JP2008505198A - Polymerization catalyst, main group coordination compound, method for producing polyolefin, and polyolefin - Google Patents

Abstract

A catalyst composition based on a compound that does not contain a transition metal is provided.
At least one chiral coordination compound of a main group element selected from the group consisting of elements consisting of Al, Si, and Ge as a central atom, and the chiral coordination compound exhibit polymerization activity for at least one olefin At least one cocatalyst that can be transformed into a chiral coordination compound comprising two bidentate chelating ligands linked together by cross-linking, and optionally one or more It is obtained by reacting with four coordinating atoms of two chelating ligands surrounding the main group element as the central atom of the coordination compound so that it is almost planar. , Two or less other ligands are located above or below the almost planar coordination sphere formed by the four coordination atoms of the two chelating ligands, In the case of two, these are mutually Isotactic polyolefin production catalyst composition present in the lance position.
[Selection figure] None

Description

  The present invention provides a main group element selected from the group consisting of Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi, and Po as central atoms. At least one chiral coordination compound, and at least one co-catalyst capable of changing the chiral coordination compound to one exhibiting polymerization activity with respect to at least one olefin. Two bidentate chelating ligands, and optionally one or more other monodentate ligands, and two surrounding the main group element as the central atom of the coordination compound to be approximately planar Obtained by reacting with four coordinating atoms of the chelating ligand of, and almost no more than two other ligands formed by the four coordinating atoms of the two chelating ligands. Above or below the coordination zone of the mold And location, to isotactic polyolefin production catalyst composition it is present in trans position to each other in the case other ligands is two.

  Furthermore, the present invention relates to a method for producing a polyolefin by polymerization or copolymerization of at least one olefin in the presence of one kind of catalyst composition of the present invention, a method for using the catalyst composition of the present invention for polyolefin production, and for olefin polymerization. Use of Chiral Coordination Compound of Main Group Element Compound for Production of Catalyst Composition, Chiral Coordination Compound of Main Group Element, Production Method of Catalyst Composition for Olefin Polymerization, Production Method of Isotactic Polyolefin, The present invention relates to polyolefins obtained by the process, polyolefin compositions comprising the polyolefins of the invention, and articles made from such polyolefin mixtures.

  Research and development on the use of organic transition metal compounds, especially metallocenes, as a catalyst composition for olefin polymerization and copolymerization aimed at producing the desired polyolefin has been intensively promoted in universities and industries over the past 15 years Has been.

  Currently, apart from metallocenes, a new class of transition metal compounds that do not contain any cyclopentadienyl ligands are increasingly being studied as catalyst compositions.

  Olefin polymerization catalysts that do not contain transition metals are likewise known. Non-Patent Document 1 discloses a cationic aluminum complex for ethylene polymerization.

J. et al. Am. Chem. Soc 1997, 119, 8125-8126

  The object of the present invention is to find a catalyst composition which makes it possible to produce highly isotactic polyolefins, in particular isotactic polypropylene having a melting point of more than 150 ° C., based on compounds which do not contain any transition metals. Furthermore, the catalyst composition must have excellent activity and be usable at industrially suitable polymerization temperatures.

  Therefore, the inventors selected from the group of elements consisting of Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi, and Po as the central atoms. At least one chiral coordination compound of a main group element and at least one cocatalyst capable of changing the chiral coordination compound to one exhibiting polymerization activity with respect to at least one olefin are bonded together by crosslinking. Two bidentate chelating ligands, and optionally one or more other monodentate ligands, and a main group atom as the central atom of the coordination compound to be substantially planar Obtained by reacting with four coordinating atoms of two surrounding chelating ligands, no more than two other ligands formed by four coordinating atoms of two chelating ligands The almost flat arrangement And on or located below the area, in the case other ligands of two found isotactic polyolefin production catalyst composition they are present in trans position to each other.

  Chiral coordination compounds of main group elements are Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi and Po, preferably Al, Si, Ga, Ge, As, In, Sn, Sb and Te, particularly preferably Al, Si, Ge and Sn, most preferably Al, Si and Ge, especially main group elements selected from the group consisting of Ge, as central atoms Including.

The bridge of the main group element's chiral coordination compound is a chiral bridge, in particular a bridge containing two chiral sp ³ -hybridized carbon atoms each directly attached to one of the two chelating ligands. Is preferred. Particular preference is given to bridges in which two chiral sp ³ -hybridized carbon atoms are bonded directly to one another.

  Each of the two bidentate chelate ligands is preferably charged to -1. The two coordinating atoms of the chelating ligand are, for example, nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium, in particular nitrogen, oxygen or sulfur. It is preferred that at least one of the two coordinating atoms of the bidentate chelate ligand, particularly exactly one, is a nitrogen atom. Particularly preferred are bidentate chelate ligands having one coordinated nitrogen atom and one coordinated oxygen atom.

  It is particularly preferable that the bidentate chelate ligand forms a 5-membered ring or a 6-membered ring, particularly a 6-membered heterocyclic ring, together with the central atom of the coordination compound.

  Preference is given to bidentate chelate ligands which are bonded to one another via one of the two coordination atoms, in particular via the respective nitrogen atom. Derived from 1,3-dicarbonyl compounds such as acetylacetone, benzoylacetone or 1,3-diphenyl-1,3-propanedione or substituted derivatives thereof, or ortho-such as 2-hydroxybenzaldehyde or 2-hydroxyacetophenone Preference is given to bidentate chelating ligands derived from carbonylphenol derivatives and substituted derivatives thereof and having an imine functional group formed by reaction of a carbonyl functional group with a primary amine.

A monodentate ligand is an anion charged to −1, in particular a fluorine, chlorine, bromine or iodine anion, in particular a halide anion such as a chlorine anion, a hydride anion, a C, such as a methyl, tert-butyl, vinyl, phenyl or benzyl anion. hydrocarbon anion of ₁ -C _40, alkoxy or aryloxy anions such as methoxy or phenyl anion, amide anion, such as dimethyl amide anion. Particularly preferred monodentate ligands are chlorine, methyl and benzyl anions, especially the chlorine anion.

  The four coordinating atoms of the two bidentate chelating ligands surround the central atom of the coordination compound so as to be substantially planar, in particular, substantially square planar. The central atom of the coordination compound need not be located exactly in the plane formed by the four coordination atoms of the two bidentate chelating ligands. For the purposes of the present invention, “substantially planar” means that the four coordinating atoms of the two chelating ligands do not have to be exactly located in the plane, but two of the first chelating ligands. Means that the coordination atoms may be slightly twisted with respect to the two coordination atoms of the second chelate ligand. In this case, the metal ion surrounded by the four coordinating atoms of the two chelate ligands so as to have a substantially planar shape, in particular, a substantially square planar shape, is defined as the second chelate ligand. A first plane formed by the coordination atom and the central atom of the coordination compound, and a second plane formed by the two coordination atoms of the second chelate ligand and the central atom of the coordination compound. It means that the angle to the plane is in the range of 0 ° to 20 °, in particular in the range of 0 ° to 10 °.

As the catalyst composition described above, the chiral coordination compound of the main group element is a coordination compound represented by the following formula (I) or an optical isomer thereof represented by the following formula (I ^* )

(Where
M is Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi or Po,
Z groups may be the same or different and each is an organic or inorganic anionic ligand;
n1 and n2 may be the same or different and each is 0 or 1, and n1 + n2 + 2 is equal to the valence of M;
R ¹ and R ² may be the same or different and each is a C ₁ -C ₄₀ group, or R ¹ and R ² together with the atoms connecting them, a cyclic or polycyclic group And the cyclic or polycyclic group contains one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si instead of carbon atoms in the cyclic group. You may,
R ³ is hydrogen or a C ₁ -C ₄₀ group, R ³ represents steric hindrance less than R ¹ ,
R ⁴ is hydrogen or a C ₁ -C ₄₀ group, R ⁴ represents a steric hindrance smaller than R ² ,
R ⁵ and R ⁶ may be the same or different and are each hydrogen or a C ₁ -C ₄₀ group, or
R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ⁵ , and / or R ² and R ⁶ together with the atoms connecting them together form a cyclic or polycyclic group, Or the polycyclic group may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si in place of the carbon atoms in the ring group;
X represents a single bond between two carbon atoms or is a divalent group,
Y ¹ and Y ² may be the same or different and are each oxygen, sulfur, selenium, tellurium, NR ⁹ group or PR ⁹ group,
R ⁷ , R ⁸ and R ⁹ may be the same or different and are each hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₂ aryl, Alkylaryl or arylalkyl having 1 to 10 carbon atoms and having 6 to 22 carbon atoms in the aryl group;
T ¹ , T ² , T ³ and T ⁴ may be the same or different and each is hydrogen or a C _{1 to} C ₄₀ group, or T ¹ and T ³ and / or T ² and T ⁴ are each A cyclic or polycyclic group together with the carbon atom to which is bonded, wherein the cyclic or polycyclic group is one or more identical or selected from the group consisting of the elements N, O, P, S and Si Which may contain different heteroatoms instead of carbon atoms in the ring group).

M ¹ is Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi or Po, preferably Al, Si, Ga, Ge, As, In, Sn, Sb and Te, particularly preferably Al, Si, Ge and Sn, most preferably Al, Si and Ge, especially Ge.

The Z groups may be the same or different, preferably the same, each being an organic or inorganic anionic ligand. Z is fluorine, chlorine, bromine or iodine, especially halogen such as chlorine, hydrogen, C ₁ -C _20, preferably an alkyl of _{C 1 ~C 4, C 2 ~C} 20, preferably alkenyl of C ₂ -C ₄ , C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl, each having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and 6 to 22 in the aryl group, Preferred is alkylaryl or arylalkyl having 6 to 10 carbon atoms, —OR ⁷ or —NR ⁷ R ⁸ . Z is particularly preferably chlorine or methyl.

  n1 and n2 may be the same or different and are each 0 or 1, and n1 + n2 + 2 corresponds to the valence of M. n1 and n2 are the same in the case of the Group 4 element of the periodic table of elements and are preferably 1 so that the oxidation number is +4 and the same in the case of the Group 10 element of the periodic table of elements. And 0, which results in an oxidation number of +2.

R ¹ and R ² may be the same or different, and are preferably the same, such as C ₁ -C ₄₀ hydrocarbon group or C ₃ -C ₄₀ -Si (R ⁷ ) ₃ , respectively. a group of C ^₁ ~C _40, R ₁ and R ² form together with atoms to bind their cyclic or polycyclic group, the cyclic or polycyclic groups, the carbon atom in the ring Alternatively, it may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, preferably N, O or S, especially N. Preferably, R ¹ and R ² are each cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl group, C ₂ -C ₂₀ , preferably C _2- C ₈ alkenyl group, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl group, having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and 6 in the aryl group An alkylaryl or arylalkyl group having from ˜22, preferably from 6 to 10 carbon atoms, which may be halogenated, or C ₃ -C ₁₈ , preferably C ₃ -C ₈ -Si (R ⁷ ) ₃ or R ¹ and R ² together with the atoms connecting them together with a cyclic 4 to 8 membered ring, preferably a 5 or 6 membered ring optionally having a C _{1 to} C ₂₀ group in order To form a cyclic group. Particularly preferably, R ¹ and R ² are each a cyclic, branched or unbranched C ₁ -C ₈ alkyl group, a C ₆ -C ₁₀ aryl group, 1-4 carbons in the alkyl group. An alkylaryl group or arylalkyl group having 6 to 10 carbon atoms in the aryl group, or a trimethylsilyl group, or R ¹ and R ² together with the atoms connecting them, cyclic, branched Jo or unbranched alkyl group of C ₁ -C _8, aryl group having C ₆ -C _10, having from 1 to 4 carbon atoms in the alkyl group, 6 to 10 carbon atoms in the aryl group A 5- or 6-membered cyclic group which may have an alkylaryl group or arylalkyl group or trimethylsilyl group in order. Particularly preferred examples of R ¹ and R ² groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, Cyclohexyl, n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4- Trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps- Butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl. Preferred ring groups formed from the R ¹ and R ² groups and the atoms connecting them are 1,2-cyclohexylene, 1,2-cyclopentylene and 1-benzylpyrrolidine-3,4-ylene.

R ³ is hydrogen or a C ₁ -C ₄₀ hydrocarbon group or a C ₁ -C ₄₀ group such as C ₃ -C ₄₀ -Si (R ₇ ) ₃ , and R ³ is less steric hindrance than R ^1. Have R ³ is preferably hydrogen, cyclic, branched or unbranched, especially unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl, C ₂ -C ₂₀ , preferably C ₂ -C ₈ alkenyl group, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl group, having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and in the aryl group It is an alkylaryl group or arylalkyl group having 6 to 22, preferably 6 to 10 carbon atoms, which may be halogenated, preferably an arylalkyl group. R ³ is particularly preferably hydrogen or an unbranched C ₁ -C ₈ alkyl group. R ³ is most preferably hydrogen.

R ⁴ is hydrogen or a C ₁ -C ₄₀ hydrocarbon group or a C ₁ -C ₄₀ group such as C ₃ -C ₄₀ -Si (R ⁷ ) ₃ , and R ⁴ is less steric hindrance than R ^2. Have R ⁴ is preferably hydrogen, cyclic, branched or unbranched, especially unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl, C ₂ -C ₂₀ , preferably C ₂ -C ₈ alkenyl group, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl group, having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and in the aryl group It is an alkylaryl group or arylalkyl group having 6 to 22, preferably 6 to 10 carbon atoms, which may be halogenated, preferably an arylalkyl group. R ⁴ is particularly preferably hydrogen or an unbranched C ₁ -C ₈ alkyl group. R ⁴ is most preferably hydrogen.

  The steric hindrance that appears by the group is determined by the degree to which it fills the space. For example, steric hindrance increases in the following order:

  Hydrogen <methyl <ethyl <isopropyl <tert-butyl

R ⁵ and R ⁶ may be the same or different, and are particularly the same, each being hydrogen or a C ₁ -C ₄₀ group. R ⁵ and R ⁶ are preferably hydrogen, cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl groups, C ₂ -C ₂₀ , preferably C ₂ -C ₈ alkenyl, C ₆ -C _22, preferably an aryl group of C ₆ -C _10, 1 to 10 carbon in the alkyl group, preferably having 1 to 4 carbon atoms, 6 in the aryl radical It is an alkylaryl group or an arylalkyl group having 22 and preferably 6 to 10 carbon atoms, which may be halogenated, preferably an arylalkyl group. R ⁵ and R ⁶ are particularly preferably hydrogen, cyclic, branched or unbranched C ₁ -C ₈ alkyl group, C ₆ -C ₁₀ aryl group, 1-4 carbons in the alkyl group. Alkylaryl or arylalkyl having an atom and having 6 to 10 carbon atoms in the aryl group. Particularly preferred examples of R ⁵ and R ⁶ groups are halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n- Hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, pentafluorophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl, p- tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl, especially hydrogen.

Furthermore, the two groups R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ⁵ , and / or R ² and R ⁶ , in each case, together with the atoms connecting them, Instead of carbon atoms, cyclic or polycyclic may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, preferably N, O or S A formula group may be formed. X represents a single bond or a divalent group between two carbon atoms. Examples of divalent groups X include CR ⁷ R ⁸ , especially CH ₂ , CR ⁷ R ⁸ —CR ⁷ R ⁸ , especially CH ₂ —CH ₂ , (CR ⁷ R ⁸ ) ₃ , (CR ⁷ R ⁸ ) ₄ Or (CR ⁷ R ⁸ ) ₅ X is preferably a single bond or CH ₂ , particularly a single bond.

Y ¹ and Y ² may be the same or different and are particularly the same and are each oxygen, sulfur, selenium, tellurium, an NR ⁹ group or a PR ⁹ group, especially oxygen.

R ⁷ , R ⁸ and R ⁹ may be the same or different and are each hydrogen, C ₁ -C ₂₀ , preferably C ₁ -C ₄ alkyl group, C ₂ -C ₂₀ , preferably C ₂ -C ₄ alkenyl, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl, having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and in the aryl group An alkylaryl group or arylalkyl group having 6 to 22, preferably 6 to 10 carbon atoms.

T ¹ , T ² , T ³ and T ⁴ may be the same or different and are each hydrogen or a C _{1 to} C ₄₀ group, or T ¹ and T ³ and / or T ² . T ⁴ includes one or more same or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, in place of the carbon atoms in the ring group, together with the carbon atoms connecting them. An optional cyclic or polycyclic group is formed. T ¹ , T ² , T ³ and T ⁴ are preferably branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl groups, C ₂ -C ₂₀ , preferably C ₂ -C ₈ alkenyl group, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl group, alkyl group having 1 to 10, preferably 1 to 4 carbon atoms, aryl group An alkylaryl group or arylalkyl group having 6 to 22, preferably 6 to 10 carbon atoms, which may be halogenated, preferably an arylalkyl group, or T ¹ and T ³ and T ² and T ⁴ may contain a heteroatom selected from the group consisting of O, S and N together with the carbon atom to which they are bonded, and become a component of a larger polycyclic group. May be substituted or unsubstituted aromatic or partially halogenated It is a 5- to 8-membered ring group, particularly a 5- or 6-membered ring group. T ¹ and T ³ and T ² and T ⁴ together with two bonded carbon atoms may be a substituted or unsubstituted phenyl ring, thiophene ring or pyrrole that may be a component of a larger polycyclic group Particular preference is given to forming a ring, in particular a phenyl ring.

In the present invention, the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , T ¹ , T ² , T ³ and T ⁴ are also represented by the catalyst of the present invention. It may have a functional group that is chemically inert under the polymerization conditions without changing the polymerization properties of the composition.

Furthermore, in the present invention, the substituent is not particularly limited and is as shown below:
The term “C ₁ -C ₄₀ group” used in the present invention means a C ₁ -C ₄₀ alkyl group, a C ₁ -C ₁₀ fluoroalkyl group, a C ₁ -C ₁₂ alkoxy group, a saturated C ₃ -C ₂₀ heterocyclic groups, C ₆ -C ₄₀ aryl groups, C ₂ -C ₄₀ heteroaromatic ring groups, C ₆ -C ₁₀ fluoroaryl groups, C ₆ -C ₁₀ aryloxy groups, C ₃ trialkylsilyl groups -C _18, means an alkenyl group, C ₂ -C ₂₀ alkynyl group, arylalkenyl group of the arylalkyl group, or C ₈ -C ₄₀ in C ₇ -C ₄₀ of C ₂ -C _20.

The term “alkyl” used in the present invention includes saturated hydrocarbons which may be cyclic, are linear or are singly or plurally branched. Preferably, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, iso C ₁ -C ₁₈ alkyl such as pentyl, isohexyl, sec-butyl or tert-butyl.

  The term “alkenyl” as used in the present invention includes linear or single or multiple branched hydrocarbons having one or more C—C double bonds that may be accumulated or alternating.

The term “saturated heterocyclic group” as used in the present invention is substituted by one or more carbon atoms, CH groups and / or CH ₂ groups by a heteroatom selected from the group consisting of O, S, N and P. Means a monocyclic or polycyclic substituted or unsubstituted hydrocarbon group. Preferred examples of the substituted or unsubstituted saturated heterocyclic group include pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, or methyl-, ethyl-, propyl- , Isopropyl- and tert-butyl-substituted derivatives, and the like.

As used herein, the term “aryl” refers to linear or branched C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₀ alkenyl, or C ₃ -C ₁₅ alkyl. By alkenyl is selected mono- or polysubstituted aromatic, where appropriate, fused polyaromatic hydrocarbon substituents. Preferred examples of the substituted or unsubstituted aryl group include phenyl, pentafluorophenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl and 4-methoxy. Phenyl, 1-naphthyl, 9-anthryl, 9-phenanthryl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-trifluoromethylphenyl, and the like.

The term “heteroaromatic group” as used in the present invention means an aromatic hydrocarbon substituent in which one or more carbon atoms are replaced by nitrogen, phosphorus, oxygen or sulfur atoms or combinations thereof. . These are selectively mono- or polysubstituted by linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkyl alkenyl, such as aryl groups. Or an aryl group. Preferred examples are furyl, thienyl, pyrrolyl, pyridyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl and their methyl-, ethyl-, propyl-, isobutyl- and tert-butyl substituted derivatives.

  As used herein, the term “alkylalkenyl” includes linear or single or multiple branched hydrocarbons having one or more separate C—C double bonds, so that the substituents are alkyl and alkenyl. Have both parts.

  The term “arylalkyl” as used herein refers to an aryl-containing substituent in which an aryl group is attached to the remainder of the molecule through an alkyl chain. Preferred examples include benzyl, substituted benzyl, phenethyl, substituted phenethyl and the like.

  Fluoroalkyl and fluoroaryl are those in which at least one, preferably two or more, and the maximum number of hydrogen atoms are replaced by fluorine atoms. In the present invention, preferred examples of the fluorine-containing organic group include trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl, 4-perfluoro-tert-butylphenyl, and the like. .

As the above-described catalyst composition, particularly preferably, the chiral coordination compound of the main group element of the formula (I) or the formula (I ^* ) is a coordination compound represented by the following formula (Ia) or the following formula (Ia ^*) Its optical isomers

(Where
M is Al, Si, Ga, Ge, As, In, Sn, Sb or Te,
Z groups may be the same or different and has a halogen respectively, hydrogen, alkyl of C ₁ -C _10, aryl of C ₆ -C _14, from 1 to 4 carbon atoms in the alkyl group An alkylaryl group or an arylalkyl group having 6 to 10 carbon atoms in the aryl group,
n1 and n2 may be the same or different and each is 0 or 1, and n1 + n2 + 2 corresponds to the valence of M;
R ¹ and R ^{2, which} may be the same or different, are each a C _{1 to} C ₄₀ group, or R ¹ and R ² together with the atoms connecting them together with the carbon atom in the ring group Instead, it forms a cyclic or polycyclic group that may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si;
R ⁵ and R ⁶ are the same and are each hydrogen or a C ₁ -C ₄₀ group;
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different and are each hydrogen, halogen or a C ₁ -C ₄₀ group, or two adjacent R ¹⁰ , R ^11. , R ¹² and R ¹³ may form a cyclic group together with the two carbon atoms bonded to them.

M ¹ is Al, Si, Ga, Ge, As, In, Sn, Sb or Te, preferably Al, Si, Ge or Sn, particularly preferably Al, Si or Ge, most preferably Si or Ge, especially Ge It is.

The Z groups may be the same or different and are preferably the same, each of fluorine, chlorine, bromine or iodine, especially halogen such as chlorine, hydrogen, C ₁ -C ₁₀ , preferably C _1- C ₄ alkyl, C ₆ -C ₁₄ , preferably C ₆ -C ₁₀ aryl and 1 to 4 carbon atoms in the alkyl group, 6 to 10 in the aryl group, preferably 6 Alkylaryl or arylalkyl having carbon atoms. Z is preferably chlorine, benzyl or methyl, especially chlorine.

The R ¹ and R ² groups may be the same or different and are particularly the same, each being a C _{1 to} C ₄₀ hydrocarbon group or a C _{3 to} C ₄₀ —Si (R ⁷ ) ₃ or other C group. _{1 to} C ₄₀ groups, or R ¹ and R ² are selected from the group consisting of the elements N, O, P, S and Si in place of the carbon atoms in the ring group, together with the atoms connecting them. To form one or more of the same or different, preferably N, O or S, in particular cyclic or polycyclic, in particular monocyclic cyclic groups, which may contain N heteroatoms. R ¹ and R ² are preferably cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl groups, C ₂ -C ₂₀ , preferably C ₂ -C ₈ , respectively. alkenyl group, C ₆ -C _22, preferably an aryl group of C ₆ -C _10, 1 to 10 carbon in the alkyl group, preferably having 1 to 4 carbon atoms, 6 to 22 pieces in the aryl radical An alkylaryl or arylalkyl group, preferably 6 to 10 carbon atoms, which may be halogenated, or C _{3 to} C ₁₈ , preferably C _{3 to} C ₈ -Si (R ⁷ ) _3. Or R ¹ and R ² may form a cyclic 4- to 8-membered ring group, preferably a 5- to 6-membered ring group, together with the atoms connecting them, and the ring groups in turn are C ₁ to it may have a C ₂₀ group. R ¹ and R ² are particularly preferably cyclic, branched or unbranched C _{1 to} C ₈ alkyl groups, C _{6 to} C ₁₀ aryl groups, and 1 to 4 carbon atoms in the alkyl group. And an aryl or arylalkyl group having 6 to 10 carbon atoms in the aryl group, or trimethylsilyl, and R ¹ or R ² is a cyclic 5- or 6-membered ring together with the atoms connecting them. Forming a cyclic group, the cyclic group having 1 to 4 carbon atoms in a cyclic, branched or unbranched C ₁ -C ₈ alkyl group, C ₆ -C ₁₀ aryl group, alkyl group. The aryl group may have an alkylaryl group or arylalkyl group having 6 to 10 carbon atoms, or a trimethylsilyl group in this order. Particularly preferred examples of R ¹ and R ² are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl Phenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl. Particularly preferred examples of the ring group formed from R ¹ , R ² and the atoms connecting them include 1,2-cyclohexylene, 1,2-cyclopentylene and 1-benzylpyrrolidine-3,4-ylene. is there.

R ⁵ and R ⁶ groups are the same and are each group of hydrogen or C ₁ -C _40. R ⁵ and R ⁶ groups are preferably hydrogen, cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl groups, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl groups, 1 to 10 carbon atoms in the alkyl group, preferably 1 to 4 carbon atoms, 6 to 22 carbon atoms in the aryl group, preferably 6 to 10 carbon atoms, halogen Optionally substituted alkylaryl or arylalkyl. R ⁵ and R ⁶ groups are particularly preferably hydrogen, cyclic, branched or unbranched C ₁ -C ₈ alkyl group, C ₆ -C ₁₀ aryl group, 1 to 4 groups in the alkyl group. An alkylaryl group or arylalkyl group having a carbon atom and having 6 to 10 carbon atoms in the aryl group. Particularly preferred examples of R ⁵ and R ⁶ groups are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl. Cyclohexyl, n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, pentafluorophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2, , 3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert- Butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl, especially methyl, phenyl or hydrogen, most hydrogen.

The R ⁷ groups may be the same or different and are each C ₁ -C ₄ alkyl, such as methyl, ethyl or tert-butyl, especially methyl, phenyl or naphthyl, especially phenyl, C ₆ -C ₁₀ Aryl, alkylaryl having 1 to 4 carbon atoms in the alkyl group, and alkylaryl or arylalkyl having 6 to 10, preferably 6 carbon atoms in the aryl group.

The R ¹⁰ , R ¹¹ , R ¹² and R ¹³ groups may be the same or different and each is hydrogen, halogen such as fluorine, chlorine, bromine or iodine, C ₁ -C ₄₀ hydrocarbon group or C C ₁ -C ₄₀ groups such as ₃ -C ₄₀ -Si (R ⁷ ) ₃ or two adjacent groups R ¹⁰ , R ¹¹ , R ¹² and R ¹³ In addition to the carbon atom in the ring group, one or more same or different, preferably N, O or S heteroatoms selected from the group consisting of the elements N, O, P, S and Si are included together with the carbon atom in the ring group To form a cyclic group which may be released. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ groups are preferably each hydrogen, fluorine, chlorine, cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl groups, C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl group, having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl group, and 6 to 22 in the aryl group, preferably having 6 to 10 carbon atoms, an optionally halogenated alkyl group, or an arylalkyl group, or a C ₃ -C _18, preferably ^{_{C 3 ~C 8 -Si (R 7}} ) 3, or two Adjacent groups R ¹⁰ , R ¹¹ , R ¹² and R ¹³ together with the atoms connecting them together are cyclic 4- to 8-membered, preferably 5- or 6-membered, especially 6-membered cyclic groups. The cyclic group may have a C _{1 to} C ₂₀ group in this order. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are particularly preferably hydrogen, cyclic, branched or unbranched C ₁ -C ₈ alkyl groups, C ₆ -C ₁₀ aryl groups, and alkyl groups, respectively. An alkylaryl group or an arylalkyl group having 6 to 10 carbon atoms in the aryl group, or a trimethylsilyl group, or two adjacent groups R ¹⁰ , R ¹¹ , R ¹² and R ¹³ together with the two carbon atoms connecting them form a cyclic 5- or 6-membered ring group, which in turn is cyclic, branched or unbranched C ₁ alkyl group -C _8, aryl group having C ₆ -C _10, having 1-4 carbon atoms in the alkyl group, alkylaryl group or arylalkyl having 6 to 10 carbon atoms in the aryl group A group or a trimethylsilyl group There. Particularly preferred examples of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, Cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, adamantyl, benzyl, triphenylmethyl, 1,1-diphenylethyl, 1-methyl-1-phenylethyl, 2-phenylethyl, phenyl, pentafluorophenyl 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4 Trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-iso-propylphenyl, p-tert-butylphenyl, p-s-butylphenyl, p- phenyl and p- trimethylsilylphenyl. Particularly preferred examples of the cyclic group formed from the two adjacent groups of R ¹⁰ , R ¹¹ , R ¹² and R ^{13 and} the two carbon atoms connecting them include other substituents in this order. It may be a phenyl ring, a pyrrole ring, or a thiophene ring.

The R ¹⁰ , R ¹¹ , R ¹² and R ¹³ groups having the same index are preferably the same group.

The R ¹⁰ group is preferably not hydrogen but a branched or cyclic C ₁ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, an alkyl group having 1 to 4 carbon atoms, and an aryl group It is a bulky group such as an alkylaryl group or an arylalkyl group having 6 to 10 carbon atoms in the group. Particularly preferred examples of the R ¹⁰ group include isopropyl, t-butyl, cyclohexyl, adamantyl, triphenylmethyl, 1,1-dimethylethyl, 1-methyl-1-phenylethyl, phenyl, pentafluorophenyl, 3 , 5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 1-naphthyl, phenanthryl, p-tert-butylphenyl. A particularly preferred example of a cyclic group formed from the groups R ¹⁰ and R ¹¹ and the two carbon atoms connecting them is a phenyl ring.

  Specific examples of the chiral coordination compound of the main group element as the central atom used as a component of the catalyst composition of the present invention include, but are not limited to:

  The production of crosslinked chelate ligands and coordination compounds prepared therefrom are known in principle from the literature and are described, for example, in WO 99/566999.

  The cocatalyst that forms the polymerization active catalyst composition of the present invention together with the above-mentioned chiral coordination compound of the main group element as the central atom can change the chirally coordinated compound of the main group element into a cationic compound. It is. The reaction step also includes substitution of the central atom.

  Preferred cation-forming compounds are, for example, aluminoxanes, strong uncharged Lewis acids, ionic compounds containing Lewis acid cations or ionic compounds containing Bronsted acids as cations. Particularly preferred as a cocatalyst is aluminoxane, especially methylaluminoxane.

  As the aluminoxane, for example, compounds described in WO00 / 31090 can be used. Particularly useful aluminoxanes are open chain or cyclic aluminoxane compounds represented by the following formula (II) or (III):

(Where
R ¹⁴ is a C ₁ -C ₄ alkyl group, preferably a methyl group or an ethyl group, and m is an integer of 5-30, preferably 10-25.

  These oligomeric aluminoxane compounds are usually prepared by reacting a trialkylaluminum solution with water. In general, the oligomeric aluminoxane compounds obtained in the process are in the form of a mixture of linear or cyclic chain molecules of various lengths, so that m is regarded as an average. The aluminoxane compound may also be present in a mixture with other metal alkyls, preferably aluminum alkyls. Furthermore, a modified aluminoxane in which some hydrocarbon groups or hydrogen atoms are substituted by alkoxy groups, aryloxy groups, siloxy groups or amide groups is replaced with aluminoxane compounds represented by the general formula (II) or (III). It can also be used.

  The chiral coordination compound and aluminoxane compound of the main group element are used in an atomic ratio of aluminum from the aluminoxane compound to the central atom of the coordination compound in the range of 10: 1 to 1000: 1, preferably 20: 1 to 500: 1. It is useful to use it in an amount within the range of 30: 1 to 400: 1.

  As a strong uncharged Lewis acid, preferably a compound represented by the following general formula (IV)

(Where
M ² is an element of Group 13 of the Periodic Table of the Elements, in particular B, Al or Ga, preferably B,
X ¹ , X ² and X ³ each independently represent hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, each having 1 to 10 carbon atoms in the alkyl group. , Alkylaryl having 6-20 carbon atoms in the aryl group, arylalkyl, haloalkyl or haloaryl, fluorine, chlorine, bromine or iodine, especially haloaryl, preferably pentafluorophenyl.

  Further examples of strong uncharged Lewis acids are disclosed in WO 00/31090.

As the compound represented by the general formula (IV), X ¹ , X ² and X ³ are particularly preferably the same, preferably tris (pentafluorophenyl) borane.

  Also preferred strong uncharged Lewis acids as cation forming compounds are reaction products from the reaction of boronic acid with two equivalents of trialkylaluminum, or acidic fluorination with trialkylaluminum, especially pentafluorophenol or bis. Mention may be made of reaction products from the reaction with two equivalents of perfluorinated hydrocarbon compounds such as (pentafluorophenyl) boronic acid.

  As a preferable ionic compound containing a Lewis acid cation, a salt-like compound of a cation represented by the general formula (V)

(Where
Y is an element of the periodic table 1-16 group,
Q ₁ to Q _{Z each} have a C _{1 to} C ₂₈ alkyl group, a C _{6 to} C ₁₅ aryl group, each having 6 to 20 carbon atoms in the aryl group, and ₁ to ₂₈ carbon atoms in the alkyl group. alkylaryl group having carbon atoms, an arylalkyl group, a haloalkyl group, a haloaryl group, a cycloalkyl group of C ₁ may have an alkyl group of ~C ₁₀ C ₃ ~C ₁₀ as substituents, halogen, C ₁ A group charged to −1, such as an alkoxy group of ˜C _28, an aryloxy group of C _{6 to} C ₁₅ , a silyl group, or a mercaptoyl group,
a is an integer of 1 to 6,
z is an integer of 0 to 5,
d corresponds to the difference of a−z, but d is an integer equal to or greater than 1).

  Particularly useful cations are carbonium cations, oxonium cations and sulfonium cations, or cationic transition metal complexes. In particular, the triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation. These preferably have uncoordinated counter ions, in particular boron compounds as described in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.

  Also, a salt having a non-coordinating anion is a second compound such as water that can react with an aluminum compound such as a boron compound or an aluminum alkyl to bind to two or more boron atoms or an aluminum atom, and ionize. It can be prepared by combining a third compound, such as triphenylchloromethane, which forms an ionic compound with a boron compound or an aluminum compound. Furthermore, you may add the 4th compound which reacts similarly with boron or aluminum compounds, such as pentafluorophenol.

  Similarly, an ionic compound containing a Bronsted acid and a cation preferably has a non-coordinating counter ion. Particularly preferred as a Bronsted acid is a protonated amine or an aniline derivative. Preferred cations are N, N-dimethylaluminum, N, N-dimethylcyclohexylammonium and N, N-dimethylbenzylammonium and the latter two derivatives.

  Preferred ionic compounds as cation-forming compounds are in particular N, N-dimethylaluminum tetrakis (pentafluorophenyl) borate, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethyl. Benzyl ammonium tetrakis (pentafluorophenyl) borate.

Two or more borate anions, divalent anions _{[(C 6 F 5) 2} B-C 6 F 4 -B (C 6 F 5) 2] mutually can be coupled ^2- as such Alternatively, the borate anion can be bound to the surface of the carrier particle by a crosslinking group having an appropriate functional group.

  Further preferred cation-forming compounds are described in WO 00/31090.

  The amount of a strong uncharged Lewis acid, an ionic compound having a Lewis acid cation, or an ionic compound containing a Bronsted acid as a cation is typically 0.1 to 20 equivalents relative to the chiral coordination compound of the main group element. , Preferably 1 to 10 equivalents.

  Preferred cation forming compounds include boron-aluminum compounds such as di [bis (pentafluorophenylboroxy)] methylalane. Examples of such boron-aluminum compounds are described, for example, in WO 99/06414.

  It is also possible to use mixtures of all the cation-forming compounds mentioned above. Preferred mixtures include aluminoxanes, in particular methylaluminoxane, and ionic compounds, in particular those containing tetrakis (pentafluorophenyl) borate anions, and / or strong uncharged Lewis acids, in particular tris (pentafluorophenyl) borate. Including.

  Both main group element coordination compounds and cation-forming compounds are preferably used in solvents, preferably aromatic hydrocarbons having 6 to 20 carbon atoms, in particular xylene and toluene.

  The catalyst composition of the present invention further comprises a metal compound represented by the following general formula (VI)

(Where
M ³ is an alkali metal, an alkaline earth metal or a metal of group 13 of the periodic table, that is, boron, aluminum, gallium, indium or thallium,
R ¹⁵ is hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, each having 1 to 10 carbon atoms in the alkyl group, and 6 to 20 carbon atoms in the aryl group. Having alkylaryl or arylalkyl,
R ¹⁶ and R ¹⁷ are the same or different, each having hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, each having 1 to 10 carbon atoms in the alkyl group; Alkylaryl, arylalkyl or alkoxy having 6-20 carbon atoms in it,
r is an integer from 1 to 3, and s and t are integers from 0 to 2, and the sum of r + s + t is equal to the valence of M ³ ;
Here, the metal compound of formula (VI) may usually contain a cation-forming compound).

Among the metal compounds of the general formula (VI),
It is preferable that M ³ is lithium, magnesium or aluminum and R ¹⁶ and R ¹⁷ are each C ₁ -C ₁₀ alkyl.

  Particularly preferred as metal compounds of the formula (VI) are n-butyllithium, n-butyl-n-octylmagnesium, n-butyl-n-heptylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, triethylaluminum and trimethyl. Aluminum, as well as mixtures thereof.

When a metal compound of formula (VI) is used, the metal compound has a molar ratio of M ³ from formula (VI) to the central atom of the chiral coordination compound of the main group element of 800: 1 to 1: 1. In particular, it is preferably contained in the catalyst composition of the present invention in an amount of 200: 1 to 2: 1.

  It is particularly preferred that the catalyst composition of the present invention further comprises a support.

  In order to obtain such a supported catalyst composition, an unsupported catalyst composition can be reacted with a support. The condition that the support, the chiral coordination compound of the main group element and the cocatalyst are bonded is not important in principle. The chiral coordination compound of the main group element and the cocatalyst can be immobilized on the support separately from each other or simultaneously. After each step, the solid can be washed with a suitable inert solvent such as an aliphatic or aromatic hydrocarbon.

  As the carrier, it is preferred to use a finely divided carrier which may be any organic or inorganic inert solid. In particular, the carrier may be a porous material such as talc, layered silicate, inorganic oxide, or finely divided polymer powder (for example, polyolefin).

Preferred inorganic oxides are found in Groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of Elements. Examples of preferred oxides as supports include silicon dioxide, aluminum oxide, and mixed oxides of calcium, aluminum, silicon, magnesium or titanium elements and the corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the preferred oxide support described above include, for example, MgO, ZrO ₂ , TiO _2, or B ₂ O ₃ . A preferred mixed oxide is, for example, calcined hydrotalcite.

The carrier material used preferably has a specific surface area in the range of 10 to 1000 m ² / g, a pore volume in the range of 0.1 to 5 ml / g, and an average particle size in the range of 1 to 500 μm. . Preferred are carriers having a specific surface area in the range of 50-500 m ² / g, a pore volume in the range of 0.5-3.5 ml / g, and an average particle size in the range of 5-350 μm. A carrier having a specific surface area in the range of 200 to 400 m ² / g, a pore volume in the range of 0.8 to 3.0 ml / g, and an average particle size of 10 to 100 μm is particularly preferred.

For example, the inorganic carrier can be heat treated to remove adsorbed water. Such a drying treatment is usually carried out at 80 to 300 ° C., preferably 100 to 200 ° C., and drying at 100 to 200 ° C. is a gas seal under reduced pressure and / or an inert gas (for example, nitrogen). It is preferred to carry out the process below, or the inorganic support can be calcined at a temperature of 200 to 1000 ° C. to give the desired solid structure or the desired surface OH concentration. The support can also be chemically treated with conventional desiccants such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCl ₄ or methylaluminoxane. Appropriate treatment methods are described, for example, in WO 00/31090.

In addition, the inorganic carrier material may be chemically modified. For example, treatment of silica gel with (NH ₄ ) ₂ SiF ₆ results in fluorination of the silica gel surface, and treatment of silica gel with silane-containing nitrogen-, fluorine- or sulfur-containing groups is the corresponding modified silica gel Bring the surface.

  Also, organic carrier materials such as micronized polyolefin powder (eg, polyethylene, polypropylene or polystyrene) can be used, as well as adhering moisture, using appropriate purification and drying operations prior to use, It is preferred to remove solvent residues or other impurities. It is also possible to use functionalized polymer powders such as those based on polystyrene to which at least one catalyst component is fixed via a functional group such as an ammonium group or a hydroxyl group.

  In a preferred embodiment of the preparation of the supported catalyst composition of the present invention, at least one main group element chiral coordination compound is contacted as a cation-forming compound with at least one cocatalyst in a suitable solvent, preferably Soluble reaction products, adducts and mixtures are obtained.

  The preparation obtained in the process is then contacted with a dehydrated or passivated support material, the solvent is removed, the resulting supported catalyst composition is dried, and all or most of the solvent is supported on the support. Ensure removal from material holes. The supported catalyst is obtained as a flowable powder. Examples of the industrial implementation of the above-described method are described in WO 96/00243, WO 98/40419 or WO 00/05277.

  In a further preferred embodiment, the cation-forming compound is first applied to the support component and then the supported cation-forming compound is contacted with the main group element's chiral coordination compound.

  Compounds obtained by combining the following components are likewise important as cocatalyst compositions.

First component: at least one predetermined boron or aluminum compound,
Second component: at least one uncharged compound having at least one acidic hydrogen atom,
Third component: at least one carrier, preferably an inorganic oxide carrier, and optionally as a fourth component, a base, preferably an organic nitrogen-containing salt such as an amine, aniline derivative or nitrogen heterocycle.

  The boron or aluminum compounds used in the preparation of these supported cocatalysts are preferably those represented by the following formula (VII)

(Where
The R ¹⁸ groups are the same or different and are each hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ halo arylalkyl, C ₇ -C ₄₀ alkyl aryl, C ₇ -C ₄₀ haloalkyl aryl, or R ¹⁸ is SiR ¹⁹ ₃ group And where
The R ¹⁹ groups are the same or different and are each hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ halo arylalkyl, C ₇ -C ₄₀ alkyl aryl, C ₇ -C ₄₀ haloalkyl aryl, preferably hydrogen, C ₁ -C ₈ alkyl or C ₇ -C ₂₀ arylalkyl,
M ⁴ is preferably boron or aluminum, preferably aluminum).

  Particularly preferred compounds of the formula (VII) are trimethylaluminum, triethylaluminum and triisobutylaluminum.

  As an uncharged compound having at least one acidic hydrogen atom and capable of reacting with the compound of the formula (VII), a compound represented by the following formula (VIII), (IX) or (X)

(Where
The R ²⁰ groups are the same or different and are each hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ halo arylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkyl aryl, Si (R ²²⁾ ₃ group, or CH (SiR ²² ₃ ) ₂ groups such as C ₁ -C ₄₀ groups containing no boron,
R ²² is, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ ~ C ₄₀ arylalkyl, C ₇ -C ₄₀ haloalkyl aryl, C ₇ -C ₄₀ alkylaryl, C ₁ -C ₄₀ group containing no boron, such as C ₇ -C ₄₀ haloalkyl aryl,
R ²¹ is, C ₁ -C ₂₀ alkylene, C ₁ -C ₂₀ haloalkylene, C ₆ -C ₂₀ arylene, C ₆ -C ₂₀ haloarylene, C ₇ -C ₄₀ arylalkylene, C ₇ -C ₄₀ halo arylalkylene the radical of a C ₇ -C ₄₀ halo arylalkylene, C ₇ -C _{40 alkylarylene, C 7 ~C 40 C 1 ~C} 40 divalent, such as haloalkyl arylene,
D is an element or NR ²³ groups group elements of the periodic table 16, where R ²³ is C ₁ -C ₂₀ hydrocarbon group such as hydrogen or a C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl, preferably oxygen And
h is preferably 1 or 2.

  Preferred compounds of the formula (VIII) include water, alcohols, phenol derivatives, thiophenol derivatives or aniline derivatives, with halogenated, especially perfluorinated alcohols and phenols being particularly important. Examples of particularly useful compounds are pentafluorophenol, 1,1-bis (pentafluorophenyl) methanol and 4-hydroxy-2,2 ', 3,3', 4 ', 5,5'6,6'- Nonafluorobiphenyl.

Preferred compounds of formula (IX) include boronic acids and borinic acids, in particular boronic acids having a pentafluorinated aryl group such as (C ₆ F ₅ ) ₂ BOH.

  Preferred compounds of formula (X) include dihydroxy compounds in which the divalent carbon-containing group is preferably halogenated, in particular perfluorinated. Examples of such compounds are 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl hydrate and the like. Examples of combinations of compounds of formula (VII) with compounds of formula (VIII) or (X) include trimethylaluminum / pentafluorophenol, trimethylaluminum / 1-bis (pentafluorophenyl) methanol, trimethylaluminum / 4- Hydroxy-2,2 ′, 3,3 ′, 4 ′, 5,5 ′, 6,6′-nonafluorobiphenyl, triethylaluminum / pentafluorophenol or triisobutylaluminum / pentafluorophenol or triethylaluminum / 4 Examples include 4′-dihydroxy-2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluorobiphenyl hydrate. For example, the following types of reaction products can be formed. .

  Examples of reaction products from the reaction of at least one compound of formula (VII) with at least one compound of formula (IX) include:

  The components can in principle be combined in any desired way.

  In some cases, the reaction product from the reaction of at least one compound of formula (VII), at least one compound of formula (VIII), (IX) or (X) and optionally an organic nitrogen base is Then, in order to form a supported cocatalyst composition comprising a support, it may be further combined with an organometallic compound of formula (II), (III), (IV) and / or (VI).

  In a preferred refinement, the first component, for example a compound of formula (VII), is combined with a second component, for example a compound of formula (VIII), (IX) or (X), the carrier as the third component and the fourth component Are separately combined with the base as follows, and then the mixture is reacted with each other, preferably in an inert solvent or suspending medium. The formed supported cocatalyst is reacted with a chiral coordination compound of the main group element and, optionally, a metal compound of formula (VI) to form an inert solvent or suspension before forming the catalyst composition of the present invention. The turbid medium can be removed.

The catalyst solid of the present invention can first be prepolymerized with an α-olefin, preferably a linear C ₂ -C ₂₀ -1-alkene, particularly ethylene or propylene, and then the resulting prepolymerized catalyst solid is actually used. Can be used for the polymerization of The mass ratio of the catalyst solid used in the prepolymerization and the monomer to be polymerized is usually in the range of 1: 0.1 to 1: 200.

  In addition, small amounts of olefins, preferably α-olefins such as vinylcyclohexane, styrene or phenyldimethylvinylsilane, antistatic agents as modifying components, or suitable inert compounds such as waxes or oils, It may be added as an additive during or after preparation of the catalyst composition. The molar ratio of the additive to the chiral coordination compound of the main group element is usually 1: 1000 to 1000: 1, preferably 1: 5 to 20: 1.

  According to the novel catalyst composition based on the chiral coordination compound of the main group element detailed above, compared with the conventionally known catalyst composition containing no transition metal, high melting point isotactic polyolefin, A tactic polypropylene is obtained.

  The present invention further relates to the first use of the above-described novel catalyst composition for the production of polyolefin, and secondly the polymerization or copolymerization of at least one olefin in the presence of the above-described novel catalyst composition. A manufacturing method is provided.

  The catalyst composition of the present invention is usually different from one or more metal compounds of the general formula (VI) used in the preparation of the catalyst composition of the present invention used for the polymerization or copolymerization of olefins. Also used with other metal compounds of formula (VI). Other metal compounds are usually added to the monomer or suspending medium and act to remove monomers of the material that adversely affect catalyst activity. One or more other cation forming compounds may be added to the catalyst composition of the present invention in the polymerization step.

  The olefin may be a functional olefinically unsaturated compound such as, for example, an ester or amide derivative of acrylic acid or methacrylic acid such as acrylate, methacrylate or acrylonitrile, or an apolar olefin compound containing an aryl-substituted α-olefin. Good.

Wherein ^{R m -CH = CH-R n} ( wherein, R ^m and R ⁿ are identical or different, are each hydrogen, or 1 to 20 carbon atoms, in particular be a group containing 1 to 10 carbon atoms Or R ^m and R ⁿ together with the atoms connecting them form one or more rings).

  Examples of such olefins are 2-40 such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptane, 1-octene, 1-decane or 4-methyl-1-pentene. 1-olefins preferably having 2 to 10 carbon atoms, unsubstituted or substituted vinyl aromatic compounds such as styrene and styrene derivatives, 1,3-butadiene, 1,4-hexadiene, 1,7-octadiene, 5 A diene such as ethylidene-2-norbornene, norbornadiene, ethylnorbornadiene, or a cyclic olefin such as norbornene, tetracyclododecene or methylnorbornene. Preferred are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like.

The catalyst composition of the present invention comprises propylene or ethylene, in particular propylene homopolymerization, or ethylene and C ₃ -C ₈ -α such as propylene, 1-butene, 1-pentene, 1-hexene and / or 1-octene. -Preferably used for copolymerization with olefins and / or cyclic olefins such as norbornene and / or dienes having from 4 to 20 carbon atoms such as 1,4-hexadiene, norbornadiene, ethylidenenorbornene or ethylnorbornadiene. Particularly preferred for use in the copolymerization of propylene with ethylene and / or 1-butene. Examples of such copolymers include propylene / ethylene, propylene / 1-butene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene copolymers, ethylene / propylene / ethylidene norbornene or ethylene. / Propylene / 1,4-hexadiene terpolymer.

  The polymerization can be carried out by a known method such as bulk, suspension, gas phase, or supercritical medium in a reactor used for ordinary olefin polymerization. One or more steps can be carried out batchwise, preferably continuously. Solution methods, suspension methods, stirred gas phase methods, and gas phase fluidized bed methods are all possible. As the solvent or suspending medium, isobutane or the monomer itself can be used.

  The polymerization can be carried out at temperatures in the range of −60 to 300 ° C. and pressures in the range of 0.5 to 3000 bar. Preference is given to temperatures in the range of 50 to 200 ° C., in particular 60 to 100 ° C., and pressures in the range of 5 to 100 bar, in particular 15 to 70 bar. The average residence time is usually 0.5 to 5 hours, preferably 0.5 to 3 hours. Hydrogen may be used during the polymerization as a molar mass regulator and / or to improve activity. Furthermore, you may use normal additives, such as an antistatic agent. In order to carry out the polymerization, the catalyst composition of the present invention can be used directly, i.e. only the catalyst composition may be introduced into the polymerization composition, or paraffin is used to improve the meterability. Inactive ingredients such as oil or wax may be mixed.

  The catalyst composition of the present invention is very useful for producing a propylene homopolymer having a high melting point.

The present invention relates to a chiral coordination compound of a main group element represented by the following formula (Ib) and optical isomers thereof represented by the following formula (Ib ^* )

Further provided is a method of using the variables (wherein the variables are as defined in formulas (I) and (I ^* )) in the preparation of a catalyst composition for olefin polymerization.

Chiral coordination compounds of main group elements represented by the following formulas (Ic) and (Ic ^* )

Particular preference is given to the production of catalyst compositions using the formulas, in which the variables are as defined in formulas (Ia) and (Ia ^* ).

Furthermore, the present invention relates to a chiral coordination compound of a main group element represented by the formula (Ib) or (Ib ^* ), wherein M is Si, Ga, Ge, As, In, Sn, Sb or Te, particularly Si or Ge. I will provide a.

Furthermore, the present invention provides an olefin polymerization catalyst composition comprising a step of reacting a chiral coordination compound of at least one main group element represented by the formula (Ib) or (Ib ^* ) with at least one cation-forming compound. A production method and a method for producing an isotactic polyolefin by polymerization of at least one α-olefin in the presence of a catalyst composition prepared by the method are provided.

  Furthermore, the present invention provides a polyolefin composition comprising a polyolefin obtained by one of the above-described polymerization methods, in particular, a homopolymer and a copolymer of propylene, and a polyolefin obtained using the catalyst composition of the present invention. provide.

The isotactic polypropylene obtained by the process of the present invention has a viscosity number (IV) greater than 1, a melting point (T _m ) greater than 158 ° C., preferably greater than 160 ° C., particularly preferably greater than 163 ° C. , Measured by ¹³ C-NMR pentad analysis of more than 98%, especially more than 99% polymer samples, isotacticity, at least 0.3%, in particular at least 0.25% ¹³ C of polymer samples -Having a reverse insertions fraction determined by NMR pentad analysis and a polydispersity Q = Mw / Mn of less than 3, in particular less than 2.5.

  The polymer obtained by the method of the present invention and the polyolefin composition containing the polymer are particularly useful for the production of films, fibers and molded articles.

  The present invention further provides films, fibers and molded articles made from the polyolefin composition described above.

  The present invention will be specifically described with reference to the following examples, but these examples do not limit the present invention.

Basic procedure Synthesis and manipulation of organometallic compounds and catalysts were carried out under argon and in the absence of air and moisture (glove box and Schlenk method). All solvents used were purged with argon and dried over molecular sieves before use.

  (S, S)-(+) N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane, (R, R)-(−) N, N ′ -Bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane and (S, S)-(+) N, N'-bis (3,5-di-tert-butylsalicyclic) Tylidene) -1,2-diaminocyclohexanealuminum (lll) chloride is commercially available.

Melting point measurement:
First heating phase up to 200 ° C. at a heating rate of 20 ° C./min, dynamic crystallization to cool down to 20 ° C. at a cooling rate of 20 ° C./min, again up to 200 ° C. at a heating rate of 20 ° C./min The melting point Tm was determined by DSC measurement according to ISO standard 3146 in the second heating phase.

Gel Permeation Chromatograph Gel permeation chromatograph (GPC) was performed at 145 ° C. in 1,2,4-trichlorobenzene using a Waters 150C GPC apparatus. Evaluation of the data was performed using software (HS-Endwickinggesellschaft fur wissenschaftriche Hard-und Software mbH, Oberhilberheim, Win-GPC). The column calibration was performed using a polypropylene standard having a molar mass of 100 to 10 ⁷ g / mol. The weight average (Mw) and number average (Mn) molar mass of the polymer was measured. The Q value is a ratio of the weight average (Mw) to the number average (Mn).

Measurement of Viscosity Number (IV) The viscosity number was measured with a Ubbelohde viscometer PVS1 with S5 measuring head at 135 ° C. in decalin. To prepare the sample, 20 mg of polymer was dissolved in 20 ml of decalin for 2 hours at 135 ° C. After 2 hours, 15 ml of this solution was introduced into the viscometer and performed until a consistent result was obtained with a minimum of at least 3 consumption time measurements on the instrument. I. V. I.I. V. = (T / t ₀ -1) ^* 1 / c (where t: means the number of times of operation of the solution, t ₀ : means the number of times of operation of the solvent, c: concentration of solution g / ml) Is calculated from

Example 1: (S, S)-(+)-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane silicon (IV) dichloride (1 )
1.04 g (6 mmol) of silicon tetrachloride is added at room temperature to (S, S)-(+) N, N′-bis (3,5-di-tert-butylsalicylidene) in 120 ml of diethyl ether. Added to a solution of 3 g of -1,2-diaminocyclohexane. The yellow suspension was stirred at room temperature for 18 hours and then filtered. First, the yellow solid was repeatedly washed with diethyl ether and then dried. The residue was suspended in dichloromethane and the filtrate was collected after filtration of the suspension. The filtrate was completely evaporated under reduced pressure. This gave 2 g of (1) as a yellow free-flowing powder.

Example 2: (S, S)-(+)-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane germanium (IV) dichloride (2 )
1.2 g (5.5 mmol) of germanium tetrachloride is added at room temperature in 120 ml of n-pentane in (S, S)-(+) N, N′-bis (3,5-di-tert-butylsalicyclic). Tylidene) -1,2-diaminocyclohexane was added to a solution of 3.0 g (5.38 mmol). The yellow suspension was stirred at room temperature for 18 hours and then filtered. First, the yellow solid was repeatedly washed with n-pentane and diethyl ether, and then dried under reduced pressure. This gave 1.5 g of (2) as a bright yellow free-flowing powder. Crystals were obtained from a saturated solution of (2) in toluene. X-ray structural analysis: FIG. 1 shows the structure of the compound (2).

Example P1 Homopolymerization of propene 4 ml (4 mmol, 1 M) of a triisobutylaluminum solution in hexane was placed in a 1 liter reactor. After adding 250 g of propylene at 30 ° C. and heating the reactor to 50 ° C., 50 ml of hydrogen was added. 0.7 mg (1.1 mmol) of the silicon compound (1) of Example 1 and 2.1 ml (3.32 mmol, 10% by mass) of a methylaluminoxane solution in toluene are mixed and post-reacted for 15 minutes. Thus, a catalyst solution was prepared and charged into a reactor together with 50 g of propylene at 80 ° C. The inside of the reactor was stirred at 70 ° C. for 2 hours, and the polymerization reaction was stopped by opening the reactor. 5 ml of methanol was added into the reactor. The polymer was dried overnight under reduced pressure. As a result, 2.50 g of polypropylene was obtained. The results of polymerization and polymer analysis are shown in Table 1 below.

Example P2 Homopolymerization of propene The polymerization was carried out in a similar manner to Example P1. 4 ml (4 mmol, 1M) of triisobutylaluminum solution in hexane was placed in the reactor at 30 ° C. with 250 g of propylene and heated to 50 ° C. 0.7 mg (1.1 mmol) of the silicon compound (1) of Example 1 and 2.1 ml (3.32 mmol, 10% by mass) of a methylaluminoxane solution in toluene are mixed and post-reacted for 15 minutes. The catalyst solution was prepared by this, and this was injected | thrown-in to the reactor with 50 g of propylene at 80 degreeC. The reactor was stirred at 70 ° C. for 2 hours. After stopping the reaction, the polymer was post-treated to obtain 2.5 g of propylene. The results of polymerization and polymer analysis are shown in Table 1 below.

Example 3P Homopolymerization of propene The polymerization was carried out in an analogous manner to Example P1. 4 ml (4 mmol, 1 M) of triisobutylaluminum solution in hexane and 1.9 ml (3.0 mmol, 10% by weight) of MAO were placed in the reactor at 30 ° C. with 250 g of propylene, 50 ml of hydrogen were added, The mixture was heated to 50 ° C. The germanium compound (2) 0.7 mg (1.02 micromol) of Example 2 was mixed with 1.9 ml (1.58 mmol, 10% by mass) of methylaluminoxane solution in toluene, and the reaction was continued for 15 minutes. To prepare a catalyst solution, which was put into a reactor at 80 ° C. together with 50 g of propylene. The reactor was heated to 70 ° C., and the reactor was stirred at 70 ° C. for 2 hours. After stopping the reaction, the polymer was post-treated to obtain 24.4 g of propylene. The results of polymerization and polymer analysis are shown in Table 1 below.

Example P4 Homopolymerization of propene The polymerization was carried out in an analogous manner to Example P3. 4 ml (4 mmol, 1M) of triisobutylaluminum solution in hexane and 5 ml of MAO (7.9 mmol, 10% by weight) are placed in a reactor at 30 ° C. with 250 g of propylene, 50 ml of hydrogen are added and the mixture is added. Heated to 50 ° C. (S, S)-(+)-N, N′-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexanealuminum (III) monochloride (3) (Aldrich) ) 0.7 mg (1.15 mmol) and 2.2 ml (1.58 mmol, 10% by mass) of methylaluminoxane solution in toluene were mixed and post-reacted for 15 minutes to prepare a catalyst solution, This was put into a reactor at 80 ° C. together with 50 g of propylene. The reactor was stirred at 70 ° C. for 2 hours. After stopping the reaction, the polymer was post-treated to obtain 10.8 g of propylene. The results of polymerization and polymer analysis are shown in Table 1 below.

Units and abbreviations: AI / M is the molar ratio of aluminum from MAO to the amount of coordination compound; activity (kg _polymer / (g _{coordination compound} ^* h _{polymerization time} )); weight average molar mass measured by GPC; Polydispersity Q = Mn / Mw

The structure of the compound obtained in Example 2 is shown.

Claims (14)

  At least one of main group elements selected from the group consisting of Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi, and Po as a central atom Two bidentate in which a chiral coordination compound and at least one cocatalyst capable of changing the chiral coordination compound to one exhibiting polymerization activity with respect to at least one olefin are bonded to each other by crosslinking Surrounds the main group element as the central atom of the coordination compound so that it is almost planar, with chiral coordination compounds containing chelating ligands, and optionally one or more other monodentate ligands Is obtained by reacting with four coordination atoms of two chelating ligands, and no more than two other ligands are formed by four coordination atoms of two chelating ligands. Almost planar configuration On or located below, isotactic polyolefin production catalyst compositions thereof in the case other ligands is two are present in trans position to each other. The chiral coordination compound of the main group element is a coordination compound represented by the following formula (I) or an enantiomer thereof represented by the following formula (I ^* )

(Where
M is Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi or Po,
Z groups may be the same or different and each is an organic or inorganic group,
n1 and n2 may be the same or different and are each 0 or 1,
R ¹ and R ² may be the same or different and each is a C ₁ -C ₄₀ group, or R ¹ and R ² together with the atoms connecting them together with carbon atoms in the ring group Instead of forming a cyclic or polycyclic group which may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si;
R ³ is hydrogen or a C ₁ -C ₄₀ group, R ³ exhibits a smaller steric hindrance than R ¹ ,
R ⁴ is hydrogen or a C ₁ -C ₄₀ group, R ⁴ exhibits a smaller steric hindrance than R ² ,
R ⁵ and R ⁶ are the same or different and are each hydrogen or a C ₁ -C ₄₀ group;
R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ^5, and / or R ³ and R ⁶ , together with the atoms that bind them to each other, are replaced by the elements N, O Forming a cyclic or polycyclic group that may contain one or more identical or different heteroatoms selected from the group consisting of P, S and Si;
X represents a single bond between two carbon atoms or is a divalent group,
Y ¹ and Y ² may be the same or different and are each oxygen, sulfur, selenium, tellurium, NR ⁹ group or PR ⁹ group,
R ⁷ , R ⁸ and R ⁹ may be the same or different and are each hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₂ aryl, Alkylaryl or arylalkyl having 1 to 10 carbon atoms and having 6 to 22 carbon atoms in the aryl group;
T ¹ , T ² , T ³ and T ⁴ may be the same or different and each is hydrogen or a C _{1 to} C ₄₀ group, or T ¹ and T ³ and / or T ² and T ⁴ are In addition to the carbon atom bonding them to each other, one or more same or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si are included instead of the carbon atom in the ring group. The catalyst composition according to claim 1, which may be a cyclic or polycyclic group. A chiral coordination compound of the main group element represented by the formula (I) or the formula (I ^* ) is a coordination compound represented by the following formula (Ia) or an enantiomer thereof represented by the following formula (Ia ^* )

(Where
M is Al, Si, Ga, Ge, As, In, Sn, Sb or Te,
Z groups may be the same or different and has a halogen respectively, hydrogen, alkyl of C ₁ -C _10, aryl of C ₆ -C _14, from 1 to 4 carbon atoms in the alkyl group , Arylalkyl or alkylaryl having 6 to 10 carbon atoms in the aryl group,
n1 and n2 may be the same or different and are each 0 or 1,
R ¹ and R ² may be the same or different and each is a C ₁ -C ₄₀ group, or R ¹ and R ² together with the atoms connecting them together with carbon atoms in the ring group Instead of forming a cyclic or polycyclic group which may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si;
R ⁵ and R ⁶ are the same and are each hydrogen or a C ₁ -C ₄₀ group;
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different and are each hydrogen, halogen or a C ₁ -C ₄₀ group, or two adjacent R ¹⁰ , R ^11. , R ¹² and R ¹³ may form a cyclic group together with the two carbon atoms bonded to them).   The catalyst composition according to any one of claims 1 to 3, wherein the cocatalyst is an aluminoxane.   The catalyst composition according to any one of claims 1 to 4, further comprising a support.   The method which uses the catalyst composition of any one of Claims 1-5 for manufacture of polyolefin.   A method for producing a polyolefin, wherein at least one olefin is polymerized or copolymerized in the presence of the catalyst composition according to any one of claims 1 to 5. Chiral coordination compounds of main group elements of formula (Ib) or enantiomers of formula (Ib ^* )

(Wherein the variables are as set forth in claim 2) for the production of an olefin polymerization catalyst composition. The chiral coordination compound represented by the formula (Ib) or (Ib ^* ) according to claim 8, wherein M is Si, Ga, Ge, As, In, Sn, Sb or Te. A method for producing a catalyst composition for olefin polymerization, wherein at least one coordination compound represented by formula (Ib) or formula (Ib ^* ) according to claim 8 is reacted with at least one cocatalyst.   A method for producing an isotactic polyolefin by polymerization of at least one α-olefin in the presence of a catalyst composition produced by the method according to claim 10.   A polyolefin obtained by the method according to claim 7.   An olefin composition comprising the polyolefin according to claim 12.   A film, fiber, or molded product produced from the olefin composition according to claim 13.

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