KR20070032012A - Metallocene compounds, ligands used in their preparation, preparation of 1-butene polymers and 1-butene polymers therefrom - Google Patents

Abstract

Process for preparing 1-butene polymer comprising polymerization of 1-butene and optionally ethylene, propylene or higher alpha-olefin in the presence of a catalyst system obtainable by contacting:

a) metallocene compound of formula (I):

[Wherein M is a transition metal; p is an integer from 0 to 3; X is a hydrogen atom, a halogen atom, or a hydrocarbon group different or identical to each other; L is a divalent C ₁ -C ₄₀ hydrocarbon radical; R ¹ is a C ₁ -C ₄₀ hydrocarbon radical; T ¹ is part of formula (IIa) or formula (IIb);

Wherein R ² and R ³ may together form a C ₁ -C ₄₀ hydrocarbon radical or a C ₃ -C ₇ -membered ring; R ⁴ is a C ₁ -C ₄₀ hydrocarbon radical; T ² and T ³ are part of formula (IIIa);

(Wherein R ⁶ and R ⁷ are the same or different from each other, a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon radical; R ⁵ is a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon radical); Provided that when T ¹ is part of formula (IIa) at least one of T ² and T ³ is part of formula (IIIb), and if T ¹ is part of formula (IIb) then at least one of T ² and T ³ is formula ( Part of IIIa); b) compounds capable of forming one or more alumoxane or alkylmetallocene cations.

 1-butene, 1-butene (co) polymer, 1-butene (co) polymer preparation method, metallocene catalyst, ligand

Description

METALOCENE COMPOUNDS, LIGANDS USED IN THEIR PREPARATION, PREPARATION OF 1-BUTENE POLYMERS AND 1-BUTENE POLYMERS THEREFROM}

The present invention relates to a process for polymerizing 1-butene using a crosslinked metallocene compound, wherein one II-ligand is substituted indenyl. The present invention also relates to the 1-butene polymer obtained by the above method and the metallocene compound from which the 1-butene polymer can be prepared.

1-butene polymers are known in the art. In view of the good properties of pressure resistance, creep resistance and impact strength, they are widely used, for example, in the manufacture of metal pipe replacement pipes, easily opened packages and films.

The 1-butene (co) polymers are generally prepared by polymerizing 1-butene in the presence of a TiCl ₃ -based catalyst component with diethylaluminum chloride (DEAC) as a cocatalyst. In some cases, a mixture of diethyl aluminum iodide (DEAI) and DEAC is used. However, the polymers obtained generally do not exhibit satisfactory mechanical properties. Furthermore, in view of the low yields obtainable by TiCl ₃ -based catalysts, the 1-butene polymers prepared with these catalysts have a high content of catalyst residues (typically 300 ppm or more Ti), which degrades the properties of the polymer This necessitates the subsequent deashing phase.

In addition, the 1-butene (co) polymers include (A) a solid component comprising a Ti compound and an electron-donor compound supported on MgCl ₂ ; It can be obtained by polymerizing monomers in the presence of a stereospecific catalyst comprising (B) an alkylaluminum compound and optionally (C) an external electron-donor compound. Processes of this type are disclosed in EP-A-172961 and WO 99/45043.

Recently metallocene compounds have been used in the production of 1-butene polymers. For example, in WO 02/100908, WO 02/100909, WO 03/014107, several series of metals from which high yields of 1-butene polymers can be obtained with high yields of isotacticity. Rosene-based catalyst systems are disclosed.

The 1-butene polymers described in all of these documents are given a significantly higher melting point and the same array index (mmmm pentad).

The 1-butene polymer with low isotactic index and low modulus of elasticity can be used as a blending component to replace resins based on soft polyvinyl chloride or to improve the softness of the resulting resin. Low modulus 1-butene polymers are disclosed in EP 1 260 525, which are obtained using double crosslinked metallocene compounds which are completely different from the metallocene compounds used in the process of the invention. Furthermore, the 1-butene polymer obtained by the process of the present invention shows a balance between the modulus of elasticity and the melting point, as compared to the polymer obtained in EP 1 260 525.

Therefore, a problem to be solved by the present invention is to find a method for obtaining a high yield of 1-butene polymer having a low modulus and a high molecular weight.

The object of the present invention is 1-butene and optionally ethylene, propylene or alpha-olefins of the formula CH ₂ = CHZ in which Z is a C ₃ -C ₁₀ alkyl group in the presence of a catalyst system obtainable by contacting A process for the preparation of 1-butene polymers, including polymerization of ethylene, propylene or optionally containing up to 30 mole% of units derived from one or more monomers selected from the above alpha-olefins.

a) at least one metallocene compound of formula (I):

[Meal:

M is a transition metal belonging to groups 3, 4, 5, 6 or lanthanide or actinide of the Periodic Table of the Elements, preferably M is titanium, zirconium or hafnium;

p is an integer from 0 to 3, preferably equal to the formal oxidation state of the metal M ^{- 2} ;

X is the same or different, hydrogen atom, halogen atom, or R, OR, OSO ₂ CF ₃ , OCOR, SR, NR ₂ , or PR ₂ group, wherein R is linear or branched, cyclic or acyclic, C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₂ -C ₄₀ -alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl Radicals; Optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Preferably R is a linear or branched C ₁ -C ₂₀ -alkyl radical; Or two X are substituted or unsubstituted butadienyl radicals or OR'O groups, wherein R 'is C ₁ -C ₄₀ alkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C ₄₀ alkylarylidene And a divalent radical selected from C ₇ -C ₄₀ arylalkylidene radicals; Preferably X is a hydrogen atom, a halogen atom or an R group; More preferably X is a chlorine or C ₁ -C ₁₀ -alkyl radical; For example methyl or ethyl radicals;

L is a divalent C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements or divalent sillylidene radicals containing up to 5 silicon atoms; Preferably L is C ₁ -C ₄₀ alkylidene, C ₃ -C ₄₀ cycloalkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements _A divalent bridging group selected from a ₄₀ alkylarylidene or C ₇ -C ₄₀ arylalkylidene radical and a sillylidene radical containing up to 5 silicon atoms such as SiMe ₂ , SiPh ₂ ; Preferably, L is (Z (R '') ₂ ) _n (wherein Z is a carbon or silicon atom, n is 1 or 2, and R '' optionally contains heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements. Is a C ₁ -C ₂₀ hydrocarbon radical; Preferably R '' is a linear or branched, cyclic or acyclic, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements. ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl, or C ₇ -C ₂₀ arylalkyl radical; More preferably, the (Z (R '') ₂ ) _n group is Si (CH ₃ ) ₂ , SiPh ₂ , SiPhMe, SiMe (SiMe ₃ ), CH ₂ , (CH ₂ ) ₂ and C (CH ₃ ) ₂ ; Even more preferably (Z (R '') ₂ ) _n is Si (CH ₃ ) ₃ ;

R ¹ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; Preferably R ¹ is linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ alkylaryl, or C ₇ -C ₄₀ arylalkyl radical; Optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; More preferably R ¹ is a linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl radical; More preferably R ¹ is a methyl or ethyl radical;

T ¹ is part of formula (IIa) or (IIb):

(Atoms denoted by the * symbol combine with atoms denoted by the same symbol in the compound of the formula (I);

R ² and R ³ are the same or different from each other or a C ₁ -C ₄₀ hydrocarbon radical optionally containing a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements, or they are heteroatoms belonging to a Group 13 to 16 of the Periodic Table of the Elements Together to form a condensed saturated or unsaturated C ₃ -C ₇ -membered ring, preferably C ₄ -C ₆ -membered ring, optionally containing; All atoms forming the ring are substituted with R ⁸ radicals; This means that the valence of each atom forming the ring is filled with R ⁸ groups, wherein R ⁸ is the same or different from each other, a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon radical; Preferably R ⁸ is a linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ egg optionally containing a hydrogen atom or one or more heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements. Kenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ arylalkyl radicals; More preferably R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl radical; Even more preferably R ⁸ is a hydrogen atom or a methyl or ethyl radical;

R ⁴ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; Preferably R ⁴ is linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C optionally containing one or more heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements. ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ arylalkyl radical; More preferably R ⁴ is linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ arylalkyl radicals such as methyl, ethyl, phenyl, or phenyl radicals ( The phenyl radical is optionally substituted with one or more C ₁ -C ₁₀ alkyl radicals);

Preferably the T ¹ moiety has formula (IIa):

T ² and T ³ are the same or different from each other and are part of formula (IIIa) or (IIIb):

(Atoms denoted by the symbol * combine with atoms represented by the same symbol to the compound of formula (I);

R ⁶ and R ⁷ are the same or different from each other are C ₁ -C ₄₀ hydrocarbon radicals which optionally contain a heteroatom belonging to a hydrogen atom or a group belonging to groups 13 to 17 of the Periodic Table of the Elements; Preferably R ⁶ and R ⁷ are the same or different from each other linear or branched, cyclic or acyclic, optionally containing one or more heteroatoms belonging to groups 13 to 17 of the periodic table of elements or hydrogen, C _1- C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ arylalkyl radicals; More preferably R ⁶ and R ⁷ are hydrogen atoms;

R ⁵ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements; Preferably R ⁵ is a linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ egg optionally containing a hydrogen atom or one or more heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements. Kenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ arylalkyl radicals; Even more preferably R ⁵ is a hydrogen atom or a linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ arylalkyl radicals such as methyl, ethyl, phenyl Or phenyl radicals, wherein the phenyl radicals are optionally substituted with one or more C ₁ -C ₁₀ alkyl radicals;

Preferably T ² and T ³ are the same; More preferably T ² and T ³ are part of formula (IIIb);

Provided that when T ¹ is part of formula (IIa) at least one of T ² and T ³ is part of formula (IIIb), and if T ¹ is part of formula (IIb) then at least one of T ² and T ³ is formula ( Part of IIIa);

b) compounds capable of forming one or more alumoxane or alkylmetallocene cations; And

c) optionally an organoaluminum compound.

Preferably, formula (I) has formula (IVa), (IVb), (IVc), or (IVd):

(Meal:

M, X, p, L, R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as above; R ⁹ and R ¹⁰ are the same or different from one another and are linear or branched, cyclic or acyclic, C ₁ -C ₄₀ alkyl radicals; Preferably R ⁹ and R ¹⁰ are C ₁ -C ₂₀ alkyl radicals such as methyl, ethyl and isopropyl radicals; R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl radical; More preferably R ⁸ is a hydrogen atom or a methyl radical.

A further object of the present invention is a metallocene compound of formula (I) as above; Preferably the compound of formula (I) has formula (IVa), (IVb), (IVc), or (IVd).

A further object of the present invention is a ligand of formula (V) and / or a double bond isomer thereof:

Wherein R ¹ , T ¹ , T ² , T ³ and L have the same meaning as above.

Compounds of formula (I) may be prepared by a process comprising the following steps:

a) a ligand of formula (V)

(Wherein R ¹ , T ¹ , T ² , T ³ and L have the same meaning as above)

And / or double bond isomers thereof, T ^a _j B, T ^a MgT ^b , wherein B is an alkali or alkaline-earth metal; j is 1 or 2, j is 1 when B is an alkali metal, preferably lithium When B is an alkali-earth metal, j is 2; linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, where T ^a optionally contains one or more Si or Ge atoms; , C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl group; preferably T ^a is a methyl or butyl radical; T ^b is a halogen atom or an OR '''group (wherein , R '''is a linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C, optionally containing one or more heteroatoms belonging to groups 13 to 17 of the periodic table. ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl radicals being shown below); preferably, T is ^a halogen atom, more preferably Ge bromide), contacting with a base selected from sodium hydride and potassium, metal sodium and potassium, wherein the molar ratio between said base and ligand of formula (V) is at least 2: 1; excess base may be used) ; And

b) contacting the product obtained in step a) with a compound of formula MX _{p +2} , wherein M and X have the meanings described above.

Preferably the method is carried out in a polar or nonpolar, aprotic solvent. Preferably said aprotic solvent is an optionally halogenated aromatic or aliphatic hydrocarbon or ether; More preferably it is selected from benzene, toluene, pentane, hexane, heptane, cyclohexane, dichloromethane, diethyl ether, tetrahydrofuran and mixtures thereof. The process is carried out at a temperature in the range of -100 ° C to + 80 ° C, more preferably -20 ° C to + 70 ° C.

Ligands of formula (V) may be obtained by a process comprising the following steps:

a) a compound of formula (VIa)

Wherein T ¹ and R ¹ are as defined above

And / or contacting the double bond isomer thereof with ^{a base selected} from T ^a _j B, T ^a MgT ^b (where T ^a , j, T ^b are as defined above), sodium hydride and potassium, metal sodium and potassium Step, wherein the molar ratio between the base and the compound of formula (VIa) is at least 1: 1; excess base may be used;

b) contacting the anionic compound obtained in step a) with a compound of formula (VIb):

Wherein T ² , T ³ and L are as defined above and Y is chlorine, bromine and iodine, preferably Y is chlorine or bromine.

In an alternative embodiment the method of preparing a ligand of Formula (V) comprises the following steps:

a) a compound of formula (VIc):

(T ² and T ³ are as defined above) T ^a _j B, T ^a MgT ^b (T ^a , j, B and T ^b are as defined above), sodium hydride and potassium, metallic sodium And contacting with a base selected from potassium, wherein the molar ratio between said base and the compound of formula (VIc) is at least 1: 1 and excess base may be used:

b) contacting the anionic compound obtained in step a) with a compound of formula (VId):

Wherein R ¹ , T ¹ and L are as defined above and Y is chlorine, bromine and iodine, preferably Y is chlorine or bromine.

Compounds of formula (IVa), (IVb), (IVc), or (IVd) are described above starting from a ligand of formula (Va), (Vb), (Vc) or (Vd), or a double bond isomer thereof It can be obtained by the method mentioned in:

Wherein R ¹ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and L have the meanings described above.

Ligands of formula (Va), (Vb), (Vc), or (Vd) can be prepared according to the methods described above initiated from the appropriate compounds.

The alumoxanes used as component b) in the catalyst system according to the invention are formulated with water of the formula H _j AlU _{3 -j} or H _j Al ₂ U _{6 -j} (wherein the U substituents are the same or different, hydrogen atoms, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkylaryl or C ₇ -C ₂₀ arylalkyl, optionally containing halogen atoms, silicon or germanium atoms It can be obtained by reacting with an organo-aluminum compound of the radical, provided that at least one U is different from halogen, j is in the range of 0 to 1 and is also non-integer. The molar ratio of Al / water in the reaction preferably comprises 1: 1 to 100: 1.

Alumoxanes used in the process according to the invention are believed to be linear, branched or cyclic compounds containing one or more groups of the following types:

Wherein the substituents U are the same or differently defined as above.

In particular, alumoxanes of the general formula can be used in the case of linear compounds:

Wherein n ¹ is 0 or an integer from 1 to 40 and the substituent U is defined as above; Or alumoxanes of the formula: may be used in the case of cyclic compounds:

Wherein n ² is an integer from 2 to 40 and the U substituent is defined as above.

Examples of alumoxanes suitable for use according to the invention include methylalumoxane (MAO), tetra- (isobutyl) alumoxane (TIBAO), tetra- (2,4,4-trimethyl-pentyl) alumoxane (TIOAO), Tetra- (2,3-dimethylbutyl) alumoxane (TDMBAO) and tetra- (2,3,3-trimethylbutyl) alumoxane (TTMBAO).

In particular, interesting cocatalysts in which alkyl and aryl groups have specific branched patterns are disclosed in WO 99/21899 and WO 01/21674.

Non-limiting examples of aluminum compounds disclosed in WO 99/21899 and WO 01/21674 that can be reacted with water to obtain a suitable alumoxane (b) are as follows:

Tris (2,3,3-trimethyl-butyl) aluminum, tris (2,3-dimethyl-hexyl) aluminum, tris (2,3-dimethyl-butyl) aluminum, tris (2,3-dimethyl-pentyl) aluminum, Tris (2,3-dimethyl-heptyl) aluminum, tris (2-methyl-3-ethyl-pentyl) aluminum, tris (2-methyl-3-ethyl-hexyl) aluminum, tris (2-methyl-3-ethyl- Heptyl) aluminum, tris (2-methyl-3-propyl-hexyl) aluminum, tris (2-ethyl-3-methyl-butyl) aluminum, tris (2-ethyl-3-methyl-pentyl) aluminum, tris (2, 3-diethyl-pentyl) aluminum, tris (2-propyl-3-methyl-butyl) aluminum, tris (2-isopropyl-3-methyl-butyl) aluminum, tris (2-isobutyl-3-methyl-pentyl Aluminum, Tris (2,3,3-trimethyl-pentyl) Aluminum, Tris (2,3,3-trimethyl-hexyl) Aluminum, Tris (2-ethyl-3,3-dimethyl-butyl) Aluminum, Tris (2 -Ethyl-3,3-dimethyl-pentyl) aluminum, tris (2-isopropyl-3,3-dimethyl-butyl) al Aluminum, tris (2-trimethylsilyl-propyl) aluminum, tris (2-methyl-3-phenyl-butyl) aluminum, tris (2-ethyl-3-phenyl-butyl) aluminum, tris (2,3-dimethyl-3 -Phenyl-butyl) aluminum, tris (2-phenyl-propyl) aluminum, tris [2- (4-fluoro-phenyl) -propyl] aluminum, tris [2- (4-chloro-phenyl) -propyl] aluminum, Tris [2- (3-isopropyl-phenyl) -propyl] aluminum, tris (2-phenyl-butyl) aluminum, tris (3-methyl-2-phenyl-butyl) aluminum, tris (2-phenyl-pentyl) aluminum , Tris [2- (pentafluorophenyl) -propyl] aluminum, tris [2,2-diphenyl-ethyl] aluminum and tris [2-phenyl-2-methyl-propyl] aluminum, as well as one hydrocarbyl Corresponding compounds in which groups have been replaced by hydrogen atoms, and compounds in which one or two hydrocarbyl groups have been replaced by isobutyl.

Among the aluminum compounds, trimethylaluminum (TMA), triisobutylaluminum (TIBA), tris (2,4,4-trimethyl-pentyl) aluminum (TIOA), tris (2,3-dimethylbutyl) aluminum (TDMBA) and Tris (2,3,3-trimethylbutyl) aluminum (TTMBA) is preferred.

A non-limiting example of a compound capable of forming an alkylmetallocene cation is a compound of formula D ⁺ E ^- wherein D ⁺ is Bronsted acid, capable of donating protons and methyllocene of formula (I) Can be irreversibly reacted with substituents X, and E ⁻ is a commercially available anion, capable of stabilizing active catalytic species derived from the reaction of two compounds and being sufficiently unstable and can be removed by olefin monomers. Preferably the anion E ⁻ comprises at least one boron atom. More preferably the anion E ⁻ is of the formula BAr ₄ ⁽⁻⁾ Substituents Ar, which are anions of which may be identical or different in the formula, are aryl radicals such as phenyl, pentafluorophenyl or bis (trifluoromethyl) phenyl. Tetrakis-pentafluorophenyl borate salts are particularly preferred compounds, as described in WO 91/02012. In addition, the compounds of the formula BAr ₃ can be used easily. Compounds of this type are described, for example, in international patent application WO 92/00333. Another example of a compound capable of forming an alkylmetallocene cation is a compound of the formula BAr ₃ P, wherein P is a substituted or unsubstituted pyrrole radical. Such compounds are described in WO 01/62764. Compounds containing boron atoms can be readily supported according to the description of DE-A-19962814 and DE-A-19962910. All of the compounds containing boron atoms range from about 1: 1 to about 10: 1; Preferably 1: 1 to 2.1; More preferably, it may be used in a molar ratio between boron and metallocene metal, including about 1: 1.

Non-limiting examples of compounds of formula D ⁺ E ^- are as follows:

Triethylammonium tetra (phenyl) borate,

Tributylammonium tetra (phenyl) borate,

Trimethylammonium tetra (tolyl) borate,

Tributylammonium tetra (tolyl) borate,

Tributylammonium tetra (pentafluorophenyl) borate,

Tributylammonium tetra (pentafluorophenyl) aluminate,

Tripropylammonium tetra (dimethylphenyl) borate,

Tributylammonium tetra (trifluoromethylphenyl) borate,

Tributylammonium tetra (4-fluorophenyl) borate,

N, N-dimethylbenzylammonium-tetrakispentafluorophenylborate,

N, N-dimethylhexylammonium-tetrakispentafluorophenylborate,

N, N-dimethylanilinium tetra (phenyl) borate,

N, N-diethylanilinium tetra (phenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,

N, N-dimethylbenzylammonium-tetrakispentafluorophenylborate,

N, N-dimethylhexylammonium-tetrakispentafluorophenylborate,

Di (propyl) ammonium tetrakis (pentafluorophenyl) borate,

Di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,

Triphenylphosphonium tetrakis (phenyl) borate,

Triethylphosphonium tetrakis (phenyl) borate,

Diphenylphosphonium tetrakis (phenyl) borate,

Tri (methylphenyl) phosphonium tetrakis (phenyl) borate,

Tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,

Triphenylcarbenium tetrakis (phenyl) aluminate,

Ferrocenium tetrakis (pentafluorophenyl) borate,

Ferrocenium tetrakis (pentafluorophenyl) aluminate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate, and

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The organoaluminum compound used as compound c) is of the formula H _j AlU _{3 -j} or H _j Al ₂ U _{6 -j} as described above.

The polymerization process of the invention can be carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent. The hydrocarbon solvent may be aromatic (eg toluene) or aliphatic (eg propane, hexane, heptane, isobutane, cyclohexane, and 2,2,4-trimethylpentane). Preferably, the polymerization process of the present invention is carried out by using liquid 1-butene as the polymerization medium.

The polymerization temperature is preferably 0 ° C. to 250 ° C .; Preferably from 20 ° C to 150 ° C, more particularly from 50 ° C to 90 ° C.

The molecular weight distribution can be varied by using a mixture of different metallocene compounds or by carrying out the polymerization in several different steps with respect to the polymerization temperature and / or the concentration of the molecular weight regulator and / or the monomer concentration. Furthermore, by carrying out the polymerization process by the use of a combination of two different metallocene compounds of formula (I), polymers with a wide melting point are produced.

According to the invention 1-butene can be homopolymerized or copolymerized with ethylene, propylene or alpha olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group. When 1-butene is copolymerized with the comonomer, a copolymer having a content of comonomer derived units of 30 mol% or less, preferably 20 mol% or less, more preferably 0.2 mol% to 10 mol% may be obtained. . Examples of alpha-olefins of the formula CH ₂ = CHZ include 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene, 1-decene, 1-dodecene to be. Preferred comonomers used in the process according to the invention are ethylene, propylene, and 1-hexene. Preferably, 1-butene is homopolymerized in the process of the invention.

According to the method of the present invention for obtaining 1-butene homopolymer, when 1-butene is used, the 1-butene homopolymer is endowed with a very low modulus of elasticity compared to the melting point. Furthermore, the isotactic index of the 1-butene homopolymer, expressed as the ratio of isotactic mmmm pentads measured by ¹³ C-NMR according to the procedure described in the Examples, comprises 40% to 85%. Whereas the melting point of the 1-butene homopolymer, measured according to the procedure described in the Examples, includes 40 ° C. to 85 ° C. As such, homopolymers have an optimal balance of elastomeric properties.

Thus, a further object of the present invention is a 1-butene homopolymer having the following properties, obtainable according to the process of the present invention:

Bending coefficient (FM) (ISO 527-1) comprising from 50 to 200 Mpa, preferably from 50 to 150 Mpa;

Melting point (Tm) comprising 40 ° C. to 80 ° C., preferably 45 ° C. to 75 ° C., more preferably 50 ° C. to 72 ° C .;

-Bending coefficient (FM) (Mpa) and melting point (Tm) (° C) satisfying the following relationship:

FM <0.006Tm ^{2 .44}

Preferably, the relationship is FM <0.005Tm ^{2 .44}

Intrinsic viscosity (I.V.) measured at 135 ° C., tetrahydronaphthalene (THN)> 0.5 dl / g, preferably ≧ 0.8 dl / g, more preferably> 1 dl / g; Even more preferably> 1.2 dl / g; And

Isotactic pentad (mmmm) comprising from 40% to 80%, preferably from 50% to 75%;

Preferably the 1-butene homopolymer has Mw / Mn <4, preferably <3.5; More preferably has a molecular weight distribution of <3.

1-butene polymers, in particular 1-butene homopolymers obtained according to the process of the present invention, may be suitable as components of formulations which contain 1-butene-based polymers with high modulus of elasticity and high melting point as additional components. In this way, it is possible to combine the optimal features of the two products that are completely miscible to obtain a 1-butene based polymer composition having a high melting point and a low modulus of elasticity. A further object of the present invention is therefore a 1-butene polymer composition comprising:

A) 30 mole% or less, preferably 20 mole% or less, of derivative units of ethylene, propylene, or alpha-olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group having the following properties: 10 to 90% by weight of 1-butene homopolymer or 1-butene copolymer, preferably containing 0.2 mol to 10 mol%:

Bending coefficient (FM) (ISO 178) comprising from 50 to 200 Mpa, preferably from 50 to 150 Mpa;

Melting point (Tm) comprising 40 ° C. to 80 ° C., preferably 45 ° C. to 75 ° C., more preferably 50 ° C. to 72 ° C .;

-Bending coefficient (FM) (Mpa) and melting point (Tm) (° C) satisfying the following relationship:

FM <0.006Tm ^{2 .44}

Preferably, the relationship is FM <0.005Tm ^{2 .44}

Intrinsic viscosity (I.V.) measured at 135 ° C., tetrahydronaphthalene (THN)> 0.5 dl / g, preferably ≧ 0.8 dl / g, more preferably> 1 dl / g; Even more preferably> 1.2 dl / g; And

B) homo-array homopolymer of 1-butene, homo-array copolymer of 1-butene containing 2 mol% or less of ethylene derived units, homo-array copolymer of 1-butene containing 30 mol% or less of propylene derived units Or 1 selected from the same arrangement copolymer of 1 or more of said alpha-olefins and 1-butene containing up to 20 mol% of alpha-olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group. 10-90 wt.% Butene polymer; The 1-butene polymer has the following properties:

A melting point (Tm) of at least 90 ° C., preferably at least 100 ° C .; And

At least 90%, preferably at least 94% of the same configuration pentad (mmmm).

Preferably said 1-butene polymer A) has Mw / Mn <4, preferably <3.5; More preferably has a molecular weight distribution of <3. Preferably said 1-butene polymer B) has Mw / Mn <4, preferably <3.5; More preferably has a molecular weight distribution of <3. Preferably the 1-butene polymer A) comprises 40% to 80% of the same arrangement pentad (mmmm), preferably 50% to 75%; Preferably said 1-butene polymer A) is a 1-butene homopolymer.

1-butene polymer B) is MgCl ₂ It can be obtained by using a titanium based catalyst system supported on the bed or by using a single point catalyst system such as a metallocene based catalyst system. Useful methods for obtaining polymers of this kind are described, for example, in WO 99/45043, WO 03/099883, EP 172961, WO 02/100908, WO 02/100909, WO 03/014107 and EP03101304.8.

Component B) of the composition according to the invention is equal to or less than 5 when obtained using a single point catalyst system, preferably a metallocene catalyst system; Preferably a molecular weight distribution (Mw / Mn) of 4 or less, more preferably 3 or less, is given.

3 or more when component B) is obtained using a titanium based catalyst system supported on MgCl ₂ ; Preferably a molecular weight distribution of at least 4, more preferably at least 5 is given.

Preferably said 1-butene polymer B) is a 1-butene homopolymer.

Preferably, in the 1-butene polymer composition, which is an object of the present invention, component A) is 20 to 80% by weight; More preferably 30 to 70 wt%; Even more preferably in the range from 40 to 60% by weight: component B) is from 20 to 80% by weight; More preferably 30 to 70 wt%; Even more preferably 40 to 60% by weight.

The following compositions are also possible:

Component A Component B 10 to 20 wt% 90 to 80 wt% 20 to 30% by weight 80 to 70 wt% 30 to 40 wt% 70 to 60 wt% 40 to 50 wt% 60 to 50 wt% 50 to 60 wt% 50 to 40 wt% 60 to 70 wt% 40 to 30 wt% 70 to 80 wt% 30 to 20 wt% 80 to 90 wt% 20 to 10 wt%

Further, the metallocene compound of formula (I), (Va), (Vb), (Vc) or (Vd) may be an alpha-olefin of formula CH ₂ = CHZ 'wherein Z' is hydrogen or C ₁ -C ₂₀ Alkyl group) can be used to (co) polymerize. Therefore, in the presence of a catalyst system that can be obtained is a further object of this invention is written sikimeu contacted to, one or more compounds of formula CH ₂ = CHZ 'the alpha-formula which comprises contacting an olefin under polymerization conditions CH ₂ = CHZ' Is the (co) polymerization method of alpha-olefins of:

a) metallocene compound of formula (I);

b) compounds capable of forming one or more alumoxane or alkylmetallocene cations; And

c) optionally an organoaluminum compound.

Preferably the metallocene compound has the formula (Va), (Vb), (Vc) or (Vd).

Examples of alpha-olefins of the formula CH ₂ = CHZ 'include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-heptene, 1-hexene, 1-octene, 4,6-dimethyl-1-heptene , 1-decene and 1-dodecene.

A further object of the present invention is a catalyst system comprising a product obtainable by contacting:

a) metallocene compound of formula (I);

b) compounds capable of forming one or more alumoxane or alkylmetallocene cations; And

c) optionally an organoaluminum compound.

Preferably the metallocene compound has the formula (Va), (Vb), (Vc) or (Vd).

The following examples are given for purposes of illustration and are not intended to be limiting of the invention.

Intrinsic viscosity (IV) was measured in tetrahydronaphthalene (THN) at 135 degreeC. The melting point (Tm) of the polymer was measured by differential scanning calorimetry (DSC) using a Perkin Elmer DSC-7 instrument according to standard methods. Weighing samples (5-7 mg) obtained from the polymerization reaction were sealed with aluminum pans and heated to 180 ° C. at 10 ° C./min. The sample was held at 180 ° C. for 5 minutes to allow all crystals to melt completely and then cooled to 10 ° C. at 10 ° C./min. After standing at 20 ° C. for 2 minutes, the sample was heated from 10 ° C./min to 180 ° C. for the second time. In the second heating operation, the peak temperature was taken as the melting point (Tm) and the area of the peak was the melting enthalpy (ΔH _f ).

Molecular weight parameters and molecular weight distribution for all of these samples were determined using a Waters 150C ALC / GPC instrument (Waters, Milford, Massachusetts, USA) equipped with four mixed-gel columns PLgel 20 μm Mixed-A LS (Polymer Laboratories, Church Stretton United Kingdom). ) Was measured. The unit of the column was 300 x 7.8 mm. The solvent used was TCB and the flow rate was maintained at 1.0 mL / min. The concentration of the solution was 0.1 g / dL in 1,2,4 trichlorobenzene (TCB). 0.1 g / L of 2,6-di- t -butyl-4methyl phenol (BHT) was added to prevent degradation and the injection volume was 300 μL. All measurements were carried out at 135 ° C. GPC calibration is complicated by the difficulty of obtaining standardized narrow molecular weight distribution standards for 1-butene polymers. Thus, a universal calibration curve was obtained using 12 polystyrene standard samples with a molecular weight distribution of 580 to 13,200,000. The K values of the Mark-Houwink relation are assumed to be as follows: K _PS = 1.21 × 10 ^-4 dL / g for polystyrene and K _PB = 1.78 × 10 ^-4 dL / g for poly-1-butene, respectively. Mark-Houwink's index α was assumed to be 0.706 for polystyrene and 0.725 for poly-1-butene. This approach enables relative comparisons, even though the molecular parameters obtained are merely estimates of the hydrodynamic volume of each chain.

NMR  analysis.

¹³ C-NMR spectra were obtained with a DPX-400 spectrometer operating at 120 ° C. and 100.61 MHz in Fourier transform mode. Samples were dissolved in 1,1,2,2, tetrachloroethane-d2 at 120 ° C. at 8 wt% / v concentration. Each spectrum was obtained as a 90 ° pulse with a delay of 15 seconds between the pulse and the CPD (Waltz 16) to remove ¹ H- ¹³ C coupling. Approximately 3000 transition points were stored as 32 K data points using a 6000 Hz spectrum window. The equal array index of the metallocene-prepared PB was measured by ¹³ C-NMR and was defined as the relative intensity of the mmmm pentad peak of the diagonal methylene of the ethyl branch. Peaks at 27.33 ppm were used according to internal standards. Pentad assignments are described in Macromolecules, 1992 , 25, 6814-6817 Was given according to

The side chain methylene portion of the PB spectrum was fitted using the procedure for deconvolution included in the Bruker WIN-NMR program. The pentad associated with the mmmm pentad and single unit errors (mmmr, mmrr and mrrm) was fitted using Lorenzian lineshapes, varying the strength and width of the line. These results were used for statistical modeling of the pentad distribution using an enantiomorphic site model to obtain a complete pentad distribution, from which the triad distribution was derived.

Metallocene compounds

Dimethylsilininyl -{5- (1,1,3,3,6- Pentamethyl -1,2,3,5- Tetrahydro - s - Indasenil ) -7- (2,5-dimethyl-cyclopenta [1,2-b: 4,3- b ' ]- Dithiophene }) Zirconium Dichloride [A-1]

a) 1,1,3,3- Tetramethylindan  synthesis

A mixture of 117.26 g of α-methylstyrene (Aldrich 99%, 0.98 mol) and 73.0 g of t -butanol (Aldrich 99%, 0.98 mol) was added dropwise to a mixture of 200 g of acetic acid and 200 g of sulfuric acid, preheated at 40 ° C. (About 1 hour). The resulting suspension was stirred at 40 ° C. for 30 minutes, then the two layers obtained were separated. The water layer was removed, and the organic layer was first washed with 0.7 M aqueous NaOH solution to pH 7 (3 × 50 mL) and then with water (2 × 50 mL). The resulting opaque yellow solution was distilled off by heating in vacuo. The colorless clear solution was collected at a pressure in the range of 97 ° C. to 103 ° C., 11 to 26 mbar, and purified by NMR analysis to obtain the desired pure 1,1,3,3 tetramethylindan (28.43 g, 16,6% isolation yield). ) Was obtained.

¹ H-NMR (CDC1 ₃ , δ, ppm): 1.39 (s, CH ₃ , H8 and H9, 12H); 1.99 (s, CH ₂ , H ₂ , 2H); 7.17-7. 30 (m, Ar, H4, H5, H6 and H7, 4H).

¹³ C { ¹ H} -NMR (CDC1 ₃ , δ, ppm): 31.56 (CH ₃ , C8 and C9, 4C); 42.51 (C, Cl and C3, 2C); 56.60 (CH ₂ , C ₂ , 1 C); 122.45 and 126.69 (Ar, C4, C5, C6 and C7, 4C); 151.15 (Ar, C3a and C7a, 2C).

b) 2,5,5,7,7- Pentamethyl -2,3,5,6,7- Pentahydro - s - Indasen Synthesis of -1-one

50.71 g of A1C1 ₃ (Aldrich 99%, 376.5 mmol) was charged 28.43 g (163.1 mmol) 2-bromoisobutyryl bromine 38.1 g of 1,1,3,3 tetramethylindan in 500 mL of CH ₂ Cl ₂ at 0 ° C. Aldrich 98%, 163.3 mmmol) was added drop wise (30 min). During the addition the solution turned colorless to yellow and finally became dark red. Gas evolution was also observed. The suspension was stirred for 17 hours at room temperature and then poured into 200 g of ice / water. The green organic layer was first washed with 1 M aqueous HCl solution (1 × 200 mL), then saturated NaHCO ₃ solution (2 × 200 mL), and finally water (2 × 200 mL). The organic layer was dried over Na ₂ SO ₄ , filtered and evaporated to dryness under reduced pressure to yield 38.23 g of a green solid, which was determined by GC-MS to contain 76.7% of the desired product (96.7% crude yield). The solid was treated with 50 mL of MeOH and filtered. The white residue was washed once more with 30 mL of MeOH and dried to give 20.28 g of white powder. The filtrate was stored at −20 ° C. for 24 hours and the previous one was combined to give 3.95 g of white powder. The powder showed the properties of pure 2,5,5,7,7-pentamethyl-2,3,5,6,7-pentahydro- s -indasen-1-one by NMR analysis. Isolation yield was 61.3% (24.23 g).

¹ H-NMR (CDCl ₃ , δ, ppm): 1.27 (s, CH ₃ , H9, 3H); 1.31 (s, CH ₃ , H11, 6H); 1.33 (s, CH ₃ , H10, 6H); 1.95 (s, CH ₂ , H 6, 2H),; 2.62-2.79 (m, CH ₂ and CH, H ₂ and H 3, 2H); 3.28-3.37 (m, CH ₂ , H 3, 1H); 7.15 (s, Ar, H 4, 1 H); 7.51 (s, Ar, H 8, 1 H).

¹³ C { ¹ H} -NMR (CDCl ₃ , δ, ppm): 16.34 (CH ₃ , C9, 1C); 31.28, 31.30 (CH ₃ , C10, 2C); 31.50, 31.55 (CH ₃ , C11, 2C); 34.73 (CH ₂ , C 3, 1C); 41.86 (C, C7, 1C); 42.38 (CH, C2, 1C); 42.52 (C, C5, 1C); 56.44 (CH ₂ , C ₆ , 1 C); 117.87 (Ar, C8, 1C); 120.22 (Ar, C 4, 1 C); 135.67 (Ar, C8a, 1C); 151.69 (Ar, C7a, 1C); 152.91 (Ar, C 3a, 1 C); 159.99 (Ar, C 4a, 1C); 208.96 (C = O, C1, 1C).

c) 1,1,3,3,6- Pentamethyl -1,2,3,5- Tetrahydro - s - Indasen

A suspension of 24.36 g (100.5 mmol) of pure 2,5,5,7,7-pentamethyl-2,3,5,6,7-pentahydro- s -indasen-1-one in 100 mL of ethanol at room temperature Treated with 4.06 g NaBH ₄ (Aldrich 98%, 105,2 mmol). An opaque yellow solution was obtained. After stirring at room temperature for 4.5 hours, the solution was treated with 5 mL of acetone and then evaporated to dryness under reduced pressure to give a yellow gel. The yellow gel obtained was treated with 100 mL of toluene and 40 mL of water, and after stirring for 15 minutes, the two layers were separated. The water layer was washed with 50 mL of toluene and the organic layer was washed with 10% aqueous NH ₄ Cl solution (2 × 30 mL). The organic layers were combined, dried over Na ₂ S0 ₄ and filtered. To the yellow filtrate containing the desired alcohol, 1.89 g (Aldrich 98.5%, 9.8 mmol) of p -toluenesulfonic acid monohydrate was added and heated to 80 ° C. Formation of water and separation of the two layers were observed. After 5 hours of stirring at 80 ° C. and 2 days at room temperature, the reaction mixture still contained 11% of the starting alcohol by NMR analysis. The water formed was then removed from the reaction mixture and 0.20 g (1.0 mmol) of p -toluenesulfonic acid monohydrate were added. After stirring for 1 hour at 80 ° C. and for 16 hours at room temperature, the conversion became quantitative. The final mixture was treated with 50 mL of saturated NaHCO ₃ aqueous solution. The organic layer was separated, washed once more with saturated aqueous NaHCO ₃ solution (1 × 50 mL) and water (3 × 50 mL), dried over Na ₂ SO ₄ and filtered. The yellow filtrate was evaporated to dryness under reduced pressure to yield 20.89 g of a yellow liquid which was crystallized after a few minutes at room temperature. The liquid showed the properties of pure 1,1,3,3,6-pentamethyl-1,2,3,5-tetrahydro-s-indacene by NMR. Isolation yield was 91.8%.

¹ H-NMR (CDCl ₃ , δ, ppm): 1.38 (s, CH ₃ , H9 e H10, 12H); 2.00 (s, CH ₂ , H ₂ , 2H); 2.18 (bs, CH ₃ , H11, 3H); 3.30 (s, CH ₂ , H5, 2H); 6.51 (s, CH, H7, 1H); 7.06 (s, Ar, H 8, 1 H); 7.18 (s, Ar, H 4, 1 H).

¹³ C { ¹ H} -NMR (CDCl ₃ , δ, ppm): 16.81 (CH ₃ , C11, 1C); 31.77 (CH ₃ , C9 e C10, 4C); 42.08, 42.16 (C, Cl e C3, 2C); 42.28 (CH ₂ , C5, 1C); 57.04 (CH ₂ , C2, 1C); 113.61 (Ar, C8, 1C); 117.55 (Ar, C 4, 1 C); 127.13 (CH, C7, 1C); 142.28 (Ar, C 4a, 1 C); 145.00, 145.26 (Ar and C =, C7a and C6, 2C); 146.88 (Ar, C 3a, 1 C); 149.47 (Ar, C8a, 1C).

d) chloro (1,1,3,3,6- Pentamethyl -1,2,3,5- Tetrahydro - s - Indasen Synthesis of -5-yl) dimethylsilane

A 2.5 M n -BuLi solution (3.8 mL, 9.50 mmol, n -BuLi: indacene = 1: 1) in hexane was added 1,1,3,3,6-pentamethyl-1 in 40 mL of Et ₂ O at 0 ° C. To this was added dropwise a solution of 2.16 g (9.54 mmol) of 2,3,5-tetrahydro- s -indenecene. At the end of the addition, the resulting pale yellow solution was allowed to preheat at room temperature and stirred for 1 hour with the last formation of the white suspension. Aliquots of the suspension were cooled to CD ₃ OD and dried. ¹ H NMR analysis in CDCl ₃ showed that the starting indenes were completely converted to the corresponding lithium salts. The latter was then cooled again to 0 ° C. and added to 10 mL of a solution of Me ₂ SiCl ₂ (98%, 1.27 g, d = 1.064, 9.64 mmol) in Et ₂ O. The reaction mixture was allowed to preheat at room temperature and stirred for 16 h with the final formation of a white suspension. After stirring for 40 minutes at room temperature, the conversion was determined by ¹ H NMR analysis. 80%. The solvent was removed in vacuo and the residue was extracted with 70 mL of toluene to remove LiCl. The filtrate was allowed to dry in vacuo at 40 ° C., yielding a dark yellow oil as product, which tends to hold at room temperature to crystallize. Isolation yield 97.9% (17.9% purity by ¹ H NMR analysis). Starting indene was still present at 2.1% by weight.

¹ H-NMR (CDCl ₃ , δ, ppm): 0.11 (s, 3H, Si-CH ₃ ); 0.41 (s, 3H, Si-CH ₃ ); 1.29 (s, 3 H, CH ₃ ); 1.31 (s, 9 H, CH ₃ ); 1.93 (s, 2 H, CH ₂ ); 2.24 (m, 3 H, CH ₃ ); 3.49 (s, 1 H, CH); 6.57 (m, 1 H, Cp-H); 7.03 (s, IH 3 Ar); 7.16 (s, 1 H, Ar).

e) 5- (l, l, 3,3,6- Pentamethyl -l, 2,3,5- Tetrahydro - s - Indasenil ) -7- (2,5-dimethyl-cyclopenta [1,2-b: 4,3- b ' ]- Dithiophene ) Dimethylsilane  synthesis

A 2.5 M n -BuLi solution (3.60 mL, 9.00 mmol) in hexane was added 2,5-dimethyl-7H-cyclopenta [1,2-b: 4,3-b ']-in 30 mL Et ₂ O at 0 ° C. To this was added dropwise a suspension of 1.82 g (8.82 mmol) of dithiophene. The resulting brown suspension was stirred at 0 ° C. for 1 h and then pre-cooled to 0 ° C. at 20 ° C. in chloro (1,1,3,3,6-pentamethyl-1,2 in 20 mL of Et ₂ O To a solution of 2.88 g (97.9%, 8.84 mmol) of, 3,5-tetrahydro- s -indenosen-5-yl) dimethylsilane was added. The reaction mixture was kept at 0 ° C. for 10 minutes and then allowed to preheat at room temperature and stirred overnight with the last formation of black suspension. Several mL of MeOH was added and the solution was evaporated under reduced pressure and the crude residue was extracted with 70 mL of toluene. The extract was dried in vacuo to yield 4.46 g of a pinch-dark solid, which was analyzed by ¹ H-NMR spectroscopy and GS-MS analysis. The latter shows the presence of 71.1% of the desired ligand with 1,1,3,3,6-pentamethyl-1,2,3,5-tetrahydro- s -indecene 1.8% and MeTh ₂ Cp 3.2%. A byproduct of molecular weight 340 was also present 11.8%, which was n -butyl (1,1,3,3,6-pentamethyl-1,2,3,5-tetrahydro- s -indacene-5-yl) dimethyl May be silane. Crude yield = 73.6%. Attempts to purify the product by washing with pentane failed, so the ligand was used as in the next step without further purification.

¹ H NMR (δ, ppm, CDCl ₃ ):-0.37 (s, 3H, Si -CH ₃ ); 0.34 (s, 3H, Si-CH ₃ ); 1.26 (s, 3 H, CH ₃ ); 1.28 (s, 3 H, CH ₃ ); 1.32 (s, 3 H, CH ₃ ); 1.33 (s, 3 H, CH ₃ ); 1.92 (s, 2 H, CH ₂ ); 2.21 (s, 3 H, CH ₃ ); 2.55 (d, 6H, J = 2.15 Hz, CH ₃ ); 3.73 (s, 1 H, CH); 3.95 (s, 1 H, CH); 6.59 (s, 1 H, Cp-H); 6.85 (m, 2 H, CH); 7.07 (s, 1 H, Ar); 7.15 (s, 1 H, Ar).

m / z (%): 489 (14) [M ⁺ + 1], 488 (34) [M ⁺ ], 284 (28), 283 (100), 264 (13), 263 (60), 235 (10 ), 227 (13).

f) dimethylsilanediyl {5- (1,1,3,3,6- Pentamethyl -1,2,3,5- Tetrahydro - s - Indasenil ) -7- (2,5-dimethyl- Cyclopenta [1,2-b: 4,3- b ' ]- Dithiophene )} Zirconium Of dechlorid [A-1]  synthesis

A 2.5 M n -BuLi solution (6.60 mL, 16.50 mmol) in hexane was added to 5- (1,1,3,3,6-pentamethyl-1,2,3,5-tetra in 30 mL of Et ₂ O at 0 ° C. Hydro- s -indacenyl) -7- (2,5-dimethyl-cyclopenta [1,2-b: 4,3-b ']-dithiophene)} in a light brown solution of 4.07 g (8.33 mmol) of dimethylsilane Added dropwise. The resulting brown suspension was stirred at room temperature for 1 hour and then added to a suspension of 1.95 g (8.37 mmol) of ZrCl _{4 in} 20 mL of toluene, which was again cooled to 0 ° C. and precooled at the same temperature. At the end of the addition, the reaction mixture was preheated at room temperature and stirred for 1.5 hours. The solvent was removed in vacuo and the dark orange-brown residue (containing mainly the product expected by ¹ H NMR analysis in CDCl ₃ ) was treated with 60 mL of a mixture of isobutanol / toluene 1/5 (v / v) It was. After stirring for 10 minutes at room temperature, the suspension was filtered over a G3 frit. The filtrate was removed, because its ¹ H NMR spectrum showed degradation of the product, possibly due to the use of isobutanol; Attempts to recover the complex by toluene extraction failed. The residue was dried in vacuo to yield 0.43 g of a pale orange powder, which was analyzed by ¹ H NMR to yield the desired complex (Isolation yield by LiCl = 8.0%).

¹ H NMR (δ, ppm, CDCl ₃ ): 1.31 (s, 6H, Si-CH ₃ ); 1.20 (s, 3 H, CH ₃ ); 1.27 (s, 3 H, CH ₃ ); 1.33 (s, 3 H, CH ₃ ); 1.36 (s, 3 H, CH ₃ ); 1.83 (s, 2 H, CH ₂ ); 2.33 (s, 3 H, CH ₃ ); 2.36 (d, 3H, J = 0.98 Hz, CH ₃ ); 2.57 (d, 3H, J = 0.98 Hz, CH ₃ ); 6.60 (q, 1 H, J = 0.98 Hz, CH); 6.74 (s, 1 H, Cp-H); 6.76 (q, 1 H, J = 0.98 Hz, CH); 7.18 (s, 1 H, Ar); 7.29 (s, 1 H, Ar).

Polymerization (general process)

Cocatalyst methylalumoxane (MAO) is a commercially available product available (Witco AG, 10% by weight / volume toluene solution, or Alemarlc, 30% by weight). The catalyst mixture is prepared by dissolving the metallocene in the amount indicated in Table 1 in the appropriate amount of the MAO solution (Al / Zr ratio = 500) and stirring for 10 minutes at room temperature before injecting into the autoclave. Was prepared.

Al (i -Bu) ₃ to 6 mmol (hexane of 1 M solution), and 1-butene 1350 g, at room temperature, a magnetic drive stirrer and a 35 mL stainless-steel vial, the (vial) is mounted, connected to a thermostat that temperature control It was preliminarily washed with an Al ( i- Bu) ₃ solution in hexane, purified and charged into a 4-L jacketed stainless-steel autoclave, dried at 50 ° C. with nitrogen vapor. The autoclave was then kept constant at the polymerization temperature and a toluene solution containing a catalyst / cocatalyst mixture was injected into the autoclave using nitrogen pressure through the stainless-steel vial and the polymerizations indicated in Table 1 At a constant temperature for a specified time. Agitation was then stopped and the pressure into the autoclave was raised to 20 bar-g with nitrogen. Open the bottom discharge valve and discharge the 1-butene / poly-1-butene mixture into a heated steel tank containing 70 ° C. water. Turn off the tank heating and supply a nitrogen flow of 0.5 bar-g. After cooling to room temperature, the steel tank was opened and the wet polymer was collected. The wet polymer is dried in an oven at 70 ° C. under reduced pressure. The polymerization conditions and the characteristic data of the obtained polymer are shown in Table 1.

Example compound mg Yield (g) Active (Kg / g _cat * h) I. V. dL / g T _m (Ⅱ) ℃ ΔH _f (II) J / g mmmm% One A-1 2 32 16.0 1.31 71.3 12.9 77.9 2 A-1 4 151 37.8 0.91 70.5 7.4 76.5

The physical-mechanical properties of the 1-butene homopolymer obtained in Example 2 were analyzed according to ISO 527-1 and ISO 178. The results are shown in Table 2.

Measure unit Bend Coefficient (ISO 178) Mpa 128.0 Yield Point Stress Mpa 6.5 Yield point yield % 15.0 Stress at break Mpa 26.8 Elongation at break % 485

Preparation of 1-butene homopolymer component B)

Rac dimethylsilanediylbis-6- [2,5-dimethyl-3- (2'-methyl-phenyl) cyclopentadienyl- [1,2-b] -thiophene] zirconium dichloride (A-2) Was prepared according to WO 01/44318.

Cocatalyst methylalumoxane (MAO) is a commercially available product used (Witco AG, 10 wt.% / Volume toluene solution, 1.7 M in Al).

The catalyst mixture was dissolved by dissolving 2 mg of A-2 in 8 mL of toluene with an appropriate amount of MAO solution (Al / Zr ratio = 500), and stirred for 10 minutes at room temperature before injecting into the autoclave to obtain a solution. Was prepared.

4 mmol of Al ( i- Bu) ₃ (TIBA) (1 M solution in hexane) and 712 g of 1-butene, at room temperature, fitted with a magnetically driven stirrer and a 35 mL stainless-steel vial, connected to a temperature controlled thermostat , 2.3-L jacketed stainless-steel autoclave. The autoclave was then kept at 83 ° C. and the catalyst system, prepared as described above, was injected into the autoclave using nitrogen pressure through stainless-steel vials. The temperature increased rapidly to 85 ° C. and the polymerization was carried out at a constant temperature for 1 hour.

After cooling the reactor to room temperature, the polymer was dried at 60 ° C. under reduced pressure. The polymer obtained had an intrinsic viscosity (I. V. THN at 135 ° C.) 0.9, a molecular weight distribution (Mw / Mn) 2.2, a melting point of 106 ° C., at least 98% of the same arrangement pentad (mmmm).

One- Butene  Preparation of Polymer Composition

The 1-butene polymer obtained in Example 2 (component A) was extruded into the 1-butene polymer (component B) obtained as described above using a Brandbury extruder in a 1: 1 weight ratio. 0.1 weight% Inorganox ™ 1010 was added to the composition as a stabilizer. The properties of the composition compared to the properties of the 1-butene homopolymers (components A and B) are shown in Table 3.

Tm (Ⅱ) ℃ mmmm% Bending factor (ISO 178) Component a 71 76.5 128 Component b 106 > 98 405 50:50 component a: component b 99 n.a. 277 n.a. = Unavailable

It is shown in Table 3 that the 1-butene polymer composition has a synergistic effect of maintaining a characteristic with a significantly higher melting point due to component b) at the same time as a low coefficient due to component a).

Claims (16)

Metallocene compound of formula (I):

[Meal: M is a transition metal belonging to groups 3, 4, 5, 6 or lanthanide or actinide of the Periodic Table of the Elements; p is an integer from 0 to 3, such as the formal oxidation state of metal M ^{- 2} ; X is the same or different, hydrogen atom, halogen atom, or R, OR, OSO ₂ CF ₃ , OCOR, SR, NR ₂ , or PR ₂ group, wherein R is linear or branched, cyclic or acyclic, C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₂ -C ₄₀ -alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl Radicals; Optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Or two X are substituted or unsubstituted butadienyl radicals or OR'O groups, wherein R 'is C ₁ -C ₄₀ alkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C ₄₀ alkylaryl Optionally a divalent radical selected from den and C ₇ -C ₄₀ arylalkylidene radicals; L is a divalent C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements or divalent sillylidene radicals containing up to 5 silicon atoms; R ¹ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; T ¹ , equally or different from each other, is a moiety of the formula (IIa) or (IIb):

(Atoms denoted by the * symbol combine with atoms denoted by the same symbol in the compound of the formula (I); R ² and R ³ are the same or different from each other or a C ₁ -C ₄₀ hydrocarbon radical optionally containing a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements, or they are heteroatoms belonging to a Group 13 to 16 of the Periodic Table of the Elements Together to form a condensed saturated or unsaturated C ₃ -C ₇ -membered ring optionally containing; All atoms forming the ring are substituted with R ⁸ radicals; This means that the valence of each atom forming the ring is filled with R ⁸ groups, wherein R ⁸ is the same or different from each other, a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon radical; R ⁴ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; T ² and T ³ are the same or different from each other and are part of formula (IIIa) or (IIIb):

(Atoms denoted by the symbol * combine with atoms represented by the same symbol to the compound of formula (I); R ⁶ and R ⁷ are the same or different from each other, a C ₁ -C ₄₀ hydrocarbon radical optionally containing a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements; R ⁵ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements; Provided that when T ¹ is part of formula (IIa) at least one of T ² and T ³ is part of formula (IIIb), and if T ¹ is part of formula (IIb) then at least one of T ² and T ³ is formula ( Part of IIIa). The compound of claim 1, wherein M is titanium, zirconium or hafnium; X is a hydrogen atom, a halogen atom, or an R group, where R is as defined in claim 1; L is a (Z (R '') ₂ ) _n group, where Z is a carbon or silicon atom, n is 1 or 2, and R '' optionally contains heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements A C ₁ -C ₂₀ hydrocarbon radical). 3. The compound of claim 1, wherein R ¹ is a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; R ⁴ is a linear or branched, cyclic or acyclic, C ₁ -C ₄₀ -alkyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -arylalkyl radical; R ⁶ and R ⁷ are hydrogen atoms; R ⁵ is a hydrogen atom or a linear or branched, cyclic or acyclic, C ₁ -C ₄₀ -alkyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -arylalkyl radical. 4. The metallocene compound according to claim 1, wherein T ¹ is part of formula (IIa), T ² and T ³ are the same and part of formula (IIIb). 5. The metallocene compound according to any one of claims 1 to 4, having the formulas (IVa), (IVb), (IVc) or (IVd):

(Wherein M, X, p, L, R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as in claim 1; R ⁹ and R ¹⁰ are the same or different from each other, linear or minute). Topographic, cyclic or acyclic, C ₁ -C ₄₀ alkyl radical, R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ alkyl radical). Ligands and / or double bond isomers thereof of Formula (V):

Wherein R ¹ , T ¹ , T ² , T ³ and L have the same meaning as in any one of claims 1-5. In the presence of a catalyst system obtainable by contacting the following: 1-butene and optionally polymerization of ethylene, propylene or alpha-olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group A process for the preparation of 1-butene polymers optionally containing up to 30 mole% of units derived from at least one monomer selected from ethylene, propylene or said alpha olefins: a) the metallocene compound according to any one of claims 1 to 5; And b) compounds capable of forming one or more alumoxane or alkylmetallocene cations. 8. The process according to claim 7, wherein said catalyst system is obtained by further contacting components a) and b) with c): c) organoaluminum compounds. The method of claim 7 or 8, wherein the 1-butene is homopolymerized. 10. The process according to any of claims 7 to 9, wherein the process is carried out by using liquid 1-butene as the polymerization medium. 1-butene homopolymer having the following properties: Bending coefficient (FM) including from 50 to 200 Mpa (ISO 527-1); Melting point (Tm) comprising from 40 ° C. to 80 ° C .; -Bending coefficient (FM) (Mpa) and melting point (Tm) (° C) satisfying the following relationship: FM <0.006Tm ^{2 .44} Intrinsic viscosity (I. V.) higher than 0.5 dl / g measured at 135 ° C., tetrahydronaphthalene (THN); And Coarse pentads (mmmm) comprising from 40% to 80%. 12. The 1-butene homopolymer of claim 11, having a molecular weight distribution of Mw / Mn <4. 1-butene polymer composition comprising: A) 1-butene homopolymer containing not more than 30 mol% of ethylene, propylene or alpha-olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group having the following properties: 1-90 wt% of 1-butene copolymer: Bending coefficient (FM) including 50 to 200 Mpa (ISO 527-1); A melting point (Tm) comprising from 40 ° C. to 80 ° C .; -Bending coefficient (FM) (Mpa) and melting point (Tm) (° C) satisfying the following relationship: FM <0.006Tm ^{2 .44} Intrinsic viscosity (I.V.) higher than 0.5 dl / g measured at 135 ° C., tetrahydronaphthalene (THN); And B) 1-butene homopolymer containing not more than 30 mol% of ethylene, propylene or alpha-olefins of formula CH ₂ = CHZ, wherein Z is a C ₃ -C ₁₀ alkyl group having the following properties: 10 to 90 weight percent of the butene copolymer: Melting point (Tm) of at least 90 ° C; And 90% or more coarse pentads (mmmm). 15. The 1-butene polymer composition of claim 14, wherein both 1-butene polymers A) and B) are 1-butene homopolymers. Contacting at least one alpha-olefin of formula CH ₂ = CHZ ', wherein Z' is hydrogen or an alkyl group of C ₁ -C ₂₀ , under polymerization conditions in the presence of a catalyst system obtainable by contacting (Co) polymerization method of the alpha-olefin of the formula CH ₂ = CHZ ' a) metallocene compound of formula (I); b) compounds capable of forming one or more alumoxane or alkylmetallocene cations; And c) optionally an organoaluminum compound. Catalyst system comprising a product obtainable by contacting: a) metallocene compound of formula (I); b) compounds capable of forming one or more alumoxane or alkylmetallocene cations; And c) optionally an organoaluminum compound.