Olefin polymerization catalyst and method for producing olefin polymer

Abstract

To provide an olefin polymerization catalyst which has higher polymerization activity than an embodiment using a catalyst component comprising a transition metal compound and a modified clay mineral and which enables production of an olefin polymer that preferably exhibits unique physical properties.SOLUTION: An olefin polymerization catalyst comprises: (a) a transition metal compound; and (b) a clay composition including (b-1) a specific heterocyclic compound or a heterocyclic spiro compound, and (b-2) a clay compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer.

Background Art

[0002] Since the announcement of the so-called "Ziegler catalyst," which combines a transition metal compound and an organometallic compound, in 1953, olefin polymerization catalysts have developed remarkably until now, and the development continues even at present. Among them, the so-called metallocene catalyst (for example, Patent Document 1, etc.) using a metallocene compound as a transition metal compound has characteristics that the polymerization activity is high, and the molecular weight distribution of the obtained olefin polymer and the composition distribution of the obtained olefin copolymer tend to be narrow. Development taking advantage of this characteristic has been actively carried out, and many olefin polymerization catalysts containing various transition metal compounds have been reported. The present applicants have also disclosed a number of catalysts containing transition metal compounds. (For example, Patent Documents 2 to 5, etc.) On the other hand, as the above-mentioned organometallic compound, which is generally often called a cocatalyst component, organoaluminum compounds, organoaluminum oxy compounds, specific boron-containing compounds, etc. are known, but the number of reported examples thereof tends to be smaller than that of transition metal compounds.

[0003] The organometallic compound may be used after being modified in combination with a clay mineral or a specific amine compound (salt), etc., and there are a plurality of reports regarding this modification. (For example, Patent Documents 6 to 13)

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0005] Organoaluminum oxy compounds, which are suitable as organometallic compound catalyst components used in catalysts containing transition metal compound complexes such as metallocene compounds, and methylaluminoxane, which is a representative example thereof, are generally expensive, and there is a demand for low-cost organometallic compound catalyst components. The organometallic compound containing the above-mentioned clay mineral is a promising compound. However, according to the study by the present inventor, the polymerization activity of the olefin polymerization catalyst using the conventional organometallic compound containing the clay mineral is preferably further improved when considering industrialization and the like. [Means for Solving the Problems

[0006] Therefore, the present invention has been made in view of the above technical background. Specifically, an olefin polymerization catalyst capable of producing an olefin polymer having a higher polymerization activity than a mode using a catalyst component containing a transition metal compound and a conventional modified clay mineral, and preferably having unique physical properties, and a method for polymerizing an olefin are provided. That is, the present invention is characterized by having the following configuration.

[0007] [1] A transition metal compound (a), A clay composition (b) containing a compound (b-1) specified by a structural formula selected from the following formula b1 and the following formula b2 and a clay compound (b-2) An olefin polymerization catalyst containing

[0008] [Chemical formula]

[0009] [Chemical formula]

[0010] 〔In the above formula b1 and formula b2, C represents a carbon atom, A plurality of Ys are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, A plurality of Rs are each independently a hydrogen atom, a halogen atom, or a substituent selected from a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. R and Y can be bonded to form a ring structure. A plurality of Rs can be bonded to each other to form a cyclic structure or a multiple structure. a1 to a27 are each independently an integer of 0 to 6 and satisfy any one of the following (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≥ 1, and a2 + a5 + a7 + a8 ≥ 2 (β2) All of a11 + a13 + a14 + a16 ≥ 1, a12 + a15 + a17 ≥ 1, a21 + a23 + a24 + a26 ≥ 1, and a22 + a25 + a27 ≥ 1

[0011] [2] The olefin polymerization catalyst of [1], wherein the compound (b-1) is specified by the following formula b3.

[0012] [Chemical formula]

[0013] [N is a nitrogen atom, C is a carbon atom, Y and Y 1 are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, A plurality of Rs are each independently a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. R and Y can be bonded to each other to form a ring structure. A plurality of Rs can be bonded to each other to form a cyclic structure or a multiple structure. a1 to a6 are each independently an integer from 0 to 6, and satisfy a1 + a3 ≥ 1 and a4 + a6 ≥ 1. ]

[0014] [3] One or more of the said Y and Y 1 is the olefin polymerization catalyst of [1] or [2] containing an atom of a Group 15 element of the periodic table.

[0015] [4] The olefin polymerization catalyst according to any one of [1] to [3], wherein the Group 15 element is nitrogen.

[0016] [5] The olefin polymerization catalyst of [1], wherein the said Y contains two kinds of substituents containing the said Group 15 element and an oxygen atom.

[0017] [6] One or more of the said Y and Y 1 is the olefin polymerization catalyst of [2], wherein one or more of them are oxygen atoms.

[0018] [7] The olefin polymerization catalyst according to any one of the above [1] to [6], wherein one or more of the Rs are selected from a hydrogen atom and a hydrocarbon group.

[0019] [8] A transition metal compound (a), A method for producing an olefin polymer by polymerizing an olefin in the presence of a clay composition (b) containing a compound (b-1) specified by a structural formula selected from the following formula b1 and the following formula b2 and a clay compound (b-2).

[0020] [Chemical formula]

[0021] [Chemical formula]

[0022] [In the above formula b1 and formula b2, A plurality of Ys are each independently a divalent substituent containing an atom of an element selected from Groups 15 and 16 of the periodic table. A plurality of Rs are each independently a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and a nitrogen-containing group. R and Y can combine to form a ring structure. A plurality of Rs can combine with each other to form a cyclic structure or a multiple structure. a1 to a27 are each independently an integer of 0 to 6 and satisfy any one of the following (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≥ 1 and a2 + a5 + a7 + a8 ≥ 2 (β2) All of a11 + a13 + a14 + a16 ≥ 1, a12 + a15 + a17 ≥ 1, a21 + a23 + a24 + a26 ≥ 1, and a22 + a25 + a27 ≥ 1

[0023] [9] The method for producing the olefin polymer of [8], wherein the compound (b-1) is specified by the following formula b3.

[0024]

Chemical formula

[0025] 〔N is a nitrogen atom, C is a carbon atom, Y and Y 1 are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, A plurality of Rs are each independently a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. R and Y can be bonded to each other to form a ring structure. A plurality of Rs can be bonded to each other to form a cyclic structure or a multiple structure. a1 to a6 are each independently an integer of 0 to 6, satisfying a1 + a3 ≥ 1 and a4 + a6 ≥ 1.〕

Advantages of the Invention

[0026] By using the olefin polymerization catalyst of the present invention, an olefin polymer having higher activity than the mode using a polymerization catalyst containing a transition metal compound and a conventional modified clay mineral, and preferably showing a unique profile by differential scanning calorimetry (DSC method), can be expected to be obtained in an inexpensive catalyst mode.

Embodiments for Carrying Out the Invention

[0027] [Olefin polymerization catalyst] As described above, the present invention is an olefin polymerization catalyst containing a clay composition (b) obtained from a compound (b-1) specified by the following formula b1 or the following formula b2 and a clay compound (b-2), and a transition metal compound (a). By using such a catalyst, an olefin polymer can be obtained with higher polymerization activity than the mode using a catalyst component containing a conventional modified clay compound and an organometallic compound. Hereinafter, the olefin polymerization catalyst of the present invention will be described in detail.

[0028] (Compound (b-1)) The compound (b-1) is specified by the structural formula of the following (Formula b1) or (Formula b2).

[0029] [Chemical formula]

[0030] [Chemical formula]

[0031] 〔In the above Formula b1 and Formula b2, C is a carbon atom, The plurality of Ys are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, The plurality of Rs are each independently a hydrogen atom, a halogen atom, or a substituent selected from hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups, R and Y can be bonded to each other to form a ring structure. a1 to a27 are each independently an integer from 0 to 6 and satisfy either of the following (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≥ 1 and a2 + a5 + a7 + a8 ≥ 2 (β2) a11 + a13 + a14 + a16 ≥ 1, a12 + a15 + a17 ≥ 1, a21 + a23 + a24 + a26 ≥ 1, and a22 + a25 + a27 ≥ 1 (all of them) It is self-evident that (β1) is the stipulation in Formula b1 and (β2) is the stipulation in Formula b2.

[0032] The elements selected from Group 15 and Group 16 of the periodic table contained in the plurality of Y present are specifically elements selected from nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, polonium, etc. The elements are preferably selected from nitrogen, phosphorus, oxygen and sulfur, and more preferably selected from nitrogen and oxygen. An embodiment in which one or more of Y contains nitrogen is particularly preferred.

[0033] Although there are a plurality of the above Y, in some cases, it is preferable that Y is a substituent containing an atom of a Group 15 element and an embodiment containing two kinds of oxygen atoms. Also, a preferred embodiment of the above formula b1 is formula b3.

[0034] [Chemical formula]

[0035] The above Y 1 is a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, similar to Y. When there are a plurality of Y 1 both cases where all are the same substituent and cases of different substituents are included. Also, N is a nitrogen atom.

[0036] The above formula b3 corresponds to the case where, in formula b1, a specific Y is NR and a7 is 1. In the above formula b3, a1 + a3 ≥ 1 and a4 + a6 ≥ 1 are satisfied.

[0037] In the above formula b3, the elements selected from Group 15 and Group 16 of the periodic table contained in the plurality of Y and Y 1 are specifically elements selected from nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, polonium, etc. The elements are preferably selected from nitrogen, phosphorus, oxygen and sulfur, and more preferably selected from nitrogen and oxygen.

[0038] The above Y and Y 1Among them, one or more may preferably contain atoms of Group 15 elements of the periodic table. Said Y and Y 1 Among them, one or more may preferably be oxygen atoms.

[0039] The above Y and Y 1 When they are groups containing Group 15 elements, Y and Y 1 are preferably groups containing the substituent R described later. Y and Y 1 can be represented as "NR" when they are each a substituent containing nitrogen, which is a preferred embodiment as a Group 15 element.

[0040] In the above formulas b1, b2, and b3, R is a hydrogen atom, a halogen atom, or a substituent, and this substituent is selected from hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups. Examples of the halogen atom include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom.

[0041] Next, the hydrocarbon group as the above R will be described. Specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, etc.; linear or branched alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as a vinyl group, an allyl group, an isopropenyl group, etc.; linear or branched alkynyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as an ethynyl group, a propargyl group, etc.; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc.; cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as a cyclopentadienyl group, an indenyl group, a fluorenyl group, etc.; An aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, such as a phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group; An alkyl-substituted aryl group such as a tolyl group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t-butylphenyl group; An alkylidene group having 1 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as a benzylidene group, methylidene group, ethylidene group; Examples include an aryl group-substituted alkyl group such as a benzyl group, cumyl group, diphenylethyl group, trityl group.

[0042] The hydrocarbon group may be a halogenated hydrocarbon group in which some or all of the hydrogen atoms are substituted with halogen atoms. Specific examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, pentafluorophenyl group, chlorophenyl group.

[0043] The hydrocarbon group may further be a heterocyclic compound residue; Oxygen-containing groups such as an alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group; Nitrogen-containing groups such as an amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, and an ammonium salt of an amino group; Boron-containing groups such as a borandiyl group, borantriyl group, diboranyl group; Sulfur-containing groups such as a mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothiocyanate ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; It may have a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, or a phosphato group; a silicon-containing group; a germanium-containing group; or a tin-containing group. Among these, a nitrogen-containing group and an oxygen-containing group are preferred.

[0044] Preferred specific examples among the above groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, an n-hexyl group, an adamantyl group, etc., in which the bonding terminal as the substituent R (i.e., the atom bonded to the C (carbon atom) described in the above formulas b1 to b3 or the N (nitrogen atom) described in the above formula b3) is carbon, and which are linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 2 to 10 carbon atoms; an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, an anthracenyl group, etc., having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; and a substituted aryl group in which 1 to 5 substituents such as a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aryloxy group are substituted on these aryl groups. Also, a heteroatom-containing hydrocarbon group having a structure in which hydrogen of these substituents is substituted by a heteroatom, for example, a hydrocarbon group having the structure of the above heteroatom-containing group such as an ester structure, a carbonyl structure, a carboxyl structure, an amino structure, a thioalkyl structure, etc., is also a preferred embodiment. As the above heteroatom-containing structure, a nitrogen-containing group and an oxygen-containing group are preferred.

[0045] Among the above, particularly preferred is a hydrocarbon group containing only carbon and hydrogen. In addition to the above, as a substituent in which the bonding terminal as the substituent R (i.e., the atom bonded to the C (carbon atom) described in the above formulas b1 to b3 or the N (nitrogen atom) described in the above formula b3) is a heteroatom (i.e., an oxygen-containing group or a nitrogen-containing group mentioned as the above R), an alkoxy group in which oxygen is the bonding terminal and an amino group in which nitrogen is the bonding terminal can be mentioned.

[0046] The plurality of Rs described above may all be the same or may be a plurality of different types. Among the plurality of Rs, at least one is preferably selected from a hydrogen atom and a hydrocarbon group, and more preferably is a hydrogen atom. In particular, it is preferable that at least one of the Rs bonded to the C (carbon atom) described in the above formulas b1 to b3 is a hydrogen atom.

[0047] The above a1 to a27 are each independently an integer from 0 to 6. These numerical values satisfy the following requirement (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≥ 1, and a2 + a5 + a7 + a8 ≥ 2 (β2) All of a11 + a13 + a14 + a16 ≥ 1, a12 + a15 + a17 ≥ 1, a21 + a23 + a24 + a26 ≥ 1, and a22 + a25 + a27 ≥ 1 The lower limit value of the above “a1 + a3 + a4 + a6”, “a11 + a13 + a14 + a16”, and “a21 + a23 + a24 + a26” is preferably 2, the upper limit value is preferably 5, more preferably 4, still more preferably 3, and particularly preferably 2.

[0048] In the above formula b3, it is preferable to satisfy a1 + a3 ≥ 1 and a4 + a6 ≥ 1. The lower limit value of the above “a1 + a3” is more preferably 2, the upper limit value is more preferably 5, still more preferably 4, and particularly preferably 3. The lower limit value of the above “a4 + a6” is more preferably 2, the upper limit value is more preferably 5, still more preferably 4, and particularly preferably 3.

[0049] The upper limit values of a2 and a5 in the above formula 3b are each preferably 3, and more preferably 2. The above R and Y can combine to form a ring structure. As the ring structure, in particular, a ring structure formed by the combination of R and Y bonded to N is preferable.

[0050] In addition, a plurality of the existing Rs may combine with each other to form a cyclic structure or a multiple structure. When the carbon atoms as adjacent ring member atoms, or the Rs bonded to the Group 15 atoms of Y and Y 1 directly bond to each other to form a double bond (in other words, when the bonded Rs are regarded as one single bond, or when it is regarded as forming a two-membered ring), the R may appear not to exist, but the present invention defines that this is also an aspect within the scope of the present invention.

[0051] As the R in the case of forming this ring structure, among the examples of the hydrocarbon group described above, a hydrocarbon group having 1 to 10 carbon atoms is preferable. Specific examples of such compounds include compounds represented by the following formula.

[0052]

Chemical formula

[0053] The above compound (b-1) is preferably reacted with a protonic acid compound to form a so-called protonate and then used in the preparation of the clay composition (b). In the case of such an aspect, Y and Y 1 preferably contain a Group 15 element, and particularly preferably contain nitrogen.

[0054] The protonic acid compound may be a carboxylic acid or an inorganic acid, and is preferably an inorganic acid. Examples of the inorganic acid include hydrogen chloride (hydrochloric acid), hydrogen fluoride (hydrofluoric acid), hydrogen bromide (hydrobromic acid), hydrogen iodide (hydroiodic acid), and sulfuric acid, and preferably hydrogen chloride (hydrochloric acid).

[0055] Part of the above compound (b-1) can be used in the preparation of the clay composition (b) in the present invention in the form of the protonate. In such a case, when the total of the compound (b-1) and its protonate is 100 mol%, the proportion of the protonate in the total of the compound (b-1) and its protonate is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. On the other hand, the upper limit value of the proportion of the protonate is, of course, 100 mol%.

[0056] In the present invention, when a protonic acid compound is used, or when the compound (b-1) is used as a protonate in the preparation of the clay composition (b), the ratio of the protonic acid compound (on a valence basis) to the compound (b-1) is preferably 0.1 to 50 in terms of molar ratio. The lower limit value of the molar ratio is more preferably 0.2, and still more preferably 0.3. On the other hand, the upper limit value of the molar ratio is more preferably 30, still more preferably 20, particularly preferably 10, and especially preferably 5.

[0057] The protonate in the present invention refers to a salt obtained by reacting a monovalent protonic acid compound with one molecule of the compound (b-1) regardless of the number of atoms of the Group 15 element in the periodic table in one molecule of the compound (b-1). As a method for forming the above protonate, a known method such as contacting the compound (b-1) with a protonic acid can be used without limitation.

[0058] (Clay compound (b-2)) As the clay compound (b-2), known clay compounds can be used without limitation. Specific examples of the clay compound (b-2) include kaolin minerals such as kaolinite, dickite, and halloysite; smectite group minerals such as montmorillonite, hectorite, beidellite, saponite, teniolite, and sauconite; mica group minerals such as muscovite, paragonite, and illite; vermiculite group minerals; brittle mica group minerals such as margarite and clintonite; chlorite group minerals such as donbassite, cookeite, and clinochlore; and clay minerals such as sepiolite and palygorskite (attapulgite). However, the clay compound (b-2) is not limited to these examples. These clay minerals exist naturally, but those with fewer impurities can also be obtained by artificial synthesis. In the present invention, as the clay compound (b-2), the natural clay minerals and the clay minerals obtained by artificial synthesis shown herein can be used.

[0059] Clay compounds are generally inorganic polymer compounds composed of a tetrahedron formed by the coordination of oxygen ions to silicon ions and an octahedron formed by the coordination of oxygen or hydroxide ions to ions such as aluminum, magnesium, or iron. The skeletal structures of many clay compounds form a layered structure having a silicate layer or the like, and the surface of the layer is charged positively or negatively. In order to compensate for this negative charge, cations are often present between the layers, and these interlayer cations can be ion-exchanged with other cations. The amount of such interlayer cations is represented by the milliequivalent number (meq) per 100 g of the clay compound (cation exchange capacity (CEC)).

[0060] The CEC varies depending on the type of clay compound and the like. For example, kaolinite is known to have a CEC of 3 to 15 meq / 100 g, halloysite has a CEC of 5 to 40 meq / 100 g, montmorillonite has a CEC of 80 to 150 meq / 100 g, illite has a CEC of 10 to 40 meq / 100 g, vermiculite has a CEC of 100 to 150 meq / 100 g, chlorite has a CEC of 10 to 40 meq / 100 g, sepiolite has a CEC of 20 to 30 meq / 100 g, and palygorskite has a CEC of 20 to 30 meq / 100 g.

[0061] (Clay composition (b)) In the present invention, the above compound (b-1) and the clay compound (b-2) are used to form the clay composition (b). The above clay composition (b) can be obtained by using known methods without limitation, such as contacting, preferably reacting, the compound (b-1) and the clay compound (b-2).

[0062] The ratio of the compound (b-1) to the clay compound (b-2) is not particularly limited, and it is preferable to use an equivalent amount or more of the compound (b-1) relative to the cations present in the clay compound (b-2). The specific ratio of the compound (b-1) to 1 gram of the clay compound (b-2) is preferably 0.01 to 20 mmol / g. The lower limit of the ratio is more preferably 0.05 mmol / gram, still more preferably 0.1 mmol / gram, and particularly preferably 0.15 mmol / gram. On the other hand, the upper limit of the ratio is more preferably 10 mmol / gram, still more preferably 7 mmol / gram, and particularly preferably 5 mmol / gram. The above compound (b-1) and the clay compound (b-2) can be used individually or in combination of multiple types.

[0063] When producing the above clay composition (b), it is preferable to use a solvent. Examples of such solvents include water or polar organic solvents. Specifically, alcohols such as methyl alcohol and ethyl alcohol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, methylene chloride, etc. can be exemplified. These solvents can be used alone or in combination. Among these, water or alcohol is particularly preferably used. More preferably, water is used.

[0064] Since the olefin polymerization catalyst of the present invention described below includes the clay composition (b), as described below, it tends to exhibit high polymerization activity, and also tends to easily produce a unique polymer that may have many terminal double bonds. The reason why the olefin polymerization catalyst of the present invention exhibits such performance is unclear at present, but the present inventor is considering the following presumptive hypothesis.

[0065] The compound (b-1) contained in the clay composition (b) is a cyclic compound having a plurality of heteroatoms. Such a compound (b-1) combines with the clay compound (b-2), and since it has a structure containing a plurality of heteroatoms, it is considered that the organometallic compound (c) and the compound (b-1) may easily form a structure in which the organometallic compound (c) and the compound (b-1) are cationically pseudo-crosslinked due to the interaction with the cations that may exist in the clay compound (b-2) and the organometallic compound (c) described below.

[0066] On the other hand, methylaluminoxane (MAO), which is well-known as a cocatalyst component of a metallocene catalyst, is said to have a repeating structure of '-Al-O-' structural units. Since the clay composition (b) has a crosslinked structure similar to MAO, the present inventor considers that the performance such as the above-mentioned high activity may be exhibited.

[0067] (Transition metal compound (a)) The transition metal compound (a) is not particularly limited, and a known transition metal compound used in an olefin polymerization catalyst can be used.

[0068] Examples of the transition metal compound (a) include transition metal compounds represented by the following general formula (a1). R 31 R 32 R 33 R 34 M ···(a1) (In the formula, M represents a transition metal atom, and R 31 , R 32 , R 33 and R 34may be the same as or different from each other, and represents a group having a cyclopentadienyl skeleton, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, halogen atom, alkylsilyl, alkylamide, alkylimide, -SO3R or hydrogen atom.)

[0069] M in the general formula (a1) is a transition metal atom of Groups 3 to 10 of the periodic table. Specifically, examples include scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, tantalum, chromium, manganese, iron, cobalt, nickel, palladium, niobium, etc. Preferably, they are transition metal atoms of Groups 3 to 6 of the periodic table, more preferably Groups 4 to 5 of the periodic table, and even more preferably Group 4 of the periodic table.)

[0070] In the general formula (a1), examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl; alkyl-substituted cyclopentadienyl such as methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, methylethylcyclopentadienyl, propylcyclopentadienyl, methylpropylcyclopentadienyl, butylcyclopentadienyl, methylbutylcyclopentadienyl, hexylcyclopentadienyl; indenyl; 4,5,6,7-tetrahydroindenyl; fluorenyl, azulenyl, etc. The group also includes indenyl, fluorenyl, azulenyl and groups in which one or more hydrogen atoms they have are substituted with hydrocarbon groups. In the case of groups having indenyl, fluorenyl, or azulenyl, part or all of the double bonds of the unsaturated ring condensed to cyclopentadienyl may be hydrogenated. These groups may be substituted with halogen atoms, trialkylsilyl, etc.)

[0071] In the general formula (a1), examples of the ligand other than the ligand having a cyclopentadienyl skeleton include hydrocarbon groups having 1 to 12 carbon atoms. Specifically, alkyl such as methyl, ethyl, propyl, isopropyl, butyl, pentyl; cycloalkyl such as cyclopentyl, cyclohexyl; aryl such as phenyl, tolyl; aralkyl such as benzyl, neophyl are exemplified.

[0072] Examples of the alkoxy include methoxy, ethoxy, butoxy and the like. Examples of the aryloxy include phenoxy and the like. Examples of the alkylsilyl include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, triisopropylsilyl and the like.

[0073] Examples of the alkylamide include dimethylamide, diethylamide and the like. Examples of the alkylimide include methylcarbonylaminocarbonyl, ethylcarbonylaminocarbonyl, n-butylcarbonylaminocarbonyl and the like.

[0074] Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Examples of the ligand represented by -SO3R include p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate and the like. Here, R is a monovalent functional group. Among the compounds represented by the general formula (a1) above, the following transition metal complex (a11) is preferred.

[0075] <Transition metal complex (a11)> The transition metal complex (a11) is not particularly limited as long as it is a transition metal compound that can function as a known olefin polymerization (multimerization) catalyst.

[0076] Specific examples of the transition metal complex (a11) include transition metal halides, transition metal alkyls, transition metal alkoxides, non-bridged or bridged metallocene compounds and the like. Examples of the preferred transition metal complex (a11) in the present invention are given below, but the invention is not limited thereto.

[0077] Among the above-exemplified transition metal complexes (a11), preferred examples from the viewpoints of polymerization activity and the like include non-bridged or bridged metallocene compounds having one or more, preferably one or two groups having a cyclopentadienyl skeleton, and non-bridged or bridged metallocene compounds having two cyclopentadienyl skeletons are more preferred.

[0078] The group having a cyclopentadienyl skeleton is as described above. When two or more groups having a cyclopentadienyl skeleton are included, two groups having a cyclopentadienyl skeleton may be bonded via an alkylene such as ethylene or propylene; an alkylidene such as isopropylidene or diphenylmethylene; a silylene; a substituted silylene such as dimethylsilylene, diphenylsilylene or methylphenylsilylene.

[0079] When having a cyclopentadienyl skeleton, other ligands include hydrocarbon groups having 1 to 12 carbon atoms such as alkyl, cycloalkyl, aryl and aralkyl, alkoxy, aryloxy, halogen atoms, alkylsilyl, alkylamide, alkylimide, -SO3R or hydrogen atoms. Their specific examples are as described above. As general structures of these compounds, compounds represented by the following general formula (A1) or (A2) are given as preferred examples.

[0080]

Chemical formula

[0081] In the above formulas (A1) and (A2), M represents the same transition metal atom as defined in the above general formula (a1). Specific examples of M include titanium, zirconium, hafnium, vanadium, niobium, and tantalum, and preferably titanium, zirconium, and hafnium.

[0082] In the above formulas (A1) and (A2), Q represents a hydrocarbon group which may contain a hetero atom. Examples of the hydrocarbon group include a halogen atom-containing hydrocarbon group, an oxygen-containing hydrocarbon group (for example, a group containing an oxygen atom in the form of alkoxy, carbonyl, carboxyl), a sulfur-containing hydrocarbon group (for example, a group containing a sulfur atom in the form of alkylthio, thiocarbonyl, thiocarboxyl, dithiocarboxyl), a silicon-containing hydrocarbon group (for example, a group containing a silicon atom in the form of -Si(R 20 )(R 21 )(R 22 ), a phosphorus-containing hydrocarbon group (for example, a group containing a phosphorus atom in the form of -P(R 23 )(R 24 ), a nitrogen-containing hydrocarbon group (for example, a group containing a nitrogen atom in the form of -N(R 25 )(R 26 ), or a boron-containing hydrocarbon group (for example, a group containing a boron atom in the form of -B(R 27 )(R 28 ). Specifically, it represents an alkyl which may have a substituent, an alkenyl which may have a substituent, an alkynyl which may have a substituent, or an aryl which may have a substituent. The number of carbon atoms of the hydrocarbon group is preferably 1 to 8, more preferably an alkyl having 1 to 8 carbon atoms, an alkenyl having 1 to 8 carbon atoms, an alkynyl having 1 to 8 carbon atoms which may have a substituent, or an aryl having 1 to 8 carbon atoms which may have a substituent, and most preferably an alkyl having 1 to 8 carbon atoms.

[0083] In the above formulas (A1) and (A2), j represents an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2 or 3. When j is an integer of 2 or more, the plurality of Qs may be the same or different from each other.

[0084] In formulas (A1) and (A2), Cp 1 and Cp 2 may be the same as or different from each other, and represent a cyclopentadienyl or substituted cyclopentadienyl that can form a sandwich structure with M. A substituted cyclopentadienyl is a group in which at least one hydrogen atom of cyclopentadienyl is substituted with a substituent. For these groups, reference can also be made to the foregoing.

[0085] Examples of the substituent in the substituted cyclopentadienyl include a hydrocarbon group (hereinafter sometimes referred to as "the group (f1)") or a silicon-containing hydrocarbon group (hereinafter sometimes referred to as "the group (f2)"). In addition, examples of the substituent in the substituted cyclopentadienyl include heteroatom-containing hydrocarbon groups such as a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, and a nitrogen-containing hydrocarbon group (excluding the silicon-containing hydrocarbon group (f2)).

[0086] The group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include a linear or branched hydrocarbon group (e.g., alkyl, alkenyl, alkynyl), a cyclic saturated hydrocarbon group (e.g., cycloalkyl), and a cyclic unsaturated hydrocarbon group (e.g., aryl). The hydrocarbon group (f1) also includes a group in which any two hydrogen atoms bonded to adjacent carbon atoms among the above-exemplified groups are simultaneously substituted to form an alicyclic or aromatic ring.

[0087] Specific examples of the group (f1) include linear aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, and allyl; branched aliphatic hydrocarbon groups such as isopropyl, isobutyl, sec-butyl, t-butyl, amyl, 3-methylpentyl, neopentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, and 1-methyl-1-isopropyl-2-methylpropyl; cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl; cyclic unsaturated hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthryl, and anthracenyl, and nuclear alkyl-substituted derivatives thereof; and groups in which at least one hydrogen atom of a saturated hydrocarbon group is substituted with aryl, such as benzyl and cumyl.

[0088] Among these groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, n-butyl, n-hexyl, isopropyl, isobutyl, sec-butyl, t-butyl, and neopentyl are preferred examples.

[0089] The group (f2) is preferably a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include a group in which a silicon atom is directly covalently bonded to the ring carbon of cyclopentadienyl. Specifically, alkylsilyl (e.g., trimethylsilyl) and arylsilyl (e.g., triphenylsilyl) can be mentioned.

[0090] Specific examples of the heteroatom-containing hydrocarbon group (excluding the group (f2)) include methoxy, ethoxy, phenoxy, N-methylamino, trifluoromethyl, tribromomethyl, pentafluoroethyl, and pentafluorophenyl.

[0091] In formula (A2), Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO2-, -Ge-, -Sn(tin)-, -NR a -, -P(R a )-, -P(O)(R a )-, -BR a - or -AlR a -. However, R a is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen compound residue (-NRH or -NR 2 ; R is a hydrocarbon group having 1 to 20 carbon atoms) in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a nitrogen atom.

[0092] Among these metallocene compounds, the compound represented by the general formula (A2) is preferred, and a bridged metallocene compound represented by the following general formula (II) (hereinafter also referred to as "bridged metallocene compound (II)") as disclosed in WO 2001 / 27124 pamphlet is more preferred.

[0093] [Chemical formula]

[0094] The bridged metallocene compound (II) structurally has the following characteristics [m1] to [m3]. [m1] Among the two ligands, one is a cyclopentadienyl which may have a substituent, and the other is a fluorenyl having a substituent (hereinafter also referred to as "substituted fluorenyl"). [m2] The two ligands are bonded by an aryl group-containing covalent bond bridge portion (hereinafter also referred to as "bridge portion") composed of a carbon atom or a silicon atom having an aryl. [m3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium.

[0095] Hereinafter, the optionally substituted cyclopentadienyl, substituted fluorenyl, bridging moiety and other features of the bridged metallocene compound (II) will be sequentially described.

[0096] (Optionally substituted cyclopentadienyl) In formula (II), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group. A hydrogen atom, a hydrocarbon group or a silicon-containing group is preferred, and two adjacent groups may be bonded to each other to form a ring.

[0097] For example, R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, or one or more of R 1 , R 2 , R 3 and R 4 is a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms) or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms). In addition, heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups can also be mentioned.

[0098] R 1 , R 2 , R 3 and R 4 When two or more of them are substituents other than hydrogen atoms, the substituents may be the same or different from each other; R 1 , R 2 , R 3 and R 4 Two adjacent groups among them may be bonded to each other to form an alicyclic or aromatic ring.

[0099] R 1 ~R 4Examples of and preferred groups for the hydrocarbon group in include the hydrocarbon group (f1) defined at the position of the substituted cyclopentadienyl above. R 1 ~R 4 Examples of and preferred groups for the silicon-containing group in include the silicon-containing group (f2) defined at the position of the substituted cyclopentadienyl above. R 1 ~R 4 Examples of the heteroatom-containing group in include the groups exemplified at the position of the substituted cyclopentadienyl above.

[0100] (Substituted fluorenyl) In formula (II), R 5 , R 8 , R 9 and R 12 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group or a silicon-containing group is preferred. R 6 and R 11 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group and a silicon-containing group are preferred; R 7 and R 10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing group other than a silicon-containing group, and a hydrogen atom, a hydrocarbon group and a silicon-containing group are preferred; R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring; provided that "R 6 , R 7 , R 10 and R 11 are all hydrogen atoms" does not occur.

[0101] From the perspective of polymerization activity, it is preferred that neither R 6 nor R 11 is a hydrogen atom. R 6 , R 7 , R 10and R 11 It is more preferable that neither is a hydrogen atom. R 6 and R 11 are the same group selected from hydrocarbon groups and silicon-containing groups, and R 7 and R 10 are the same group selected from hydrocarbon groups and silicon-containing groups is particularly preferred. Further, R 6 and R 7 are bonded to each other to form an alicyclic or aromatic ring, and it is also preferable that R 10 and R 11 are bonded to each other to form an alicyclic or aromatic ring.

[0102] Examples and preferred groups of the hydrocarbon group in R 5 ~R 12 include the hydrocarbon group (f1) defined at the position of the above-mentioned substituted cyclopentadienyl. R 5 ~R 12 Examples and preferred groups of the silicon-containing group in R 5 ~R 12 include the silicon-containing group (f2) defined at the position of the above-mentioned substituted cyclopentadienyl. Examples of the heteroatom-containing group in R

[0103] 6 and R 7 (R(R 10 and R 11 ) When bonded to each other to form an alicyclic or aromatic ring, examples of the substituted fluorenyl include groups derived from the compounds represented by the general formulas (III) to (VII) described later as preferred examples.

[0104] (Crosslinking part) In formula (II), R 13 and R 14 each independently represent aryl, and Y1 represents a carbon atom or a silicon atom. An important point in the method for producing the olefin polymer of the present invention is that on the crosslinking atom Y1 of the crosslinking part, aryl (aryl) [R 13 and R 14is bonded. From the viewpoint of ease of production, R 13 and R 14 are preferably the same as each other.

[0105] Examples of the aryl include phenyl, naphthyl, anthracenyl, and groups in which one or more of the aromatic hydrogens (sp2-type hydrogens) they have are substituted with substituents. Examples of the substituent include the hydrocarbon group (f1) and the silicon-containing group (f2) defined in the above-mentioned substituted cyclopentadienyl moiety, a halogen atom, and a halogenated hydrocarbon group.

[0106] Specific examples of the aryl include unsubstituted aryl having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, anthracenyl, and biphenyl; alkyl-substituted aryl such as tolyl, dimethylphenyl, isopropylphenyl, n-butylphenyl, and t-butylphenyl; cycloalkyl-substituted aryl such as cyclohexylphenyl; halogenated aryl such as chlorophenyl, bromophenyl, dichlorophenyl, and dibromophenyl; halogenated alkyl-substituted aryl such as (trifluoromethyl)phenyl and bis(trifluoromethyl)phenyl. The position of the substituent is preferably the meta-position and / or the para-position. Among these, substituted phenyl in which the substituent is located at the meta-position and / or the para-position is more preferable.

[0107] (Other characteristics of the bridged metallocene compound) In formula (II), Q represents an alkyl which may contain a hetero atom, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same as or different from each other. Examples of the alkyl in Q include the same atoms or groups as Q in formulas [A1] and [A2].

[0108] (Examples of the preferred bridged metallocene compound (II)) Specific examples of the crosslinked metallocene compound (II) are shown below. In the exemplified compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from the compound having the structure represented by formula (III), octamethyltetrahydrodicyclopentapentafluorenyl refers to a group derived from the compound having the structure represented by formula (IV), dibenzofluorenyl refers to a group derived from the compound having the structure represented by formula (V), 1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentapentafluorenyl refers to a group derived from the compound having the structure represented by formula (VI), and 1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentapentafluorenyl refers to a group derived from the compound having the structure represented by formula (VII).

[0109]

Chem.

[0110] The above metallocene compounds can be produced by known methods, and the production method is not particularly limited. Examples of known methods include the methods described in, for example, International Publication No. 2001 / 27124 pamphlet, International Publication No. 2004 / 029062 pamphlet, and International Publication No. 2004 / 87775 pamphlet by the present applicant. Specific compounds of the transition metal compound in which M of the general formula (a1) is zirconium are exemplified below, but are not limited thereto.

[0111] Bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconium bis(p-toluenesulfonate), bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methy zirconium monochloride, ethylenebis(indenyl)zirconium bis(methanesulfonate), ethylenebis(indenyl)zirconium bis(p-toluenesulfonate), ethylenebis(indenyl)zirconium bis(trifluoromethanesulfonate), ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, Isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl-methylcyclopentadienyl)zirconium dichloride, Dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium bis(trifluoromethanesulfonate), rac-Dimethylsilylenebis{1-(2-methyl-4,5-ace naphthocyclopentadienyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methyl-4-isopropyl-7-methylindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methylindenyl)}zirconium dichloride, Dimethylsilylenebis(4,5,6,7 - tetrahydroindenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl - fluorenyl)zirconium dichloride, diphenylsilylenebis(indenyl)zirconium dichloride, methylphenylsilylenebis(indenyl)zirconium dichloride, Bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methy zirconium monochloride, bis(cyclopentadienyl)ethyl zirconium monochloride, bis(cyclopentadienyl)cyclohexyl zirconium monochloride, bis(cyclopentadienyl)phenyl zirconium monochloride, bis(cyclopentadienyl)benzyl zirconium monochloride, bis(cyclopentadienyl)zirconium monochloride monohydride, bis(cyclopentadienyl)methyl zirconium monohydride, bis(cyclopentadienyl)dimethyl zirconium, bis(cyclopentadienyl)diphenyl zirconium, bis(cyclopentadienyl)dibenzyl zirconium, bis(cyclopentadienyl)zirconium methoxychloride, bis(cyclopentadienyl)zirconium ethoxychloride, bis(cyclopentadienyl)zirconium bis(methanesulfonate), bis(cyclopentadienyl)zirconium bis(p - toluenesulfonate), bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonate), Bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium ethoxychloride, bis(dimethylcyclopentadienyl)zirconium bis(trifluoromethanesulfonate), bis(ethylcyclopentadienyl)zirconium dichloride, bis(methylethylcyclopentadienyl)zirconium dichloride, bis(propylcyclopentadienyl)zirconium dichloride, bis(methylpropylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconium dichloride, bis(methylbutylcyclopentadienyl)zirconium dichloride, bis(methylbutylcyclopentadienyl)zirconium bis(methanesulfonate), bis(trimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(hexylcyclopentadienyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconium dichloride, 8-octamethylfluoren-12‘-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]inden))zirconium dichloride, bis(1,3-n-butylmethylcyclopentadienyl)zirconium(IV) dichloride, di-p-tolylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di-p-tolylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium(IV) dimethyl, dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium(IV) dichloride Examples thereof include the following.

[0112] In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-disubstituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-trisubstituted products. In addition, alkyl groups such as propyl and butyl include isomers such as n-, i-, sec-, and tert-.

[0113] In the present invention, in the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. Specific examples of the compound in which zirconium metal is replaced with hafnium metal include bis(t-butylcyclopentadienyl)hafnium dichloride. In addition to titanium compounds and hafnium compounds having a similar steric structure, and bromides and iodides, for example, transition metal compounds as described in Organometallics, Vol. 13, pp. 954-963, 1994, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, JP-A-3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300887, WO 2001 / 27124 pamphlet, JP-A-2010-144035, JP-A-2012-92199, JP-A-2013-60518, etc. can be mentioned.

[0114] In addition, as the transition metal compound (a), a transition metal compound represented by the following general formula (a2) as described in JP-A-11-315109, JP-A-2000-239312, WO 2001 / 55231 pamphlet, Chemical Review, Vol. 111, pp. 2363-2449, 2011 can also be mentioned.

[0115] [Chemical formula]

[0116] In the general formula (a2), M represents a transition metal atom of Groups 4 to 10 of the periodic table. m represents an integer from 1 to 6, R 19 ~R 24 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Two or more of these may be linked to each other to form a ring. Also, when m is 2 or more, two of the groups represented by R 19 ~R 24 may be linked. n is a number that satisfies the valence of M. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same as or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

[0117] Specifically, examples include bis{N-(5-adamantyl-3-methylsalicylidene)-2-methylcyclohexylaminato}zirconium(IV) dichloride, bis{N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato}titanium(IV) dichloride, and the like.

[0118] Also, as the transition metal compound (a), for example, transition metal complexes having a crosslinked bisaromatic ligand described in International Publication No. 2003 / 091262 pamphlet, US Patent Application No. 2004 / 0010103, and International Publication No. 2007 / 136496 pamphlet can also be mentioned.

[0119] Specifically, examples thereof include bis((2-oxoyl-3-(3,5-bis(1,1-dimethylethyl)phenyl)-(5-(1,1-dimethylethyl)phenyl)-(4-(1,1-dimethylethyl)-2-phenoxy)-propane-1,3-diyl)zirconium(IV) dichloride).

[0120] Examples of the transition metal compound (a) also include compounds represented by the following general formula (a3) as described in, for example, Pamphlet of International Publication No. 2009 / 5003, JP-A-2011-178682, and JP-A-2011-195584.

[0121] [Chemical formula]

[0122] (In the general formula (a3), R 25 ~R 30 may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. Further, R 25 may be linked to Z. M represents a transition metal atom selected from Groups 3 to 10 of the periodic table. n represents the valence of M. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and the atoms or groups represented by X may be the same as or different from each other, and the groups represented by X may be bonded to each other to form a ring. Y represents an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom. Z represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent, and the shortest number of bonds connecting Y and N is 4 to 6. In the formula, the bond connecting Y and Z may be a double bond or a triple bond, and the bond connecting Y and R 25 may also be a double bond or a triple bond. In the formula, the dotted line indicates a coordination bond.)

[0123] Examples of the compound represented by the general formula (a3) include trichloro{6-[(2'-methoxy-κO 1 -biphenyl-2-yl)imino-κN 1 -methyl]-4-methyl-2-(tricyclo[3.3.1.1 3,7 decane-1-yl)phenolato}titanium(IV).

[0124] (Olefin polymerization catalyst) The olefin polymerization catalyst of the present invention is characterized by containing the transition metal compound (a) and the clay composition (b).

[0125] There is no particular limitation on the amount ratio of the two components. For example, the known range of the amount ratio of the transition metal compound and the clay mineral (or modified clay mineral) employed in a known olefin polymerization catalyst containing a known clay mineral (or modified clay mineral) instead of the clay composition (b) can be applied.

[0126] The amount of the clay composition (b) is preferably an amount sufficient for the transition metal compound (a) to react. More specifically, the amount of the cation in the clay composition (b) relative to the transition metal compound (a) is preferably 1 to 10,000 molar times. The lower limit of this ratio is more preferably 10 molar times, and even more preferably 20 molar times. On the other hand, the upper limit of this ratio is more preferably 5,000 molar times, even more preferably 1,000 molar times, and particularly preferably 800 molar times.

[0127] If the ratio is too small, sufficient polymerization activity may not be obtained. On the other hand, if the ratio is too large, the proportion of the clay compound (b-2) in the obtained olefin polymer may become too large, and optical problems such as the generation of fish eyes and physical property problems such as a decrease in impact resistance may occur.

[0128] When preparing the olefin polymerization catalyst of the present invention, it is preferable to use a metal organic compound (c) such as an organoaluminum compound in combination. Considering the effect of inactivating impurities in the polymerization reaction system, the metal organic compound (c) can also be regarded as an essential component. In this case, the amount of the metal organic compound (c) is preferably 1 to 10,000 times the amount of the transition metal compound (a) (based on the number of moles of metal atoms). The lower limit of the above range is more preferably 10 times the molar ratio, and even more preferably 20 times the molar ratio. On the other hand, the upper limit of the above range is more preferably 5,000 times the molar ratio, even more preferably 2,000 times the molar ratio, particularly preferably 1,500 times the molar ratio, and especially preferably 1,000 times the molar ratio. If the amount of the metal organic compound (c) is too small, the polymerization activity may decrease, and if it is too large, the effect on improving the activity may be reduced.

[0129] The ratio of the metal organic compound (c) (based on the number of moles of metal atoms) to the clay composition (b) (by weight) is preferably 0.01 to 200 mmol / g. The lower limit of the above ratio is more preferably 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. On the other hand, the upper limit of the above ratio is more preferably 100 mmol / g, even more preferably 50 mmol / g, and particularly preferably 20 mmol / g.

[0130] As the metal organic compound (c), compounds containing Group 13 metals, for example, organoaluminum compounds, complex alkylates of Group 1 metals and aluminum, and organometallic compounds of Group 2 metals can be used. Among these, organoaluminum compounds are preferred.

[0131] Specific examples of the metal organic compound (c) include the metal organic compound catalyst components described in the known literature of EP0585869A1 as preferred examples. Among these, organoaluminum compounds are preferred. More specifically, examples include trialkylaluminum compounds such as triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; halogen-containing organoaluminum compounds such as diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride; and alkylaluminum alkoxides such as diethylaluminum ethoxide, dibutylaluminum butoxide. Among these, trialkylaluminum is preferred. Further, considering ease of acquisition and price, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, and trioctylaluminum can be cited as preferred specific examples. Even more preferably, triethylaluminum and triisobutylaluminum are used.

[0132] In addition, the olefin polymerization catalyst of the present invention may be used in combination with a solid carrier as necessary, as long as the effects of the present invention are not inhibited. Examples of the solid carrier include solid inorganic carriers such as silica, alumina, silica-alumina, and magnesium chloride, or solid organic carriers such as polystyrene beads.

[0133] (Method for forming olefin polymerization catalyst) The method for forming the olefin polymerization catalyst of the present invention is arbitrary, and known methods can be used without limitation. For example, · A method in which the transition metal compound (a) and the clay composition (b) are contacted and then used for olefin polymerization · A method in which the transition metal compound (a) and the clay composition (b) are contacted in a polymerization solvent described below and then used for olefin polymerization · A method in which the clay composition (b) and the organometallic compound (c) are contacted, and then contacted with the transition metal compound (a) and used for olefin polymerization · A method in which the clay composition (b) and the transition metal compound (a) are sequentially added to an olefin polymerization reactor and used for olefin polymerization · A method of sequentially adding a clay composition (b), an organometallic compound (c), and a transition metal compound (a) to a reactor for olefin polymerization and using them for the polymerization of olefins Examples such as the above can be cited as suitable examples.

[0134] The olefin polymerization catalyst of the present invention tends to have higher polymerization activity than the prior art. It is presumed that this is because in the olefin polymerization catalyst of the present invention, as described above, the clay composition (b) forms a special structure and exhibits an effect similar to that of MAO.

[0135] [Method for Producing Olefin Polymer] The method for producing an olefin polymer of the present invention includes a step of polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention. The olefin polymerization catalyst of the present invention may be used as a catalyst as it is or as a catalyst component, or may be used as a prepolymerization catalyst obtained by prepolymerizing an olefin. The olefin polymer can be produced by a known method as long as the step is included. The olefin polymer includes homopolymers of olefins and copolymers such as block copolymers and random copolymers produced from two or more olefins.

[0136] Examples of the polymerization method include a slurry polymerization method using a nonpolar solvent such as butane, pentane, hexane, heptane, octane, etc., a gas-phase polymerization method in which a monomer in a gaseous state is brought into contact with a catalyst for polymerization, or a bulk polymerization method in which a liquefied monomer is used as a solvent and polymerization is carried out therein. Further, the polymerization may be any of multi-stage polymerization such as one-stage polymerization and two-stage polymerization, continuous polymerization, and batch polymerization.

[0137] Specific examples of the inert hydrocarbon medium used in the slurry polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Olefins themselves can also be used as solvents.

[0138] When performing the polymerization of olefins using the above olefin polymerization catalyst, the transition metal atoms derived from the transition metal compound (a) are usually in an amount of 1×10 -12 ~1×10 -1 mol, preferably 1×10 -10 ~1×10 -2 mol, more preferably 1×10 -8 ~1×10 -2 mol per liter of the reaction volume, and the olefin polymerization catalyst is used.

[0139] In addition, in the polymerization of olefins using the above olefin polymerization catalyst, the polymerization temperature is usually in the range of -50 to 200°C, preferably 0 to 170°C, and particularly preferably 40 to 170°C. The polymerization time is usually in the range of 10 seconds to 20 hours. The polymerization pressure is usually 0.001 MPa to 250 MPa, preferably 0.005 MPa to 50 MPa, and more preferably 0.005 MPa to 10 MPa. The polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

[0140] The molecular weight of the resulting olefin polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. During polymerization, at least one compound selected from polyalkylene oxide block, higher aliphatic amide, polyalkylene oxide, polyalkylene oxide alkyl ether, alkyldiethanolamine, and polyoxyalkylene alkylamine may coexist for the purpose of suppressing fouling or improving particle properties.

[0141] Examples of the olefin used in the method for producing an olefin polymer of the present invention include α-olefins having 2 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, and diene compounds having 4 to 20 carbon atoms, but are not limited thereto as long as the effects of the present invention are achieved. In the present invention, these olefins can be used alone or in admixture of two or more.

[0142] Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. Preferably, they are ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.

[0143] Examples of the cyclic olefin having 3 to 20 carbon atoms include cyclopropene, cyclopentene, cyclohexene, cycloheptene, norbornene, tetracyclododecene and the like. Preferably, they are norbornene and tetracyclododecene.

[0144] Examples of the diene compound having 4 to 20 carbon atoms include butadiene, isoprene, 1,5 - hexadiene, 1,7 - octadiene, 1,3 - cyclohexadiene, 1,4 - cyclohexadiene, 1,5 - cyclooctadiene, dicyclopentadiene, norbornadiene, 5 - vinyl - 2 - norbornene, 5 - ethylidene - 2 - norbornene, etc. Preferably, they are butadiene, isoprene, 5 - vinyl - 2 - norbornene, 5 - ethylidene - 2 - norbornene, etc.

[0145] Furthermore, monomers having a ring structure such as styrene, α - methylstyrene and vinylcyclohexane, polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, and halogen - substituted olefins such as bisfluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoropropene and chloroethylene can also be used.

[0146] The olefin polymer obtained by the polymerization reaction is preferably separated and recovered from the polymerization solvent by a conventionally known method after the polymerization is completed, dried and used for various applications. When the olefin polymer obtained by the olefin polymerization method of the present invention is analyzed by, for example, differential scanning calorimetry (DSC method), it may show an unexpected tendency that the melting point (Tm) is high but the heat of fusion is low. (Generally, an olefin polymer with a high melting point tends to have a high heat of fusion.) This can be considered to suggest that the polymer obtained by the olefin polymerization catalyst of the present invention may have a unique structure.

[0147] The present inventor presumes that there is a high possibility that a relatively large amount of polymers having a terminal double bond are generated among the olefin polymers obtained by the olefin polymerization method of the present invention for the following reasons.

[0148] The DSC method attempts to obtain information about the properties of a sample by supplying and quantifying thermal energy to a polymer so that the temperature of the sample rises or falls at a constant rate. Usually, the melting point, crystallization temperature, heat capacity, etc. can be measured.

[0149] Despite the high melting point of the olefin polymer obtained by the method for producing an olefin polymer of the present invention which is the sample, the reason why the heat of fusion does not increase correspondingly is that if the polymer which is the sample reacts and generates heat during the measurement, in the DSC method, the amount of heat added for raising the temperature becomes small, so it is expected that the heat of fusion amount will be low.

[0150] Normally, olefin polymers are stable in an inert gas atmosphere in a temperature range of about 200°C or lower, so heat generation and heat absorption are unlikely. However, for example, if it has a highly reactive structure such as a terminal double bond, it is considered that this double bond may react during DSC measurement and generate thermal energy. Therefore, it is conceivable that the olefin polymer obtained from the olefin polymerization catalyst of the present invention is a polymer having some reactivity.

[0151] As described above, one of the features of the olefin polymerization catalyst of the present invention is that it contains a clay composition (b) having a unique structure containing the compound (b-1). As also described above, the compound (b-1) may easily form a pseudo-crosslinked structure. By using such a compound, during the olefin polymerization reaction, the reaction environment of the reaction using the transition metal of the transition metal compound as the active species becomes relatively diversified, and reactions different from addition reactions such as β-hydrogen elimination are likely to occur simultaneously. Therefore, it is considered that there is a tendency to easily produce an olefin polymer having a highly reactive structure such as a terminal double bond.

[0152] For an olefin polymer having such high reactivity as described above, when the same polymer is subjected to hot melt molding such as injection molding or T-die molding, it is expected to have effects such as forming a partially branched structure and improving moldability, and being suitable as a base polymer for graft reaction.

[0153] On the other hand, olefin copolymers obtained by copolymerizing olefins, such as copolymerization of ethylene and hexene, using the olefin polymerization method of the present invention may not exhibit the surprising relationship between the melting point (Tm) and the heat of fusion as described above. This is thought to be because in a system containing two or more olefins, an environment is created in which olefins with different polymerization reactivities coexist, allowing for the formation of various reaction fields, and therefore the proportion of reaction fields that induce the β-hydrogen elimination reaction described above is relatively reduced, making it difficult for the above-mentioned unique tendency to become apparent. In other words, it can be considered that the degree of specificity of the relationship between the melting point and the heat of fusion can be adjusted by adjusting the copolymerization conditions of the olefin. It is believed that the use of the compound (b-1) makes it possible to more precisely adjust the comonomer content in the copolymer. Furthermore, in the olefin polymerization method of the present invention, when olefin copolymerization is carried out, activity may be improved compared to homopolymerization, as shown in the examples described later. The reason why the olefin polymerization catalyst of the present invention exhibits such performance is currently unknown, but the present inventors have hypothesized the following. It is thought that the protons of the comonomer fixed to the anionic clay layer interact with the protons on the ammonium cation derived from the amine, making it easier for the comonomer to exist in the vicinity of the active species, promoting the monomer insertion reaction and improving activity. In addition to the above, various reactions that are said to go through a dormant state (resulting in a slower polymerization rate), such as a beta-hydrogen elimination reaction, are relatively less likely to occur in an embodiment using multiple types of olefins, and therefore, it is conceivable that the polymerization activity may be increased in copolymerization.

[0154] As described above, the olefin polymers obtained using the olefin polymerization catalyst of the present invention may exhibit performance different from that of polymers obtained using conventional catalysts, and therefore can be suitably used in applications suited to their physical properties. For example, they can be expected to be used appropriately in known applications such as films produced by T-die molding or inflation molding, structures produced by injection molding, and containers produced by blow molding or vacuum molding. In addition, since it may be a polymer having reactivity, it is expected to be suitable as a raw material for a compound combined with other (olefin) polymers.

[0155] On the other hand, according to the olefin polymerization method of the present invention, an olefin copolymer having the same characteristics as those of the prior art can also be produced. From these facts, it was suggested that the olefin polymerization method of the present invention has the possibility of producing various olefin polymers. Therefore, the industrial value of the present invention can be expected to be high.

Examples

[0156] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. In the following examples, the molecular weight distribution, melting point, crystallization temperature, and heat of fusion were measured by the following methods.

[0157] (Molecular weight distribution) · Gel permeation chromatograph: HLC-8321 GPC / HT type manufactured by Tosoh Corporation · Detector: Differential refractometer · Columns: Two TSKgel GMH6-HT manufactured by Tosoh Corporation and two TSKgel GMH6-HTL were connected in series. (Column size (all the same size): 7.5 mm I.D. × 30 cm) · Mobile phase medium: o-dichlorobenzene (containing 0.025% of dibutylhydroxytoluene (BHT) as an antioxidant) · Flow rate: 1.0 ml / min · Measurement temperature: 140 °C · Method for preparing calibration curve: Standard polystyrene samples manufactured by Tosoh Corporation were used. · Sample concentration: 0.01% (w / v) · Sample solution volume: 0.4 ml · Sampling interval: 0.5 seconds

[0158] Measurements were performed under the above conditions, and the resulting chromatograms were analyzed by known methods to calculate the weight-average molecular weight (Mw) and the Mw / Mn value, which is an index of molecular weight distribution (MWD). The measurement time per sample was 40 minutes.

[0159] (Intrinsic viscosity [η]) The ethylene polymer was dissolved in decalin, and the viscosity was measured in decalin at a temperature of 135°C using a fully automatic viscosity measuring device (VMR-053UPC manufactured by Rigo Co., Ltd.).

[0160] (Polymer melting point (Tm), crystallization temperature (Tc), heat of fusion (ΔH)) The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymers of the present invention were measured by differential scanning calorimetry (DSC) using a Hitachi High-Tech Science DSC7020 device. 5 to 10 mg of sample was sealed in an aluminum pan and heated from room temperature to 200°C at 100°C / min. The sample was held at 200°C for 10 minutes and then cooled to 30°C at 10°C / min. The peak temperature in this cooling test was taken as the crystallization temperature (Tc). After holding at 30°C for 1 minute, the sample was heated a second time to 200°C at 10°C / min. In this second heating test, the peak temperature was taken as the melting point (Tm), and the endothermic heat was taken as the heat of fusion (ΔH).

[0161] [Example 1] (Preparation of Clay Composition) A 300 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 15 mL of deionized water, 5 mL of 1N hydrochloric acid, and a previously prepared solution of 0.56 g (5.0 mmol) of 1,4-diazabicyclo[2.2.2]octane (a product of Fujifilm Wako Pure Chemical Industries, Ltd.) in 20 mL of ethanol at room temperature, all of which were stirred. Stirring was continued for an additional 15 minutes, after which 5 g of montmorillonite (trade name: Kunipia-F, manufactured by Kunimine Industries, Ltd.) was added (amine / hydrochloric acid = 1 / 1 m.r.).

[0162] After heating this to 60°C, it was held at the same temperature for 2 hours. After gradually cooling this to room temperature, the resulting suspension was filtered, and the obtained solid was thoroughly washed with water to confirm that the pH value had reached 7. This solid was dried at 80°C under reduced pressure (0.09 MPa) for 10 hours, and then the dried solid was pulverized using a mortar to obtain a clay composition (1).

[0163] (Preparation of solid catalyst) 150 mg of the above clay composition (1) was charged into a Schlenk tube containing a stirrer rotor with an internal volume of 30 mL that had been sufficiently purged with nitrogen, and dried under reduced pressure (70 Pa) at 80°C for 3 hours. Next, after setting the Schlenk tube under a nitrogen atmosphere, 9.15 mL of toluene was charged, and while stirring, 1.35 milliliters of a decane solution of triisobutylaluminum (1.0 M) and 4.5 mL of a toluene solution of bis(N-butylcyclopentadienyl)zirconium(IV) dichloride (1.0 mmol / L in terms of Zr) were sequentially charged, and the temperature was raised to 60°C and held for 2 hours. After a predetermined time, it was gradually cooled to room temperature and allowed to stand until a solid precipitated. After removing 10 mL of the supernatant therefrom, it was washed once by the decantation method using 10 mL of toluene to obtain a solid catalyst slurry (1-1) with a solid content concentration of the clay composition of 10.0 g / L.

[0164] (Polymerization of ethylene) Into a 1-liter SUS autoclave with a stirrer, which had been sufficiently purged with nitrogen, 500 milliliters of heptane was charged under a nitrogen atmosphere. After that, while stirring, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al), 0.25 mL of a decane solution of polyoxyethylene polyoxypropylene condensate (trade name: L-71, manufactured by ADEKA Corporation) (1.0 mol / L), and 50 mg equivalent of the solid content of the above-obtained solid catalyst slurry (1-1) were charged into the reactor. Then, by raising the temperature and supplying ethylene, the temperature and pressure inside the reactor were raised to 80 °C and 0.8 MPaG, and the mixture was held for 60 minutes under stirring to carry out the ethylene polymerization reaction. After a predetermined time, it was cooled to room temperature and unreacted ethylene was purged. Next, the white solid component in the reactor was filtered, thoroughly washed with heptane, and then dried under reduced pressure at 80 °C for 10 hours to obtain 56.86 g of an ethylene polymer (white solid component). The weight average molecular weight (Mw) of the obtained ethylene polymer was 430,000.

[0165] [Example 2] (Preparation of clay composition) A clay composition (2) was obtained in the same manner as in Example 1, except that the amount of deionized water was changed to 10 mL and the amount of 1N hydrochloric acid was changed to 10 mL (2 equivalents to the amine), and 0.44 g (5.0 mmol) of morpholine (purchased from Fujifilm Wako Pure Chemical Corporation) was used instead of 1,4-diazabicyclo[2.2.2]octane.

[0166] (Preparation of solid catalyst) A solid catalyst slurry (2-1) was obtained in the same manner as in Example 1, except that the clay composition (2) was used instead of the clay composition (1).

[0167] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (2-1) was used instead of the solid catalyst slurry (1-1). 54.25 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 420,000.

[0168] [Example 3] (Preparation of clay composition) A clay composition (3) was obtained in the same manner as in Example 2, except that 0.51 g (5.0 mmol) of 4-methylmorpholine (purchased from Fujifilm Wako Pure Chemical Corporation) was used instead of morpholine.

[0169] (Preparation of solid catalyst) A solid catalyst slurry (3-1) was obtained in the same manner as in Example 1, except that the clay composition (3) was used instead of the clay composition (1).

[0170] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (3-1) was used instead of the solid catalyst slurry (1-1). 54.85 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 440,000.

[0171] [Example 4] (Preparation of clay composition) A clay composition (4) was obtained in the same manner as in Example 2, except that 0.82 g (5.0 mmol) of 4-phenylmorpholine (purchased from Fujifilm Wako Pure Chemical Corporation) was used instead of morpholine.

[0172] (Preparation of solid catalyst) A solid catalyst slurry (4-1) was obtained in the same manner as in Example 1, except that the clay composition (4) was used instead of the clay composition (1).

[0173] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (4-1) was used instead of the solid catalyst slurry (1-1). 36.63 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 450,000.

[0174] [Example 5] (Preparation of clay composition) A clay composition (5) was obtained in the same manner as in Example 2, except that 0.40 g (5.0 mmol) of pyrazine (purchased from Fujifilm Wako Pure Chemical Corporation) was used instead of morpholine.

[0175] (Preparation of solid catalyst) A solid catalyst slurry (5-1) was obtained in the same manner as in Example 1, except that the clay composition (5) was used instead of the clay composition (1).

[0176] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (5-1) was used instead of the solid catalyst slurry (5-1). 16.43 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 500,000.

[0177] [Example 6] (Preparation of clay composition) A clay composition (6) was obtained in the same manner as in Example 2, except that deionized water was not used, the amount of 1N hydrochloric acid was changed to 20 mL (4 equivalents to the amine), and 0.70 g (5.0 mmol) of hexamethylenetetramine (purchased from Fujifilm Wako Pure Chemical Corporation) was used instead of morpholine.

[0178] (Preparation of solid catalyst) A solid catalyst slurry (6-1) was obtained in the same manner as in Example 1, except that the clay composition (6) was used instead of the clay composition (1).

[0179] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (6-1) was used instead of the solid catalyst slurry (1-1). 20.89 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 470,000.

[0180] [Example 7] (Preparation of solid catalyst) A Schlenk tube containing a rotor for stirring with an internal volume of 30 mL that had been sufficiently purged with nitrogen was charged with 100 mg of the above-mentioned clay composition (1) produced in the process of Example 1, and dried under reduced pressure (70 Pa) at 80 °C for 3 hours. Next, after setting the Schlenk tube under a nitrogen atmosphere, 6.75 mL of toluene was charged, and while stirring, 0.25 mL of a decane solution of triisobutylaluminum (1.0 M) and 3.0 mL of a toluene solution of bis(n-butylcyclopentadienyl)zirconium(IV) dichloride (1.0 mmol / L in terms of Zr) were sequentially charged. After continuing stirring at room temperature for 30 minutes, a solid catalyst slurry (1-2) with a solid content concentration of the clay composition of 10.0 g / L was obtained.

[0181] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that 30 mg of the solid content equivalent of the solid catalyst slurry (1-2) was charged into the reactor. 3.03 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 8,230,000.

[0182] [Example 8] (Preparation of solid catalyst) A solid catalyst slurry (2-2) was obtained in the same manner as in Example 7, except that the clay composition (2) produced in the process of Example 2 was used instead of the clay composition (1).

[0183] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 7, except that the solid catalyst slurry (2-2) was used instead of the solid catalyst slurry (1-2). 21.02 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 8,290,000.

[0184] [Comparative Example 1] (Preparation of clay composition) A clay composition (7) was obtained in the same manner as in Example 2, except that morpholine was not used.

[0185] (Preparation of solid catalyst) A solid catalyst slurry (7-1) was obtained in the same manner as in Example 1, except that the clay composition (7) was used instead of the clay composition (1).

[0186] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (7-1) was used instead of the solid catalyst slurry (1-1). 2.9 g of an ethylene polymer (white solid component) was obtained.

[0187] [Comparative Example 2] (Preparation of clay composition) A clay composition (8) was obtained in the same manner as in Example 1, except that 1.49 g (5.0 mmol) of N,N-dimethyl-n-octadecylamine (product of Tokyo Chemical Industry Co., Ltd.) was used instead of 1,4-diazabicyclo[2.2.2]octane.

[0188] (Preparation of solid catalyst) A solid catalyst slurry (8-1) was obtained in the same manner as in Example 1, except that the clay composition (8) was used instead of the clay composition (1).

[0189] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (8-1) was used instead of the solid catalyst slurry (1-1). 31.35 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 460,000.

[0190] [Comparative Example 3] (Preparation of clay composition) A clay composition (9) was obtained in the same manner as in Example 1, except that 1.07 g (5.0 mmol) of N,N-dimethyldodecylamine (purchased from Tokyo Chemical Industry Co., Ltd.) was used instead of 1,4-diazabicyclo[2.2.2]octane.

[0191] (Preparation of solid catalyst) A solid catalyst slurry (9-1) was obtained in the same manner as in Example 1, except that the clay composition (9) was used instead of the clay composition (1).

[0192] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst slurry (9-1) was used instead of the solid catalyst slurry (1-1). 30.71 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 450,000.

[0193] [Comparative Example 4] (Preparation of solid catalyst) A solid catalyst slurry (8-2) was obtained in the same manner as in Example 7, except that the clay composition (8) produced in the process of Comparative Example 2 was used instead of the clay composition (1).

[0194] (Polymerization of ethylene) Ethylene was polymerized in the same manner as in Example 7, except that the solid catalyst slurry (8-2) was used instead of the solid catalyst slurry (1-2). 0.8 g of an ethylene polymer (white solid component) was obtained. The weight average molecular weight (Mw) of the obtained ethylene polymer was 7,830,000.

[0195] The above results and various physical properties are summarized in Tables 1 and 2. It can be seen that when using the olefin polymerization catalyst of the present invention, olefin polymers such as ethylene polymers can be obtained with relatively high activity compared to the prior art. In addition, it can be seen that olefin polymers such as the obtained ethylene polymer show a unique tendency that while having a relatively higher melting point than the polymers obtained by the prior art, the heat of fusion is equal to or lower.

[0196]

Table 1

[0197]

Table 2

[0198] [Example 9] (Preparation of Solid Catalyst) A solid catalyst slurry (2-3) with a solid content concentration of 10.0 g / L of the clay composition was obtained in the same manner as in Example 2, except that bis(1-n-butyl-3-methylcyclopentadienyl)zirconium(IV) dichloride was used instead of bis(n-butylcyclopentadienyl)zirconium(IV) dichloride.

[0199] (Polymerization of Ethylene) Ethylene was polymerized in the same manner as in Example 2, except that the solid catalyst slurry (2-3) was used instead of the solid catalyst slurry (2-1), to obtain a white solid (ethylene polymer). The analysis results of the obtained solid are shown in Table 3.

[0200] [Comparative Example 5] (Preparation of Solid Catalyst) A solid catalyst slurry (8-3) was obtained in the same manner as in Comparative Example 4, except that bis(1-n-butyl-3-methylcyclopentadienyl)zirconium(IV) dichloride was used instead of bis(n-butylcyclopentadienyl)zirconium(IV) dichloride.

[0201] (Polymerization of Ethylene) Ethylene was polymerized in the same manner as in Comparative Example 4, except that the solid catalyst slurry (8-3) was used instead of the solid catalyst slurry (8-2), to obtain a white solid (ethylene polymer). The analysis results of the obtained solid are shown in Table 3.

[0202] [Table 3]

[0203] [Example 10] (Ethylene / Hexene Copolymerization) Ethylene and 1-hexene were copolymerized in the same manner as in Example 9, except that 20 milliliters of 1-hexene purified for olefin polymerization was subsequently charged into heptane, to obtain a white solid (ethylene / hexene copolymer). The analysis results of the obtained solid are shown in Table 4.

[0204] [Comparative Example 6] (Ethylene / Hexene Copolymerization) Ethylene and 1-hexene were copolymerized in the same manner as in Comparative Example 5, except that 20 milliliters of 1-hexene purified for olefin polymerization was subsequently charged into heptane, to obtain a white solid (ethylene / hexene copolymer). The analysis results of the obtained solid are shown in Table 4.

[0205]

Table 4

Claims

1. A transition metal compound (a), and a clay composition (b) containing a compound (b-1) specified by a structural formula selected from the following formula b1 and the following formula b2 and a clay compound (b-2) An olefin polymerization catalyst comprising 【Chemical Formula 1】 [Chemical 2] 〔In the above formula b1 and formula b2, C represents a carbon atom, A plurality of Ys are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, A plurality of Rs are each independently a hydrogen atom, a halogen atom, or a substituent selected from a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. R and Y can combine to form a ring structure. A plurality of Rs can combine with each other to form a cyclic structure or a multiple structure. a1 to a27 are each independently an integer from 0 to 6 and satisfy either of the following (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≧ 1 and a2 + a5 + a7 + a8 ≧ 2 (β2) All of a11 + a13 + a14 + a16 ≧ 1, a12 + a15 + a17 ≧ 1, a21 + a23 + a24 + a26 ≧ 1, and a22 + a25 + a27 ≧ 1〕

2. The olefin polymerization catalyst according to claim 1, wherein the compound (b-1) is specified by the following formula b3 【Chemical Formula 3】 〔N is a nitrogen atom, C is a carbon atom, Y and Y 1 are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, A plurality of Rs are each independently a hydrogen atom, a halogen atom, or a substituent selected from a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. R and Y can combine with each other to form a ring structure. A plurality of Rs can combine with each other to form a cyclic structure or a multiple structure. a1 to a6 are each independently an integer from 0 to 6 and satisfy a1 + a3 ≧ 1 and a4 + a6 ≧ 1.〕

3. Said Y and Y 1 wherein one or more of Claims 1 or 2 contain atoms of Group 15 elements of the periodic table The olefin polymerization catalyst described in

4. The olefin polymerization catalyst according to claim 1 or 2, wherein the Group 15 element is nitrogen.

5. The olefin polymerization catalyst according to claim 1, wherein the Y includes two types, a substituent containing the Group 15 element and an oxygen atom.

6. Said Y and Y 1 The olefin polymerization catalyst according to claim 2, wherein one or more of them are oxygen atoms.

7. The olefin polymerization catalyst according to claim 1, wherein one or more of the Rs are selected from a hydrogen atom and a hydrocarbon group.

8. A transition metal compound (a), and a method for producing an olefin polymer by polymerizing an olefin in the presence of an olefin polymerization catalyst containing a clay composition (b) containing a compound (b-1) specified by a structural formula selected from the following formula b1 and the following formula b2 and a clay compound (b-2). [Chemical Formula 4] 【Chemical Formula 5】 〔In the above formula b1 and formula b2, The plurality of Y's are each independently a divalent substituent containing an atom of an element selected from Groups 15 and 16 of the periodic table, The plurality of R's are each independently a hydrogen atom, a halogen atom, or a substituent selected from hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, and nitrogen-containing groups. R and Y can be bonded to form a ring structure. The plurality of R's can be bonded to each other to form a cyclic structure or a multiple structure. a1 to a27 are each independently an integer of 0 to 6 and satisfy either of the following (β1) or (β2). (β1) a1 + a3 + a4 + a6 ≥ 1 and a2 + a5 + a7 + a8 ≥ 2 (β2) All of a11 + a13 + a14 + a16 ≥ 1, a12 + a15 + a17 ≥ 1, a21 + a23 + a24 + a26 ≥ 1, and a22 + a25 + a27 ≥ 1

9. The method for producing an olefin polymer according to claim 8, wherein the compound (b-1) is specified by the following formula b3. 【Chemical Formula 6】 [N is a nitrogen atom, C is a carbon atom, Y and Y 1 are each independently a divalent or trivalent substituent containing an atom of an element selected from Group 15 and Group 16 of the periodic table, The plurality of R's are each independently a hydrogen atom, a halogen atom, or a substituent selected from hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups. R and Y can be bonded to each other to form a ring structure. The plurality of R's can be bonded to each other to form a cyclic structure or a multiple structure. a1 to a6 are each independently an integer of 0 to 6 and satisfy a1 + a3 ≥ 1 and a4 + a6 ≥ 1.]

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