overnight and 60 ml of toluene are added. The reaction mixture was concentrated and the residue was extracted twice with 50 ml of toluene. The resulting solution is concentrated to a volume of 15 ml and kept at room temperature for 15 hours. Red crystals are isolated, washed twice with 10 ml of cooled pentane and dried. Yield: 2.1 g.

NMR-H¹ (toluene-d⁸): 7.68 (d, 1H); 7.61 (d, 1H); 7.20 (dd, 1H); 6.94 (dd, 1H); 6.13 (s, 1H); 2.88 (s, 3H); 1.98 (s, 3H); 1.41 (s, 9H); 0.73 (s, 3H); 0.51 (s, 3H), 0.05 (s, 3H); -0.04 (s, 3H).

Example 4

Synthesis of dimethylsilyl (tert-butylamido) (N-ethyl-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyltitanium (B-4)

<img file="ES2326537T3_D0021.tif" />

(a) Synthesis of 5,6-dihydroindeno [2,1-b] indole

In a flask of 11 are deposited 36.55 g of 2-indanone (Aldrich, MW = 132.16, 276.6 mmol), 40 g of phenylhydrazine hydrochloride (Aldrich, 99%, MW = 144.61, 276.6 mmol) and 0.3 l of i-Pr-OH. The suspension is heated at 80 ° C for 30 minutes and with stirring the suspension turns from yellow to dark brown. The reaction mixture was stirred at 80 ° C for 1.5 hours and cooled to room temperature in about 30 minutes. By siphoning the suspension is poured over 1.0 l of water containing 34.85 g of NaHCO₃, forming a fine dispersion of a green product (no heat release is observed). The suspension is filtered on a G4 frit, washed with water, dried under a moderate vacuum for 24 hours, until constant weight.

51.81 g of the desired product are obtained, in the form of a green powder, in a yield of 92.8% (purity 99.8%, according to GC).

NMR-H¹ (CDCl₃, δ, ppm): 3.72 (s, 2H, CH₂); 7.12 (td, 1H, H8, J = 7.48, 1.17 Hz); 7.16-7.29 (m, 2H, H2, H3); 7.31-7.39 (m, 2H, H1, H9); 7.42 (dt, 1H, H7, J = 7.24 Hz), 7.66 (dt, 1H, H10, J = 7.48 Hz); 7.85-7.89 (m, 1H, H4), 8.26 (broad s, 1H, NH).

C-NMR¹³ (CD13, δ, ppm): 31.51 (CH2); 112.18 (C-H1); 118.77 (C-H10); 119.56 (C-H4); 120.73, 121.84 (C-H2, CH3), 122.47 (C10c), 122.91 (C-H8), 125.05 (C-H7), 127.38 (C-H9); 140.32 (C10b); 140.93 (C4a); 142.88 (C6a, 10a),

146.44 (C5a).

ES 2 326 537 T3 (b) Synthesis of N-ethyl-5,6-dihydroindeno [2,1-b] indole

15.00 g of 5,6-dihydroindeno [2,1-b] indole (99.8% according to GC, MW = 205.26, 73.1 mmol) are dissolved in a 0.5 l flask at room temperature in 200 ml of 1,3-dioxolane (Aldrich). 8.28 g of tert-BuOK (Fluka, 99%, MW = 112.22, 73.1 mmol) are added and the reaction mixture turns from a green suspension to a brown solution. Stir at room temperature for 30 minutes, add 5.51 ml of EtBr (Fluka, 99%, MW = 108.97, d = 1.46, 7.31 mmol), forming a brown suspension. Stirring was continued for 2 hours and then the reaction mixture was poured into water containing 8 g of NH₄Cl (Carlo Erba RPE, purity: 99.5%). After 2 hours of stirring, the green-brown suspension is filtered on a G4 frit, the solid is dried with air with a moderate vacuum, obtaining a brown powder (8.98 g), which is analyzed by H-NMR¹. Purity: 98.9% by weight according to NMRNH¹ (yield = 52.1%).

NMR-H¹ (CDCh, δ, ppm): 1.48 (t, 3H, CH3, J = 7.26 Hz), 3.73 (s, 2H, CH2); 4.24 (q, 2H, CH2, J = 7.26 Hz); 7.047.90 (m, 8H, Ar).

(c) Synthesis of (tert-butylamino) dimethylchlorosilane

15.95 ml of M are added dropwise at 0 ° C₂SiCl₂ (MW = 129.06, d = 1.064, 130.21 mmol) in 20 ml of Et₂Or to a solution of 20.41 g of tert-BuNH₂ (MW = 73.14, d = 0.696, 273.54 mmol, tert-BuNH₂: Me2SiCl₂ = 2.1: 1) in 40 ml of Et2O. The resulting milky solution is allowed to warm to room temperature and stir for 30 minutes. The solvent is removed and the residue is extracted with 50 ml of pentane, forming 13.76 g of a colorless oil, which according to H-NMR analysis¹ it turns out to be the desired product, of a purity of 83.7% by weight, together with 16.3% by weight of di (tert-butylamino) dimethylsilane. Silylamine is used for the next step without further purification. Yield: 53.4%.

NMR-H¹ (CD2Cl2, δ, ppm): 0.44 (s, 6H, Si-CIF); 1.21 (s, 9H, tert-Bu).

(d) Synthesis of 6- [dimethylsilyl (tert-butylamino)] N-ethyl-5,6-dihydroindeno [2,1-b] indole

8.02 ml of 2.5 M n-BuLi in hexane (20.04 mmol) are added dropwise at 0 ° C to a solution of 4.30 g of Netyl-5,6-dihydroindeno [2,1-b ] indole (MW = 233.31, purity: 98.9%, 18.22 mmol) in Et₂O. At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirred for two hours. The dark brown solution obtained is added at 0 ° C to a solution of 4.32 g of (tert-butylamino) -dimethylchlorosilane (MW = 165.74, purity: 83.7%, d = 0.887, 21.86 mmol) in Et₂O. The final mixture is allowed to warm to room temperature and stir for three hours. The solvents are then evaporated under reduced pressure, obtaining a residue (8.73 g), which is extracted with 50 ml of toluene. The extract, a brown sticky solid (7.48 g), is washed with pentane, obtaining 4.23 g of a brown powder, which is analyzed by H-NMR.¹. H-NMR analysis¹ indicates a purity of 96.6% by weight of the desired ligand, together with 3.4% by weight of the starting N-ethyl-5,6-dihydroindeno [2,1-b] -indole. Yield = 63.1%.

NMR-H¹ (C₆D₆, δ, ppm): -0.23 (s, 3H, Si-CH3); -0.01 (s, 3H, Si-CH3); 0.41 (broad s, 1H, NH); 0.99 (s + t, 12H, tert-Bu + CH3); 3.56 (s, 1H, CH), 4.07 (m, 2H, CH2); 7.15-8.07 (m, 8H, Ar).

NMR-H¹ (CDCh, δ, ppm): -0.13 (s, 3H, Si-CH3); 0.03 (s, 3H, Si-CH3); 0.75 (broad s, 1H, NH); 1.26 (s, 9H, tertBu); 1.37 (t, 3H, CH3, J = 7.14 Hz); 3.84 (s, 1H, CH), 4.50 (m, 2H, CH2); 6.90-8.00 (m, 8H, Ar).

(e) Synthesis of dimethylsilyl (tert-butylamido) (N-ethyl-5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyl-titanium

16.3 ml of a 1.6 M solution of MeLi in diethyl ether (25.80 mmol) are added dropwise at 0 ° C to a solution of 2.30 g of 6- [dimethylsilyl (tert-butylamino)] N-ethyl-5,6-dihydro-indeno [2,1-b] indole (MW = 362.60, 6.34 mmol), obtained as just described, in 40 ml of Et2O. The resulting dark brown solution is allowed to warm to room temperature and stir for 3 hours. Then 0.70 ml of TiCl4 (MW = 189.71, d = 1.730, 6.34 mmol) in 4 ml of pentane are slowly added at room temperature and the resulting dark brown suspension is stirred for 1 hour. The solvents are removed under reduced pressure and the residue is extracted with 50 ml of toluene. The extract (2.27 g of sticky dark brown powder) is washed with pentane and the residue is dried, obtaining a powder (1.7 g) which is analyzed by H-NMR.¹. H-NMR analysis¹ indicates a purity of 97.6% by weight of the desired catalyst, together with 2.4% by weight of the starting ligand. Yield = 79.7%.

NMR-H¹ (C6D6, δ, ppm): -0.002 (q, 3H, Ti-CH3, J = 0.41 Hz); 0.09 (q, 3H, Ti-CH3, J = 0.41 Hz); 0.61 (s, 3H, Si-CH₃); 0.73 (s, 3H, Si-CH₃); 1.05 (t, 3H, CH₃, J = 7.26); 1.41 (s, 9H, tert-Bu); 3.78 (q, 2H, CH₂, J = 7.26 Hz); 6.98-7.06 (m, 2H, H3, H8); 7.24-7.33 (m, 3H, H1, H4 and H9); 7.80 (dt, 1H, J = 8.67 Hz, H7); 7.88-7.93 (m, 2H, H2, H10).

ES 2 326 537 T3

C-NMR¹³ (C6D6, δ, ppm): 6.62 (Si-CH₃); 7.63 (Si-CH₃); 14.48 (CH₃); 34.51 (tert-Bu); 40.00 (CH₂); 56.90 (TiCH3); 57.01 (Ti-CH₃); 57.81 (C-tert-Bu); 67.98 (C-Si); 109.81 (C-H3); 114.56 (C-H10c); 120.48 (C-H1); 120.59 (CH2); 123.67 (C-10-a); 124.08 (C-H10); 124.32 (C-H8); 124.49 (C-H4); 125.27 (C-H9); 128.62 (C-H7); 134.89 (C6a), 145.50 (C4a); 147.34 (C5a).

Example 5

Synthesis of dimethylsilyl (tert-butylamido) (2,5-dimethyl-7H-thieno [3 ', 2': 3,4] cyclopenta [1,2-b] thiophen-7-yl) dimethyl-titanium (A-1 )

N (a) chloro (2,5-dimethyl-7H-thieno [3 ', 2': 3,4] cyclopenta [1,2-b] thiophen-7-yl) dimethylsilane

A suspension of 4.13 g (20 mmol) of 2,5-dimethyl-7H-cyclopenta [1,2b: 4,3-b '] dithiophene in 80 ml of ether is treated dropwise with stirring at -40 ° C. with 15 ml (24 mmol, 20% excess) of 1.6 M BuLi in hexane. The mixture is stirred for 3 hours and then treated with 4.82 ml (40 mmol) of Me2SiCl₂ in 10 ml of Et₂O. The precipitate is filtered and used without further purification. Yield: 4.84 g (81%), taking into account the presence of LiCl (1.02 g, 24 mmol).

NMR-H¹ (CDCl₃, 30 ° C) δ = 6.85 (q, 2H), 3.93 (s, 1H), 2.57 (broad s, 6H), 0.25 (s, 6H).

(b) N- (tert-butyl) (2,5-dimethyl-7H-thieno [3 ', 2': 3,4] -cyclopenta [1,2-b] thiophen-7-yl) dimethylsilanamine

A suspension of 2.12 ml (20 mmol) of tert-butylamine in 70 ml of ether is drop-treated at -30 ° C with 12.5 ml (20 mmol) of 1.6M BuLi in hexane. The reaction mixture was stirred at room temperature for 3 hours and the resulting suspension was treated at -70 ° C with a solution of 4.84 g (16.2 mmol) of chlorine (2,5-dimethyl-7H-thieno [3 ', 2': 3,4] cyclopenta [1,2-b] thiophen-7-yl) di-methylsilane in 30 ml of ether. The resulting suspension is allowed to warm to room temperature and stir overnight. Separate the LiCl solution and concentrate. Yield: 4.47 g (82%) of a brown solid, which is used without further purification.

NMR-H¹ (CDCl₃, 30 ° C) δ = 6.85 (q, 2H), 3.80 (s, 1H), 2.58 (broad s, 6H); 1.31 (s, 9H); 0.05 (s, 6H).

(c) Me₂Si (tert-BuN) 2,5-dimethyl-7H-thieno [3 ', 2': 3,4] -cyclopenta [1,2-b] thiophen-7-yl) TiMe₂

To a solution of N- (tert-butyl) (2,5-dimethyl-7H-thieno [3 ', 2': 3,4] -cyclopenta [1,2-b] -thiophen-7-yl) dimethylsilanamine in 30 ml of ether are added at -40 ° C with stirring 23 ml of 1.2M MeLi in ether (28.7 mmol). The reaction mixture was then stirred under reflux for 3 hours. The resulting mixture is cooled to -60 ° C and a solution of 0.63 ml (5.7 mmol) of TiCl is added.₄ in 30 ml of hexane. The mixture was allowed to warm to room temperature and stir overnight. The resulting mixture is concentrated and the residue is extracted with hexane (3 times with 50 ml). The hexane solution is concentrated to a volume of 10 ml and kept at room temperature for 10 hours. The crystalline product is separated from the mother liquor, washed twice with cold pentane and dried. Yield: 0.27 g (11%) of dark red crystals.

NMR-H¹ (C7D8, 30 ° C) δ = 6.76 (q, 2H); 2.20 (d, 6H); 1.49 (s, 9H), 0.56 (s, 6H), 0.36 (s, 6H). C-NMR¹³ (C7D8, 30 ° C) δ = 146.51, 139.67, 133.08, 116.65, 78.16, 58.00, 56.82, 34.56, 16.29, 3.21.

ES 2 326 537 T3

Comparative Example 6

Synthesis of dimethylsilyl (tert-butylamido) (indenyl) -dimethyltitanium (C-3)

<img file="ES2326537T3_D0022.tif" />

11.3 ml of a 1.6 M solution of methyl lithium in diethyl ether (18.04 mmol) are slowly added at -78 ° C to a solution of 1.08 grams (4.40 mmol) of IndMe₂SiNH-t-Bu in 23 ml of diethyl ether. During the addition an increasing turbidity forms, resulting in a yellow suspension. This mixture is allowed to warm to room temperature and is stirred for two hours.

50 ml of TiCl are diluted₄ (4.40 mmol) in 23 ml of pentane. This solution is added very slowly and carefully at room temperature to the suspension of the lithium salt in diethyl ether. The resulting dark solution is stirred at room temperature overnight. The reaction mixture was concentrated to dryness under reduced pressure. The dark solution is extracted with 60 ml of toluene and the filtrate is concentrated to dryness, under reduced pressure, obtaining 0.99 g (yield = 70%) of a gray-black solid. H-NMR¹ confirms the formation of [Me₂Si (Ind) (tert-BuN)] TiMe₂.

NMR-H¹ (CeD₆, δ, ppm): -0.15 (q, J = 0.48 Hz, 3H, Ti-CH₃); 0.36 (s, 3H, Si-CH₃); 0.53 (s, 3H, Si-CH₃); 0.82 (q, J = 0.48 Hz, Ti-CH3); 1.44 (s, 9H, tert-Bu); 6.05 (d, J = 3.21 Hz, 1H, Cp-H2); 6.88 (ddd, J = 8.50, 6.64, 1.04 Hz, 1H, Ar-H6); 7.01 (dd, J = 3.21, 0.83 Hz, 1H, Cp-H3); 7.07 (ddd, J = 8.50, 6.64, 1.04 Hz, 1H, Ar-H5); 7.46 (dq, J = 8.50, 1.04 Hz, 1H, Ar-H7); 7.48 (dt, J = 8.50, 1.04 Hz, 1H, Ar-H4).

Comparative Example 7

Synthesis of dimethylsilyl (tert-butylamido) (2-methyl-1-indenyl) -dimethyltitanium (C-4)

<img file="ES2326537T3_D0023.tif" />

The dimethylsil (tert-butylamido) (2-methyl-1-indenyl) dimethyltitanium complex is obtained from the corresponding ligand in 71%, using the same procedure.

(a) Synthesis of (2Me-Ind) SiMe₂(t-BuNH)

5.02 g of (2-Me Ind) SiMe are added at 0 ° C₂Cl (25.23 mmol) in Et₂Or to a t-BuNH solution₂ (56.16 mmol), forming a yellow suspension. The mixture is allowed to warm to room temperature for 16 hours. Evaporate

ES 2 326 537 T3 solvents under reduced pressure and the product is extracted with toluene, obtaining, after filtering and evaporation of the solvent, 5.52 g of an orange oil. H-NMR analysis¹ indicates the presence of two isomers (allyl: 60% and vinyl: 40%). Yield: 83.4%.

NMR-H¹ (C₆D₆, δ, ppm): allyl isomer: -0.09 (s, 3H, Si-CH₃); 0.11 (s, 3H, Si-CH₃); 1.02 (s, 9H, t-Bu); 2.14 (s, 3H, CH3; 3.21 (s, 1H, CH); 6.52 (s, 1H, CH); vinyl isomer: 0.46 (s, 6H, Si-CH3); 1, 1 (s, 9H, t-Bu), 2.06 (s, 3H, CH3), 3.05 (s, 2H, CH2), both isomers: 6.98-7.82 (m, 8H, Ar) ;

(b) Synthesis of Me2Si (2-Me-Ind) (t-BuN) TiMe2

At 0 ° C, 25 ml of 1.6 M MeLi in Et₂Or (40 mmol) to a solution of 2.53 g (2MeInd) SiMe₂(t-BuNH) (9.75 mmol) and after stirring at room temperature for 1.5 hours add 1.07 ml of TiCl₄ in pentane (9.75 mmol). After 2 hours, the solvents are evaporated under reduced pressure and the mixture is taken up in 50 ml of toluene, stirred for 30 minutes and filtered, obtaining, after evaporation of the solvent, 2.68 g of a powder. The powder is collected in pentane, filtered and the filtrate is concentrated to dryness, under reduced pressure, obtaining 2.31 g of an ocher powder. Yield: 70.6%.

NMR-H¹ (C6D6, δ, ppm): -0.11 (q, 3H, J = 0.48 Hz, Ti-CH3); 0.46 (broad s, 3H, Si-CH3); 0.56 (broad s, 3H, SiCH₃); 0.85 (q, 3H, J = 0.48 Hz, Ti-CH₃); 1.47 (s, 9H, t-Bu); 1.99 (s, 3H, CH₃); 6.76 (broad s, 1H, H3); 6.89 (ddd, 1H, H6, J = 8.41, 6.77, 1.08 Hz); 7.07 (ddd, 1H, H5; J = 8.41, 6.77, 1.08 Hz); 7.44 (dt, 1H, H4, J = 8.41, 1.08 Hz); 7.51 (dq, 1H, H7, J = 8.41, 1.08 Hz).

C-NMR¹³ (C6D6, δ, ppm): 5.30 (C-Si); 5.55 (C-Si); 17.98 CH3); 33.85 ((CH₃)₃); 50.82 (C-Ti); 56.57 (C-Ti); 57.55 (Ct-Bu); 115.64 (C-H3); 124.72 (C-H6); 124.9 (C-H4); 125.17 (C-H5); 127.81 (C-H7); 131.57 (C-C3a); 133.82 (CC7a); 140.97 (C-CH3).

Example 8

Obtaining the supported catalyst

The polyethylene (PE) used as support has a particle diameter of 250-300 μιη, the porosity, measured by the Mercury porosimeter technique (MA 17302) is approximately 50% v / v, the surface area is 5 , 6 m²/ g and the mean diameter of the pores is 8923 A.

Impregnation

The apparatus used for the support operation is a cylindrical glass container, equipped with a vacuum pump, a dosing pump for supplying catalytic solution on the support and a stirrer to allow good mixing during the impregnation stage. The preparation of the supported catalyst is carried out in a stream of nitrogen at room temperature.

In a flask, 5 g of the PE support described above are deposited and it is mechanically stirred in a stream of nitrogen, 3 ml of MAO solution (Witco, 100 g / l in toluene) are metered in in a single addition step on the prepolymer , in order to sequester residual impurities and achieve incipient wetting. The solvent is then evaporated in vacuo.

The catalytic solution is prepared by dissolving 17 mg of B-4 in 9 ml of the same MAO solution, in order to achieve an Al / Ti ratio = 400 mol / mol. After stirring this for 15 minutes, it is added to the support in 3 aliquots; After each addition, once incipient wetting has been achieved, the solvent is evaporated in vacuo.

Analysis of the supported catalysts obtained indicates Al = 7.3%, Ti = 0.03%.

Polymerization tests

The batch (discontinuous) polymerizations are carried out in a 1 l or 4.25 l stainless steel reactor, fitted with a stirrer. The reactor is washed with a solution of TIBA (Al (i-Bu)₃) in hexane and then purge dried with propylene at 80 ° C for one hour. The catalyst / cocatalyst mixture is prepared by dissolving the Ti complex in the required amount of MAO / toluene solution and allowing it to stand for 10 minutes.

ES 2 326 537 T3

Examples 9-11

Propylene polymerization

MAO (commercial product from Witco, 10% w / w in toluene, 1.7M in Al) is used as supplied. The catalyst system is prepared by dissolving the amount of dimethylsilyl (tert-butylamido) (N-methyl-2-methyl5,6-dihydroindeno [2,1-b] indol-6-yl) dimethyl-titanium (B-1) prepared in Example 1, first synthetic route, as indicated in Table 1, with the amount of MAO indicated in Table 1; The solution obtained is stirred at room temperature for 10 minutes, before being injected into the autoclave.

In a 1 l jacketed stainless steel autoclave fitted with a mechanical stirrer, charge 1 mmol of Al (i-Bu) at room temperature₃ (TIBA) (in the form of a 1 M solution in hexane) and 300 g of propylene, which is also provided with a 35 ml stainless steel vial, connected to a thermostat for temperature control, and which has previously been purified by means of washed with a solution of Al (i-Bu) in hexane and dried at 50 ° C in a propylene stream. The autoclave is then adjusted to 2 ° C below the polymerization temperature by means of a thermostat and the catalyst system, prepared in the manner described above, is injected under nitrogen pressure through the stainless steel vial. The temperature is rapidly raised to the polymerization temperature, as indicated in Table 1 and the polymerization is carried out at a constant temperature, for the time indicated in Table 1.

After discharging the unreacted monomer and cooling the reactor to room temperature, the polymer is dried under reduced pressure, at 60 ° C.

The polymerization data and the characterization data of the polymers obtained are indicated in table 1.

The results obtained demonstrate that the titanium complexes according to the present invention can provide high molecular weight amorphous polypropylene.

Example 12

Propylene polymerization

The propylene polymerization is carried out according to the procedure indicated in examples 9-11, with the difference that, as a catalyst, the B-1 obtained in example 1, second synthetic route, is used.

The polymerization data, yields and characteristics of the polymer obtained are shown in table I.

Example 13

Influence of hydrogen

In order to evaluate the influence of hydrogen on the molecular weight of the polymers obtained, the polymerization of propylene was carried out according to the procedure indicated in Examples 9-11, with the only difference being the introduction of 100 ml of hydrogen before adding propylene. The polymerization data are collected in table I.

The results obtained confirm that the titanium complexes of the present invention are sensitive to hydrogen as a regulator of molecular weight.

Example 14

Propylene / Ethylene Copolymerization

The propylene polymerization is carried out according to the procedure of Examples 9-11, with the only difference that, before loading the amount of propylene indicated in Table I, 4.1 g of ethylene are loaded into the autoclave.

The resulting copolymer has an ethylene content of 0.8% by weight (C-NMR¹³) and the other data on polymerization, performance and characteristics of the copolymer obtained are indicated in table I.

The results obtained demonstrate a good activity of the titanium complexes of the invention in the propylene / ethylene copolymerization; inserting small amounts of ethylene into propylene polymers can serve to regulate the molecular weight of the final polymers, at the same time without adversely affecting intrinsic viscosity values ​​or process performance. The use of small amounts of ethylene in the propylene polymerization process according to the present invention makes it possible to regulate the molecular weight of the polymers obtained.

ES 2 326 537 T3

Example 15

Propylene homopolymerization

1200 g of liquid propylene are charged at 30 ° C into a 4.25 ml stainless steel reactor, fitted with a stirrer, and then 1 mmol of TIBA in hexane, used as sequestrant. The reactor temperature rises to 60 ° C.

The polymerization is started by injecting 2.1 ml of a solution of MAO in toluene (approx. 6 mmol of Al), containing 1.4 mg of B-3, into the autoclave at 60 ° C, by means of an overpressure of nitrogen and then the temperature is maintained at 60 ° C for 37 minutes. The polymerization is stopped by purging and cooling the reactor.

530 of an amorphous, soft, non-sticky product are obtained, equivalent to an approximate yield of 600 kg / (g_catxh). The properties of the polymer are:

IV = 3.65 dl / g, no melting point (DSC), rr = 72.16, rrrr = 51.7 (C-NMR¹³).

The polymerization data, performance and characteristics of the polymer obtained are summarized in table I.

Example 16

Propylene homopolymerization

2 ml of TIBA solution in hexane (1 mmol of TIBA is used as sequestrant) and 271 g of liquid propylene are charged to a 1 l stainless steel reactor, fitted with a stirrer. The reactor temperature is then raised to 70 ° C.

The polymerization is started by injecting in the autoclave at 70 ° C 3 ml of a solution of MAO in toluene (0.64 mmol of Al, MAO / Zr = 500), containing 0.5 mg of B-3, by means of an overpressure of nitrogen and then the temperature is maintained at 70 ° C for 60 minutes. The polymerization is interrupted by pressurization with CO, purging and cooling of the reactor.

53 g of a soft, non-sticky amorphous product are obtained, equivalent to an approximate yield of 106 kg / (g_catxh). The properties of the polymer are:

IV = 4.92 dl / g, no melting point (DSC).

The polymerization data, yields and characteristics of the polymer obtained are summarized in table I.

Example 17

Propylene / Ethylene Copolymerization

In a 4.25 l stainless steel reactor, fitted with a stirrer, 2 l of hexane are charged at 30 ° C and then 2 mmol of TIBA in hexane, used as sequestrant. 397 g of propylene and 38 g of ethylene are introduced into the reactor under excess pressure and the temperature of the reactor is raised to 50 ° C, resulting in a pressure of 9.3 bar-g.

The polymerization is started by injecting 4.3 ml of a toluene solution containing MAO (1.29 mmol of Al) and 0.5 mg of B-3 into the autoclave at 50 ° C with nitrogen overpressure, maintaining the temperature at 50 ° C and ethylene is continuously fed to the reactor in order to maintain a constant pressure. After introducing 7 g of ethylene in 23 minutes, the polymerization is interrupted by pressurizing 1.5 l of CO into the reactor, purging and cooling the reactor. The propylene / ethylene copolymer is recovered in a hexane solution by precipitation in acetone and subsequent drying under reduced pressure, at 70 ° C, for 4 hours.

104 g of amorphous, non-sticky copolymer are obtained, equivalent to an approximate yield of 540 kg / (g_catxh). The copolymer contains 20% by weight of ethylene (analysis by NMR-H¹), it is completely amorphous, has a Tg = -26 ° C and an intrinsic viscosity of 6.65 dl / g.

Example 18

Propylene / Butene Copolymerization

2 ml of a solution of TIBA in hexane (1 mmol of TIBA is used as sequestrant), 158 g of propylene and 154 g of 1- butene.

ES 2 326 537 T3

The reactor temperature is raised to 60 ° C (15 bar-g).

The polymerization is started by injecting in the autoclave at 60 ° C 3 ml of a solution of MAO in toluene (approx. 2.6 mmol of Al), containing 1 mg of B-3, with a nitrogen overpressure and then maintaining the temperature at 60 ° C for 60 minutes. The polymerization is interrupted by pressurization with CO, purging and cooling of the reactor.

13 are obtained from a soft, non-sticky amorphous product. The properties of the polymer are:

IV = 0.9 dl / g, without melting point and T_g = -7 ° C, butene = 47% (measured by C-NMR¹³).

Example 19

Propylene / Butene Copolymerization

Example 18 is repeated with an Al / Zr ratio of 500, obtaining a copolymer with IV = 2.11 dl / g.

Example 20

Polymerization of propylene at 80 ° C

Applying the usual procedure, in a reactor of 21 1 mmol of TIBA and 585 g of propylene are charged and it is heated to 80 ° C. 1 mg of B-3 is dissolved in 1.07 ml of a 10% MAO solution (1.82 mmol of Al) in toluene, diluted with toluene (total volume: 3 ml), left to stand for 10 minutes and is injected into the reactor. Polymerization with CO is discontinued after 60 minutes at 80 ° C. The results of the analysis of the polymer are collected in table I.

Example 21

Propylene polymerizations at 80 ° C

Applying the usual procedure, 1 mmol of TIBA and 585 g of propylene are charged to a 2 l reactor, then it is heated to 80 ° C. 0.5 mg of B-3 is dissolved in 1.07 ml of a 10% MAO solution (1.82 mmol of Al) in toluene, diluted with toluene (total volume: 3 ml), left to stand 10 minutes and injected into the reactor. Polymerization with CO is discontinued after 60 minutes at 80 ° C. The results of the polymer analysis are shown in Table I.

Examples 22-23

A propylene polymerization is carried out according to the procedure of Examples 9-11, with the difference that B-4 is used as catalyst instead of B-1.

The polymerization data, yields and characteristics of the polymer obtained are shown in table I.

Example 24

Polymerization with supported catalysts

In a 4.25 ml stainless steel reactor, fitted with a stirrer, 1200 g of liquid propylene are charged at 30 ° C and then 1 mmol of TIBA in hexane, used as sequestrant. 200 ml of hydrogen are added before the catalyst. Afterwards, 650 mg of the solid catalyst prepared in Example 8 are injected into the reactor under nitrogen overpressure, through a stainless steel vial and in 15 minutes the temperature of the reactor is raised to the reaction temperature.

After one hour the polymerization is interrupted by discharge purge and reactor cooling, the amorphous product is collected and dried.

The polymerization data, yields and characteristics of the polymer obtained are summarized in table I.

ES 2 326 537 T3

Example 25

Propylene polymerizations at 80 ° C

Applying the usual procedure, 1 mmol of TIBA and 585 g of propylene are charged to a 2 l reactor, then it is heated to 80 ° C. 1.5 mg of A-1 are dissolved in 1.07 ml of a 10% MAO solution (1.82 mmol of Al) in toluene and diluted with toluene (total volume: 3 ml), left to stand for 10 minutes and injected into the reactor. Polymerization with CO is discontinued after 60 minutes at 80 ° C. 85 g of an amorphous and rubbery polypropylene are recovered, equivalent to a catalyst activity of 56.6 kg_pp/ (g_cat xh). The results of the analysis of the polymer are collected in table I.

Comparative Examples 26-28

The propylene polymerization is carried out according to the procedure of Examples 9-11, with the difference that, as a catalyst, dimethylsilyl (tert-butylamido) (tetramethylcyclopentadienyl) titanium dichloride is used instead of the titanium complex of the invention. The polymerization data, yields and characteristics of the polymer obtained are summarized in table 1. The results obtained demonstrate that the titanium complexes of the invention are capable of exerting polymerization activities superior to those of the restricted geometry catalysts, corresponding to the state of the art.

Comparative Example 29

The propylene polymerization is carried out according to the procedure of Example 9, with the difference that, as a catalyst, dimethylsilyl (tert-butylamido) (tetramethylcyclopentadienyl) titanium dichloride is now used instead of the titanium complex of the invention. The polymerization data are collected in table I.

Comparative Example 30

The propylene copolymerization is carried out according to the procedure of Examples 9-11, with the difference that 4.5 g of ethylene are added to the reactor, before adding 288 g of propylene; Dimethylsilyl (tert-butylamido) (tetramethylcyclopentadienyl) -titanium dichloride (supplied by the Witco company) is used as catalyst, instead of the titanium complex of the invention and 15.7 g of ethylene are introduced into the reactor along polymerization time of 1 hour, in order to maintain a constant pressure of 25.6 bar-g (of which 0.3 bar is due to nitrogen). The resulting copolymer has an ethylene content of 4.5% by weight (according to C-NMR¹³), the other polymerization data are listed in Table I.

Comparative Examples 31-32

The propylene polymerization is carried out according to the procedure reported in examples 9-11, with the difference that, as a catalyst, dimethylsilyl (tert-butyl-amido) (indenyl) titanium-dimethyl is used, instead of the titanium complex of the invention.

The polymerization data, yields and characteristics of the polymer obtained are summarized in Table I. The results obtained demonstrate that the titanium complexes of the invention are capable of exerting polymerization activities superior to those of the restricted geometry catalysts, corresponding to the state of technique.

Comparative Example 33

The propylene polymerization is carried out according to the procedure of Examples 9-11, with the difference that, as catalyst, dimethylsilyl (tert-butyl-amido) (2-methyl-indenyl) titanium-dimethyl is used, instead of titanium complex of the invention.

The polymerization data, yields and characteristics of the polymer obtained are summarized in table 1. The results obtained demonstrate that the titanium complexes of the invention are capable of exerting polymerization activities superior to those of the obligate geometry catalysts, corresponding to the state of the art.

ES 2 326 537 T3

TABLE 1

<td rowspan="2">ex-</td><td rowspan="2">Ti complex</td><td rowspan="2">mg of complex</td><td rowspan="2">proport. molar MAO / Ti</td><td rowspan="2">Tpol ° C</td><td rowspan="2">time (min)</td><td rowspan="2">exercise kgpp / gcat</td><td rowspan="2">IV dl / g</td><td colspan="3">tacticity (%)</td>

<td>rr I</td><td>rrrr |</td><td> 2,1</td>

<td> 9</td><td>B-1</td><td> 1</td><td> 500</td><td> 50</td><td> 60</td><td> 41.6</td><td> 5.97</td><td> 73.8</td><td> 57.5</td><td> &lt;0.5</td>

<td> 10</td><td>B-1</td><td> 1</td><td> 1000</td><td> 60</td><td> 30</td><td> 49.4</td><td> 3.14</td><td> 72.4</td><td> 53.3</td><td> &lt;0.5</td>

<td> 11</td><td>B-1</td><td> 0.7</td><td> 1000</td><td> 70</td><td> 60</td><td> 26.9</td><td> 3.06</td><td> 69.2</td><td> 48.4</td><td> &lt;0.5</td>

<td> 12</td><td>B-1</td><td> 1</td><td> 500</td><td> 70</td><td> 60</td><td> 37.9</td><td> 4.69</td><td> -</td><td> -</td><td> -</td>

<td> 13^to&gt;</td><td>B-1</td><td> 1</td><td> 1000</td><td> 60</td><td> 60</td><td> 12.2</td><td> 1.84</td><td> -</td><td> -</td><td> -</td>

<td> 14^b&gt;</td><td>B-1</td><td> 1</td><td> 1000</td><td> 60</td><td> 30</td><td> 81.7</td><td> 2.41</td><td> -</td><td> -</td><td> -</td>

<td> 15^c)</td><td>B-3</td><td> 1.4</td><td> 1000</td><td> 60</td><td> 37</td><td> 530</td><td> 3.65</td><td> 72.2</td><td> 51.7</td><td> 0</td>

<td> 16</td><td>B-3</td><td> 0.5</td><td> 500</td><td> 70</td><td> 60</td><td> 106</td><td> 4.92</td><td> -</td><td> -</td><td> -</td>

<td> 20</td><td>B-3</td><td> 1</td><td> 500</td><td> 80</td><td> 60</td><td> 288</td><td> 4.16</td><td> 68.9</td><td> 48.1</td><td> 0</td>

<td> 21</td><td>B-3</td><td> 0.5</td><td> 500</td><td> 80</td><td> 60</td><td> 320</td><td> 5.01</td><td> 70.2</td><td> 50.69</td><td> 0</td>

<td> 22</td><td>B-4</td><td> 0.3</td><td> 1000</td><td> 60</td><td> 60</td><td> 113</td><td> 7.89</td><td> 73.0</td><td> 57.1</td><td> 0.3</td>

<td> 23</td><td>B-4</td><td> 0.5</td><td> 1000</td><td> 70</td><td> 60</td><td> 106</td><td> 5.96</td><td> 72.8</td><td> 54.1</td><td> 0</td>

<td> 24^c)</td><td>B-4</td><td> 6100</td><td></td><td> 60</td><td> 60</td><td> 0.283)</td><td> 5.85</td><td> -</td><td> -</td><td> -</td>

<td> 25</td><td>A-1</td><td> 1.5</td><td> 500</td><td> 80</td><td> 60</td><td> 56.7</td><td> 4.25</td><td> 33.4</td><td> 10.6</td><td> 0.5</td>

<td> 26*</td><td>C-1^and&gt;</td><td> 2</td><td> 1000</td><td> 60</td><td> 60</td><td> 29.5</td><td> 3.56</td><td> 50.2</td><td> 25.3</td><td> 1.3</td>

<td> 27*</td><td>C-1^and)</td><td> 2</td><td> 1000</td><td> 70</td><td> 60</td><td> 31.5</td><td> 2.58</td><td> -</td><td> -</td><td> -</td>

<td> 28*</td><td>C-1^and&gt;</td><td> 2</td><td> 500</td><td> 70</td><td> 60</td><td> 25.8</td><td> 2.70</td><td> -</td><td> -</td><td> -</td>

<td> 29 *^to)</td><td>C-1^and)</td><td> 2</td><td> 1000</td><td> 60</td><td> 60</td><td> 23.8</td><td> 2.42</td><td> 52.1</td><td> 25.4</td><td> 1.5</td>

<td> 30 *^d)</td><td>C-1^and)</td><td> 2</td><td> 1000</td><td> 60</td><td> 60</td><td> 32.3</td><td> 4.84</td><td> -</td><td> -</td><td> -</td>

<td> 31*</td><td>C-3</td><td> 2</td><td> 1000</td><td> 60</td><td> 60</td><td> 12.7</td><td> 1.12</td><td> -</td><td> -</td><td> -</td>

<td> 32*</td><td>C-3</td><td> 2</td><td> 500</td><td> 70</td><td> 60</td><td> 7.1</td><td> 0.92</td><td> -</td><td> -</td><td> -</td>

<td> 33*</td><td>C-4</td><td> 1</td><td> 1000</td><td> 60</td><td> 60</td><td> 18.3</td><td> 3.15</td><td> 51.4</td><td> 28.3</td><td> 0.6</td>

a) H₂ = 100 ml;

b) C₂~ = 4.1 g;

c) 4.25 1 reactor;

d) C₂"= 17 g;

e) dimethylsilyl (tert-butyl-amido) (tetramethyl cyclopentadienyl) titanium dichloride (Witco);

f) mg of supported catalyst;

g) kg_pol/ g_dozeyou * comparative