JP2006117642A - Method for producing low molecular weight olefin polymer and olefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a low molecular weight olefin polymer using a chromium-based catalyst, capable of highly selectively producing a trimer of an olefin in a high yield, capable of preventing adhesion by recovering a by-product polymer in a particulate state, and therefore improved so that the low molecular weight olefin is industrially advantageously produced by effectively conducting separation, and further capable of economically advantageously producing the low molecular weight olefin by making a polymerization catalyst coexist. <P>SOLUTION: This method for producing the low molecular weight olefin polymer comprises using the catalyst which contains chromium, wherein the contact of the olefin with the catalyst is conducted in the presence of a carrier which is preliminarily treated with a metal alkyl compound. Further, the method for producing the low molecular weight olefin polymer is conducted in the presence of a particulate solid catalyst component which contains at least one of the metal alkyl compound and a reaction product thereof as one component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an olefin low polymer, and more specifically, to stably produce an olefin low polymer mainly composed of an olefin trimer from olefin with high yield and high selectivity. The present invention relates to a process for producing an industrially advantageous olefin low polymer. In addition, the present invention provides a low polymer having a polymerizable unsaturated bond among the olefin low polymers produced by the method by carrying out the method for producing the olefin low polymer in the presence of a polymerization catalyst. The present invention relates to a method for producing an olefin copolymer economically by further copolymerizing olefins.

Conventionally, a method of using a chromium-based catalyst comprising a combination of a specific chromium compound and a specific organoaluminum compound is known as a low polymerization method for olefins such as ethylene. For example, a method for obtaining 1-hexene and polyethylene from ethylene using a catalyst system comprising a transition metal compound of group VIA containing chromium and polyhydrocarbyl aluminum oxide is disclosed (for example, see Patent Document 1).
Also disclosed is a method of trimerizing olefins using a catalyst obtained by previously reacting a chromium-containing compound having a chromium-pyrrolyl bond with a metal alkyl or Lewis acid (see, for example, Patent Document 2). It describes the use of a carrier.
Further, a method for obtaining 1-hexene from ethylene in high yield and high yield using a catalyst comprising a chromium compound in combination with one or more compounds selected from the group of amine, amide and imide and an alkylaluminum compound ( For example, Patent Documents 3 and 4) are disclosed.

By the way, by any of the above methods, the production of a polymer as a by-product is unavoidable. In particular, in the implementation on an industrial scale, how to separate and recover the by-product polymer is an important issue. . In particular, by-product polyethylene when 1-hexene is obtained from ethylene using the above-described chromium-based catalyst is used as a so-called “string”, “beard” on the inner wall surface, stirring shaft, stirring blade, baffle, etc. of the reactor. ”,“ Block ”, and“ sheet ”are easily attached and formed in an indeterminate state, so that recovery is difficult or heat removal of the reactor is obstructed.
In order to solve these problems, several methods have been reported. For example, a method of separating and recovering a trimer solution from by-product polyethylene and a catalyst component by distillation separation after reaction (for example, patent documents). 5), and reports that the effect of forming the by-product polymer in a powdery form with little adhesion is obtained by carrying out the low polymerization reaction in the presence of hydrogen (see, for example, Patent Document 6). ) Has been. Further, a low polymerization reaction is carried out at a high temperature at which no by-product polymer is precipitated, or a process is carried out in a molten state while maintaining from the reactor outlet to the product recovery system at a high temperature at which no by-product polymer is precipitated (for example, Patent Document 7). Reference.).

  However, although some improvement effect can be obtained by these methods, the adhesion prevention effect is insufficient, or the catalyst deterioration is advanced by carrying out the reaction at a high temperature, and the yield and selectivity of the olefin low polymer are reduced. There was a problem of falling. Furthermore, these by-product polymers tend to have a high molecular weight, and there is a problem that fluidity is poor because labor is required to remove adhesion from the vessel wall or the like, and the viscosity becomes high even when melt processing is performed. It was. On the other hand, a technique in which a catalyst system for mixing a metal source, a pyrrole-containing compound, and a metal alkyl is brought into contact with a support such as an inorganic oxide (see, for example, Patent Document 8) has been disclosed. There's a problem.

On the other hand, conventionally, an olefin reaction is performed in the presence of an olefin polymerization catalyst such as ethylene and an olefin polymerization catalyst to further copolymerize the polymerizable low polymer and the olefin contained in the resulting olefin low polymer. There have been attempts to produce olefin copolymers with an economic advantage. For example, a method of synthesizing a linear low density polyethylene using an ethylene trimerized 1-hexene highly selective production catalyst and a polymerization catalyst simultaneously (for example, see Patent Documents 9 and 10) is disclosed. In addition, it is necessary to carry out the reaction at a high temperature in order to ensure the polymerization activity, the generated 1-hexene purity is low, or a by-product polymer derived from a trimerization catalyst is mixed to form a non-uniform resin product. was there.
Japanese Patent Publication No. 43-18707 Japanese Patent Laid-Open No. 3-128904 JP-A-7-165815 JP-A-10-101724 JP-A-8-295705 JP-A-6-157655 JP-A-10-101724 JP-A-6-239920 JP-A-8-333407 Japanese Patent Laid-Open No. 10-60043

  In view of the above problems, an object of the present invention is to produce an olefin trimer with high yield and high selectivity in a method for producing a low olefin polymer using a chromium-based catalyst, and to form a by-product polymer in a granular form. It is an object of the present invention to provide an industrially advantageous production method of an olefin low polymer which is improved so that it can be efficiently separated by recovering it and preventing adhesion. Another object of the present invention is to provide a highly active, highly selective, by-product optimum for use in the production of an economically superior olefin copolymer in which the method for producing the olefin low polymer is carried out in the presence of a polymerization catalyst. An object of the present invention is to provide a method for producing an olefin low polymer and an olefin copolymer having polymer properties.

  As a result of intensive studies to solve the above problems, the present inventor has previously treated the contact of the olefin and the chromium-containing catalyst with a metal alkyl compound in the method for producing an olefin low polymer using a chromium-containing catalyst. The present invention was completed by conducting the reaction in the presence of the supported carrier to prevent the by-product polymer from adhering without reducing the yield and selectivity of the low olefin polymer and to facilitate the recovery thereof. I let you.

  That is, according to the first invention of the present invention, in the method for producing an olefin low polymer using a chromium-containing catalyst, the contact between the olefin and the catalyst is carried out in the presence of a carrier previously treated with a metal alkyl compound. A method for producing an olefin low polymer is provided.

According to the second invention of the present invention, in the first invention, the catalyst containing chromium comprises:
(A) Component: Chromium compound represented by the following general formula (1) CrX _n (1)
(In the formula (1), X represents an arbitrary organic group or inorganic group, a negative atom or an electron donating ligand, n represents an integer of 1 to 6, and when n is 2 or more, X is the same. (They may be different from each other. The valence of chromium is 0 to 6.)
A process for producing an olefin low polymer is provided.

According to the third invention of the present invention, in the first invention, the catalyst containing chromium is
(A) component: the chromium compound represented by the following general formula (1),
CrX _n (1)
(In the formula (1), X represents an arbitrary organic group or inorganic group, a negative atom or an electron donating ligand, n represents an integer of 1 to 6, and when n is 2 or more, X is the same. (They may be different from each other. The valence of chromium is 0 to 6.)
(B) Component: One or more compounds selected from the group of amines, amides and imides, and (C) Component: A catalyst system comprising an alkylaluminum compound is provided. Is done.

  According to a fourth aspect of the present invention, there is provided the method for producing an olefin low polymer according to any one of the first to third aspects, wherein the carrier is an inorganic oxide solid.

According to the fifth invention of the present invention, in any one of the first to fourth inventions, the catalyst further contains a component (D) represented by the following general formula (2) or (3). A process for producing a low olefin polymer is provided.
[L] ⁺ · [M ¹ R ¹ R ² R ³ R ⁴ ] ⁻ (2)
M ² R ⁵ R ⁶ R ⁷⁻ (3)
(Wherein M ¹ and M ² are elements selected from Group IIIB, IVB, VB and VIB of the periodic table, R ^{1 to} R ⁷ are organic groups, inorganic groups or negative atoms, and [L] ⁺ is (Indicates a cation containing an element selected from Groups IA, VIIA, VIIIA, IB, and IIIB to VIB of the periodic table.)

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the low polymerization reaction of olefin is performed at a temperature lower than the melting point of the olefin polymer as a by-product. A method for producing a low olefin polymer is provided.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the component collected by the sieve having an opening of 5.6 mm in the olefin polymer as a by-product. A method for producing a low olefin polymer, characterized in that the proportion is 10% by weight or less.

  According to an eighth invention of the present invention, in any one of the first to seventh inventions, the olefin polymer as a by-product has a weight average molecular weight by GPC of 1,000,000 or less. A method for producing a low polymer is provided.

According to a ninth invention of the present invention, the olefin low polymer according to any one of the first to eighth inventions, wherein the olefin is ethylene and the olefin low polymer is mainly 1-hexene. A manufacturing method is provided.
Is provided.

  According to the tenth aspect of the present invention, in the method for producing the olefin low polymer according to any one of the first to ninth aspects, the carrier previously treated with the metal alkyl compound is a metal alkyl compound or a reaction product thereof. There is provided a method for producing an olefin low polymer and an olefin copolymer, which is a particulate solid polymerization catalyst containing at least one of the above as a component.

  According to an eleventh aspect of the present invention, in the tenth aspect, the particulate solid polymerization catalyst is a Ziegler catalyst or a metallocene catalyst, and the method for producing an olefin low polymer and an olefin copolymer Is provided.

  According to the twelfth aspect of the present invention, in the tenth or eleventh aspect, the ratio of the low polymer having a polymerizable unsaturated bond in the olefin low polymerization reaction product excluding the olefin polymer is 70% by weight. % Of olefin, a method for producing an olefin copolymer and an olefin copolymer are provided.

  According to the thirteenth invention of the present invention, in the tenth to twelfth inventions, the olefin polymer to be produced has an Mw / Mn by GPC of 10 or less, and the olefin low polymer and olefin copolymer A method for producing a coalescence is provided.

  The method for producing an olefin low polymer according to the present invention efficiently produces an olefin trimer with high yield and high selectivity, and further recovers the by-product polymer in a granular form to prevent adhesion. How to get. In addition, the method for producing an olefin low polymer of the present invention can be applied to the synthesis of an olefin (co) polymer such as linear low density polyethylene, and the olefin (co) polymer can be produced at a high yield even at a low temperature. It is a method that can be produced economically by suppressing the production of unnecessary low polymers and high molecular weight polymers.

  The present invention relates to a method for producing an olefin low polymer using a chromium-containing catalyst system, wherein the contact of the olefin with the catalyst is carried out in the presence of a carrier previously treated with a metal alkyl compound. It is a method for producing an olefin low polymer that prevents the by-product polymer from adhering and facilitates its recovery without lowering the yield and selectivity. Hereinafter, the present invention will be described in detail for each item.

1. Catalyst containing chromium The catalyst containing chromium used in the present invention is not particularly limited as long as it has low olefin polymerization ability, but at least the following component (A) chromium compound, The catalyst system is a combination of (B) one or more compounds selected from the group of amine, amide and imide, and (C) an alkylaluminum compound, if necessary.

(A) Component (A) The chromium compound is a chromium compound represented by the following general formula (1).
CrX _n (1)
In general formula (1), X represents an arbitrary organic group or inorganic group or negative atom, n represents an integer of 1 to 6, and when n is 2 or more, X is the same or different from each other. Also good. The valence of chromium is 0 to 6, and n in the above formula is preferably 2 or more. Most preferably n is 3. When n is 2 or more, a plurality of Xs may be bonded to each other (that is, a multidentate ligand is formed).
Examples of the organic group include various groups having usually 1 to 30 carbon atoms. Specific examples include a hydrocarbon group, a carbonyl group, a carboxyl group, a β-diketonate group, a β-ketocarboxyl group, a β-ketoester group and an amide group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group, and a cyclopentadienyl group.
Inorganic groups include chromium salt-forming groups such as nitric acid groups and sulfuric acid groups, and negative atoms include oxygen and halogen.

Preferred chromium compounds are an alkoxy salt, a carboxyl salt, a β-diketonate salt, a salt with an anion of a β-keto ester, or a chromium halide, specifically, chromium (IV) -t-butoxide, Chromium (III) acetylacetonate, Chromium (III) trifluoroacetylacetonate, Chromium (III) hexafluoroacetylacetonate, Chromium (III) (2,2,6,6-tetramethyl-3,5-heptanedio Nato), Cr (PhCOCHCOPh) ₃ (where Ph represents a phenyl group), chromium (II) acetate, chromium (III) -2-ethylhexanoate, chromium (III) benzoate, chromium (III) naphthenate _{, Cr (CH 3 COCHCOOCH 3)} 3, chloride Chromous, chromic chloride, bromide chromous bromide chromic, first chromium iodide, chromic iodide, first chromium fluoride, and the second chromium fluoride.

Moreover, the complex which consists of said chromium compound and an electron donor can also be used conveniently. The electron donor is selected from compounds containing nitrogen, oxygen, phosphorus or sulfur.
Nitrogen-containing compounds include nitriles, amines, amides, and the like. Specifically, acetonitrile, pyridine, dimethylpyridine, dimethylformamide, N-methylformamide, aniline, nitrobenzene, tetramethylethylenediamine, diethylamine, isopropylamine, hexa Examples thereof include methyldisilazane and pyrrolidone.
Examples of the oxygen-containing compound include esters, ethers, ketones, alcohols, aldehydes, and the like. Specifically, ethyl acetate, methyl acetate, tetrahydrofuran, dioxane, diethyl ether, dimethoxyethane, diglyme, triglyme, acetone, methyl ethyl ketone, methanol. , Ethanol, acetaldehyde and the like.
Examples of phosphorus-containing compounds include hexamethylphosphoamide, hexamethylphosphorustriamide, triethylphosphite, tributylphosphine oxide, triethylphosphine, and the like. On the other hand, examples of the sulfur-containing compound include carbon disulfide, dimethyl sulfoxide, tetramethylene sulfone, thiophene, and dimethyl sulfide.

Accordingly, examples of the complex composed of a chromium compound and an electron donor include an ether complex, an ester complex, a ketone complex, an aldehyde complex, an alcohol complex, an amine complex, a nitrile complex, a phosphine complex, and a thioether complex of chromium halide. As with X described above, a plurality of electron donors may be bonded to each other (that is, forming a multidentate ligand). Specifically, CrCl ₃ · 3THF, CrCl ₃ · 3dioxane, CrCl ₃ · (CH ₃ CO ₂ n-C ₄ H ₉ ), CrCl ₃ · (CH ₃ CO ₂ C ₂ H ₅ ), CrCl ₃ · 3 ( _{i-C 3 H 7 OH)} , CrCl 3 · 3 [CH 3 (CH 2) CH (C 2 H 5) CH 2 OH], CrCl 3 · 3pyridine, CrCl 3 · 2 (i-C 3 H 7 NH 2 ), [CrCl ₃ · 3CH ₃ CN] · CH ₃ CN, CrCl ₃ · 3PPh ₃ , CrCl ₂ · 2THF, CrCl ₂ · ₂ pyridine, CrCl ₂ · 2 [(C ₂ H ₅ ) ₂ NH], CrCl ₂ · 2CH ₃ CN, CrCl ₂ .2 [P (CH ₃ ) ₂ Ph] and the like.

Further, as the chromium compound, a compound that is soluble in a hydrocarbon solvent is preferable. Examples include carbene complexes, various cyclopentadienyl complexes, alkyl complexes, and phenyl complexes. Specific examples of chromium carbonyl complexes, carbene complexes, cyclopentadienyl complexes, alkyl complexes, and phenyl complexes include Cr (CO) ₆ , (C ₆ H ₆ ) Cr (CO) ₃ , and (CO) _5. Cr (= CCH ₃ (OCH ₃ )), (CO) ₅ Cr (= CC ₆ H ₅ (OCH ₃ )), CpCrCl ₂ (where Cp represents a cyclopentadienyl group), (Cp ^* CrClCH ₃ ) ₂ (where Cp ^* represents a pentamethylcyclopentadienyl group), (CH ₃ ) ₂ CrCl, and the like.

Component (B): One or more compounds selected from the group of amine, amide and imide In the catalyst system containing chromium of the present invention, 1 selected from the group of (B) amine, amide and imide, if necessary. More than one type of compound can be used.
The amine used as the component (B) is a primary or secondary amine. Examples of the primary amine include ethylamine, isopropylamine, cyclohexylamine, benzylamine, aniline, naphthylamine, and the like. Examples of the secondary amine include diethylamine, diisopropylamine, dicyclohexylamine, dibenzylamine, bis (trimethylsilyl) amine, morpholine. Imidazole, indoline, indole, pyrrole, 2,5-dimethylpyrrole, 3,4-dimethylpyrrole, 3,4-dichloropyrrole, 2,3,4,5-tetrachloropyrrole, 2-acylpyrrole, pyrazole, pyrrolidine Etc. are exemplified.

  Examples of the amide used as the component (B) in the present invention include metal amides derived from primary or secondary amines. For example, the primary or secondary amines described above and the groups IA, IIA, IIIB And amides obtained by reaction with metals selected from the group IVB and group IVB. Specific examples of such metal amides include lithium amide, sodium ethylamide, calcium diethylamide, lithium diisopropylamide, potassium benzylamide, sodium bis (trimethylsilyl) amide, lithium indolide, sodium pyrrolide, lithium pyrrolide, potassium pyrrolide. And aluminum diethylpyrrolide, ethylaluminum dipyrrolide, aluminum tripyrrolide and the like.

  In the present invention, the above-mentioned secondary amine, metal amide derived from the secondary amine, or a mixture thereof is preferably used. In particular, secondary amines include pyrrole, 2,5-dimethylpyrrole, 3,4-dimethylpyrrole, 3,4-dichloropyrrole, 2,3,4,5-tetrachloropyrrole, 2-acylpyrrole, Suitable metal amides derived from secondary amines are aluminum pyrrolide, ethylaluminum dipyrrolide, aluminum tripyrrolide, sodium pyrrolide, lithium pyrrolide, and potassium pyrrolide. Of the pyrrole derivatives, derivatives having a hydrocarbon group in the pyrrole ring are particularly preferred.

  Examples of the amide or imide compound other than the above used as the component (B) in the present invention include compounds represented by the following general formulas (4) to (6).

In the general formula (4), ^{M 3} is IA hydrogen atom or the periodic table, IIA, a metal element selected from Group IIIB, ^{R 8} is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group , An aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, R ⁹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, An aralkyl group, an aryl group which may have a substituent, an aryl group which may contain a hetero element, or an acyl group C (═O) R ¹⁰ (R ¹⁰ has the same definition as R ⁸ . R ⁸ may be different from R ⁸ ), and R ⁸ and R ⁹ may form a ring.

In the general formula (5), M ⁴ and M ⁵ are a hydrogen atom or a metal element selected from the groups IA, IIA, and IIIB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a carbon number of 1 to 30 An alkyl group, an alkenyl group, an aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, and R ¹¹ and R ¹² may form a ring In addition, A represents an alkylene group which may contain an unsaturated bond.

In general formula (6), M ⁶ is a hydrogen atom or a metal element selected from groups IA, IIA, and IIIB of the periodic table, and R ¹³ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and an alkenyl group. , An aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, aralkyl group, an optionally substituted aryl group, or an aryl group which may contain a hetero element _{^{or,, SO 2 R 15 (R}} 15 is the same definition as ^{R 13,} different from ^{R 13} R ¹³ and R ¹⁴ may form a ring.

  Examples of the amides represented by the general formula (4) or the general formula (5) include acetamide, N-methylhexaneamide, succinamide, maleamide, N-methylbenzamide, imidazole-2-carboxamide, and di-2- Thenoylamine, β-lactam, δ-lactam, ε-caprolactam, and salts of these with metals of Groups IA, IIA and IIIB of the periodic table can be mentioned. Examples of imides include 1,2-cyclohexanedi Carboximide, succinimide, phthalimide, maleimide, 2,4,6-piperidinetrione, perhydroazesin-2,10-dione, and salts thereof with metals of Groups IA, IIA, IIIB of the Periodic Table It is done.

Examples of the sulfonamides and sulfonimides represented by the general formula (6) include benzenesulfonamide, N-methylmethanesulfonamide, N-methyltrifluoromethylsulfonamide, and IA of the periodic table. And salts with IIA and IIIB metals.
Among these amide or imide compounds, a compound represented by the general formula (4) is preferable. In particular, R ⁹ in the general formula (4) represents an acyl group C (═O) R ¹⁰ , and R ⁸ and R An imide compound in which ⁹ forms a ring is preferable.

Component (B) is an amine, the amount of a compound selected from the group of amides and imides, per chromium compound 1mol as the component (A) is usually ¹⁰ -3 ^{to 10} 3 mol, preferably ^10-2 It is -10 < ² > mol, More preferably, it is 10 < ^-1 > -5 * 10 < ¹ > mol.

(C) Component: Alkyl Aluminum Compound In the catalyst system containing chromium of the present invention, an (C) alkyl aluminum compound component can be used as necessary. As the alkylaluminum compound used as the component (C), an alkylaluminum compound represented by the following general formula (7) is preferably used.
R ¹⁶ _m Al (OR ¹⁷ ) _{pH q} Y _r (7)
In general formula (7), R ¹⁶ and R ¹⁷ are hydrocarbon groups or silicon-containing hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, and may be the same or different from each other. Y is a halogen atom, m is 0 <m ≦ 3, p is 0 ≦ p <3, q is 0 ≦ q <3, r is 0 ≦ r <3, and m + p + q + r = Represents a number that is 3.

Further, as the alkylaluminum compound, a condensation reaction product of the alkylaluminum compound and water (so-called aluminoxane compound), a condensation reaction product of the alkylaluminum compound and alkylboronic acid (so-called aluminum boronate compound), A condensation reaction product of an alkylaluminum compound and various metal hydroxides can also be used. In this case, a condensation reaction product of two or more different alkylaluminum compounds and water can also be used. The aluminoxane compound can be produced by a conventionally known method by a hydrolysis reaction of an alkylaluminum compound. For example, the molar ratio of water to the alkylaluminum compound in a hydrocarbon solvent is 0.8: 1 to 1.3: 1. The method of reacting preferably in the range of 0.9: 1 to 1.2: 1 can be exemplified. The boronic acid aluminum compound is a reaction of 10: 1 to 1: 1 (molar ratio) between one type of trialkylaluminum or two or more types of trialkylaluminum and the alkylboronic acid represented by the following general formula (8). Can be obtained. In the general formula (8), R ¹⁸ represents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
R ¹⁸ B (OH) ₂ (8)

Examples of the alkylaluminum compound include a trialkylaluminum compound represented by the following general formula (9), a halogenated alkylaluminum compound represented by the general formula (10), an alkoxyaluminum compound represented by the general formula (11), Examples thereof include an alkylaluminum hydride compound represented by the general formula (12). The meanings of R ¹⁶ , Y and R ¹⁷ in each formula are the same as described above. Among these, the trialkylaluminum compound represented by the general formula (9) is preferable in that there are few by-products of the polymer.
R ¹⁶ ₃ Al (9)
R ¹⁶ _m AlY _3-m (10)
(In the formula (10), m is 1.5 ≦ m <3)
R ¹⁶ _m Al (OR ¹⁷ ) _3-m (11)
(In the formula (11), m is 0 <m <3, preferably 1.5 ≦ m <3)
R ¹⁶ _m AlH _3-m (12)
(M is 0 <m <3, preferably 1.5 ≦ m <3)

  Specific examples of the above alkylaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal octylaluminum, diethylaluminum monochloride, diethylaluminum ethoxide, diethylaluminum hydride, (trimethylsilyl) diethylaluminum, (Trimethylsiloxy) diethylaluminum, (dimethylboroxy) diethylaluminum, (methylmagnesiumoxy) diethylaluminum, methylaluminoxane, ethylaluminoxane, i-propylaluminoxane, isobutylaluminoxane and the like. Of these, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormaloctylaluminum, and the like are preferable in that there are few by-products of the polymer. The alkylaluminum compound may be a mixture of two or more.

The amount of the alkylaluminum compound as component (C) is usually 10 ⁻³ to 10 ⁴ mol, preferably 10 ⁻² to 10 ³ mol, per mol of the chromium compound as component (A), Preferably it is 10 < ^-1 > -10 < ² > mol.

  In addition, although the manufacturing method of the olefin low polymer of this invention is implemented by performing the contact of an olefin and the above-mentioned catalyst in presence of the support | carrier previously processed with the metal alkyl compound, it processed with the metal alkyl compound beforehand. The carrier means a carrier that has not been in contact with the catalyst containing chromium (in the case where the catalyst contains the component (A) when the catalyst contains the component (A)) used for the production of the olefin low polymer. A carrier obtained by contact treatment with an alkyl compound. Here, since the alkylaluminum compound as the component (C) is a kind of metal alkyl compound, the metal alkyl compound used for the contact treatment is the same compound as the alkylaluminum compound as the component (C). Also good.

2. Carrier (component (E))
The carrier (component (E)) used in the present invention is a carrier previously treated with a metal alkyl compound.
As the metal alkyl compound used for the treatment of the carrier, the following general formula (13)
M ⁷ R ¹⁹ _s Z _(ts) (13)
The metal alkyl compound shown by these is used suitably. Moreover, the condensation reaction product of the metal compound shown by General formula (13) and water can be used as a metal alkyl compound in the range in which a metal alkyl bond exists. In this case, a condensation reaction product of two or more different metal alkyl compounds and water can also be used.

In the general formula (13), M ⁷ is a metal element selected from the groups IA, IIA, IIB, and IIIB of the periodic table, and preferably any one of Li, Na, K, Mg, Zn, B, and Al It is a metal atom, More preferably, it is a metal atom of Mg, Zn, B, or Al.
R ¹⁹ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group here is a halogen atom-containing hydrocarbon group, an oxygen-containing hydrocarbon group (for example, an oxygen atom is an alkoxy group, Carbonyl group, group containing carboxyl group), sulfur-containing hydrocarbon group (for example, group containing sulfur atom in the form of alkylthio group, thiocarbonyl group, thiocarboxyl group, dithiocarboxyl group), silicon-containing hydrocarbon group ( For example, a silicon atom in the form of —Si (R ²⁰ ) (R ²¹ ) (R ²² ), a phosphorus-containing hydrocarbon group (for example, a phosphorus atom in the form of —P (R ²³ ) (R ²⁴ )) including group), a nitrogen-containing hydrocarbon group (e.g., nitrogen atom and ^-N (R 25) group contains in the form of ^{(R 26)),} or a boron-containing hydrocarbon group (e.g., a boron atom -B ^{(R 27} Also include groups) including in the form of (R ^28), specifically, it may have a substituent alkyl group, an alkenyl group which may have a substituent, have a substituent Represents an alkynyl group which may be substituted or an aryl group which may have a substituent. R ¹⁹ is preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group which may have a substituent, and more preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group which may have a substituent, and a substituent. Most preferred is an alkyl group having 1 to 8 carbon atoms.
Z is hydrogen, halogen, an alkoxy group having 1 to 30 carbon atoms, a substituted silyl group having 1 to 30 carbon atoms, a substituted siloxy group having 1 to 30 carbon atoms, a substituted amino group having 1 to 30 carbon atoms, represents either, or mixtures of these substituted amide group having a carbon number of 1 to 30, s is a number of 1 ≦ s ≦ t, t denotes the valence of M ^7.

  Specific examples of the compound include methyl lithium, ethyl lithium, i-propyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, lithium acetylide, lithium cyclopentadienide, lithium phenyl acetylide, lithium trimethylsilyl acetylide. , (Trimethylsilylmethyl) lithium, phenyl lithium, hexyl lithium, octyl lithium, dodecyl lithium, octadecyl lithium, allyl lithium, methyl sodium, ethyl sodium, propyl lithium, butyl lithium, sodium cyclopentadienide, (trimethylsilylmethyl) sodium, phenyl Sodium, hexyl sodium, octyl sodium, methyl potassium, ethyl potassium, propyl potassium, butyl potassium , Potassium cyclopentadienide, (trimethylsilylmethyl) potassium, phenyl potassium, hexyl potassium, octyl potassium, dimethyl magnesium, methyl magnesium chloride, divinyl magnesium, vinyl magnesium bromide, diethyl magnesium, ethyl magnesium bromide, 1-propynyl magnesium chloride, Allylmagnesium bromide, i-propenylmagnesium bromide, cyclopropylmagnesium bromide, 3-thienylmagnesium iodide, 3-butenylmagnesium bromide, 1-methyl-1-propenylmagnesium bromide, 2-methyl-1-propenylmagnesium bromide, i -Butylmagnesium bromide, (trimethylsilylmethyl) magnesium chloride, cyclo Nethylmagnesium bromide, 3,4-difluorophenylmagnesium bromide, 3,5-difluorophenylmagnesium bromide, phenylmagnesium chloride, cyclohexylmagnesium chloride, o-tolylmagnesium bromide, 2-methoxyphenylmagnesium bromide, heptylmagnesium bromide, phenyl Ethynyl magnesium bromide, 2,3-dimethylphenyl magnesium bromide, α-methylbenzyl zinc bromide, octyl magnesium chloride, butyl ethyl magnesium, dibutyl magnesium, 2-mesityl magnesium bromide, 4-t-butylphenyl magnesium bromide, decyl magnesium bromide 2-methyl-1-naphthylmagnesium bromide, 4-biphenyl magnesium Bromide, dodecyl magnesium bromide, tetradecyl magnesium chloride, pentadecyl magnesium chloride, octadecyl magnesium chloride, dimethyl zinc, propyl zinc bromide, 2-thienyl zinc bromide, butyl zinc bromide, diethyl zinc, diisopropyl zinc, butyl ethyl zinc, dibutyl zinc, 2-pyridyl zinc bromide, 1,1-dimethylpropyl zinc bromide, 3,5-difluorophenyl zinc bromide, 3-chloro-4-fluorophenyl zinc iodide, phenyl zinc bromide, (2-chloro-5-pyridyl) methyl Zinc chloride, 1-ethylbutyl zinc chloride, 2,3,4,5,6-pentafluorobenzyl zinc bromide, 2-cyanophenyl zinc bromide 3-fluoro-4-methylphenyl zinc iodide, exo-2-norbornyl zinc bromide, 1-phenyl vinyl zinc bromide, 1-naphthyl zinc iodide, diphenyl zinc, trimethylborane, butyldichloroborane, triethylborane, tributyl Borane, triphenylborane, dimesitylboron fluoride, dimesitylborane, trimesitylborane, methylboroxan, bis (dimethylamino) methylborane, methoxydimethylborane, oxybis (dimethylborane), ethylenebis (dichloroborane), 1-propyl Bolinane, trimethylboroxine, ethylaluminum dichloride, dimethylaluminum chloride, i-butylaluminum dichloride, ethylaluminum sesquichloride, dii-butylal Minium chloride, dii-butylaluminum fluoride, dii-butylaluminum hydride, tetraethyldialuminoxane, tripropylaluminum, tetrai-butyldialuminoxane, triphenylaluminum, trioctylaluminum, (trimethylsilyl) diethylaluminum, (trimethylsiloxy ) Diethylaluminum, Al compounds defined as component (C), and the like.

  Among these, the yield and selectivity of the olefin low polymer are high, and there are few polymers that are produced in an indeterminate state called "string", "beard", "bulk", or "sheet". Dimethylmagnesium, divinylmagnesium, diethylmagnesium, butylethylmagnesium, dibutylmagnesium, dimethylzinc, diethylzinc, diisopropylzinc, butylethylzinc, dibutylzinc, diphenylzinc, trimethylborane, triethylborane, tributylborane, triphenylborane , Trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, trioctylaluminum, methylaluminoxane, isobutylaluminoxane are preferred, trimethylaluminum Um, triethylaluminum, triisobutylaluminum, tri-octyl aluminum, methylaluminoxane more preferred. The metal alkyl compound may be a mixture of two or more.

  The carrier before being treated with the metal alkyl compound is not particularly limited with respect to its elemental composition and compound composition. For example, the support | carrier consisting of an inorganic or organic compound can be illustrated. Examples of the inorganic carrier include inorganic oxide solids, inorganic sulfide solids, inorganic halide solids, and simple metals. Examples of the organic carrier include polymer particle carriers. Furthermore, a mixture or complex of two or more selected from these compound groups can also be used as a carrier. Alternatively, these compounds are used after one or more of chemical modification treatment (acid treatment, alkali treatment, salt treatment, organic treatment, etc.), heat denaturation treatment, photo-denaturation treatment, electromagnetic treatment, and ultrasonic treatment are added. You can also The metal alkyl compound used for the metal alkyl compound treatment may itself have a carrier function.

Specific examples of the inorganic carrier include inorganic oxide solids such as vanadium oxide, titania, zeolite, silica, alumina, magnesia, zirconia, antimony oxide, ruthenium oxide, molybdenum oxide, rhenium oxide, phosphorus oxide, bismuth oxide. , Zinc oxide, iron oxide, tin oxide, and the like, and these composite oxides such as silica / alumina, silica / magnesia, silica / titania, alumina / magnesia, various ceramics (cordylite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ), Mullite (3Al ₂ O ₃ · 2SiO _{2 to} 2Al ₂ O ₃ · SiO ₂ ), etc., lanthanum β-alumina, etc., and inorganic sulfide solids include zinc sulfide, S-based chalcogenides (MoS ₂ , WS ₂ , TiS ₂ etc.), inorganic halide solids include potassium chloride Um, potassium bromide, sodium chloride, magnesium chloride, magnesium fluoride, calcium chloride, calcium fluoride, manganese chloride, iron chloride, copper chloride, zinc chloride, aluminum chloride, etc. Copper, metallic aluminum, metallic magnesium, various alloys, etc. Others include silicon carbide, glass, clays, inorganic silicate compounds such as ion-exchange layered silicate, aluminum phosphate, zirconium phosphate, titanate , Molybdate, diatomaceous earth, acid clay, pumice, diamond, graphite, carbon black, activated carbon, brick, calcium carbonate, calcium sulfate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, heteropolyacid, molecular sieve, calcium hydroxyapatite Etc. Apatite such, chalcogenides other than S system (TiSe _2, etc.), _{hydrotalcite,} LiCa ₂ Bi ₃ O 4 Cl metal oxyhalides such as _6, K ₄ Nb _{6 O 17} layered perovskite compounds such like.

  Specific examples of the polymer particle carrier include poly α-olefins such as polyethylene and polypropylene, polyisoolefins such as polyisobutene, polycycloolefins, diene polymers such as polybutadiene, polystyrene, polyvinylpyridine, and the like. Aromatic unsaturated hydrocarbon polymers, polyacetylenes, cellulose, polyacrylonitrile, perfluorosulfonic acid resin, polyacrylic acid ester, polymethacrylic acid ester, polyethylene terephthalate resin, polylactic acid and other polyester resins, nylon 6, nylon 66, etc. Various nylon resins, various polyamide resins, vinyl chloride resins, polycarbonate resins, silicone resins, urethane resins and the like.

  Among these, α-olefin low polymer has a high yield and selectivity, and a polymer produced in an indeterminate state called “string”, “beard”, “block”, or “sheet”. It is preferably used in terms of low titania, zeolite, silica, alumina, magnesia, zirconia, silica-alumina, silica-magnesia, silica-titania, alumina-magnesia, magnesium chloride, aluminum chloride, ion exchange layered Silicates, aluminum phosphates, acid clays, molecular sieves, polyethylene, polypropylene, polystyrene are used, and silica, alumina, magnesia, silica-alumina, silica-magnesia, alumina-magnesia, ion exchange are more preferable. Layered silicate. Particularly preferred are ion-exchangeable layered compounds.

Here, the ion-exchange layered silicate (hereinafter simply referred to as silicate) includes, for example, various layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995), Specifically, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, smectite group such as stevensite, vermiculite group such as vermiculite, mica group such as mica, illite, sericite, sea green stone, attapulgite, Examples include sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group, layered silicates in which these form a mixed layer, and the like. Among these, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite.
Since the above-mentioned carrier usually contains adsorbed water and interlaminar water, it is preferable to use after removing moisture by heat dehydration under an inert gas flow.

It is also preferable to control the size and shape of the carrier particles so that the by-product polymer does not easily adhere to the reactor or the like and can be easily collected. The shape of the carrier particles is particularly preferably spherical, and if the particle shape is spherical, natural products or commercially available products may be used as they are, or the shape and particle size are controlled by granulation, sizing, fractionation, etc. May be used. In the present invention, in order to control the shape and particle size of the carrier, pulverization, granulation, sizing, fractionation, etc. may be performed before chemical treatment, during treatment, after treatment, before treatment with metal alkyl compound, during treatment, You may perform after a process. The size of the carrier particles is usually 1 μm to 10 mm, preferably 5 μm to 1 mm, and more preferably 10 to 200 μm as measured by a laser diffraction method. Surface area of the support particles, typically 10~1100m ² / g as measured by the BET method, preferably has a range of 100~800m ² / g. The pore volume of the carrier particles is usually in the range of 0.1 to ⁴ cm ³ / g, preferably 0.5 to ² cm ³ / g as measured by mercury porosimetry. Various known methods can be employed for granulation, and preferably, stirring granulation method and spray granulation method are exemplified.
In the present invention, the carrier previously treated with the metal alkyl compound can be obtained by bringing the carrier mentioned above into contact with the metal alkyl compound.

Contact between the support and the metal alkyl compound is usually carried out in an inert hydrocarbon medium. The contact method is not particularly limited, and the following methods (I) to (X) can be exemplified.
(I) A method of adding an inert hydrocarbon medium to a support to form a slurry, and then adding a metal alkyl compound to the slurry.
(II) A method in which a metal alkyl compound is added to a support, and finally an inert hydrocarbon medium is added to obtain a uniform slurry solution.
(III) A method of adding an inert hydrocarbon medium to a support to form a slurry, and then adding a mixed solution of a metal alkyl compound and an inert hydrocarbon medium to the slurry.
(IV) A method of adding a mixed solution of a metal alkyl compound and an inert hydrocarbon medium to a support.
(V) A method in which an inert hydrocarbon medium is added to a metal alkyl to form a mixed solution, and then a carrier is added to this solution.
(VI) A method in which a carrier is added to a metal alkyl compound, and finally an inert hydrocarbon medium is added to obtain a uniform slurry solution.
(VII) A method in which an inert hydrocarbon medium is added to a metal alkyl to form a mixed solution, and then a slurry solution of a carrier and an inert hydrocarbon medium is added to the solution.
(VIII) A method of adding a slurry solution of a support and an inert hydrocarbon medium to a metal alkyl.
(IX) A method of simultaneously mixing a support, a metal alkyl and an inert hydrocarbon medium.
(X) A method of continuously mixing a slurry solution of a support and an inert hydrocarbon medium and a mixed solution of a metal alkyl compound and an inert hydrocarbon medium.

  In view of carrying out the contact reaction more uniformly, (I), (III), (V), (VII), (VIII), (X) are preferred, and (III), (V), (VII), (X) is particularly preferred. An inert hydrocarbon medium for concentration adjustment can be newly added at the end of each contact method of (I) to (X). Moreover, the addition speed | rate or mixing speed | rate of each component or each solution can be selected arbitrarily. At this time, when a large exotherm is caused by the contact reaction, it goes without saying that the temperature of the contact reaction solution is suddenly increased.

  Here, the inert hydrocarbon medium is a liquid inert hydrocarbon compound having a carbon number of about 3 to 30 and optionally containing heteroatoms such as halogen, silicon, oxygen, nitrogen and the like. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, propylene, butene, hexene, Unsaturated hydrocarbons such as butadiene, isoprene, cyclohexene, vinylcyclohexene, aromatic hydrocarbons such as benzene, toluene, xylene, styrene, oxygen-containing hydrocarbons such as diethyl ether, tetrahydrofuran, dioxane, ethylene chloride, chlorobenzene, dichloromethane, etc. Halogenated hydrocarbons or mixtures of these Mention may be made of things like.

Upon contact, the metal alkyl compound is usually used in an amount of 10 ⁻⁵ to 10 ¹ mol, preferably 10 ⁻⁴ to 10 ⁻¹ mol, more preferably 5 × 10 ⁻⁴ to 10 ⁻² mol, relative to 1 g of the carrier. . The concentration of the carrier at the time of contact is usually ¹⁰ -3 ^~10 3 g / L, preferably ^{10 0 ~6 × 10 2 g /} L, more preferably ^{10 1 ~3 × 10 2 g /} L, the concentration of the metal alkyl compound is used usually ¹⁰ -5 ^~10 1 mol / L, preferably ¹⁰ -3 ^~10 0 mol / L, further preferably in the range of from ^{10 -2 ~5 × 10 -1 mol /} L . The contact temperature is usually −100 to 150 ° C., preferably −70 to 120 ° C., more preferably 0 to 100 ° C. The contact time varies depending on the reaction temperature, but is usually 0.01 to 100 hours, preferably 0. It is about 1 to 10 hours, more preferably about 0.2 to 5 hours.

  After the contact reaction, all or a part of the suspension may be used for the low polymerization reaction of olefin, or the inert hydrocarbon medium is removed by filtration or decantation and the remaining solid component is used. Alternatively, a solid component obtained by evaporating an inert hydrocarbon medium from the suspension may be used. Further, the washing of the solid component with a new inert hydrocarbon medium of the same kind as described above removes excess metal alkyl compounds and by-products that have not been used in the catalytic reaction, so that the olefin content is reduced. This is preferable because it may prevent a decrease in polymerization reaction activity, reduce the amount of by-product polymer, and increase the yield of a desired low olefin polymer in the low olefin polymerization reaction product.

  The suitable form of the support | carrier (component (E)) previously processed with the metal alkyl compound can be illustrated concretely as following (E-1)-(E-3).

(E-1) Silica on which an aluminoxane compound is supported (C) Homogeneous mixing by adding commercially available silica particles continuously or in small portions to a hydrocarbon solvent dispersion of the same aluminoxane compound used as the component (C). Use liquid. By adding the aluminoxane compound or its hydrocarbon solvent dispersion continuously or in small portions to the silica particle hydrocarbon solvent dispersion, or by synthesizing the aluminoxane compound directly in the presence of silica particles. A method for producing a homogeneous mixed solution may also be employed. Next, the mixed liquid is washed with a hydrocarbon solvent or the like as necessary, and then the aluminoxane-supported silica particles as a product are obtained by removing the solvent. The ratio of silica to aluminoxane compound in the product can be varied within a relatively wide range. According to the present invention, the aluminum content in the product is 1 to 40% by weight, preferably 5 to 30% by weight. %, More preferably 10 to 25% by weight is selected to be present in the form of an aluminoxane compound.

(E-2) Silica contact-treated with trialkylaluminum By adding commercially available silica particles continuously or in small portions to a hydrocarbon solution of the same trialkylaluminum compound used as component (C). Use a homogeneous mixture. A method of obtaining a homogeneous mixed solution by adding a trialkylaluminum compound or a hydrocarbon solution thereof continuously or in small portions to a hydrocarbon solvent dispersion of silica particles may be employed. Next, the mixed solution is washed with a hydrocarbon solvent or the like as necessary, and then the solvent is removed to obtain trialkylaluminum-treated silica particles as a product. The ratio of silica to alkylaluminum compound in the product can be varied within a relatively wide range. According to the invention, the aluminum content in the product is 0.01 to 10% by weight, preferably 0 .1 to 5% by weight, more preferably 0.5 to 3% by weight.

(E-3) Ion exchange layered silicate contact treated with trialkylaluminum (C) Commercial ion exchange layered layer such as montmorillonite in a hydrocarbon solution of the same trialkylaluminum compound used as component (C) A homogeneous mixture is obtained by adding silicate particles continuously or in small portions. A method of obtaining a homogeneous mixed solution by adding a trialkylaluminum compound or a hydrocarbon solution thereof continuously or in small portions to a hydrocarbon solvent dispersion of ion-exchange layered silicate particles can also be employed. Next, the mixed solution is washed with a hydrocarbon solvent or the like as necessary, and then the solvent is removed to obtain trialkylaluminum-treated ion-exchange layered silicate particles as a product. The ratio of ion-exchange layered silicate and alkylaluminum compound in the product can be varied within a relatively wide range. According to the present invention, the aluminum content derived from the alkylaluminum compound in the product is 0. 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight.

In the catalyst for low olefin polymerization of the present invention, (E-1) to (E-3) are each used alone, and these three components and other metal alkyl compound-treated carriers are used in appropriate combination. Can do.
As the carrier (component (E)) previously treated with the metal alkyl compound used in the present invention, a particulate solid polymerization catalyst containing at least one of the metal alkyl compound or its reaction product as one component can be used. . In this case, the olefin low polymer is produced in the presence of the polymerization catalyst, and the low polymer having a polymerizable unsaturated bond (polymerizable low polymer) of the olefin low polymer is present in the presence of the polymerization catalyst. Is further copolymerized with an olefin to form an olefin copolymer. Therefore, if the low polymerization activity and the decrease in polymerization activity are not remarkable, the production selectivity of the polymerizable low polymer is high, and the production of the amorphous by-product polymer is suppressed, this method is an extremely economically advantageous olefin. It becomes the manufacturing method of a copolymer. This method will be described in detail later in section 6.

The amount of the carrier used in advance for the production of the olefin low polymer is a carrier pre-treated with the chromium compound as the component (A) and the metal alkyl compound as the component (E). component is usually ¹⁰ -8 ^{to 10} 0 mol, preferably ¹⁰ -7 ^{to 10} -1 mol, the range of more preferably ¹⁰ -6 ^~10 -2 mol. When the amount of component (A) used is small, not only is the activity of the low olefin polymerization reaction inadequate, which is economically disadvantageous, but also the amount of carrier used increases, so that labor is required for its removal. Also, when the amount of component (A) used is large, the amount of polymer produced in an indeterminate state such as “string”, “beard”, “block”, or “sheet” increases, which is not preferable.

3. (D) component In this invention, (D) component can further be added as a catalyst as needed. As the component (D), it is preferable to use a compound represented by the following general formula (2) or (3). When these compounds are used to produce an olefin low polymer, the reaction activity of the olefin low polymerization is reduced, or the yield of the desired olefin low polymer is reduced in the olefin low polymerization reaction product. Therefore, it is possible to reduce the molecular weight of the by-product polymer without removing the by-product polymer. It is possible to avoid problems such as poor fluidity.

[L] ⁺ · [M ¹ R ¹ R ² R ³ R ⁴ ] ⁻ (2)
M ² R ⁵ R ⁶ R ⁷⁻ (3)
In formulas (2) and (3), M ¹ and M ² are elements selected from the IIIB group, IVB group, VB group and VIB group of the periodic table, and B, Al, etc. are particularly preferable.
R ^{1 to} R ⁷ are an organic group, an inorganic group, or a negative atom, a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an alkoxyaryl group having 1 to 20 carbon atoms, It is selected from a halogen-substituted alkoxyaryl group having 1 to 20 carbon atoms, an organic metalloid group, a halogen atom or the like, and two or more of them may be bonded to each other to form a ring.
Specific examples of R ^{1 to} R ⁷ include dimethylamino group, diethylamino group, pyrrolyl group, 2,5-dimethylpyrrolyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, and t-butoxy. Group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-t-butylphenoxy group, naphthylphenoxy group, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, phenyl group 3-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2 , 3,5-trimethylphenyl group, 2,3,4-trimethylphenyl group, 3-t-butylphenyl group, 2,6-di-t-butylphenyl group, benzyl group p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 3-methoxy Phenyl group, 2,4-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,4-trimethoxyphenyl Group, 3,5-bis (1-methoxy-2,2,2-trifluoro-1- (trifluoromethyl) ethyl) phenyl group, 3- (1-methoxy-2,2,2-trifluoro-1) -(Trifluoromethyl) ethyl) -5- (trifluoromethyl) phenyl group, 3- (2,2,2-trifluoro-1- (2,2,2-trifluoroethoxy) ) -1- (trifluoromethyl) ethyl) -5- (trifluoromethyl) phenyl group, 3,5-bis (2,2,2-trifluoro-1- (2,2,2-trifluoroethoxy) ) -1- (trifluoromethyl) ethyl) phenyl group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, pentafluorotelluroxy group, F, Cl, Br, I and the like.

[L] ^{+ in} the general formula (2) represents a cation containing an element selected from Group IA, Group VIIA, Group VIIIA, Group IB, and Group IIIB to VIB of the periodic table. L is represented by M ⁸ , M ⁹ R ²⁹ R ³⁰ , E ¹ R ³¹ R ³² R ³³ or E ² R ³⁴ R ³⁵ R ³⁶ R ³⁷ , and M ⁸ is a group IA or IB in the periodic table element selected from the group and group IIIB, ^{M 9} represents an element selected from group VIIA and VIII, ^{E 1} is a carbon atom, an oxygen atom or a sulfur atom, ^{E 2} is a nitrogen atom or a phosphorus atom.
M ⁸ is particularly preferably Li, Na, K, Ag or the like, and M ⁹ is particularly preferably Mn, Fe, Co, Ni or the like.
R ²⁹ and R ³⁰ are substituents selected from a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group, and may be bonded to each other to form a ring. The substituent of the substituted cyclopentadienyl group of R ²⁹ and R ³⁰ is usually an alkyl group having 1 to 6 carbon atoms, and the number of substituents is an integer of 1 to 5. Specific examples include a methylcyclopentadienyl group, an n-butylpentadienyl group, and a pentamethylcyclopentadienyl group.
R ^{31 to} R ³⁷ are selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, or an organic metalloid group. Specifically, hydrogen, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, cyclohexyl group, phenyl group, benzyl group, 3-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,4- Examples include trimethylphenyl group, 3-t-butylphenyl group, 2,6-di-t-butylphenyl group, F, Cl, Br, and I.

Among the compounds represented by the general formula (2) or (3), those in which M ¹ or M ² is Al or boron are preferred, those in which boron is particularly preferred, and represented by the general formula (2). Among the compounds, specifically, the following are particularly preferable.
The L is a compound of M ^8, tetraphenylborate silver tetraphenylborate, sodium tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) borate lithium, tetrakis (pentafluorophenyl tellurium oxy) borate silver tetrafluoroborate Silver, silver tetrafluoroarsenate, silver tetrafluoroantimonate, etc. are mentioned.
Examples of compounds in which L is M ⁹ R ²⁹ R ³⁰ include tetraphenylborate ferrocenium, tetraphenylborate manganese (tetraphenylporphyrin), tetrakis (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate decamethyl. Examples include ferrocenium, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) borateformylferrocenium, tetrakis (pentafluorophenyl) borate cyanoferrocenium, and the like.
Examples of the compound in which L is E ¹ R ³¹ R ³² R ³³ include tetraphenylborate trityl, tetrakis (pentafluorophenyl) borate trityl, tetraphenylboratetrimethylsulfonium, tetraphenylboratebenzyldimethylsulfonium, tetrakis (pentafluorophenyl) boratebenzyl Examples include dimethylsulfonium.

Examples of the compound in which L is E ² R ³⁴ R ³⁵ R ³⁶ R ³⁷ include tetraphenylborate ammonium, tetraphenylborate triethylammonium, tetraphenylboratetri (n-butyl) ammonium, tetraphenylboratetrimethylammonium, tetraphenylboratepyrrolinium. , Tetraphenylborate 2,5-dimethylpyrrolium, tetrakis (pentafluorophenyl) borate ammonium, tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) boratetri (n-butyl) ammonium, tetrakis (pentafluorophenyl) ) Borate trimethylammonium, tetrakis (pentafluorophenyl) borateanilinium, tetrakis ( Ntafluorophenyl) borate monomethylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate tetraphenylphosphonium, tetrakis (pentafluorophenyl) borate tetrabutylammonium, tetrakis (pentafluorophenyl) borate methyl Diphenylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) boratepyridinium, tetrakis (pentafluorophenyl) boratedimethyl (m-nitroanilinium), tetrakis (pentafluorophenyl) boratedimethyl (p- Bromoanilinium), tetrakis (pentafluorophenyl) boret (P-cyanopyridinium), tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate dimethyldiphenylammonium, tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium, tetrakis (pentafluorophenyl) boratemethyltriphenylammonium , Tetrakis (pentafluorophenyl) borate pyrrolinium, tetrakis (pentafluorophenyl) borate 2,5 -Dimethylpyrrolinium, tetrakis (3,5-di (trifluoromethyl) phenyl) borate dimethylanilinium, triethylammonium hexafluoroarsenate, tetrakis (3,5-bis (1-methoxy-2,2,2,-) Trifluoro-1- (trifluoromethyl) ethyl)) phenyl) boratedimethylanilinium, tetrakis (3- (1-methoxy-2,2,2, -trifluoro-1- (trifluoromethyl) ethyl) -5 -(Trifluoromethyl)) phenyl) boratedimethylanilinium, tetrakis (3- (2,2,2, -trifluoro-1- (2,2,2-trifluoroethoxy) -1- (trifluoromethyl) Ethyl) -5- (trifluoromethyl)) phenylborate dimethylanilinium, tetrakis (3 -Bis (2,2,2, -trifluoro-1- (2,2,2-trifluoroethoxy) -1- (trifluoromethyl) ethyl) phenylborate dimethylanilinium, tetraphenylboratetetraethylammonium, tetraphenyl Boratemethyltri (n-butyl) ammonium, tetraphenylboratebenzyltri (n-butyl) ammonium, tetraphenylboratetrimethylanilinium, tetraphenylboratedimethyldiphenylammonium, tetraphenylboratemethyltriphenylammonium, tetraphenylboratemethylpyridinium, Tetraphenylborate benzylpyridinium, tetraphenylboratemethyl (2-cyanopyridinium), tetrakis (pentafluorophenyl) borate (te Raethylammonium), tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) boratemethyl (4- Cyanopyridinium), tetrakis (pentafluorophenyl) borate benzylpyridinium, and the like.

  Among the compounds represented by the general formula (3), specifically, tris (pentafluorophenyl) boron, tris (3,5-bis (1-methoxy-di-2,2,2-trifluoro-) 1- (trifluoromethyl) ethyl) -5- (trifluoromethyl)) phenyl boron, tris (3- (2,2,2-trifluoro-1- (2,2,2-trifluoroethoxy) -1 -(Trifluoromethyl) ethyl) -5- (trifluoromethyl)) phenyl boron, tris (3,5-bis (2,2,2-trifluoro-1- (2,2,2-trifluoroethoxy)) -1- (Trifluoromethyl) ethyl) phenyl boron, triphenyl boron, tris (pentafluorotelluroxy) boron and the like are particularly preferable.

As the usage-amount of the compound represented by General formula (2) or (3), it is 10 ^<-5 > ^-10 < ³ > mol normally with ^respect to 1 mol of chromium compounds which are (A) components, Preferably it is 10 ^<-4 > ^-10 < ¹ >. a mol, more preferably from ¹⁰ -3 ^{to 10} 0 mol, and most preferably ¹⁰ -2 ^~1.5 × ¹⁰ -1 mol.

4). (F) component In the present invention, as a catalyst component, in addition to the components (A) to (E), if necessary, if a halogen-containing compound is further used as the component (F), the yield of the olefin low polymer and It is preferable because the selectivity is improved and the ratio of the amount of by-product polymer produced in the entire product can be reduced. As the halogen-containing compound, a halogen-containing compound containing an element selected from the group of groups IIIA, IIIB, IVA, IVB, VA, and VB in the periodic table is preferably used. As the halogen, chlorine or bromine is preferable.
Specific examples of the halogen-containing compound include scandium chloride, yttrium chloride, lanthanum chloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, boron trichloride, aluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, and gallium chloride. , Carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, hexachloroethane, hexachlorobenzene, 1,3,5-trichlorobenzene, hexachlorocyclohexane, trityl chloride, silane tetrachloride, trimethylchlorosilane, germanium tetrachloride, tetra Tin chloride, tributyltin chloride, phosphorus trichloride, antimony trichloride, trityl hexachloroantimonate, antimony pentachloride, bismuth trichloride, triodor Boron, aluminum tribromide, carbon tetrabromide, bromoform, bromobenzene, iodomethane, silicon tetrabromide, hexafluorobenzene, include aluminum fluoride, and the like.
Among the above halogen-containing compounds, those having a large number of halogen atoms are preferred, and compounds soluble in the reaction solvent are preferred. Examples of particularly preferred halogen-containing compounds include carbon tetrachloride, chloroform, dichloroethane, tetrachloroethane, hexachloroethane, titanium tetrachloride, germanium tetrachloride, tin tetrachloride and the like. In addition, a halogen containing compound can also be used as a 2 or more types of mixture.

(F) As the usage-amount of the halogen-containing compound which is a component, it is 10 ^<-3 > ^-10 < ³ > mol normally with respect to 1 mol of chromium compounds which are (A) components, Preferably it is 10 < ^-1 > -10 < ² > mol, Preferably it is 10 < ⁰ > -5 * 10 < ¹ > mol.

5. Production of Olefin Low Polymer The method for producing an olefin low polymer of the present invention comprises an olefin and a chromium compound such as component (A) in the presence of a carrier pretreated with a metal alkyl compound as component (E). It is carried out by contacting the catalyst. The contact mode in this case is not particularly limited, but the following methods (1) to (11) can be exemplified.
(1) A method of introducing the component (A) after introducing the olefin into the reactor containing the component (E).
(2) A method of introducing an olefin after introducing the component (A) into a reactor containing the component (E).
(3) A method of separately introducing the olefin and the component (A) into the reactor containing the component (E).
(4) A method of simultaneously introducing an olefin and a component (A) into a reactor containing the component (E).
(5) A method of introducing the component (A) after introducing the component (E) into the reactor containing olefin.
(6) A method of introducing an olefin after introducing the component (E) into a reactor containing the component (A).
(7) A method of simultaneously introducing the component (E) and the component (A) into a reactor containing olefin.
(8) A method of simultaneously introducing the component (E) and the olefin into the reactor containing the component (A).
(9) A method of introducing a mixture of component (E) and component (A) into a reactor containing olefin.
(10) A method of introducing a mixture of component (E) and olefin into a reactor containing component (A).
(11) A method of simultaneously introducing the component (E), the component (A) and the olefin into the reactor.

  In addition, the component (B), the component (C), the component (D), and the component (F) that are used as needed are the above-described contact between the olefin in the presence of the component (E) and the component (A), When the low polymerization reaction is carried out during contact or intermittently, it can be used by contacting with the component (A) at any time between contact and does not contradict the purpose of the present invention. In the range, the contact method, order, and the like are not limited. These components are introduced into the reactor as an arbitrary mixture with (A) component, (E) component or olefin described in each of the above contact methods (1) to (11), for example ( It is possible to contact the component A). Of course, it goes without saying that these components can be introduced directly into the reactor together with the medium or alone.

The contact between the component (E) and the component (A) is usually performed at a temperature of −100 to 300 ° C. Contact at a high temperature exceeding 300 ° C. is not preferable because it promotes the degenerative reaction of the component (A) and deteriorates the activity and selectivity of the low polymer. The degree of progress of the alteration reaction also depends on the contact concentration of each component. For example, when the product of the concentrations of the component (E) and the component (A) at the time of contact is 10 ⁻¹ (unit: g · mol / L ² ) or more, the preferred contact temperature is −50 to 200 ° C. A preferable contact temperature is 0 to 150 ° C, and a particularly preferable contact temperature is 20 to 110 ° C.

Moreover, contact with any of (B) component, (C) component, (D) component, (F) component, and (E) component or (A) component used as needed is also high concentration and high temperature. The contact at is not preferred because it promotes the alteration reaction of the catalyst. In the case of contact with the component (E), the standard is the same as the contact between the component (E) and the component (A). At this time, when a plurality of components are brought into contact with the component (E), the determination is made based on the sum of the concentrations of the components. Furthermore, in the case of contact with the component (A), the product of the concentration of the component (A) at the time of contact and the concentration of each component (the sum of the concentration of each component when a plurality of components are used) is 10 ⁻⁴ (unit: mol ² / L ²⁾ case described above, the preferred contact temperature is -50 to 200 ° C., more preferred contact temperature is 0 to 150 ° C., are particularly preferred contact temperature is 20 to 110 ° C..

  In the method for producing a low olefin polymer of the present invention, the raw material olefin is preferably a substituted or unsubstituted olefin having 2 to 30 carbon atoms, particularly preferably an α- having 2 to 30 carbon atoms. Olefin is used. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, and the like. In particular, ethylene is suitable as a raw material olefin, and 1-hexene, which is a trimer thereof, can be obtained from ethylene with high yield and high selectivity.

  In the present invention, the low polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon. Specific examples of the solvent include 1 to 1 carbon atoms such as butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, and decalin. Twenty linear or alicyclic saturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, and tetralin, olefins as reaction raw materials themselves, or olefins other than the main raw materials can be used. These can be used alone or as a mixed solvent. For the reaction solvent, a chain saturated hydrocarbon having 4 to 10 carbon atoms, an alicyclic saturated hydrocarbon or an olefin having 4 to 30 carbon atoms is preferable, and it is particularly preferably liquid at normal temperature.

The temperature of the low polymerization reaction is usually −50 to 250 ° C., preferably 0 to 150 ° C., more preferably 20 to 110 ° C. In particular, it is preferable to carry out at a temperature below the melting point of the olefin polymer as a by-product.
The pressure is not particularly limited, but is preferably in the range of normal pressure to about 200 MPa, but a pressure up to about 10 MPa is usually sufficient. The residence time is usually in the range of 1 minute to 20 hours, preferably 0.5 to 6 hours. If hydrogen is allowed to coexist during the reaction, it is preferable because catalytic activity and trimer selectivity are improved. In addition, the coexistence of hydrogen also provides an effect that the properties of the by-produced polymer become powdery with little adhesion. The amount of coexisting hydrogen is usually 0.01 to 10 MPa, preferably 0.1 to 8 MPa as the hydrogen partial pressure. Preferred low polymerization methods are slurry low polymerization, gas phase low polymerization, high pressure low polymerization, and solution low polymerization. More preferred are slurry low polymerization and gas phase low polymerization.

In the low polymerization reaction of the present invention, the amount of the chromium compound used is usually 1.0 × 10 ^{−7 to} 0.5 mol, preferably 1.0 × 10 ⁻⁶ to 1 liter per liter of the solvent in the case of the slurry low polymerization method. The range is 0.1 mol, more preferably 5.0 × 10 ⁻⁶ to 10 ⁻² mol. In the case of the gas phase low polymerization method, usually 1.0 × 10 ^{−7 to} 0.5 mol, preferably 1.0 × 10 ^{−6 to} 0.2 mol, more preferably 1.0 per liter of the gas phase part. It is the range of x10 < ^-5 > -0.1 mol.

The method for producing an olefin low polymer according to the present invention can produce an olefin low polymer in a high yield and high selectivity by performing the above-mentioned catalyst and reaction conditions, and at the same time, produce a by-product olefin polymer. It is characterized in that it can be produced in granular form.
That is, the ratio of the components collected by the sieve having a mesh size of 5.6 mm in the olefin polymer as a by-product is preferably 10% by weight or less, more preferably 8% by weight or less, Preferably it becomes 4 weight% or less. Moreover, the weight average molecular weight by GPC of the olefin polymer as a by-product is preferably 1,000,000 or less, more preferably 700,000 or less, and still more preferably 500,000 or less.
As described above, according to the method of the present invention, the by-product polymer is formed in a granular form, so that it does not adhere to the reactor in an indeterminate state and becomes difficult to recover, and is an industrially stable low polymer. Can be manufactured.

6). Production of Olefin Low Polymer and Olefin Copolymer in the Coexistence of Polymerization Catalyst In the method for producing an olefin low polymer of the present invention, particularly, high-purity 1-hexene can be produced industrially advantageously from ethylene. . The 1-hexene obtained by the production method of the present invention may be homopolymerized by a polymerization reaction using a known polymerization catalyst, or may be subjected to various kinds of vinyls through or without a purification separation step by a known method such as distillation. Various polymers can be produced by copolymerization with monomers. Furthermore, by carrying out the method for producing an olefin low polymer of the present invention in the presence of a polymerization catalyst, the copolymerization of the produced 1-hexene and ethylene with other vinyl monomers introduced as necessary is the same. This is possible in the reactor. By these methods, L-LDPE, which is an industrially useful resin, can be produced particularly economically from 1-hexene obtained by the production method of the present invention.

  Thus, when implementing the manufacturing method of the olefin low polymer of this invention in the coexistence of a polymerization catalyst for the purpose of implementing manufacture of a polymer simultaneously, the preferable embodiment is (E) component. Using a particulate solid polymerization catalyst (component (E ′)) containing, as a component, at least one of a metal alkyl compound or a reaction product thereof as a carrier pretreated with a metal alkyl compound, component (E) The reaction is carried out in accordance with the conditions described in the above-mentioned "2. Support" to "5. Production of low olefin polymer", except that "E" is replaced with component (E '). Of course, it is also preferable to use the component (E) and the component (E ′) in an arbitrary ratio for the purpose of controlling the physical properties of the polymer by adjusting the ratio of the amount of polymer and low polymer produced.

The component (E ′) is preferably formed by supporting or impregnating the above-described component (E), which is a carrier, with a compound containing at least an element selected from Groups IIIA to XA of the periodic table, or the above-mentioned component (E ′) The carrier before the component (E) is treated with a metal alkyl compound is supported or impregnated with at least a compound containing an element selected from Groups IIIA to XA of the periodic table and a metal alkyl compound. As the compound containing an element selected from Group IIIA to XA of the periodic table, preferably, at least Sc, Y, La, Nd, Sm, Gd, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, A compound containing an element selected from W, Mn, Fe, Ru, Co, Ni, Pd, and Cu, and more preferably an element selected from Ti, Zr, Hf, V, Cr, Fe, Co, Ni, and Pd Particularly preferred are compounds containing an element selected from Ti, Zr, and Hf.
Here, as the carrier, all the compounds described in the above-mentioned component (E) can be used. Similarly, as the metal alkyl compound, all the same compounds described in the component (E) can be used. It is possible to use the metal alkyl compounds. In addition, the contact order of the compound containing the element selected from Groups IIIA to XA of the periodic table, the metal alkyl compound, and the carrier is arbitrary. For example, the above-described methods (I) to (I) defining the contact between the carrier and the metal alkyl compound In any step of X), it is possible to contact a compound containing an element selected from Groups IIIA to XA of the periodic table with other two components, and it is naturally possible to use a plurality of methods in combination. . These compounds and methods are the same as described in the above-mentioned component (E) with respect to preferred examples.

  Suitable forms of the particulate solid polymerization catalyst (component (E ′)) containing a metal alkyl compound as one component can be specifically exemplified as the following (E′-1) to (E′-3). .

(E'-1) A supported Ziegler catalyst in which at least a group IVA metal halide and an organoaluminum compound are supported on a carrier. As described in JP-A-54-142192 and JP-A-54-148093 An inert carrier material-supported Mg / Ti catalyst can be exemplified. That is, for example, catalyst powder obtained by impregnating porous silica previously treated with triethylaluminum with a uniform mixed solution of anhydrous MgCl ₂ in tetrahydrofuran and TiCl ₄ and drying to dryness. Further, a catalyst obtained by subjecting a Mg / Ti catalyst to olefin prepolymerization in the presence of organoaluminum as described in JP-A-63-117019 can also be exemplified. That is, for example, a catalyst obtained by introducing a mixed solution of TiCl ₄ and methylhydrogen polysiloxane into a solid component obtained by the reaction of MgCl ₂ , Ti (OnBu) ₄ and methyl hydrogen polysiloxane is present in the presence of triethylaluminum. The following are prepolymerized catalysts obtained by ethylene prepolymerization.

(E'-2) A supported metallocene catalyst in which at least a group IVA metal metallocene compound and an organoaluminum compound are supported on a carrier. Examples of support-supported metallocene / alumoxane catalysts as described in JP-A-61-296008 I can do it. That is, for example, a solid catalyst obtained by dropping dicyclopentadienylzirconium dichloride on silica treated with alumoxane. Further, a support-supported metallocene / non-metallocene transition metal compound / alumoxane catalyst as described in JP-A-1-503715 can also be exemplified. That is, for example, a solid catalyst obtained by dropping methylalumoxane, ZrCl ₄ and bis (n-butylcyclopentadienyl) zirconium dichloride onto dehydrated silica. Furthermore, the catalyst for olefin polymerization obtained by contacting a metallocene transition metal compound / clay etc./organoaluminum compound as described in JP-A-5-301917 can also be exemplified. That is, for example, a solid catalyst obtained by bringing a contact reaction product of montmorillonite and trimethylaluminum into contact with a contact reaction product of biscyclopentadienylzirconium dichloride and trimethylaluminum.

(E′-3) a bridged nonmetallocene compound wherein a nitrogen atom or an oxygen atom is directly coordinated to at least a group IVA to XA metal, and a bulky substituent is present on the nitrogen atom and the oxygen atom; Supported post-metallocene catalyst in which organoaluminum is supported on a carrier (examples of a group 4 metal compound in the periodic table include a bisamide compound having an NN type ligand and a salicylaldi having an NO type ligand. Minato compounds.Examples of compounds of Group 8-10 metals in the periodic table include biimino compounds having an NN type ligand and salicyl aldiminato compounds having an NO type ligand)
A bridged nonmetallocene compound as described in JP-A-10-513289 is prepared together with an organoaluminum compound and an organoaluminum oxy compound by the method described in JP-A-9-278821 and JP-A-9-302021. A catalyst supported on a particulate carrier can be exemplified. That is, for example, the reaction product of trimethylaluminum and hydrous silica is a solid catalyst obtained by contacting the following complex (A).

  In addition, it can be obtained from various nonmetallocene compounds described in JP-A-10-298216, JP-A-11-315109, JP-A-2000-336110, JP-T-2001-515930, and the like by a similar supporting method. The obtained solid catalyst can also be illustrated.

  The component (E ′) is preferably composed of at least one of a metal alkyl compound represented by the above-exemplified examples (E′-1) and (E′-2) or a reaction product thereof as one component. Particulate solid Ziegler catalyst or metallocene catalyst.

  The component (E ′) is used in a reaction system that satisfies the conditions described in the above-mentioned section “5. Production of Low Olefin Polymer”. As with the component (E), the contact mode with the component (A), which is the main catalyst component of the low polymerization reaction, is preferably replaced with the component (E ′) by the method (1) to (11). The method can be illustrated. When the component (E) and the component (E ′) are used in combination for the purpose of controlling the polymer physical properties by adjusting the production ratio of the polymer and the low polymer, the component (E) mixed at a predetermined ratio in advance The component (E ′) may be used in any one of the methods (1) to (11), or may be used separately according to any one of the methods (1) to (11).

In the component (E ′) which is a particulate solid polymerization catalyst, the content of the element selected from the group IIIA to XA derived from the compound containing the element selected from the group IIIA to XA of the periodic table is the condition of the reaction to be performed. and be appropriately adjustments are made by the desired polymer properties, in general, a ¹⁰ -8 ^{to 10} 0 mol per component (E ') 1 g, preferably from ¹⁰ -7 ^{to 10} -1 mol, further Preferably it is 10 ^{< -6} > -10 ^<-2 > mol. When the content of an element selected from the group IIIA to XA is small, the activity of the olefin polymerization reaction is insufficient, resulting in a shortage of the production amount of the olefin polymer, or a relatively high production amount of the olefin low polymer. As a result, the concentration of the low polymer in the system becomes high, so that the low polymer content in the polymer increases excessively, resulting in a disadvantage that a polymer having desired physical properties cannot be obtained. Further, when the content of an element selected from the IIIA to XA groups is large, the olefin low polymerization reaction active site is poisoned to reduce the amount of low polymer produced, or a desired low content having a polymerizable unsaturated bond. The production selectivity of the polymer (polymerizable low polymer) decreases, and the activity of the olefin polymerization reaction becomes too high, and the production amount of the olefin low polymer is relatively short, resulting in low weight in the system. When the coalescence concentration is lowered, there is a disadvantage that a polymer having a desired physical property cannot be obtained because the content of the low polymer in the polymer is excessively lowered.

The molar ratio of Cr derived from component (A) and the elements selected from the groups IIIA to XA is also appropriately adjusted depending on the conditions of the reaction to be carried out and the desired polymer physical properties. ^{It is −5 to} 1000, preferably 10 ^{−3 to} 100 mol, and more preferably 10 ^{−2 to} 50 mol. If it is smaller than this range, the olefin low polymerization reaction is reduced, the low polymerization active sites are easily poisoned, the production amount of the low polymer is reduced, or a desired low polymer having a polymerizable unsaturated bond ( The production selectivity of the polymerizable low polymer) is lowered, and the low polymer content in the polymer is lowered too much, so that a polymer having desired physical properties cannot be obtained. On the other hand, if it is larger than this range, the low polymer content in the polymer is increased by increasing the low olefin polymerization activity, increasing the low polymer production amount and increasing the low polymer concentration in the system. If the polymer increases too much, a polymer having the desired physical properties cannot be obtained, the polymerization activity is relatively lowered, or the polymerization active site becomes susceptible to poisoning, resulting in a shortage of polymer production. Occurs. The copolymerization content of the polymerizable low polymer in the olefin polymer is arbitrary depending on the desired physical properties of the olefin polymer, so it is generally 0.001 to 100 mol%, preferably 0.01 to 50 mol%, Preferably it is 0.1-20 mol%, Most preferably, it is 0.5-10 mol%. When the copolymerization content is small, the economic merit is small and it is not practical to adopt this method. Further, when the copolymerization content is large, particularly when slurry polymerization or gas phase polymerization is carried out, the low melting point component that hinders the particle polymerization is increased, resulting in a problem in the polymerization operation. However, this is not the case when a solution polymerization method or a bulk polymerization method is performed, and when a polymerization catalyst capable of stereoregular polymerization of a low polymer is used.

  When the method for producing an olefin low polymer of the present invention is carried out in the presence of a polymerization catalyst for the purpose of simultaneously carrying out production of a polymer, by selecting appropriate conditions from the above-mentioned various conditions, Polymerization is performed under high-selection reaction conditions in which the production selectivity of the desired low polymer (polymerizable low polymer) having a polymerizable unsaturated bond in the low-olefin polymerization reaction product excluding the polymer is at least 70% or more. It is preferable in terms of economy. In particular, when the olefin is ethylene and the olefin low polymer is mainly 1-hexene, the proportion of 1-hexene in the ethylene low polymerization reaction product excluding the ethylene (co) polymer is 80% by weight or more, preferably It is desirable that it is 90% by weight or more, more preferably 95% by weight or more, particularly preferably 97% by weight or more. The upper limit is 100% by weight. If the ratio of 1-hexene is low, not only is an unnecessary low polymer produced, it is uneconomical, but also the product that acts as a poison for the polymerization activity and low polymerization activity increases, resulting in a decrease in productivity. This is not preferable because it may cause the formation of a non-uniform polymer in terms of molecular weight distribution or comonomer composition distribution.

Regarding the molecular weight distribution, it is desired from the practical performance of the polymer that the Mw / Mn by GPC of the olefin polymer to be produced is 10 or less, preferably 6 or less, more preferably 5 or less, and particularly preferably 4 or less. The lower limit is not particularly limited, but is generally 2 or more. If Mw / Mn is too large, the high molecular weight component increases, causing fish eyes and gels, or the melt elasticity is too strong, causing appearance deterioration due to surface unevenness of the molded product and physical property deflection due to extreme orientation. Or low molecular weight components are increased, which may cause stickiness on the surface of the product and eyes during molding, or may deteriorate transparency.
Here, Mw / Mn by GPC refers to the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, the measuring method used for an Example and a comparative example is as follows.

(1) Measurement of polymer molecular weight by GPC In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC). Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation by the least square method.
The viscosity equation [η] = K × M ^α used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733
PP: K = 1.03 × 10−4, α = 0.78
The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: ο-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
(2) Sieving of produced polymer All the polymers were put in a standard sieve having an inner diameter of 75 mm (mesh opening 5.6 mm), shaken for 20 minutes, and the weight of the polymer remaining on the sieve was measured.
(3) Measurement of ethylene low polymer composition by gas chromatographic analysis The product with 6 to 20 carbon atoms contained in the product was quantified by Shimadzu Corporation gas chromatograph equipped with a GL Science capillary column (TC-1). This was carried out using a graph GC-14 (FID detector). That is, He was used as the carrier gas, the injection temperature was set to 300 ° C., the detector temperature was set to 300 ° C., and cyclopentane was used as the internal standard. The analysis was performed by injecting 1.0 μl of the reaction solution into this gas chromatograph and then raising the column temperature from 60 ° C. to 300 ° C.
In addition, the quantification of the product having 6 carbon atoms contained in the product was performed by a gas chromatograph GC-14 (FID detector) manufactured by Shimadzu Corporation equipped with a capillary column (Al ₂ O ₃ / KCl, PLOT Fused Silica) manufactured by GL Science. ). That is, He was used as the carrier gas, the injection temperature was set to 250 ° C., the detector temperature was set to 300 ° C., and cyclopentane was used as the internal standard. The analysis was performed by injecting 1.0 μl of the reaction solution into this gas chromatograph and then raising the column temperature from 100 ° C. to 190 ° C.
(4) Measurement of melting point (Tm) of polymer by DSC It was measured according to JIS K7121. 5 mg of sample was melted at 170 ° C. for 5 minutes, cooled to 20 ° C. at a rate of 10 ° C./minute, held for 1 minute, and then a melting curve was measured at a temperature increase rate of 10 ° C./minute up to 170 ° C. (° C.) was defined as the melting point (Tm-DSC).
(5) Measurement of MI and FR MI was measured according to JIS K6760 at 190 ° C. and a load of 2.16 kg. FR was calculated from the ratio of I _{10 kg} to MI (= I _{10 kg} / MI), which is the melt index measured in the same manner under the conditions of 190 ° C. and 10 kg load.
(6) Measurement of density The density was measured by a density gradient tube method after the strand obtained at the time of melt index measurement was heat-treated at 100 ° C for 1 hour and further allowed to stand at room temperature for 1 hour.

Example 1
(1) Chemical treatment and drying of clay mineral 40 kg of a granulated and classified product of commercially available swellable montmorillonite (“Ben Clay SL”, manufactured by Mizusawa Chemical Co., Ltd., average particle size 38 μm) was dispersed in 160 kg of 25% sulfuric acid, and 90 ° C. For 2 hours. This was filtered and washed with demineralized water to pH 3.5, and then the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours to obtain acid-treated montmorillonite. Of this pre-dried montmorillonite, 200 g of particles that passed through a sieve having an opening of 150 mesh were placed in a 2 L flask with 115 g of zinc sulfate heptahydrate (Zn (SO ₄ ) · 7H ₂ O), 10 g of sulfuric acid, and 675 g of demineralized water. The mixture was dispersed in the dissolved mixture and stirred at 30 ° C. for 2 hours. After the treatment, this solid component was washed with demineralized water and pre-dried to obtain a treated montmorillonite. This pre-dried zinc-treated montmorillonite was placed in a 1 L flask and subjected to heat dehydration treatment at 200 ° C. for 2 hours under a reduced pressure of 1 mmHg.
(2) Organoaluminum treatment of clay mineral In a nitrogen atmosphere, 25 mL of n-heptane and 1.0 g of the dried montmorillonite particles obtained in (1) above were introduced into a 100 mL flask. The system was kept at 20 ° C. and 3.2 mL of a triethylaluminum n-heptane solution (concentration 0.613 mol / L) was added. The reaction was carried out for 1 hour while maintaining the temperature, and after washing with n-heptane until the washing rate became 1/100, the total amount was adjusted to 100 mL.
(3) Low polymerization reaction of ethylene Under a nitrogen atmosphere, in a 3 L autoclave with an induction stirrer, 1.5 L of n-heptane, 3.0 mmol of triethylaluminum (n-heptane solution with a concentration of 0.613 mol / L), 2, 5 -1.87 mmol of dimethylpyrrole (0.187 mmol / ml n-heptane solution) was added in order while stirring at room temperature, then the temperature was raised to 80 ° C., and ethylene was introduced to increase the pressure to 2.0 MPa-G. (Ethylene partial pressure 1.8 MPa). Then, while maintaining the temperature, 300 mg of chromium (III) 2-ethylhexanoate (chromium (III) 2-ethylhexanoate, 70% in mineral spirits manufactured by STREM CHEMICAL Inc.) was diluted with n-heptane. (Used as a 20 mg / ml solution) and 100 mg of the organoaluminum-treated montmorillonite obtained in (2) above (10 mg / ml n-heptane slurry solution) were sequentially added into the catalyst feeder connected to the inside of the autoclave via a valve. After mixing for 5 minutes, the mixture in the feeder is pressurized with ethylene to press into the autoclave and the introduction of ethylene is continued to bring the total pressure to 2.2 MPa-G (ethylene partial pressure 2.0 MPa). Keep 80 In was carried out for 1 hour oligomerization. After 1 hour, ethanol was added to stop the reaction.
(4) Post-treatment of the product After the reaction was stopped, the autoclave was cooled to room temperature and the inside was confirmed. Almost no solid matter was found on the inner wall of the autoclave or the stirring blade. The composition of the ethylene low polymer produced was measured by gas chromatographic analysis of the supernatant of the contents. Subsequently, all the contents were collected, and suction filtration was performed with 5A filter paper to separate the solid matter. This solid was dried in a vacuum dryer at a temperature of 80 ° C. for 10 hours or longer to remove the solvent and the like to obtain 1.0 g of a polymer. When this was sieved with a sieve having an opening of 5.6 mm, the weight of the polymer remaining on the sieve (the component collected by the sieve with an opening of 5.6 mm) was 0.035 g.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 1)
A low polymerization reaction of ethylene was carried out in the same manner as in Example 1 except that the organoaluminum-treated montmorillonite was not used in Example 1 (3). After the reaction was stopped, the inside of the autoclave was confirmed. As a result, solid matter was extremely attached to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 2)
A low polymerization reaction of ethylene was performed in the same manner as in Example 1 except that the dried montmorillonite obtained in Example 1 (1) was used instead of the organoaluminum-treated montmorillonite in Example 1 (3). The total amount of product and the amount of 1-hexene produced were less than in Example 1. After the reaction was stopped, the inside of the autoclave was confirmed, and solid matter adhered to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 2)
A low polymerization reaction of ethylene was carried out in the same manner as in Example 1 except that 50 mg of organoaluminum-treated montmorillonite was used in Example 1 (3). When the inside of the autoclave was checked after the reaction was stopped, the solid matter adhered to the inner wall of the autoclave and the stirring blade was slight.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 3)
A low polymerization reaction of ethylene was carried out in the same manner as in Example 1 except that diethylaluminum chloride was used instead of triethylaluminum in Example 1 (2). After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

Example 4
In Example 1 (3), ethylene was subjected to a low polymerization reaction in the same manner as in Example 1 except that pyrrole was used instead of 2,5-dimethylpyrrole and the temperature was changed to 90 ° C. instead of 80 ° C. . After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 3)
A low polymerization reaction of ethylene was performed in the same manner as in Example 4 except that the organoaluminum-treated montmorillonite was not used. After the reaction was stopped, the inside of the autoclave was confirmed. As a result, solid matter was extremely attached to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 5)
In Example 1 (3), triethylaluminum was adjusted to 6.0 mmol (an n-heptane solution having a concentration of 0.613 mol / L), and 1.25 mmol (1,1,1,2,2,2-hexachloroethane) was added to the autoclave. A low polymerization reaction of ethylene was carried out for 23 minutes in the same manner as in Example 1 except that 0.125 mmol / ml n-heptane solution) was added. After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 6)
A low polymerization reaction of ethylene was carried out for 27 minutes in the same manner as in Example 5 except that 124 mg of methylaluminoxane-supported silica (manufactured by Witco, Al content 22.3% by weight) was used instead of the organoaluminum-treated montmorillonite. After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 4)
A low polymerization reaction of ethylene was carried out for 23 minutes in the same manner as in Example 5 except that the organoaluminum-treated montmorillonite was not used. After the reaction was stopped, the inside of the autoclave was confirmed. As a result, solid matter was extremely attached to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 5)
In place of the organoaluminum-treated montmorillonite, a low-polymerization reaction of ethylene was carried out in the same manner as in Example 5 except that commercially available silica particles (Carriert P10 manufactured by Fuji Silysia Chemical Co., Ltd.) were baked under reduced pressure at 600 ° C. for 3 hours. It went for 39 minutes. After the reaction was stopped, the inside of the autoclave was confirmed, and solid matter adhered to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 7)
(1) Organoaluminum treatment of silica Except for using the calcined silica of Comparative Example 5 in place of the dried montmorillonite particles, the organoaluminum treated silica was treated in the same manner as the organoaluminum treatment of the clay mineral of Example 1 (2). Obtained.
(2) Low polymerization reaction of ethylene The organoaluminum-treated silica of (1) above is used instead of the organoaluminum-treated montmorillonite, and in the catalyst feeder, 2-ethylhexanoic acid chromium (III), the silica, and A low polymerization reaction of ethylene was performed for 29 minutes in the same manner as in Example 5 except that 50 μmol of tetrakis (pentafluorophenyl) borate dimethylanilinium (10 μmol / ml toluene solution) was added. After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 8)
A low polymerization reaction of ethylene was carried out for 27 minutes in the same manner as in Example 7 except that the organoaluminum-treated montmorillonite of Example 1 (2) was used instead of the organoaluminum-treated silica. After the reaction was stopped, the inside of the autoclave was checked, and almost no solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

Example 9
A low polymerization reaction of ethylene was carried out for 25 minutes in the same manner as in Example 8, except that 125 μmol (10 μmol / ml toluene solution) of tetrakis (pentafluorophenyl) borate dimethylanilinium was used. When the inside of the autoclave was checked after the reaction was stopped, the solid matter adhered to the inner wall of the autoclave and the stirring blade was slight.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Comparative Example 6)
A low polymerization reaction of ethylene was carried out for 25 minutes in the same manner as in Example 7 except that the organoaluminum-treated silica was not used. After the reaction was stopped, the inside of the autoclave was confirmed. As a result, solid matter was extremely attached to the inner wall of the autoclave and the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 1, and the results of the low polymerization reaction are shown in Table 2.

(Example 10)
(1) Preparation of Clay Mineral Metallocene Polymerization Catalyst Under a nitrogen atmosphere, 34.4 mL of n-heptane and 10 g of the dried montmorillonite particles obtained in Example 1 (1) were introduced into a 200 mL flask. While maintaining the system at 30 ° C., 48.9 mL of an n-heptane solution of triethylaluminum (concentration 0.613 mol / L) was added with stirring. The reaction was continued for 1 hour while maintaining the temperature by continuing stirring, and then washing with n-heptane was performed until the washing rate became 1/270, and the total amount was adjusted to 20 mL. After adding 80 mL of toluene, the whole amount of a solution in which 2.40 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 90 mL of toluene was added while stirring at 30 ° C. The reaction was carried out for 1 hour while being held, and then washed with toluene until the washing rate became 1 / 100,000, and the total amount was adjusted to 200 mL to obtain a slurry solution of clay mineral metallocene polymerization catalyst.
(2) Preparation of prepolymerization catalyst In a nitrogen atmosphere, 237 mL of n-heptane was added to a 1 L autoclave equipped with an induction stirrer, and further 4.8 mmol of triethylaluminum at 20 ° C. (an n-heptane solution having a concentration of 0.613 mol / L). And the whole slurry solution of the clay mineral metallocene polymerization catalyst produced in (1) was added and contacted for 10 minutes, and then the temperature was raised to 40 ° C. and further contacted for 10 minutes. Ethylene was supplied here at a rate of 0.375 g / min, and polymerization was continued for 90 minutes while maintaining the temperature. After the ethylene supply rate was increased to 0.938 g / min, the temperature of the system was increased to 10 ° C./4 min. The polymerization was continued at a rate of 80 ° C. until the cumulative supply of ethylene reached 112.5 g, and finally the ethylene gas in the system was purged to stop the polymerization. The entire slurry solution in the system was collected and washed with toluene until the washing rate became 1/23, and then the solvent was distilled off at 70 ° C. to obtain 114 g of a clay mineral metallocene prepolymerized catalyst powder having good properties. It was.
(3) Low polymerization reaction of ethylene In a 3 L autoclave with an induction stirrer in a nitrogen atmosphere, 1.5 L of n-heptane, 1.0 mmol of triethylaluminum (n-heptane solution with a concentration of 0.613 mol / L), 2, 5 -0.311 mmol of dimethylpyrrole (0.187 mmol / ml n-heptane solution) and 0.208 mmol of hexachloroethane (0.125 mmol / ml n-heptane solution) were sequentially added at room temperature with stirring, and then 80 ° C. Then, ethylene was introduced and the pressure was increased to 2.0 MPa-G (ethylene partial pressure 1.8 MPa). Next, while maintaining the temperature, 50 mg of chromium (III) 2-ethylhexanoate (Chromium (III) 2-ethylhexanoate, 70% in mineral spirits manufactured by STREM CHEMICAL Inc.) was diluted with n-heptane, and chromium 2-ethylhexanoate was diluted. Used as a 30 mg / ml solution) and 1.143 g of the clay mineral metallocene prepolymerized catalyst obtained in (2) above (5 mg / ml n-heptane slurry solution as montmorillonite) were connected to the inside of the autoclave via a valve. After sequentially adding to the catalyst feeder and mixing for 5 minutes, the mixture in the feeder is pressurized with ethylene to press fit into the autoclave, and the introduction of ethylene is continued to bring the total pressure to 2.2 MPa-G (ethylene content). Pressure 2.0MPa To keep, was 32 minutes oligomerization at 80 ° C.. After 32 minutes, ethanol was added to stop the reaction.
(4) Post-treatment of the product After stopping the reaction, the autoclave was cooled to room temperature and the inside was confirmed. As a result, no solid matter was found on the inner wall of the autoclave or the stirring blade. The composition of the ethylene low polymer produced was measured by gas chromatographic analysis of the supernatant of the contents. Subsequently, all the contents were collected, and suction filtration was performed with 5A filter paper to separate the solid matter. The solid was dried in a vacuum dryer at a temperature of 80 ° C. for 10 hours or longer to remove the solvent and the like to obtain 45.5 g of polymer. This was sieved with a sieve having an opening of 5.6 mm, but there was no polymer remaining on the sieve (component collected by a sieve with an opening of 5.6 mm).
The polymerization catalyst composition and reaction conditions are shown in Table 3, and the results of the low polymerization reaction and olefin copolymerization reaction are shown in Table 4.

(Example 11)
(1) Preparation of solid catalyst for olefin polymerization Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-neck flask equipped with an electromagnetic induction stirrer, and then 3.3 g of tetrapropoxyzirconium (Zr (On-Pr) ₄ ) and indene 9. 3 grams was added and stirred at room temperature for 30 minutes, and the system was maintained at 0 ° C., and 11.1 grams of triethylaluminum (AlEt ₃ ) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction system was brought to room temperature for 5 hours. Stir. This solution is designated as solution A. The Zr concentration of the solution A was 0.057 mmol / ml as Zr. Next, 200 ml of purified toluene was added to another 3 L three-necked flask equipped with a stirrer under nitrogen, and 96 ml of the solution A, and then 548 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) were added and reacted. This is designated as solution B. Next, 400 ml of purified toluene was added to a 3 L three-necked flask equipped with a stirrer under nitrogen, and then 100 g of silica (made by Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 600 ° C. for 5 hours was added. After the addition, the entire amount of the solution B was added and stirred at room temperature for 2 hours. Then, the solvent was removed by nitrogen blowing to obtain a powdery solid catalyst for olefin polymerization having good fluidity.
(2) Low polymerization reaction of ethylene Example 10 (except for using 100 mg of the solid catalyst for olefin polymerization (5 mg / ml n-heptane slurry solution) obtained in the above (1) instead of the clay mineral metallocene prepolymerization catalyst. The low polymerization reaction of ethylene was conducted for 39 minutes in the same manner as 2). No solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 3, and the results of the low polymerization reaction and olefin copolymerization reaction are shown in Table 4.

(Example 12)
(1) Preparation of solid catalyst for olefin polymerization Silica (made by Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 600 ° C. for 4 hours with flowing nitrogen in a 1 L reactor equipped with an electromagnetic induction stirrer under nitrogen 68 g was dispersed in 526 mL of isopentane and stirred at 40 ° C. for 30 minutes. To this, 33.3 mmol of triethylaluminum (n-heptane solution with a concentration of 0.613 mol / L) was added at room temperature and stirred for another 30 minutes, and then the temperature was raised to 60 ° C. and the solvent was evaporated with a nitrogen stream to triethyl. Dry particles of aluminized silica were obtained. A total amount of a uniform solution obtained by dissolving 22.71 mmol in terms of Ti in 68.14 mmol of anhydrous magnesium chloride and a mixture of titanium trichloride / aluminum trichloride (3TiCl ₃ .AlCl ₃ ) separately in 310 mL of anhydrous tetrahydrofuran was added to the dry particles at 60 ° C. After the addition and stirring for 30 minutes, the temperature was raised to 75 ° C., and drying was performed with a nitrogen stream until the remaining amount of tetrahydrofuran in the system reached 15.0% by weight. Next, 664 mL of isopentane, 52.84 mmol of diethylaluminum chloride and 52.82 mmol of trinormal hexylaluminum were added at room temperature, and the stirring was continued for 30 minutes. Then, the temperature was raised to 70 ° C. and the solvent was evaporated in a nitrogen stream to olefin. Dry particles of a solid catalyst for polymerization were obtained.
(2) Low polymerization reaction of ethylene 100 mg (5 mg / ml n-heptane slurry solution) of the solid catalyst for olefin polymerization obtained in the above (1) is used instead of the clay mineral metallocene prepolymerization catalyst, and the gas at the start of the reaction The composition was set to 1 MPa in the same manner as in Example 10 (2) except that the ethylene partial pressure was 1.0 MPa and the hydrogen partial pressure was 0.5 MPa, and thereafter the introduction of ethylene was continued and the total pressure was maintained at 1.7 MPa-G. The time low polymerization reaction was performed. No solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 3, and the results of the low polymerization reaction and olefin copolymerization reaction are shown in Table 4.

(Example 13)
Instead of 100 mg of organoaluminum-treated montmorillonite (10 mg / ml n-heptane slurry solution), 200 mg of the same organoaluminum-treated montmorillonite (10 mg / ml n-heptane slurry solution) and 16 ml of 1.0 μmol / ml toluene solution of zirconocene dichloride A low polymerization reaction of ethylene was carried out in the same manner as in Example 4 except that was used. No solid matter was found on the inner wall of the autoclave or the stirring blade.
The polymerization catalyst composition and reaction conditions are shown in Table 3, and the results of the low polymerization reaction are shown in Table 4.

  The method for producing an olefin low polymer according to the present invention efficiently produces an olefin trimer with high yield and high selectivity, and further recovers the by-product polymer in a granular form to prevent adhesion. Since it is a method to obtain, especially 1-hexene of high purity can be manufactured industrially advantageously from ethylene. And L-LDPE which is useful resin can be manufactured from the 1-hexene obtained by the manufacturing method of this invention by the polymerization reaction using a well-known polymerization catalyst.

It is a figure explaining the baseline and the section of a chromatogram in the measurement of the polymer molecular weight by GPC.

Claims (13)

  A method for producing an olefin low polymer using a chromium-containing catalyst, wherein the contact between the olefin and the catalyst is carried out in the presence of a carrier previously treated with a metal alkyl compound. . A catalyst containing chromium,
(A) Component: Chromium compound represented by the following general formula (1) CrX _n (1)
(In the formula (1), X represents an arbitrary organic group or inorganic group, a negative atom or an electron donating ligand, n represents an integer of 1 to 6, and when n is 2 or more, X is the same. (They may be different from each other. The valence of chromium is 0 to 6.)
The method for producing a low olefin polymer according to claim 1, comprising: A catalyst containing chromium,
(A) component: the chromium compound represented by the following general formula (1),
CrX _n (1)
(In the formula (1), X represents an arbitrary organic group or inorganic group, a negative atom or an electron donating ligand, n represents an integer of 1 to 6, and when n is 2 or more, X is the same. (They may be different from each other. The valence of chromium is 0 to 6.)
The olefin low-weight according to claim 1, which is a catalyst system comprising (B) component: one or more compounds selected from the group of amine, amide and imide, and (C) component: alkylaluminum compound. Manufacturing method of coalescence.   The method for producing an olefin low polymer according to any one of claims 1 to 3, wherein the support is an inorganic oxide solid. The method for producing an olefin low polymer according to any one of claims 1 to 4, wherein the catalyst further comprises a component (D) represented by the following general formula (2) or (3). .
[L] ⁺ · [M ¹ R ¹ R ² R ³ R ⁴ ] ⁻ (2)
M ² R ⁵ R ⁶ R ⁷⁻ (3)
(Wherein M ¹ and M ² are elements selected from Group IIIB, IVB, VB and VIB of the periodic table, R ^{1 to} R ⁷ are organic groups, inorganic groups or negative atoms, and [L] ⁺ is (Indicates a cation containing an element selected from Groups IA, VIIA, VIIIA, IB, and IIIB to VIB of the periodic table.)   The method for producing an olefin low polymer according to any one of claims 1 to 5, wherein the olefin low polymerization reaction is performed at a temperature lower than the melting point of the olefin polymer as a by-product.   The ratio of components collected by a sieve having an opening of 5.6 mm in the olefin polymer as a by-product is 10% by weight or less, according to any one of claims 1 to 6. The manufacturing method of the olefin low polymer of description.   The weight average molecular weight by GPC of the olefin polymer which is a by-product is 1 million or less, The method for producing an olefin low polymer according to any one of claims 1 to 7.   The method for producing an olefin low polymer according to any one of claims 1 to 8, wherein the olefin is ethylene and the olefin low polymer is mainly 1-hexene.   The carrier previously treated with a metal alkyl compound in the method for producing a low olefin polymer according to any one of claims 1 to 9, wherein at least one of the metal alkyl compound or a reaction product thereof is a component. A method for producing an olefin low polymer and an olefin copolymer, which is a particulate solid polymerization catalyst.   The method for producing an olefin low polymer and an olefin copolymer according to claim 10, wherein the particulate solid polymerization catalyst is a Ziegler catalyst or a metallocene catalyst.   The olefin low polymer according to claim 10 or 11, wherein the ratio of the low polymer having a polymerizable unsaturated bond in the olefin low polymerization reaction product excluding the olefin polymer is 70% by weight or more. And a method for producing an olefin copolymer.   The method for producing an olefin low polymer and an olefin copolymer according to any one of claims 10 to 12, wherein Mw / Mn by GPC of the produced olefin polymer is 10 or less.

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