JP6771946B2 - New solid-supported olefin polymerization catalyst and its production method - Google Patents

Description

The present invention relates to a novel solid-supported olefin polymerization catalyst and a method for producing the same.

Olefin (co) polymers and copolymers of olefins and polar monomers play a very important role as industrial materials. In particular, a copolymer of an olefin and a polar monomer is important because it is possible to design a molecule in which essential functions covered by additives such as adhesiveness, antioxidant function, and photostabilizing effect are directly linked to the polymer molecule. In order to efficiently produce this important (co) polymer and for the maintenance of the plant, it is desired that the polymer produced in the plant be obtained in the form of particles (Non-Patent Document 1). Olefin (co) polymers are produced in the form of particles using a Ziegler-based catalyst or a metallocene-supported catalyst, but are very expensive co-catalysts (methylaluminoxane) for catalyst activation and removal of toxic substances. , Organic aluminum compound and boron compound) are used in large quantities (see, for example, Non-Patent Document 1). Furthermore, since these polymerization catalysts are poisoned by polar monomers, it is not possible to produce copolymers of olefins and polar monomers (see, for example, Non-Patent Document 2). It is also known to use the bis (phenoxyimine) (FI) catalyst of the pre-cycle transition metal catalyst, but a relatively large amount of co-catalyst is required to detoxify the toxic substance, or with the olefin moiety. Only a copolymer with a polar monomer whose polar part is relatively separated can be synthesized, which limits the design of the polymer (see, for example, Non-Patent Document 3).

On the other hand, the recently discovered diimine-based complexes and bis (imino) pyridine-based complex catalysts having late-period transition metals such as nickel, palladium, iron, and cobalt as the central metal, which Brookhardt and Gibson et al. Have recently discovered, are expensive aids. It has also been reported that an olefin can be polymerized without using a catalyst, and that a copolymer of an olefin and a polar monomer can be produced (see, for example, Non-Patent Document 4). Further, there is a report that a particulate polymer can be produced by using a heterogeneous catalyst in which those catalysts are supported on a solid (see, for example, Non-Patent Documents 5 and 6).

Recently, by using phosphine-sulfonate-based palladium catalysts and phosphine-phenol-based catalysts for diimine-based catalysts and bis (imino) pyridine-based catalysts, olefin polymers and olefins / polarities with excellent mechanical and thermal properties There are reports that monomer copolymers are produced (see, for example, Non-Patent Document 7, Patent Documents 1 and 2). It has also been reported that a particulate olefin (co) polymer can be produced by supporting a phosphine-phenolic catalyst on a carrier that has been subjected to a specific treatment (see, for example, Patent Documents 3 and 4). ..

International Release 2010/050256 Special Table 2011-525211 Japanese Unexamined Patent Publication No. 2016-017134 Japanese Unexamined Patent Publication No. 2016-029170

Chem. Rev. 2005, Volume 105, p4073. Chem. Rev. 2000, Volume 100, p1479. J. Am. Chem. Soc. 2008, Volume 130, p17636. Chem. Rev. 2000, Volume 100, p1169. Maromocules, 2010, Vol. 43, p3624. Maromocules, 2002, Vol. 35, p6074. Chem. Rev. 2009, Vol. 109, p5215.

In order to obtain particulate (co) polymers, heterogeneous catalysts mainly supported on solids have been developed. However, for example, the polymer produced from the diimine-based supported catalyst described in Non-Patent Document 6 has many methyl branches, so that the melting point of the polymer is low. Further, for example, the catalysts reported so far as described in Patent Document 4, including the supported catalyst, do not necessarily have high copolymerizability and polymerization activity, and obtain a polymer chain having a high proportion of polar functional groups. Was not done. For this reason, there is a need for development of a technique for an olefin (co) polymerization catalyst for obtaining a particulate olefin (co) polymer having high copolymerizability and activity.
In such a situation, the problem to be solved by the present invention is an olefin (co) polymer for obtaining a particulate olefin (co) polymer, which has high copolymerizability and activity, is easy to handle, and is suitable for process production. It is an object of the present invention to provide a novel catalyst for production and a method for producing an olefin (co) polymer using the same.

As a result of diligent research, the present inventors have obtained copolymerizability and polymerization activity by using an olefin polymerization catalyst containing a catalyst mixture of a late-period transition metal having a specific structure and a solid carrier subjected to a specific treatment. We have found that it is possible to produce a particulate olefin (co) polymer with a high value, and have completed the present invention.

［式中、Ｚは、水素であり、ｍはＺの価数を表し、Ｅ^１は、リン、砒素又はアンチモンであり、Ｘ^１は、酸素又は硫黄であり、Ｒ^２及びＲ^３は、それぞれ独立に、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基又は基−Ｑ−Ｒ^ａを含有し、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基（ここで、Ｑは、ヘテロ原子を含有してもよい炭素数１〜２０の炭化水素基を表し、Ｒ^ａは、先に定義されたとおりである）であるか、又はＲ^２及びＲ^３は、互いに結合してＥ^１とともに環を形成していてもよく、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子、ハロゲン原子、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基、シアノ基、ニトロ基、又は基−Ｑ−Ｒ^ａであり、Ｒ^７は、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基であり、ただし、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６のうちの少なくとも１つは基−Ｑ−Ｒ^ａを含む置換基である］
で示される化合物と、周期表９族、１０族又は１１族に属する遷移金属Ｍを含む遷移金属化合物（Ｃ）とを含有する、前記［１］記載のオレフィン重合触媒である。
［３］前記金属触媒成分（２）が、下記一般式（Ｄ）：

［式中、Ｅ^１、Ｘ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、先に定義したとおりであり、Ｍは周期表９族、１０族又は１１族に属する遷移金属であり、Ｌ^１は、Ｍに配位することができるリガンドであり、Ｒ^１は、水素原子又はヘテロ原子を含有していてもよい炭素数１〜２０の炭化水素基である］
で示される金属錯体を含む、前記［２］記載のオレフィン重合触媒である。
［４］前記一般式（Ｄ）中、Ｍが、ニッケル、パラジウム、白金、コバルト又はロジウムである、前記［３］記載のオレフィン重合触媒である。
［５］前記固体担体（１）が、無機酸化物又はポリマー担体である、前記［１］〜［４］のいずれかに記載のオレフィン重合触媒である。
［６］Ｒ^ａが、ＯＲ^８、ＣＯ_２Ｒ^８、Ｃ（Ｏ）Ｎ（Ｒ^８）_２、Ｃ（Ｏ）Ｒ^８、ＳＲ^８、Ｐ（Ｒ^９）_２、ＮＨＲ^８、Ｎ（Ｒ^８）_２又はＳｉ（ＯＲ^８）_３−ｘ（Ｒ^８）_ｘ（ここで、Ｒ^８は、水素原子又は炭素数１〜１０の炭化水素基であり、Ｒ^９は、炭素数１〜１０の炭化水素基である）である、前記［１］〜［５］のいずれかに記載のオレフィン重合触媒である。
［７］固体担体（１）をＭ^１Ｒ^ｃ _３及びＢ（ＯＲ^ｂ）_ｎＲ^ｃ _３−ｎで処理する工程、及び、該処理された固体担体（１）を、金属触媒成分（２）で処理する工程を含む、前記［１］〜［６］のいずれかに記載のオレフィン重合触媒の製造方法である。
［８］固体担体（１）をＭ^１Ｒ^ｃ _３及びＢ（ＯＲ^ｂ）_ｎＲ^ｃ _３−ｎで処理する工程、該処理された固体担体（１）を、一般式（Ａ）又は（Ｂ）で示される化合物を接触させて混合物を調製する工程、及び、得られた該混合物に前記遷移金属化合物（Ｃ）を接触させる工程を含む、前記［１］〜［６］のいずれかに記載のオレフィン重合触媒の製造方法である。
［９］固体担体（１）をＭ^１Ｒ^ｃ _３で処理した後、更にＢ（ＯＲ^ｂ）_ｎＲ^ｃ _３−ｎで処理する工程を含む、前記［７］又は［８］記載のオレフィン重合触媒の製造方法である。
［１０］更に、前記［７］〜［９］のいずれか記載の方法で得られたオレフィン重合触媒を、α−オレフィンで予備重合する工程を含む、オレフィン予備重合触媒の製造方法である。
［１１］前記予備重合がルイス塩基の存在下で行われる、前記［１０］記載のオレフィン予備重合触媒の製造方法である。
［１２］前記α−オレフィンがエチレン又はプロピレンである、前記［１０］又は［１１］記載のオレフィン予備重合触媒の製造方法である。
［１３］前記［１］〜［６］のいずれかに記載のオレフィン重合触媒又は前記［７］〜［１２］のいずれか記載の方法により得られるオレフィン重合触媒若しくはオレフィン予備重合触媒の存在下、オレフィンを単独重合又は共重合する工程を含む、オレフィン重合体の製造方法である。
［１４］前記［１］〜［６］のいずれかに記載のオレフィン重合触媒又は前記［７］〜［１２］のいずれか記載の方法により得られるオレフィン重合触媒若しくはオレフィン予備重合触媒の存在下、オレフィンと（メタ）アクリル酸エステルを共重合する工程を含む、α−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法である。 That is, the present invention relates to the inventions of the following items.
[1] The compound represented by M ¹ R ^c ₃ and the compound represented by B (OR ^b ) _n R ^c _3-n (where M ¹ represents aluminum or boron, and R ^b and R ^c are respectively. Independently, a solid carrier (1) contacted with a hydrocarbon group having 1 to 20 carbon atoms and n representing an integer of 1 to 3), and
OR ⁸ , CO ₂ R ⁸ , CO ₂ M', C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , SO ₃ R ⁸ , P (O) (OR ⁸ ) _2-y (R ⁹ ) _y , P (OR ⁹ ) _3-x (R ⁹ ) _x , NHR ⁸ , N (R ⁸ ) ₂ , Si (OR ⁸ ) _3-x (R ⁸ ) _x , OSi (OR ⁸ ) _{3 ^{-x (R 8) x, SO}} 3 M ', PO 3 M' 2, PO 3 M ", P (O) (oR 9) 2 M ' and epoxy-containing group (wherein, ^{R 8} is a hydrogen atom or R ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms, M'represents an alkali metal, ammonium, quaternary ammonium or phosphonium, and M'represents alkaline soil. Represents a class metal, x represents an integer of 0 to 3, y represents an integer of 0 to 2), and has ^a reactive group Ra selected from the group consisting of Group 9, Group 10, or Group 11 of the Periodic Table. It is an olefin polymerization catalyst containing a metal catalyst component (2) containing a transition metal compound containing a transition metal M belonging to the group.
[2] The metal catalyst component (2) has the following general formula (A) or (B):

[In the formula, Z is hydrogen, m is the valence of Z, E ¹ is phosphorus, arsenic or antimony, X ¹ is oxygen or sulfur, and R ² and R ³ are respectively. Independently, a hydrocarbon group having 1 to 30 carbon atoms or a group −Q—R ^a which may contain a heteroatom and a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. (Here, Q represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and ^Ra is as defined above) or R ² and R ^{3 May} form a ring together with E ¹ by bonding to each other, and R ⁴ , R ⁵ and R ⁶ may independently contain a hydrogen atom, a halogen atom and a hetero atom, respectively. ~ 30 hydrocarbon groups, cyano groups, nitro groups, or groups −Q—R ^a , where R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, provided that At least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a substituent containing the group -Q-R ^a ].
The olefin polymerization catalyst according to the above [1], which contains the compound represented by (1) and the transition metal compound (C) containing the transition metal M belonging to Group 9, Group 10, or Group 11 of the periodic table.
[3] The metal catalyst component (2) has the following general formula (D):

[In the formula, E ¹ , X ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above, and M is in Group 9, Group 10, or Group 11 of the Periodic Table. The transition metal to which it belongs, L ¹ is a ligand capable of coordinating with M, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom].
The olefin polymerization catalyst according to the above [2], which comprises the metal complex represented by.
[4] The olefin polymerization catalyst according to [3] above, wherein M in the general formula (D) is nickel, palladium, platinum, cobalt or rhodium.
[5] The olefin polymerization catalyst according to any one of [1] to [4] above, wherein the solid carrier (1) is an inorganic oxide or polymer carrier.
[6] R ^a is OR ⁸ , CO ₂ R ⁸ , C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , P (R ⁹ ) ₂ , NHR ⁸ , N (R ^8). ) ₂ or Si (OR ⁸ ) _3-x (R ⁸ ) _x (Here, R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁹ is a hydrocarbon having 1 to 10 carbon atoms. The olefin polymerization catalyst according to any one of the above [1] to [5], which is a (hydrocarbon group).
[7] The step of treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , and the treated solid carrier (1) being subjected to the metal catalyst component (2). The method for producing an olefin polymerization catalyst according to any one of [1] to [6] above, which comprises the step of treating with.
[8] A step of treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , and the treated solid carrier (1) is subjected to the general formula (A) or (B). ), The step of contacting the transition metal compound (C) with the obtained mixture, and the step of contacting the transition metal compound (C) with the obtained mixture, according to any one of [1] to [6] above. This is a method for producing an olefin polymerization catalyst.
[9] The olefin polymerization according to the above [7] or [8], which comprises a step of treating the solid carrier (1) with M ¹ R ^c ₃ and then further treating with B (OR ^b ) _n R ^c _3-n. This is a method for producing a catalyst.
[10] Further, the method for producing an olefin prepolymerization catalyst, which comprises a step of prepolymerizing the olefin polymerization catalyst obtained by the method according to any one of [7] to [9] above with α-olefin.
[11] The method for producing an olefin prepolymerization catalyst according to the above [10], wherein the prepolymerization is carried out in the presence of a Lewis base.
[12] The method for producing an olefin prepolymerization catalyst according to the above [10] or [11], wherein the α-olefin is ethylene or propylene.
[13] In the presence of the olefin polymerization catalyst according to any one of [1] to [6] or the olefin polymerization catalyst or olefin prepolymerization catalyst obtained by the method according to any one of [7] to [12]. A method for producing an olefin polymer, which comprises a step of homopolymerizing or copolymerizing an olefin.
[14] In the presence of the olefin polymerization catalyst according to any one of [1] to [6] or the olefin polymerization catalyst or olefin prepolymerization catalyst obtained by the method according to any one of [7] to [12]. This is a method for producing an α-olefin / (meth) acrylic acid ester copolymer, which comprises a step of copolymerizing an olefin and a (meth) acrylic acid ester.

According to the present invention, an olefin (co) polymer having high activity and in the form of particles can be produced without using a large amount of an expensive cocatalyst, so that the olefin (co) polymer can be produced at low cost. Can be done.

One aspect of the present invention is a solid carrier in contact with a specific aluminum or boron compound M ¹ R ^c ₃ and a boron compound B (OR ^b ) _n R ^c _3-n containing an alkoxy group, and Group 9 of the Periodic Table. A olefin polymerization catalyst and a method for producing the same, which contains a transition metal M belonging to Group 10 or Group 11 and a metal catalyst component having ^a reactive group Ra. In addition, another aspect of the present invention is an olefin prepolymerization catalyst in which the polymerization catalyst is prepolymerized and a method for producing the same. Another aspect of the present invention is an α-olefin / (meth) acrylic acid ester obtained by copolymerizing an olefin polymer or an olefin with a (meth) acrylic acid ester, which is carried out in the presence of the polymerization catalyst or prepolymerization catalyst. This is a method for producing a copolymer.

Hereinafter, the constituent monomers of the polymer, the polymerization catalyst, the method for producing the polymerization catalyst, the polymerization method and the like will be described in detail. In the following description, the term "polymerization" is a general term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers, and is a general term when it is not necessary to distinguish between the two. Is simply described as "polymerization". Further, "(meth) acrylic acid" means acrylic acid or methacrylic acid (methacrylic acid).

1. 1. Constituent Monomer of Copolymer The olefin polymerization catalyst of the present invention can be homopolymerized or copolymerized with an α-olefin (a) as a monomer, or a combination of an α-olefin (a) and a (meth) acrylic acid ester (b). It is preferably used during polymerization.

(A) α-olefin The component (a), which is a monomer used for (co) polymerization, is an α-olefin represented by the general formula: CH ₂ = CHR ¹¹ . Here, R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branched, ring and / or unsaturated bond. When the number of carbon atoms of R ¹¹ is larger than 20, sufficient polymerization activity tends not to be exhibited. Therefore, preferred components (a) include α-olefins in which R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Further preferable components (a) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene and vinyl. Cyclohexene and styrene can be mentioned. In the polymerization, one kind of component (a) may be used alone, or a plurality of kinds of component (a) may be used in combination.

(B) (Meta) Acrylic Acid Ester The component (b), which is a monomer used for copolymerization, is a (meth) acrylic acid ester represented by the general formula: CH ₂ = C (R ¹² ) CO ₂ (R ¹³ ). Is. Here, R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branched, ring, and / or unsaturated bond. R ¹³ is a hydrocarbon group having 1 to 30 carbon atoms and may have a branched, ring, and / or unsaturated bond. Further, a hetero atom may be contained at an arbitrary position in R ¹³ . When the number of carbon atoms of R ¹² is at 11 or higher, there is a tendency that sufficient polymerization activity is not exhibited. Preferred (b) components include (meth) acrylic acid esters in which R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. More preferable component (b) includes a methacrylic acid ester in which R ¹² is a methyl group or an acrylic acid ester in which R ¹² is a hydrogen atom. Further, when the carbon number of R ¹³ exceeds 30, the polymerization activity tends to decrease. R ¹³ preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Further, examples of the heteroatom that may be contained in R ¹³ include oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, and boron. Of these heteroatoms, oxygen, silicon and fluorine are preferred, and oxygen is even more preferred. Further, R ¹³ may also be preferably used those that do not contain heteroatoms.

Further preferable components (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (Meta) nonyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate , (Meta) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, -2-aminoethyl (meth) acrylate, -2-methoxyethyl (meth) acrylate, -3-methoxypropyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) ethylene oxide, (meth) trifluoromethyl acrylate, (meth) -2-trifluoromethyl ethyl acrylate, (meth) perfluoroethyl acrylate, (meth) Examples thereof include acrylamide, (meth) acrylic dimethylamide, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. In the polymerization, one kind of component (b) may be used alone, or a plurality of kinds of component (b) may be used in combination.

2. Solid Carrier The solid carrier is composed of an inorganic or organic compound and usually has a particle size of 5 μm or more, preferably 10 μm or more, and usually 5 mm or less, preferably 2 mm or less. As the carrier that can be used, any carrier can be used as long as the gist of the present invention is not impaired. In general, inorganic oxides and polymer carriers can be preferably used. Specific examples of the inorganic oxide include metal oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , and SiO _2- Al. Examples thereof include mixed oxides such as ₂ O ₃ , SiO _2- V ₂ O ₅ , SiO _2- TiO ₂ , SiO _2- MgO, SiO _2- Cr ₂ O ₃ , inorganic silicates, or mixtures thereof. As the polymer carrier, a polyethylene carrier, a polypropylene carrier, a polystyrene carrier, a polyacrylic acid carrier, a polymethacrylic acid carrier, a polyacrylic acid ester carrier, a polyester carrier, a polyamide carrier, a polyimide carrier and the like can be used. As for these carriers, any carrier having a particle size in the above range is not particularly limited in terms of particle size distribution, pore volume, specific surface area, and the like, and any carrier can be used.

As specific examples of the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth and the like can be used. As these, synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clay and clay minerals include allophen groups such as allophen, kaolin groups such as dikite, nacrite, kaolinite and anokisite, halosite groups such as metahaloisite and halosite, and serpentine such as chrysotile, lizardite and antigolite. Smectite such as stones, montmorillonite, sauconite, biderite, nontronite, saponite, hectrite, vermiculite minerals such as vermiculite, mica minerals such as illite, serpentine, seagreen stone, attapargit, sepiolite, paigolskite, bentonite, wood section Examples include clay, gairome clay, hisingelite, vermiculite, and rhokuday stones. These may form a mixed layer. Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite and the like.

Of these specific examples, preferably, kaolins such as dikite, nacrite, kaolinite, and anokisite, halosites such as metahalosites and halosites, vermiculites such as chrysotile, lysardite, and antigolite, and montmorillonite. Examples include smectites such as zauconite, biderite, nontronite, saponite and hectrite, vermiculite minerals such as vermiculite, mica minerals such as illite, serpentine and seagreen stone, synthetic mica, synthetic hectrite, synthetic saponite and synthetic teniolite. Particularly preferably, smectites such as montmorillonite, zauconite, biderite, nontronite, saponite and hectrite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectrite, synthetic saponite and synthetic teniolite can be mentioned.

These carriers may be used as they are, but may be treated with acid such as hydrochloric acid, nitrate, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , dsm ₄ , ZnSO ₄ , Ti (SO). ₄ ) Salt treatment such as ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ may be performed. In the treatment, the corresponding acid and base may be mixed to form a salt in the reaction system for the treatment. Further, shape control treatment such as crushing and granulation and drying treatment may be performed.

3. 3. Aluminum or Boron Compound The polymerization catalyst of the present invention contains a solid carrier (1) in which M ¹ R ^c ₃ and B ¹ (OR ^b ) _n R ^c _3-n are brought into contact with the solid carrier. Here, M ¹ represents aluminum or boron, R ^b and R ^c each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3 carbon atoms. The metal M ¹ is preferably aluminum.

In specific R ^b and R ^c , the hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Here, examples of alkyl groups and cycloalkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , Decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl -2-Propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4 -Heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclo Dodecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, mentyl group, neomentyl group Examples thereof include a neopentyl group and a 5-decyl group. Methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group and octyl group are preferable.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group and a styryl group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group, and these aryl groups may have a substituent on the aromatic ring, and examples of possible substituents include. It is an alkyl group, an aryl group, a fusion aryl group, a phenylcyclohexyl group, a phenylbutenyl group, a trill group, a xsilyl group, a p-ethylphenyl group and the like. Among these, preferred substituents are a methyl group, an ethyl group, an isopropyl group, a butyl group and a phenyl group. These are examples and are not limited to these.

Specific examples of preferred ^M 1 ^R _{c 3,} trimethylaluminum (AlMe _3), triethyl aluminum _(AlEt 3: TEAL), triisobutylaluminum _{^{(Al i Bu 3: TIBA)}} , tri-n- octyl aluminum (TNOA) and the like Can be mentioned. From the viewpoint of availability and the like, triethylaluminum or triisobutylaluminum is more preferable.

Specific examples of preferred ^{_{B (OR b) n R c}} 3-n, BMe 2 BHT, BMeBHT 2, BEt 2 BHT, BEtBHT 2, B i Pr 2 BHT, B i PrBHT 2, BBu 2 BHT, BBuBHT 2, Bet ₂ (Oet), Bet (Oet) ₂ , Bet (O ⁱ Pr) ₂ , Bet ₂ (O ⁱ Pr), BBu ₂ (OEt), BBu (OEt) ₂ , BBu ₂ (O ⁱ Pr), BBu ( Examples thereof include O ⁱ Pr) ₂ , B (OMe) ₃ , B (OEt) ₃ , and B (OBu) ₃ . Here, Me is methyl, Et is ^ethyl, i Pr is an isopropyl group, Bu a butyl group (n- butyl group, isobutyl group), BHT is 2,6-di -t- butyl-4-methyl phenolate Represents a group. B (OEt) ₃ is more preferable from the viewpoint of availability.

As used herein, the term "contact" with a solid support means that at least a portion of the compound of interest, such as M ¹ R ^c ₃ or B (OR ^b ) _n R ^c _3-n , interacts with the surface of the solid carrier. It means forming an action. The actual state of interaction includes physical adsorption, electrostatic action, formation of covalent bond, coordination bond, etc., and is not particularly limited.
The solid carrier (1) to which M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n are contacted is changed to another functional group by a chemical reaction with the compound contacted with the functional group on the surface of the solid carrier. It is conceivable that the compound is in various states such as being substituted or the contacted compound being physically adsorbed on the surface of the solid support. Therefore, it is difficult to unambiguously specify the structure of the solid support (1) after contacting M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n . However, without being bound to a particular theory, by the surface of the solid support is taking such various conditions, the metal catalyst component having a reactive group R ^a (2) a solid support (1) It is thought that it can be supported on top. When M ¹ R ^c ₃ or B (OR ^b ) _n R ^c _3-n is not contacted, the functional groups on the surface of the solid carrier (1) have sufficient properties to support the metal catalyst component (2). It does not have, and the metal catalyst component (2) cannot be supported or becomes insufficient.

4. Metal catalyst component metal catalyst component (2) is the periodic table 9, having a transition metal compound containing a transition metal M which belongs to Group 10 or Group 11 (C), and a reactive group R ^a. Metal catalyst component (2) may contain a compound having a reactive group R ^a transition metal compound (C) containing a transition metal M, include a transition metal M and the compound having a reactive group R ^a May contain, and may be a mixture thereof.

<Metal type>
In the metal catalyst component (2), the transition metal M is a metal element belonging to Group 9, Group 10, or Group 11 of the periodic table, but preferably Group 10 nickel, palladium, platinum, Group 9 cobalt, and the like. It is rhodium, Group 11 copper, more preferably Group 10 nickel, palladium or platinum, and most preferably Group 10 nickel or palladium.
As the transition metal compound (C), a compound capable of reacting with a compound represented by the general formulas (A), (B) and the like described later to form a complex having a polymerizable ability is used. These may also be referred to as precursors, precursors.
For example, examples of the transition metal compound (C) containing nickel include Ni (COD) ₂ (COD: 1,5-cyclooctadiene), bis (cyclopentadienyl) nickel (II), and the general formula (CH ₂ CR ^17). CH _{2) 2 Ni,} may be used complexes represented by ^{_{Ni (CH 2 SiR 17 3)}} 2 L 1 or ^NiR _{17 2} ^L ₁ 2. Here, R ¹⁷ is a hydrocarbon group having 1 to 20 carbon atoms, OR ⁸ or CO ₂ R ⁸ , which may contain a hydrogen atom, a halogen atom, and a hetero atom, and L ¹ is coordinated to nickel. A ligand, R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
The transition metal compound (C) containing the transition metal M of group 9, group 10, or group 11 has a general formula: MR ¹⁷ _p L ¹ _q (where M is group 9, group 10, or 11 of the periodic table. Group transition metals, R ¹⁷ and L ¹ are as defined above, p and q are integers greater than or equal to 0 and are selected to satisfy the 18-electron rule of the transition metal complex). Can be used.

Among these transition metal compounds (C), those preferably used are complexes represented by bis (1,5-cyclooctadiene) nickel (0), general formula: (CH ₂ CR ¹⁷ CH ₂ ) ₂ Ni. general ^{_{formula: Ni (CH 2 SiR 17 3}} ) complex represented by ^{2 L} _{1 2,} the general ^formula: _NiR 17 in ^{2 L} ₁ of ₂ in complex represented (these ^formulas, R 17, ^{L 1} is previously (As defined in), Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ (where dba stands for dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ , (1). , 5-Cyclooctadiene) Pd (methyl) (chloride). Particularly preferably, bis (1,5-cyclooctadien) nickel (0), (CH ₂ CHCH ₂ ) ₂ Ni, (CH ₂ CMeCH ₂ ) ₂ Ni, Ni (CH ₂ SiMe ₃ ) ₂ (Py) ₂ ( Hereinafter, Py represents pyridine), Ni (CH ₂ SiMe ₃ ) ₂ (Lut) ₂ (hereinafter Lu represents 2,6-rutidine), NiPh ₂ (Py) ₂ (hereinafter Ph represents phenyl). , Ni (Ph) ₂ (Lut) ₂ , Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ , Pd (OCOCH ₃ ) ₂ , (1,5-cyclooctadien) Pd (methyl) ) (Chloride).

<Reactive group ^Ra >
The metal catalyst component (2) includes OR ⁸ , CO ₂ R ⁸ , CO ₂ M', C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , SO ₃ R ⁸ , P ( O) (OR ⁸ ) _2-y (R ⁹ ) _y , P (OR ⁹ ) _3-x (R ⁹ ) _x , NHR ⁸ , N (R ⁸ ) ₂ , Si (OR ⁸ ) _3-x (R ⁸⁾ ) _x, consisting _{^{OSi (oR 8) 3-x}} (R 8) x, SO 3 M ', PO 3 M' 2, PO 3 M ", P (O) (oR 9) 2 M ' and an epoxy-containing group is selected from the group, it includes reactive groups ^{R a.} wherein, ^{R 8} represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, ^{R 9} is a hydrocarbon group having 1 to 10 carbon atoms , M'represents alkali metal, ammonium, quaternary ammonium or phosphonium, M'represents alkaline earth metal, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. Of these, considering ligand and complex synthesis, ^Ra is OR ⁸ , CO ₂ R ⁸ , C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , P (R). ⁹ ) ₂ , NHR ⁸ , N (R ⁸ ) ₂ or Si (OR ⁸ ) _3-x (R ⁸ ) _x is preferable.

Examples of specific structures of ^Ra include -OH, -OMe, -CO ₂ H, -CO ₂ Me, -C (= O) NMe ₂ , -CHO, -C (= O) Me, -SH. , -SMe, -PPh ₂ , -NH ₂ , -NMe ₂ , and -Si (OMe) ₃ .

［式中、Ｚは、水素であり、ｍはＺの価数を表し、Ｅ^１は、リン、砒素又はアンチモンであり、Ｘ^１は、酸素又は硫黄であり、Ｒ^２及びＲ^３は、それぞれ独立に、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基又は基−Ｑ−Ｒ^ａを含有し、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基（ここで、Ｑは、ヘテロ原子を含有してもよい炭素数１〜２０の炭化水素基を表し、Ｒ^ａは、先に定義したとおりである）であるか、又はＲ^２及びＲ^３は、互いに結合してＥ^１とともに環を形成していてもよく、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子、ハロゲン原子、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基、シアノ基、ニトロ基、又は基−Ｑ−Ｒ^ａであり、Ｒ^７は、ヘテロ原子を含有していてもよい炭素数１〜３０の炭化水素基であり、ただし、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６のうちの少なくとも１つは基−Ｑ−Ｒ^ａを含む置換基である］
で示される化合物と、周期表９族、１０族又は１１族に属する遷移金属Ｍを含む遷移金属化合物（Ｃ）とを含有することが好ましい。 The metal catalyst component (2) has the following general formula (A) or (B): as a specific structure.

[In the formula, Z is hydrogen, m is the valence of Z, E ¹ is phosphorus, arsenic or antimony, X ¹ is oxygen or sulfur, and R ² and R ³ are respectively. Independently, a hydrocarbon group having 1 to 30 carbon atoms or a group −Q—R ^a which may contain a heteroatom and a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. (Here, Q represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and ^Ra is as defined above), or R ² and R ³ are. , They may be bonded to each other to form a ring together with E ¹ , and R ⁴ , R ⁵ and R ⁶ may independently contain a hydrogen atom, a halogen atom and a hetero atom, respectively. 30 hydrocarbon groups, cyano groups, nitro groups, or groups −Q—R ^a , where R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, provided that R ^At least one of ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a substituent containing the group −Q—R ^a ].
It is preferable to contain the compound represented by (C) and the transition metal compound (C) containing the transition metal M belonging to Group 9, Group 10, or Group 11 of the periodic table.

In the general formula (A) or (B), Z is a hydrogen atom.

Although the general formula (B) is expressed in the form of an anion, any counter cation can be used as long as it does not inhibit the reaction with the transition metal compound (C).

Specifically, as the counter cation, ammonium (NH ₄ ⁺ ), quaternary ammonium (R ¹⁵ ₄ N ⁺ ) or phosphonium (R ¹⁶ ₄ P ⁺ ) (where R ¹⁵ and R ¹⁶ have 1 carbon atoms). It is a hydrocarbon group of ~ 20, and R ¹⁵ and R ¹⁶ of each may be the same or different), and metal ions of Groups 1 to 14 of the Periodic Table can be mentioned. Of these, NH ₄ ⁺ , R ¹⁵ ₄ N ⁺ , R ¹⁶ ₄ P ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ are preferable, and more preferably R ¹⁵ ₄ N. ⁺ , Li ⁺ , Na ⁺ , K ⁺ .

In the general formula (A) or (B), X ¹ is an oxygen atom or a sulfur atom. Of these, an oxygen atom is preferred. E ¹ is a phosphorus atom, an arsenic atom or an antimony atom. Of these, the phosphorus atom is preferred. R ² and R ³ each independently contain a hydrocarbon group having 1 to 30 carbon atoms or a group −Q—R ^a, which may contain a heteroatom, and may contain a heteroatom. The number 1 to 30 hydrocarbon groups (where Q and ^Ra are as defined above) or R ² and R ³ are bonded to each other to form a ring with E ^1. You may. R ² and R ³ are in the vicinity of the transition metal M and interact sterically and / or electronically with the transition metal M. In order to exert such an effect, R ² and R ³ are preferably bulky substituents. The preferred carbon number of R ² and R ³ is 3 to 30, and more preferably 6 to 30.

The more specific structures of R ² and R ³ are linear hydrocarbon groups that may contain hydrogen atoms or heteroatoms, and branched hydrocarbons that may contain heteroatoms, respectively. Examples thereof include a group, an alicyclic hydrocarbon group which may contain a heteroatom, and an aryl group which may contain a heteroatom. As described above, since it is preferable that R ² and R ³ are bulky, an alicyclic hydrocarbon group which may contain a hetero atom or an aryl group which may contain a hetero atom may be contained. Is preferable, and an aryl group which may contain a hetero atom is most preferable. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is particularly preferable.

In R ² and R ³ , examples of the hetero atom contained in the hetero atom-containing group include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine, and boron. As the hetero atom contained in the hetero atom-containing group, one capable of coordinating with a transition metal is preferable. Specific examples of the heteroatom-containing group containing such a transition metal-possible heteroatom include the following.
That is, as the oxygen-containing group, an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a t-butoxy group, a phenoxy group, a p-methylphenoxy group and a p-methoxyphenoxy group. Examples thereof include an acyl group such as an aryloxy group, an acetyl group and a benzoyl group, an acetoxy group, an ethyl carboxylate group, a t-butyl carboxylate group, a carboxylate group such as a phenyl carboxylate group and the like.
Examples of the nitrogen-containing group include a dialkylamino group such as a dimethylamino group, a diethylamino group, a di-n-propylamino group and a cyclohexylamino group.
Examples of the sulfur-containing group include a thioalkoxy group such as a thiomethoxy group, a thioethoxy group, a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, a thio-t-butoxy group and a thiophenoxy group, and p-methylthio. Examples thereof include a thioaryroxy group such as a phenoxy group and a p-methoxythiophenoxy group.
Examples of the phosphorus-containing substituent include a dialkylphosphino group such as a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, and a cyclohexylphosphino group.
Examples of the selenium-containing group include a serenyl group such as a methylselenyl group, an ethylserenyl group, an n-propylserenyl group, an n-butylserenyl group, a t-butylserenyl group and a phenylserenyl group.
Among these, alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group, p-methylphenoxy group, p-methoxyphenoxy group and the like. Dialkylamino groups such as allyloxy group, dimethylamino group, diethylamino group, di-n-propylamino group, cyclohexylamino group, thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n Phioalkoxy groups such as -butoxy group, thio-t-butoxy group and thiophenoxy group, and thioaryroxy groups such as p-methylthiophenoxy group and p-methoxythiophenoxy group are preferable, and methoxy group, ethoxy group and n-propoxy Alkoxy groups such as groups, isopropoxy groups, n-butoxy groups and t-butoxy groups, and allyloxy groups such as phenoxy groups, p-methylphenoxy groups and p-methoxyphenoxy groups are more preferable.

When R ² or R ³ is an aryl group which may contain a heteroatom and the heteroatom-containing group is bonded to the aromatic skeleton of the aryl group, the heteroatom-containing group is the aromatic skeleton as a bonding mode. It may be attached directly to or to the aromatic skeleton via a spacer such as an alkylene group. When the heteroatom-containing group is bonded to the aromatic skeleton via the alkylene group, the number of carbon atoms is preferably one, that is, it is preferably a methylene group. The substitution position is preferably the ortho position with respect to the carbon bonded to E ¹ in the aromatic skeleton of R ² or R ³ . By doing so, the heteroatom of R ² or R ³ can be spatially arranged so as to interact with M.
Specific examples of preferred R ² and R ³ are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-. 2,6-dimethoxyphenyl group, 1,3-dimethoxy-2-naphthyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl Group, 4-t-butyl-2,6-diethoxyphenyl group, 1,3-diethoxy-2-naphthyl group, 2,6-diisopropoxyphenyl group, 2,4,6-triisopropoxyphenyl group, 4-Methyl-2,6-diisopropoxyphenyl group, 4-t-butyl-2,6-diisopropoxyphenyl group, 1,3-diisopropoxy-2-naphthyl group, 2,6-diphenoxyphenyl Group, 2,4,6-triphenoxyphenyl group, 4-methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group, 1,3-diphenoxy-2-naphthyl Group, 2,6-di (methoxymethyl) phenyl group, 2,4,6-tri (methoxymethyl) phenyl group, 4-methyl-2,6-di (methoxymethyl) phenyl group, 4-t-butyl- 2,6-di (methoxymethyl) phenyl group, 1,3-di (methoxymethyl) -2-naphthyl group, 2,6-di (ethoxymethyl) phenyl group, 2,4,6-tri (ethoxymethyl) Phenyl group, 4-methyl-2,6-di (ethoxymethyl) phenyl group, 4-t-butyl-2,6-di (ethoxymethyl) phenyl group, 1,3-di (ethoxymethyl) -2-naphthyl Group, 2,6-di (isopropoxymethyl) phenyl group, 2,4,6-tri (isopropoxymethyl) phenyl group, 4-methyl-2,6-di (isopropoxymethyl) phenyl group, 4-t -Butyl-2,6-di (isopropoxymethyl) phenyl group, 1,3-di (isopropoxymethyl) -2-naphthyl group, 2,6-di (phenoxymethyl) phenyl group, 2,4,6- Tri (phenoxymethyl) phenyl group, 4-methyl-2,6-di (phenoxymethyl) phenyl group, 4-t-butyl-2,6-di (phenoxymethyl) phenyl group, 1,3-di (phenoxymethyl) ) -2-Naftyl group and the like can be mentioned.

Of these, preferred are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-2,6- Dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl group, 4-t-butyl-2,6-diethoxyphenyl Group, 2,6-diisopropoxyphenyl group, 2,4,6-triisopropoxyphenyl group, 4-methyl-2,6-diisopropoxyphenyl group, 4-t-butyl-2,6-diiso Propoxyphenyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4-methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl Group, 2,6-di (methoxymethyl) phenyl group, 2,4,6-tri (methoxymethyl) phenyl group, 4-methyl-2,6-di (methoxymethyl) phenyl group, 4-t-butyl- 2,6-di (methoxymethyl) phenyl group, 2,6-di (ethoxymethyl) phenyl group, 2,4,6-tri (ethoxymethyl) phenyl group, 4-methyl-2,6-di (ethoxymethyl) ) Phenyl group, 4-t-butyl-2,6-di (ethoxymethyl) phenyl group, 2,6-di (isopropoxymethyl) phenyl group, 2,4,6-tri (isopropoxymethyl) phenyl group, 4-Methyl-2,6-di (isopropoxymethyl) phenyl group, 4-t-butyl-2,6-di (isopropoxymethyl) phenyl group, 2,6-di (phenoxymethyl) phenyl group, 2, Examples thereof include 4,6-tri (phenoxymethyl) phenyl group, 4-methyl-2,6-di (phenoxymethyl) phenyl group, 4-t-butyl-2,6-di (phenoxymethyl) phenyl group, and in particular. Preferred are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-2,6-dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl group, 4-t-butyl-2,6-diethoxyphenyl group, 2, 6-Diisopropoxyphenyl group, 2,4,6-triisopropoxyphenyl group, 4-methyl-2,6-diisopropoxyphenyl group, 4-t-butyl-2,6-diisopropoki Siphenyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4-methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group Can be mentioned.

R ⁴ , R ⁵ and R ⁶ each independently contain a hydrogen atom, a halogen atom and a hetero atom, which may contain a hydrocarbon group having 1 to 30 carbon atoms, a cyano group, a nitro group, or a group −Q−. it is an R ^a. In R ^{4 to} R ⁶ , examples of the hetero atom contained in the hetero atom-containing group include oxygen, silicon, and fluorine.
Among these, preferred as R ^4, R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom, chlorine atom, a halogen atom bromo atom, a methyl group, an ethyl group, an alkyl group such as isopropyl group, an aryl such as a phenyl group Perfluoroalkyl groups such as groups, trifluoromethyl groups, perfluoroaryl groups such as pentafluorophenyl groups, trialkylsilyl groups such as trimethylsilyl groups, alkoxy groups such as methoxy groups and ethoxy groups, allyloxy groups such as phenoxy groups, Examples thereof include a cyano group and a nitro group. Particularly preferred are hydrogen atom, fluorine atom, methyl group, phenyl group, trifluoromethyl group, pentafluorophenyl group, trimethylsilyl group, cyano group, nitro group and the like.

R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom. As for R ⁷ , a bulky substituent tends to give a high molecular weight polymer, so a bulky substituent is preferable. Therefore, the number of carbon atoms of R ⁷ is preferably 3 to 30. Specifically mentioned examples of R ^7, a hydrocarbon group, an isopropyl group, an isobutyl group, t- butyl group, a phenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 2-anthracenyl group, Examples thereof include a 9-anthrasenyl group, a 4-t-butylphenyl group, a 2,4-di-t-butylphenyl group, a 9-fluorenyl group, a cyclohexyl group, and the heteroatom-containing hydrocarbon group includes a trimethylsilyl group. Examples thereof include a triethylsilyl group, a tri-n-propylsilyl group, a triphenylsilyl group, a 2,6-difluorophenyl group, a 2,4,6-trifluorophenyl group, a pentafluorophenyl group and a carbazole group.
Among these, preferred ^{R 7,} t-butyl group, a phenyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4-di -t- butyl-phenyl Group, 9-fluorenyl group, cyclohexyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triphenylsilyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, penta Examples thereof include a fluorophenyl group and a carbazole group. Further, particularly preferable ones include a t-butyl group, a 9-anthrasenyl group, a trimethylsilyl group, a pentafluorophenyl group and a carbazole group.

In the general formula (A) or (B), at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a substituent containing the group −Q—R ^a . Here, ^Ra is as defined above.

In the group −Q—R ^a , Q represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. One of the two bonds of Q is bound to ^Ra . Specific examples of Q include −CH ₂ −, −CH ₂ CH ₂ −, − (CH ₂ ) ₃ − as hydrocarbon groups.
As mentioned as a hetero atom, an oxygen atom, a sulfur atom, and nitrogen atom, _-CH 2 _-O-CH 2 as a hydrocarbon group which may contain an oxygen atom _{-, - CH 2 - (O} -CH ₂ ) _2- , -CH _2- (O-CH ₂ ) _3- , -CH _2- O-CH ₂ CH _2- , -CH _2- (O-CH ₂ CH ₂ ) _2- , -CH _2- O −CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ −O−CH ₂ −, −CH ₂ CH ₂ −O−CH ₂ CH ₂ −, −CH ₂ CH ₂ −O−CH ₂ CH ₂ CH ₂ − Can be mentioned.
Further, as hydrocarbon groups which may contain sulfur atoms, -CH _2- S-CH ₂ CH _2- , -CH _2- (S-CH ₂ CH ₂ ) _2- , -CH ₂ CH ₂ -SCH ₂ CH ₂ −, −CH ₂ −S−CH ₂ CH ₂ CH ₂₋ can be mentioned.
Further, _-CH 2 _-N as a hydrocarbon group which may contain a nitrogen atom _{(CH 3) -CH 2 CH 2} -, - CH 2 - (N (CH 3) -CH 2 CH 2) 2 -, - CH ₂ CH ₂ −N (CH ₃ ) −CH ₂ CH ₂ −, −CH ₂ −N (CH ₃ ) −CH ₂ CH ₂ CH ₂ −.

When Q has a certain length, it tends to be easily supported on a carrier. Therefore, preferred Qs are −CH ₂ CH ₂ −, − (CH ₂ ) ₃ − hydrocarbon groups, −CH ₂ −O−CH ₂ CH ₂ −, −CH ₂ −O−CH ₂ CH ₂ CH. ₂ −, −CH ₂ CH ₂ −O−CH ₂ CH ₂ −, −CH ₂ CH ₂ −O−CH ₂ CH ₂ CH ₂ −. Further, as hydrocarbon groups that may contain sulfur atoms, -CH _2- S-CH ₂ CH _2- , -CH ₂ CH _2- S-CH ₂ CH _2- , -CH _2- S-CH ₂ CH ₂ CH _2- can be mentioned. Further, as a hydrocarbon group which may contain a nitrogen atom, -CH _2- N (CH ₃ ) -CH ₂ CH _2- , -CH ₂ CH _2- N (CH ₃ ) -CH ₂ CH _2- , -CH _2- N (CH ₃ ) -CH ₂ CH ₂ CH _2-

Further preferable Qs from the viewpoint of synthesizing the ligand or complex component are the hydrocarbon groups of −CH ₂ CH ₂ −, − (CH ₂ ) ₃ −, −CH ₂ −O−CH ₂ CH ₂ −, −. CH ₂ −O−CH ₂ CH ₂ CH ₂₋ can be mentioned. Further, examples of the hydrocarbon group which may contain a sulfur atom include -CH _2- S-CH ₂ CH _2- and -CH ₂ CH _2- S-CH ₂ CH _2- . Further, examples of the hydrocarbon group which may contain a nitrogen atom include -CH _2- N (CH ₃ ) -CH ₂ CH _2- .

Specific structures of the group −Q—R ^a include −CH ₂ CH ₂ OH, − (CH ₂ ) ₃ OH, −CH ₂ OCH ₂ CH ₂ OH, −CH ₂ OCH ₂ CH ₂ CH ₂ OH, − CH ₂ CH ₂ OMe,-(CH ₂ ) ₃ OMe, -CH ₂ OCH ₂ CH ₂ OMe, -CH ₂ OCH ₂ CH ₂ CH ₂ OMe, -CH ₂ CH ₂ CO ₂ H,-(CH ₂ ) ₃ CO ₂ H, -CH ₂ OCH ₂ CH ₂ CO ₂ H, -CH ₂ OCH ₂ CH ₂ CH ₂ CO ₂ , -CH ₂ CH ₂ CO ₂ Me,-(CH ₂ ) ₃ CO ₂ Me, -CH ₂ OCH ₂ CH ₂ CO ₂ Me, -CH ₂ OCH ₂ CH ₂ CH ₂ CO ₂ Me, -CH ₂ CH ₂ CONMe ₂ ,-(CH ₂ ) ₃ CONMe ₂ , -CH ₂ OCH ₂ CH ₂ CONMe ₂ , -CH ₂ OCH ₂ CH ₂ CH ₂ CONMe ₂ , -CH ₂ CH ₂ CHO,-(CH ₂ ) ₃ CHO, -CH ₂ CH ₂ COMe,-(CH ₂ ) ₃ COMe, -CH ₂ OCH ₂ CH ₂ COMe, -CH ₂ OCH ₂ CH ₂ CH ₂ COMe, -CH ₂ CH ₂ SH,-(CH ₂ ) ₃ SH, -CH ₂ SCH ₂ CH ₂ SH, -CH ₂ (SCH ₂ CH ₂ ) ₂ SH, -CH ₂ CH _2- SCH ₂ CH ₂ SH, -CH ₂ CH ₂ SMe,-(CH ₂ ) ₃ SMe, -CH ₂ SCH ₂ CH ₂ SMe, -CH ₂ CH ₂ SCH ₂ CH ₂ SMe, -CH ₂ CH ₂ PPh ₂ ,- (CH ₂ ) ₃ PPh ₂ , -CH ₂ OCH ₂ CH ₂ PPh ₂ , -CH ₂ OCH ₂ CH ₂ CH ₂ PPh ₂ , -CH ₂ CH ₂ NH ₂ ,-(CH ₂ ) ₃ NH ₂ , -CH ₂ N (CH ₃ ) CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NMe ₂ ,-(CH ₂ ) ₃ NMe ₂ , -CH ₂ N (CH ₃ ) CH ₂ CH ₂ NMe ₂ , -CH ₂ CH ₂ Si (OMe) ₃ ,-(CH ₂ ) ₃ Si (OMe) ₃ are listed. Is done.

Of these, the preferred ones are -CH ₂ CH ₂ OH,-(CH ₂ ) ₃ OH, -CH ₂ OCH ₂ CH ₂ OH, -CH ₂ CH ₂ OME,-(CH ₂ ) ₃ OME, -CH ₂ CH ₂ CO ₂ H,-(CH ₂ ) ₃ CO ₂ H, -CH ₂ OCH ₂ CH ₂ CO ₂ H, -CH ₂ OCH ₂ CH ₂ CH ₂ CO ₂ H, -CH ₂ CH ₂ CO ₂ Me,-(CH ₂ ) ₃ CO ₂ Me, -CH ₂ OCH ₂ CH ₂ CO ₂ Me, -CH ₂ OCH ₂ CH ₂ CH ₂ CO ₂ Me, -CH ₂ CH ₂ CONMe ₂ ,-(CH ₂ ) ₃ CONMe ₂ , -CH ₂ OCH ₂ CH ₂ CONMe ₂ , -CH ₂ OCH ₂ CH ₂ CH ₂ CONMe ₂ , -CH ₂ CH ₂ CHO,-(CH ₂ ) ₃ CHO, -CH ₂ CH ₂ COMe,-(CH ₂ ) ₃ COMe, -CH ₂ OCH ₂ CH ₂ COMe, -CH ₂ OCH ₂ CH ₂ CH ₂ COMe, -CH ₂ CH ₂ SH,-(CH ₂ ) ₃ SH, -CH ₂ SCH ₂ CH ₂ SH, -CH ₂ (SCH ₂₎ CH ₂ ) ₂ SH, -CH ₂ CH ₂ -SCH ₂ CH ₂ SH, -CH ₂ CH ₂ PPh ₂ ,-(CH ₂ ) ₃ PPh ₂ , -CH ₂ OCH ₂ CH ₂ PPh ₂ , -CH ₂ OCH ₂ CH ₂ CH ₂ PPh ₂ , -CH ₂ CH ₂ NH ₂ ,-(CH ₂ ) ₃ NH ₂ , -CH ₂ N (CH ₃ ) CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ Si (OMe) ₃ , − (CH ₂ ) ₃ Si (OMe) ₃ can be mentioned.

More preferably,-(CH ₂ ) ₃ OH, -CH ₂ OCH ₂ CH ₂ OH, -CH ₂ CH ₂ CO ₂ Me,-(CH ₂ ) ₃ CO ₂ Me, -CH ₂ CH ₂ CONMe ₂ ,- Examples thereof include (CH ₂ ) ₃ CONMe ₂ , -CH ₂ CH ₂ COMe,-(CH ₂ ) ₃ COMe, -CH ₂ CH ₂ Si (OMe) ₃ ,-(CH ₂ ) ₃ Si (OMe) ₃ .

In formula (A) and (B), the position of the group ^{-Q-R a} is not particularly limited, group ^{-Q-R a} is disposed a part of ^{R 2} or ^{R 3,} or as ^{R 5} or ^{R 6} It is preferable that it is arranged as a part of R ² or R ³ or as R ⁵ . A particularly preferred basic skeleton of R ² and R ³ is a phenyl group, but the group -Q-R ^a may be attached to the 2-position, 3-position or 4-position of the phenyl group. The preferred bond position is the 3- or 4-position of the phenyl group, and the more preferred bond position is the 4-position of the phenyl group.

Hereinafter, specific examples of the compound used as the compound represented by the general formula (A) or (B) are shown in Tables 1 to 5, but the present invention is not limited to the following examples. Here, Q ¹ =-(CH ₂ ) ₃ OH, Q ² = -CH ₂ OCH ₂ CH ₂ OH, Q ³ = -CH ₂ CH ₂ CO ₂ Me, Q ⁴ =-(CH ₂ ) ₃ CO ₂ Me , Q ⁵ = -CH ₂ CH ₂ CONMe ₂ , Q ⁶ =-(CH ₂ ) ₃ CONMe ₂ , Q ⁷ = -CH ₂ CH ₂ COMe, Q ⁸ =-(CH ₂ ) ₃ COMe, Q ⁹ = -CH ₂ CH ₂ Si (OMe) ₃ , Q ¹⁰ =-(CH ₂ ) ₃ Si (OMe) ₃ , Me is a methyl group, Ph is a phenyl group, and Carb is a carbazole group.

In order to understand the structure of the compound, the structural formulas and names of the compounds of compound number 7 shown in Table 1 above are shown. The compound having this structural formula is referred to as 2-bis (2,6-dimethoxyphenyl) phosphanyl-4- (3-butanone-1-yl) -6-pentafluorophenylphenol (B-195).

As the metal catalyst component (2), in addition to the compound represented by the general formula (A) or (B), a compound represented by the following general formulas (E), (F) and (G) may be used. Good. These are examples and are not limited to these.

In the above general formulas (E), (F), and (G), R ^{20 to} R ²⁶ are hydrocarbons having 1 to 30 carbon atoms which may independently contain a hydrogen atom, a halogen atom, and a hetero atom. Represents ^a group, a cyano group, a nitro group or a group −Q—R ^a . However, at least one of R ^{20 to} R ²⁶ is a substituent containing the group −Q—R ^a . Q and ^Ra are as defined above.

In R ^{20 to} R ²⁶ , preferred specific examples of the halogen atom are fluorine, chlorine and bromine. Of these, a more preferred halogen atom is chlorine.

In R ^{20 to} R ²⁶ , examples of the heteroatom which may be contained in the hydrocarbon group having 1 to 30 carbon atoms include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine and boron. Of these, oxygen, nitrogen, sulfur and silicon are preferred. Examples of the heteroatom-containing group containing these heteroatoms include an alkoxy group, an aryloxy group, an acyl group, an aroyl group, and a carboxylate group as oxygen-containing groups. Examples of the nitrogen-containing group include an amino group and an amide group. Examples of the sulfur-containing group include a thioalkoxy group and a thioaryroxy group. Examples of the phosphorus-containing substituent include a phosphino group. Examples of the selenium-containing group include a serenyl group. Examples of the silicon-containing group include a trialkylsilyl group, a dialkylarylsilyl group and an alkyldiarylsilyl group, and examples of the fluorine-containing group include a fluoroalkyl group and a fluoroaryl group. Examples of the boron-containing group include an alkylboron group and an arylboron group.

Specific examples of the heteroatom-containing group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group, p-methylphenoxy group and p-methylphenoxy group as oxygen-containing groups. -Methoxyphenoxy group, acetyl group, benzoyl group, acetoxy group, ethyl carboxylate group, t-butyl carboxylate group, phenyl carboxylate group and the like can be mentioned.
Examples of the nitrogen-containing group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a cyclohexylamino group and the like.
Sulfur-containing groups include thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n-butoxy group, thio-t-butoxy group, thiophenoxy group, p-methylthiophenoxy group, p- Examples thereof include a methoxythiophenoxy group.
Examples of the phosphorus-containing group include a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, a cyclohexylphosphino group and the like.
Examples of the selenium-containing group include a methylselenyl group, an ethylserenyl group, an n-propylserenyl group, an n-butylserenyl group, a t-butylserenyl group, a phenylserenyl group and the like.

In R ^{20 to} R ²⁶ , the hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Here, examples of alkyl groups and cycloalkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , Decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl -2-Propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4 -Heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclo Dodecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, mentyl group, neomentyl group It is a neopentyl group, a 5-decyl group, or the like. Among these, preferred substituents are an isopropyl group, an isobutyl group and a cyclohexyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group and a styryl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthrasenyl group and a fluorenyl group, and examples of substituents that can be present in the aromatic ring of these aryl groups include an alkyl group, an aryl group, a fused aryl group and a phenylcyclohexyl. A group, a phenylbutenyl group, a tolyl group, a xsilyl group, a p-ethylphenyl group and the like. Among these specific examples, a particularly preferable substituent is a methyl group, an ethyl group, and a phenyl group, and further particularly preferably a methyl group. These are examples, and it is self-evident that they are not limited to these.

［式中、Ｅ^１、Ｘ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、先に定義したとおりであり、Ｍは周期表９族、１０族又は１１族に属する遷移金属であり、Ｌ^１は、Ｍに配位することができるリガンドであり、Ｒ^１は、水素原子又はヘテロ原子を含有していてもよい炭素数１〜２０の炭化水素基である］
で示される金属錯体が含まれることが好ましい。一般式（Ｄ）で示される金属錯体は、例えば、一般式（Ａ）又は（Ｂ）で表される化合物と遷移金属Ｍを含む遷移金属化合物（Ｃ）との接触により得ることができる。 5. The metal complex metal catalyst component (2) contains the following general formula (D) as a component having both a reactive group and a transition metal element.

[In the formula, E ¹ , X ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above, and M is in Group 9, Group 10, or Group 11 of the Periodic Table. The transition metal to which it belongs, L ¹ is a ligand capable of coordinating with M, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom].
It is preferable that the metal complex represented by is contained. The metal complex represented by the general formula (D) can be obtained, for example, by contacting the compound represented by the general formula (A) or (B) with the transition metal compound (C) containing the transition metal M.

M is a transition metal belonging to Group 9, Group 10, or Group 11 of the periodic table, but is preferably Group 10 nickel, palladium, platinum, Group 9 cobalt, rhodium, and Group 11 copper, and further. Group 10 nickel, palladium and platinum are preferred, and Group 10 nickel or palladium is most preferred.

The valence of M is preferably divalent. Here, the valence of M means a formal oxidation number used in organometallic chemistry. That is, it refers to the number of charges remaining on the atom of an element when an electron pair in a bond involving an element is assigned to an element having a high electronegativity. For example, in the general formula (D), E ¹ is phosphorus, X ¹ is oxygen, M is nickel, R ¹ is a phenyl group, L ¹ is pyridine, and nickel is phosphorus, oxygen, carbon of phenyl group, nitrogen of pyridine. When forming a bond with, the formal oxidation number of nickel, that is, the valence of nickel, is divalent. Based on the above definitions, in these bonds, electron pairs are assigned to phosphorus, oxygen, carbon, and nitrogen, which have higher electronegativity than nickel, and the charges are 0 for phosphorus, -1 for oxygen, and-for phenyl groups. This is because the pyridine is 0 and the complex is electrically neutral as a whole, so that the charge remaining on nickel is +2. As the divalent transition metal, for example, nickel (II), palladium (II), platinum (II), cobalt (II) are preferable, and copper (I) or rhodium (III) is also preferably used other than divalent. Can be done.

R ¹ represents a hydrocarbon group which may contain a hydrogen atom or a hetero atom having 1 to 20 carbon atoms. Polymerization or copolymerization reaction by the binding of M and R ¹ is (a) alpha-olefin component or (b) (meth) acrylic acid ester component to insert is believed to be initiated. Therefore, if the carbon number of R ¹ is excessively large, this initiation reaction tends to be inhibited. Therefore, the preferred R1 is ^{1 to} 16 carbon atoms, and more preferably 1 to 10 carbon atoms.
Specific examples of R ¹ include hydride group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, n-octyl group and n-decyl group. Examples thereof include n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenyl group, p-methylphenyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group and the like.

L ¹ represents a ligand coordinated to M. Ligand L ¹ is a hydrocarbon compound having 1 to 20 carbon atoms having oxygen, nitrogen, and sulfur as atoms that can be coordinated. Further, as L ¹ , a hydrocarbon compound having a carbon-carbon unsaturated bond that can be coordinated to the transition metal (which may contain a hetero atom) can also be used. Preferably, L ¹ has 1 to 16 carbon atoms, and more preferably 1 to 10 carbon atoms. Further, as L ¹ to coordinate-bond with M in the general formula (D), a compound having no electric charge is preferable.

L ¹ forms a coordinate bond with M, but in order to promote the polymerization of (a) α-olefin component and the copolymerization of (a) α-olefin component and (b) (meth) acrylic acid ester component. , It is not necessary to use a compound that removes L ¹ from M.

In the so-called SHOP type metal complex, instead of L ^1, a phosphine, for example, be used trimethylphosphine and triphenylphosphine, it can be synthesized similar complexes with the present invention. However, when such a ligand is used, it is known that it is essential to use a compound that removes the ligand from the transition metal M as a scavenger in order to express the polymerizable ability of the olefin (for example, U.S.A. Klabunde et al., "J. Polymer. Sci .: Part A: Polymer. Chem.", 1987, Vol. 25, p. 1989). Known scavengers used for such purposes include Ni (COD) ₂ , B (C ₆ F ₅ ) ₃ , aluminoxans, and rhodium complexes.

Preferred L ^1, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters, aromatic Examples thereof include esters, amines, cyclic unsaturated hydrocarbons and the like. Further preferable L ¹ includes pyridines, cyclic ethers, aliphatic esters, aromatic esters, and cyclic olefins, and particularly preferable L ¹ is pyridine, lutidine (dimethylpyridine), picoline (methylpyridine). , R ⁹ CO ₂ R ⁸ (R ⁸ and R ⁹ are as defined above). In addition, R ¹ and L ¹ may be bonded to each other to form a ring. An example of such is the cycloocta-1-enyl group, which is also a preferred embodiment.

6. Polymerization catalyst The polymerization catalyst of the present invention contains the above-mentioned solid carrier (1) and metal catalyst component (2). Of these, a polymerization catalyst obtained by contacting the metal catalyst component (2) with the solid carrier (1) is preferable. Furthermore, coordinating compound and the solid support (1) a mixture obtained by contacting the transition metal compound constituting the metal catalyst component (2) having a reactive group R ^a which constitutes the metal catalyst component (2) (C ) polymerization catalyst is preferably obtained by contacting, as a compound having a reactive group R ^a, formula (a) or (B) a compound represented by the solid support (1) and more be contacted with preferable.
That is, one aspect of the present invention is a step of treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , and the treated solid carrier (1). The present invention relates to a method for producing an olefin polymerization catalyst, which comprises a step of treating with the metal catalyst component (2). In yet another aspect, the present invention comprises treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , the treated solid carrier (1). Production of an olefin polymerization catalyst, which comprises a step of contacting a compound represented by the general formula (A) or (B) to prepare a mixture, and a step of contacting the obtained mixture with the transition metal compound (C). Regarding the method. In yet another aspect, the present invention comprises the steps of treating the solid support (1) with M ¹ R ^c ₃ and then further with B (OR ^b ) _n R ^c _3-n for an olefin polymerization catalyst. Regarding the manufacturing method.

Further, the contact order of each component is not particularly limited. That is,
(1) A solid in which a coordinating compound having ^a reactive group R ^a and a transition metal compound (C) are brought into contact with each other, and then M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n are brought into contact with each other. It may be in contact with the carrier (1) or
(2) A transition metal after contacting a solid carrier (1) to which M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n have been contacted with a coordinating compound having ^a reactive group Ra. Compound (C) may be contacted or
(3) After the coordinating compound having the reactive group R ^a and the transition metal compound (C) are brought into contact with each other, M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n and a solid carrier are combined. You can contact them at the same time
(4) After contacting the coordinating compound having the reactive group R ^a with the transition metal compound (C) to isolate the metal complex represented by the general formula (D), M ¹ R ^c ₃ and B (OR ^b ) may be brought into contact with _n R ^c _3-n .
As an example of the coordinating compound having the reactive group Ra, ^a compound represented by the general formula (A) or (B) can be mentioned.

In addition, solids of inorganic oxides such as olefin polymers, silica, and alumina may coexist or be brought into contact with each other at the time of contact or after contact with each component of the catalyst. Further, the Lewis base described later may coexist or be brought into contact with each other at the time of contact with each component of the catalyst or after the contact. The contact pressure and time are not particularly limited, and the polymerization catalyst can be obtained in 1 second to 24 hours from pressurization to reduced pressure.

The contact may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. It is preferable to use these solvents that have been subjected to an operation for removing toxic substances such as water and sulfur compounds. The contact temperature is preferably between −20 ° C. and the boiling point of the solvent used, and particularly preferably between room temperature and the boiling point of the solvent used.
The ratio of each component of the catalyst is not particularly limited, but when an ion-exchange layered compound other than silicate or an inorganic silicate is used as the solid carrier, the transition metal compound is 0.0001 per 1 g of the solid carrier. 10 mmol, preferably 0.001 to 5 mmol, so that M ¹ R ^c ₃ or B (OR ^b ) _n R ^c _3-n is 0.001 to 10,000 mmol, preferably 0.01 to 100 mmol. By setting, suitable results can be obtained in terms of polymerization activity and the like. Further, the ratio of boron and aluminum in the transition metal M in the transition metal compound (C) and M ¹ R ^c ₃ or B (OR ^b ) _n R ^c _3-n is preferably 1: 0.1 to 100 in terms of molar ratio. Is preferably controlled so as to be 1: 0.5 to 50 in terms of polymerization activity and the like. The amount of Lewis base is 0.0001 equivalent to 1000 equivalent, preferably 0.1 equivalent to 100 equivalent, and more preferably 0.3 equivalent to 30 equivalent with respect to the transition metal M in the catalyst component.

The catalyst thus obtained may be used after being washed with an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, or xylene, or may be used without washing. Good. At the time of washing, if necessary, the above-mentioned M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n may be newly used in combination. The amounts of M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n used in this case are such that the ratio of boron to aluminum to the transition metal M in the transition metal compound (C) is 1: 0 in molar ratio. It is preferably 1 to 100.
Further, an olefin polymer may be produced via an olefin prepolymerization catalyst obtained by prepolymerizing the obtained catalyst with an α-olefin. That is, an olefin prepolymerization catalyst is obtained by prepolymerizing the obtained catalyst with α-olefin. The prepolymerization catalyst may be washed if necessary. This prepolymerization may be carried out in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene or xylene. The α-olefin used is preferably one having a small molecular weight, and specifically, ethylene or propylene is preferable. Further, when the olefin polymerization catalyst is prepolymerized, a Lewis base described later may be contained and prepolymerized with an α-olefin in the presence of the Lewis base. The obtained prepolymerization catalyst can be washed if necessary and used for the production of an olefin polymer.
That is, still another aspect of the present invention relates to a method for producing an olefin prepolymerization catalyst, which further comprises a step of prepolymerizing the olefin polymerization catalyst obtained by the above method with an α-olefin. In yet another aspect, the present invention relates to a method for producing an olefin prepolymerization catalyst in which the prepolymerization is carried out in the presence of a Lewis base. In yet another aspect, the present invention relates to a method for producing an olefin prepolymerization catalyst in which the α-olefin is ethylene or propylene.

The structure of the olefin prepolymerization catalyst after prepolymerization includes a polymer produced by prepolymerization as a part of the catalyst component as compared with that before prepolymerization, but the structure is uniquely defined. That is difficult. The polymerization catalyst or the polymerization catalyst component can be macroscopically analyzed as a component thereof, such as a metal component contained therein or a polymer species produced by prepolymerization. On the other hand, regarding the microstructure such as what part or partial structure of the prepolymerization catalyst selectively proceeds with prepolymerization, and as a result, what kind of catalyst part the prepolymerized polymer is unevenly distributed. Can take various morphologies, and it is difficult to specifically define the morphology of these microstructures using the current analytical techniques.

The polymerization catalyst of the present invention contains, for example, a compound represented by the general formula (A) or (B) and a transition metal compound (C) in ((A) + (B)) :( C) = 1:99. It can be obtained by contacting the mixture in an amount of ~ 99: 1 (molar ratio) in an organic solvent such as toluene or benzene at 0 to 100 ° C. for 1 to 86400 seconds under reduced pressure to pressurized pressure. When a toluene or benzene solution of Ni (COD) ₂ is used as the transition metal compound (C), the formation of the reaction product can be confirmed by changing the color of the solution from yellow to, for example, red.
After the reaction, the components constituting the transition metal compound (C) other than the transition metal of the transition metal compound (C) are the portions of the component represented by the general formula (A) excluding Z. Substitution by the component represented by the general formula (B) produces a metal complex represented by the general formula (D).
It is preferable that this substitution reaction proceeds quantitatively, but in some cases, it does not have to proceed completely. After completion of the reaction, other components derived from the starting material coexist in addition to the metal complex represented by the general formula (D), but these other components are removed when the polymerization reaction or copolymerization reaction is carried out. It may or may not be removed. In general, it is preferable to remove these other components because high activity can be obtained.

When carrying out the reaction may be allowed to coexist ligands L ¹ coordinated to the transition metal M. As the transition metal M, in the case of using a nickel or palladium, by the coexistence of L ¹ Lewis basic in the system, it is the stability of the metal complex represented by the generated general formula (D) is increased There, in such a case, as long as L ¹ does not inhibit the polymerization reaction or copolymerization reaction, it is preferable to coexist L ^1.

The reaction for preparing the metal complex represented by the general formula (D) is carried out in advance in a container different from the reactor used for the polymerization of the olefin and the copolymerization of the olefin and the (meth) acrylic acid ester, and then the reaction is carried out. The obtained metal complex represented by the general formula (D) may be subjected to polymerization of an olefin or copolymerization of an olefin with a (meth) acrylic acid ester, or the reaction may be carried out in the presence of these monomers. Good. Further, the reaction for preparing the metal complex represented by the general formula (D) may be carried out in a reactor used for polymerization of an olefin or copolymerization of an olefin and a (meth) acrylic acid ester. At this time, these monomers may or may not be present. Further, for the components represented by the general formula (A) or (B), a single component may be used, or a plurality of types of components may be used in combination. In particular, the combined use of these plurality of types is useful for the purpose of expanding the molecular weight distribution and the comonomer content distribution.

7. Olefin Polymerization The polymerization reaction using the catalyst of the present invention is not particularly limited in its polymerization form. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or a polymer produced in a monomer liquefied at high temperature and high pressure High-pressure ion polymerization or the like in which at least a part of the above is dissolved is preferably used. Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Further, it may be a living polymerization, or the polymerization may be carried out while causing chain transfer. Further, a so-called chain transfer agent (CSA) may be used in combination to perform chain shooting or coordinative chain transfer polymerization (CCTP).
The polymerization reaction involves hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, and methylcyclohexane, liquids such as liquefied α-olefin, and diethyl ether and ethylene glycol dimethyl ether. , Tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol and the like may be used in the presence or absence of polar solvents. Moreover, you may use the mixture of the liquid compound described here as a solvent. Further, ionic liquids can also be used as solvents. From the viewpoint of obtaining high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent and ionic liquid are more preferable.

The polymerization reaction can be carried out in the presence or absence of a known additive. As the additive, a polymerization inhibitor that prohibits radical polymerization and an additive that has an action of stabilizing the produced copolymer are preferable. For example, quinone derivatives, hindered phenol derivatives and the like are examples of preferable additives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of tetravalent titanium alcoxide and BHT, etc. Can be used. Inorganic and / or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers. Further, it may be used ligand L ¹ and the ionic liquid is as defined above as an additive.

Lewis bases are preferred additives. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylic acid ester can be improved. The amount of Lewis base is 0.0001 equivalent to 1000 equivalent, preferably 0.1 equivalent to 100 equivalent, and more preferably 0.3 equivalent, relative to the transition metal M in the catalyst component present in the polymerization system. ~ 30 equivalents. The method for adding the Lewis base to the polymerization system is not particularly limited, and any method can be used. For example, it may be added by mixing with the catalyst component of the present invention, may be added by mixing with a monomer, or may be added to the polymerization system independently of the catalyst component and the monomer. Moreover, you may use a plurality of Lewis bases in combination. Further, the same Lewis base as L1 according to the present invention may be used, or may be different.

Lewis bases include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters. , Aromatic esters, phosphates, phosphites, thiophenes, thianslens, thiazoles, oxazoles, morpholines, cyclic unsaturated hydrocarbons and the like. Of these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters and aromatic esters, and among them, preferred Lewis bases are pyridine derivatives, pyrimidine derivatives and piperidine. Derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, furan derivatives, aliphatic ester derivatives.

Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-rutidine, 2,4-rutidine, 3,5-rutidine, pyrimidine, N, N-dimethylaminopyridine, N-methylimidazole, 2, 2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tris (2-pyridyl) -S-triazine, quinoline, 8-methylquinolin, phenazine, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo- [5.4.0] -undeca-7-ene, 1,4 -Diazabicyclo- [2,2,2] -octane, triethylamine, benzonitrile, picolin, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholin, benzoxazole, benzothiazole, furan, 2,5- Dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrolidinophosphine, Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methyl butyrate, methyl salicylate, ethyl formate, ethyl butyrate, ethyl caproate, pentyl acetate, isopentyl acetate, pentyl valerate, pentyl butyrate, acetate Octyl, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) ) T-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate , (Meta) decyl acrylate, (meth) dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, diethylaminoethyl (meth) acrylate, -2-aminoethyl (meth) acrylate, -2-methoxyethyl (meth) acrylate, -3-methoxypropyl (meth) acrylate, (meth) acrylic Glycidyl acid acid, ethylene oxide (meth) acrylate, trifluoromethyl (meth) acrylate, -2-trifluoromethylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, (meth) acrylamide, (meth) Acrylic dimethylamide, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like can be mentioned.

Lewis acid is also mentioned as a preferred additive. By selecting an appropriate Lewis acid, the activity, molecular weight, and copolymerizability of the acrylic acid ester can be improved. The amount of Lewis acid is 0.0001 equivalent to 100 equivalents, preferably 0.1 equivalent to 50 equivalents, and more preferably 0.3 equivalents, relative to the transition metal M in the catalyst component present in the polymerization system. ~ 30 equivalents. The method for adding the Lewis acid to the polymerization system is not particularly limited, and any method can be used. For example, it may be added by mixing with the catalyst component of the present invention, may be added by mixing with a monomer, may be added to the polymerization system independently of the catalyst component or the monomer, or may be added to the monomer or the monomer. It may be added by mixing with a Lewis base. Moreover, you may use a plurality of Lewis acids in combination.

As the Lewis acid to be added, a modified Lewis acid produced by mixing with a monomer or a Lewis base may be used, but the order of mixing thereof is not particularly limited, and a monomer or a Lewis base may be added to the Lewis acid. However, Lewis acid may be added to the monomer or Lewis base.
The conditions for preparing the modified Lewis acid, for example, the contact pressure and the time are not particularly limited, and the modified Lewis acid can be obtained in 1 second to 24 hours under pressure and reduced pressure. The contact may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. It is preferable to use these solvents that have been subjected to an operation for removing toxic substances such as water and sulfur compounds. The contact temperature is preferably between −20 ° C. and the boiling point of the solvent used, and particularly preferably between room temperature and the boiling point of the solvent used.

The ratio of Lewis acid to the monomer or Lewis base is not particularly limited, but the molar ratio of Lewis acid to the monomer or Lewis base is 1: 0.5 to 10,000, preferably 1: 0.8 to 1,000. It is preferable to control the above in terms of polymerization activity and the like.
Specific examples of Lewis acid include trimethylaluminum, triethylaluminum, tripropylaluminum, trin-butylaluminum, triisobutylaluminum, trin-pentylaluminum, trin-octylaluminum, and trin-decylaluminum.

The unreacted monomer or medium may be separated from the produced copolymer and recycled for use. Upon recycling, these monomers and media may be purified and reused, or may be reused without purification. A conventionally known method can be used for separating the produced copolymer from the unreacted monomer and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, but usually, the optimum setting can be made from the following ranges in consideration of productivity and process capacity. That is, the polymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 250 MPa, and the polymerization time is 0.1 minutes. It can be selected from the range of 10 to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours. The polymerization is generally carried out in an inert gas atmosphere. For example, a nitrogen, argon or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. In addition, a small amount of oxygen or air may be mixed.

The supply of the catalyst and the monomer to the polymerization reactor is not particularly limited, and various supply methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to take a method in which a predetermined amount of monomer is supplied to the polymerization reactor in advance and a catalyst is supplied there. In this case, additional monomers and additional catalysts may be supplied to the polymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the polymerization reactor to carry out the polymerization reaction continuously.
Regarding the control of the composition of the copolymer, a method of supplying a plurality of monomers to the reactor and controlling by changing the supply ratio can be generally used. In addition, there are a method of controlling the copolymerization composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method of controlling the copolymerization composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. ..

A conventionally known method can be used for controlling the molecular weight of the polymer. That is, a method of controlling the polymerization temperature, a method of controlling the monomer concentration, a method of using a chain transfer agent, a method of controlling the ligand structure in the transition metal complex, and the like can be mentioned. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl and the like can be used.

When the (b) (meth) acrylic acid ester component itself is a kind of chain transfer agent, the ratio of the (b) (meth) acrylic acid ester component to the (a) α-olefin component and (b) The molecular weight can also be adjusted by controlling the concentration of the components. By controlling the ligand structure of the transition metal complex, in case of the molecular weight modifier, the kind of heteroatom-containing group in the R ^2, R ^3, several, or control the placement, bulk around the transition metal M or to place high substituent by or to introduce a heteroatom in R ⁶ described above, can be utilized tend to generally increase the molecular weight. It is preferable to arrange the electron donating group with respect to the transition metal M so that the electron donating group such as an aryl group or a heteroatom-containing substituent can interact with each other. Whether or not such an electron-donating group can interact with the metal M can be generally determined by measuring the distance between the electron-donating group and the metal M by a molecular model or molecular orbital calculation.

Since the copolymer of the present invention contains many monomer units having a polar group, it has good coatability, printability, antistatic property, inorganic filler dispersibility, and other resins due to the effect based on the polar group of the copolymer. Adhesiveness, compatibility with other resins, etc. are more strongly expressed. Taking advantage of these properties, the copolymer of the present invention can be used for various purposes. For example, it can be used as a film, a sheet, an adhesive resin, a binder, a compatibilizer, a wax and the like.

The present invention will be described in more detail in the following Examples and Comparative Examples, but the present invention is not limited thereto. In the following synthesis examples, unless otherwise specified, the operation was carried out in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxidized.

1. 1. Evaluation method (1) Weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution Mw / Mn:
It was determined by the following GPC measurement.
First, a sample (about 20 mg) was collected in a vial for the high-temperature GPC pretreatment device PL-SP260VS manufactured by Polymer Laboratory, and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L). Was added to adjust the polymer concentration to 0.1 wt%. The polymer was dissolved by heating to 135 ° C. in the above-mentioned pretreatment device for high temperature GPC PL-SP260VS, and filtered through a glass filter to prepare a sample. In the GPC measurement, no polymer was captured by the glass filter. Next, as a column, GPC measurement was performed using TSKgel GMH-HT (30 cm × 4) manufactured by Tosoh Corporation and GPCV2000 manufactured by Waters Co., Ltd. equipped with an RI detector. As the measurement conditions, the sample solution injection amount: about 520 μL, the column temperature: 135 ° C., the solvent: o-dichlorobenzene, and the flow rate: 1.0 mL / min were adopted. The molecular weight was calculated as follows. That is, using a commercially available monodisperse polystyrene as a standard sample, a calibration curve regarding the retention time and molecular weight is created from the polystyrene standard sample and the viscosity formula of the ethylene polymer, and the molecular weight is calculated based on the calibration curve. went. As the viscosity formula, [η] = K × M ^α is used, K = 1.38E ^-4 and α = 0.70 are used for polystyrene, and ethylene-based polymer is used. , K = 4.77E ^-4 , α = 0.70 was used.

(2) IR analysis:
The comonomer content ([RA]) was determined by IR measurement of the sample sheeted by hot pressing. At that time, the ethylene / acrylic ester copolymer is a value obtained by converting the area ratio of 1,740 to 1,690 cm ^-1 / 730 to 720 cm ^-1 using the following formula.
[RA] = 1.3503 (area ratio) -0.2208
(3) Measurement of polymer bulk density (BD): Measured according to JIS K 7365.

2. Synthesis of Ligand Synthesis Example 1: Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphanyl-4- (3-butanone-1-yl) -6-pentafluorophenylphenol ligand (B-195) [1] Synthesis of 1,3-dimethoxy-2-iodobenzene (2) 1,3-dimethoxybenzene (50 g, 0.36 mol) was dissolved in dehydrated tetrahydrofuran (500 mL). To this, an n-hexane solution of n-butyllithium (166 mL, 2.5 M, 0.42 mol) was gradually added at 0 ° C. under a nitrogen atmosphere. A solution of iodine (96.5 g, 0.38 mol) dissolved in dehydrated tetrahydrofuran (200 mL) was added dropwise to the solution obtained here at 0 ° C. over 40 minutes. The resulting solution was stirred at room temperature overnight. After completion, methanol (80 mL) was added dropwise, the obtained mixture was concentrated under reduced pressure, water (200 mL) was added, and the mixture was extracted 3 times with ethyl acetate (250 mL). The extract was washed with aqueous sodium thiosulfate and saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated to give 1,3-dimethoxy-2-iodobenzene (2) as a yellow solid (63 g). , 66% yield).

[2] Synthesis of bis (2,6-dimethoxyphenyl) phosphine chloride (3) Compound (2) (19.4 g, 73.5 mmol) was dissolved in dehydrated tetrahydrofuran (50 mL), and a solution of isopropylmagnesium chloride in tetrahydrofuran (36). (0.8 mL, 2.0 M, 73.6 mmol) was added slowly at −30 ° C. and the resulting mixture was stirred at 15 ° C. for 1 hour. The mixture was then cooled to −78 ° C. and phosphorus trichloride (5.0 g, 36.4 mmol) was slowly added thereto. The temperature was gradually raised to 15 ° C., the mixture was stirred at 15 ° C. for 1 hour, and then the solvent was removed by vacuum. Dehydrated tetrahydrofuran (150 mL) was added to the reaction intermediate containing the obtained bis (2,6-dimethoxyphenyl) phosphine chloride (3) and used in the next reaction.

[3] Synthesis of 4- (3,5-dibromo-4-hydroxyphenyl) -2-butanone (B-195_5) 4- (4-Hydroxyphenyl) -2-butanone (150 g, 0.91 mol) of acetone ( After adding sodium bromide (231 g, 2.25 mol) and Oxone (registered trademark) (monosulfate compound) (843 g, 1.37 mol) to a 1 L) / water (1 L) mixed solution at 0 ° C. under an argon atmosphere. , The mixture was stirred for 14 hours. The reaction mixture was filtered and the filtrate was washed with ethyl acetate (500 mL x 3). The filtrate and washing solution were concentrated under reduced pressure, and the obtained concentrate was extracted with ethyl acetate (800 mL × 3). The extract was dehydrated with anhydrous sodium sulfate and then filtered, and the filtrate was concentrated to obtain the target compound (B-195_5) (250 g, 0.78 mol, 86% yield).

[4] Synthesis of 2-methyl-2- (2- (3,5-dibromo-4-hydroxyphenyl) ethyl) -1,3-dioxalane (B-195_6) Compound (B-195_5) (430 g, 1. Trimethyl orthoformate (709 g, 6.68 mol) and p-toluenesulfonic acid (43 g, 0.20 mol) were added to a mixed solution of 34 mol) and ethylene glycol (415 g, 6.69 mol) at 15 ° C. under an argon atmosphere. The mixture was stirred for 14 hours. Saturated aqueous sodium hydrogen carbonate (500 mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (1 L × 3). The extract was dehydrated with anhydrous sodium sulfate, filtered, and then the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain the target compound (B-195_6) as a white solid (420 g, 1.15 mol, 86% yield). ..

[5] Synthesis of 2-methyl-2- (2- (3,5-dibromo-4- (methoxymethoxy) phenyl) ethyl) -1,3-dioxalane (B-195_7) Sodium hydride (54.4 g, Compound (B-195_6) (246 g, 0.67 mol) was added to a suspension of dehydrated tetrahydrofuran (500 mL) of 1.36 mol (40 wt% of mineral oil) at 0 ° C. in an argon atmosphere, and then the mixture was stirred for 1 hour. Chloromethyl methyl ether (112 g, 1.39 mol) was added at 0 ° C. under an argon atmosphere, and the mixture was stirred for 4 hours. After adding ice water (500 mL) to the mixture, the mixture was extracted with ethyl acetate (500 mL × 3). The obtained extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain the target compound (B-195_7) as a colorless transparent liquid (250 g, 0.61 mol, 90% yield). ).

[6] 2-Methyl-2- (2- (3-bromo-4- (methoxymethoxy) -5-bis (2,6-dimethoxyphenyl) phosphanylphenyl) ethyl) -1,3-dioxalane (B-) Synthesis of 195_8) n-hexane solution of n-butyllithium (29.4 mL, 2.) in dehydrated tetrahydrofuran (75 mL) solution of compound (B-195_7) (30.2 g, 73.6 mmol) at -78 ° C. 5M, 73.5 mmol) was added dropwise and the mixture was stirred for 1 hour. The solution (73.5 mmol) of the compound (3) obtained in [2] was added dropwise to the reaction mixture cooled to −78 ° C., the temperature was gradually raised to 15 ° C., and the mixture was stirred for 14 hours. Ice water (100 mL) was added to the reaction mixture, and the mixture was extracted with methylene chloride (150 mL × 3). The extract was washed with saturated brine (50 mL) and then dehydrated with anhydrous sodium sulfate. The dehydrated extract was concentrated, and the obtained crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain the target compound (B-195_8) as a colorless transparent liquid (15). .0 g, 23.6 mmol, 32% yield).

[7] 2-Methyl-2- (2- (3- (pentafluorophenyl) -4- (methoxymethoxy) -5-bis (2,6-dimethoxyphenyl) phosphanylphenyl) ethyl) -1,3- Synthesis of dioxalane (B-195_9) n-hexane solution of n-butyllithium (5.) in dehydrated tetrahydrofuran (40 mL) solution of compound (B-195_8) (8.0 g, 12.6 mmol) at −78 ° C. in an argon atmosphere. 0 mL, 2.5 M, 12.5 mmol) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. Hexafluorobenzene (7.7 g, 41.4 mmol) was added dropwise to the reaction mixture at −78 ° C., the temperature was gradually raised to 15 ° C., and the mixture was stirred for 14 hours. Ice water (50 mL) was added to the reaction mixture, and the mixture was extracted with methylene chloride (75 mL × 3). The extract was washed with saturated brine (50 mL) and then dehydrated with anhydrous sodium sulfate. The dehydrated extract was concentrated, and the obtained crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain the target compound (B-195_9) as a colorless liquid (4). 0.0 g, 5.5 mmol, 44% yield).

[8] Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphanyl-4- (3-butanone-1-yl) -6-pentafluorophenylphenol ligand (B-195) Compound (B-195_9) An ethyl acetate solution of hydrogen chloride (4M, 40 mL) was added to a solution of (4.0 g, 5.5 mmol) in ethyl acetate (20 mL) at 0 ° C. under an argon atmosphere. The mixture was gradually heated to 25 ° C. and stirred for 1 hour. Saturated aqueous sodium hydrogen carbonate (50 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (60 mL × 2). The extract was washed with saturated aqueous sodium chloride solution (30 mL) and then dehydrated with anhydrous sodium sulfate. The dehydrated extract is concentrated under reduced pressure, and the obtained crude product is purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5/1) to obtain the target compound (B-195) as a white powder. (1.3 g, 2.1 mmol, 38% yield).
^{1 1} HNMR (C ₆ D ₆ , δ, ppm): 7.72 (dd, J = 14.0, 2.0 Hz, 1H), 7.73 (s, 1H), 6.99 (t, J = 8) .4Hz, 2H), 6.89 (s, 1H), 6.20 (dd, J = 8.4, 2.4Hz, 4H), 3.17 (s, 12H), 2.73 (t, J) = 7.6Hz, 2H), 2.16 ( t, J = 7.6Hz, 2H), 1.55 (s, 3H); 31 PNMR (C 6 D 6, δ, ppm): - 58.4 ( s).

Synthesis Example 2: 2- (2,6-dimethoxyphenyl) (2,6-diphenoxyphenyl) phosphanyl-4- (3-butanone-1-yl) -6-pentafluorophenylphenol ligand (B-203) (1) 2-Methyl-2- (2- (3-bromo-4- (methoxymethoxy) -5- (2,6-dimethoxyphenyl) (2,6-diphenoxyphenyl) phosphanylphenyl) Synthesis of (ethyl) -1,3-dioxalane (B-203_11A) (1-1) 1,3-Dimethoxy-2-iodobenzene (13.2 g, 50.0 mmol) was dissolved in dehydrated tetrahydrofuran (60 mL) and isopropyl. A solution of magnesium chloride in tetrahydrofuran (25.0 mL, 2.0 M, 50.0 mmol) was gradually added at −30 ° C., and the obtained mixture was stirred at 15 ° C. for 1 hour. The mixture was then cooled to −78 ° C., phosphorus trichloride (8.40 g, 61.2 mmol) was added thereto, and the mixture was further stirred for 1 hour. Then, after removing the solvent and excess phosphorus trichloride in a vacuum, dehydrated tetrahydrofuran (80 mL) was added to the residue and used for the next reaction.
(1-2) A solution of 1,3-diphenoxybenzene (13.1 g, 49.9 mmol) in dehydrated tetrahydrofuran (40 mL) at 0 ° C. in an argon atmosphere with an n-hexane solution of n-butyllithium (20.0 mL, 2). .50 M, 50.0 mmol) was added dropwise, and then the temperature was gradually raised to 15 ° C. and stirred for 2 hours. The mixed solution was added dropwise to the tetrahydrofuran solution obtained in (1-1) at −78 ° C., the temperature was gradually raised to 15 ° C., and the mixture was stirred for 1 hour.
(1-3) 2-Methyl-2- (2- (3,5-dibromo-4- (methoxymethoxy) phenyl) ethyl) -1,3-dioxalane (B-195_7) (20.5 g, 50.0 mmol) ) Was added dropwise to the dehydrated tetrahydrofuran (50 mL) solution of n-butyllithium in n-hexane (20.0 mL, 2.50 M, 50.0 mmol) at −78 ° C. under an argon atmosphere, and the mixture was further stirred for 1 hour. The mixture was added dropwise to the solution of the mixture obtained in (1-2) at −78 ° C., the temperature was gradually raised to 15 ° C., and the mixture was stirred for 16 hours. After adding ice water (300 mL) to the reaction mixture, the organic solvent was distilled off under reduced pressure and extracted with ethyl acetate (150 mL × 3). The extract was washed with saturated brine (300 mL), dehydrated with anhydrous sodium sulfate, and filtered. Then, the filtrate was concentrated, and the obtained crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20/1) to obtain the target compound (B-203_11A) as a white solid (13). 8.8 g, 18.2 mmol, 36% yield).

[2] 2-Methyl-2- (2- (3- (pentafluorophenyl) -4- (methoxymethoxy) -5- (2,6-dimethoxyphenyl) (2,6-diphenoxyphenyl) phosphanylphenyl ) Ethyl) -1,3-Dioxalan (B-203_12A) Synthesis Compound (B-203_11A) (13.8 g, 18.2 mmol) in dehydrated tetrahydrofuran (50 mL) solution in an argon atmosphere at −78 ° C. to n-butyllithium The n-hexane solution (7.3 mL, 2.5 M, 18.3 mmol) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. Hexafluorobenzene (12.5 g, 67.2 mmol) was added dropwise thereto, and then the temperature was gradually raised to 15 ° C. and the mixture was stirred for 16 hours. After adding ice water (100 mL) to the reaction mixture, the organic solvent was distilled off under reduced pressure. The residue was extracted with ethyl acetate (150 mL x 3). The extract was washed with saturated brine (150 mL), dehydrated with anhydrous sodium sulfate, and filtered. The filtrate was concentrated and the obtained crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20/1) to obtain the target compound (B-203_12A) as a white solid (9. 50 g, 11.2 mmol, 62% yield).

(3) 2- (2,6-dimethoxyphenyl) (2,6-diphenoxyphenyl) phosphanyl-4- (3-butanone-1-yl) -6-pentafluorophenylphenol ligand (B-203) Synthesis of compound (B-203_12A) (0.403 g, 0.486 mmol) was added dropwise to a solution of ethyl acetate (8 mL) in an ethyl acetate solution (4M, 15 mL) of hydrogen chloride at 0 ° C. under an argon atmosphere. The mixture was gradually heated to 25 ° C., stirred for 1 hour, and then the organic solvent was distilled off under reduced pressure. Saturated sodium hydrogen carbonate water (30 mL) was added to the obtained residue, and then the mixture was extracted with ethyl acetate (30 mL × 2). The extract was washed with saturated aqueous sodium chloride solution (30 mL), dehydrated with anhydrous sodium sulfate, and filtered. When the filtrate was concentrated under reduced pressure, the target compound (B-203) was obtained as a white powder (0.36 g, 0.474 mmol, 98% yield).
^{1 1} HNMR (CDCl ₃ , δ, ppm): 7.68 (s, 1H), 7.64 (dd, J = 13.2,2.0 Hz, 1H), 6.99-6.94 (m, 4H) ), 6.90 (t, J = 8.4Hz, 1H), 6.80-6.71 (m, 8H), 6.50 (dd, J = 8.0, 2.8Hz, 2H), 6 .09 (dd, J = 8.0, 2.8Hz, 2H), 3.17 (s, 6H), 2.53 (t, J = 7.6Hz, 2H), 1.98 (t, J = 7.6 Hz, 2H), 1.53 (s, 3H); ³¹ NMR (CDCl ₃ , δ, ppm): −59.2 (s).

Preparation of Polymerization Catalyst 1 Preparation of Solid Carrier 1: 1.03 g of silica (Grace Grace 948) was collected and 4 mL of toluene was added thereto. Thereafter, stirring was added ^Al i Bu ₃ in toluene (0.4 M, 5.0 mL, 2.0 mmol) at room temperature with and allowed to react for 1 hour. To a mixture obtained, a toluene solution of B (OEt) ₃ (0.245 M, 8.2 mL, 2.0 mmol) was added at room temperature with stirring, and the mixture was stirred at 70 ° C. for 1 hour. The toluene solution containing silica was washed with 20 mL of toluene three times and then dried under reduced pressure to obtain 1.10 g of solid support 1.
Preparation of Polymerization Catalyst 1: A toluene solution (5.0 mL) of B-195 (0.20 mmol) was added to a solid carrier, and the mixture was stirred at room temperature for 30 minutes. To this, 5.0 mL of a toluene solution of Ni (COD) ₂ (55.0 mg, 0.20 mmol) was added, and the mixture was stirred at 60 ° C. for 1 hour. After washing 3 times with 20 mL of toluene and 2 times with 20 mL of hexane, the mixture was dried under reduced pressure to obtain 1.20 g of the polymerization catalyst 1.

Preparation of polymerization catalyst 2 Preparation of solid support 2: 1.01 g of silica (Grace Grace 948) was collected, and 4 mL of toluene was added thereto. Thereafter, stirring was added ^Al i Bu ₃ in toluene (0.4 M, 5.0 mL, 2.0 mmol) at room temperature with and allowed to react for 1 hour. To a mixture obtained, a toluene solution of B (OEt) ₃ (0.410M, 4.9 mL, 2.0 mmol) was added at room temperature with stirring, and the mixture was stirred for 1 hour. The toluene solution containing silica was washed with 20 mL of toluene three times and then dried under reduced pressure to obtain 1.10 g of solid support 2.
Preparation of Polymerization Catalyst 2: To a solid support 2 (1.10 g) was added a toluene solution (5.0 mL) of B-195 (0.20 mmol), and the mixture was stirred at room temperature for 30 minutes. To this, 5.0 mL of a toluene solution of Ni (COD) ₂ (55.0 mg, 0.20 mmol) was added, and the mixture was stirred at 60 ° C. for 1 hour. After washing 3 times with 20 mL of toluene and 2 times with 20 mL of hexane, the mixture was dried under reduced pressure to obtain 1.18 g of the polymerization catalyst 2.

Preparation of Polymerization Catalyst 3 Preparation of Polymerization Catalyst 3: With a toluene solution of B (OEt) ₃ (0.410M, 4.0 mL, 2.0 mmol) and a toluene solution of B-195 (0.20 mmol) (5.0 mL). Was mixed and stirred at room temperature for 30 minutes. The obtained solution and solid carrier 1 (1.12 g) are mixed and stirred at room temperature for 30 minutes, and then 5.0 mL of a toluene solution of Ni (COD) ₂ (55.0 mg, 0.20 mmol) is added to room temperature. Was stirred for 30 minutes. After washing 3 times with 20 mL of toluene and 2 times with 20 mL of hexane, the mixture was dried under reduced pressure to obtain 1.18 g of the polymerization catalyst 3.

Preparation of adjusting polymerization catalyst 4 of the polymerization catalyst 4: Solid support 2 (1.11 g) in a toluene solution of B-195 (0.20mmol) to (5.0 mL) was added and stirred for 30 minutes at room temperature. To the obtained mixture, 5.0 mL of a toluene solution of Ni (COD) ₂ (55.0 mg, 0.20 mmol) was added, and the mixture was stirred at 60 ° C. for 1 hour. After washing 3 times with 20 mL of toluene and 2 times with 20 mL of hexane, the mixture was dried under reduced pressure to obtain 1.19 g of the polymerization catalyst 4.
Preparation of prepolymerization catalyst 4: Dry hexane (200 mL), hexane solution of tri-n-octyl aluminum (0.1 M, 1 mL, 0.1 mmol), n-butyl acrylate (nBA) in an induction stirring autoclave with an internal volume of 2 L. (0.2 mmol) was introduced. After heating to 40 ° C., ethylene (0.1 MPa) was introduced and the polymerization catalyst 4 (1.0 g) was added. Ethylene was introduced at 0.1 MPa each time the pressure of ethylene became 0, and the process was repeated 4 times in total. By this operation, a prepolymerization catalyst 4 containing 6.63 g of polyethylene per 1 g of the polymerization catalyst was obtained.

Preparation of Polymerization Catalyst 5 Preparation of Solid Carrier 3: 1.02 g of silica (Grace Grace 948) was collected and 4 mL of toluene was added thereto. Then, a toluene solution of AlEt ₃ (0.4M, 5.0 mL, 2.0 mmol) was added at room temperature with stirring, and the mixture was reacted for 1 hour. To the mixture was added a toluene solution of B (OEt) ₃ (0.245 M, 8.2 mL, 2.0 mmol) at room temperature with stirring and stirred for 1 hour. The toluene solution containing silica was washed 3 times with 20 mL of toluene and then dried under reduced pressure to obtain 1.09 g of solid support 3.
Preparation of Polymerization Catalyst 5: A toluene solution (8.0 mL) of B-203 (0.20 mmol) was added to the solid support 3 (1.09 g), and the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 5.0 mL of a toluene solution of Ni (COD) ₂ (55.0 mg, 0.20 mmol) was added, and the mixture was stirred at 60 ° C. for 1 hour. After washing 3 times with 20 mL of toluene and 2 times with 20 mL of hexane, the mixture was dried under reduced pressure to obtain 1.12 g of the polymerization catalyst 5.

[Examples 1 to 7]
Copolymerization of ethylene / acrylic acid ester using polymerization catalysts 1 to 5 and homopolymerization of ethylene

(1) Copolymerization of ethylene / acrylic acid ester [Examples 1 to 5]
Dry hexane (0.6 L) and a predetermined amount of acrylic acid ester as a conomonomer were introduced into an induction stirring autoclave having an internal volume of 2 L. After raising the temperature of the autoclave to 90 ° C. with stirring, ethylene was supplied to the autoclave at 3.0 MPa. After completion of the adjustment, a hexane slurry of a polymerization catalyst was supplied to initiate copolymerization. After polymerizing for 1 hour, the unreacted gas was removed, and then the autoclave was opened, and filtration, solvent washing, and heat drying were performed to obtain a copolymer.

The types and amounts of comonomer used in the copolymerization are shown in Table 6. The comonomer was used after purification at room temperature in a high-purity nitrogen atmosphere using a column packed with Aldrich Inhibitor Remover manufactured by Aldrich.

[Comparative Examples 1 and 2]
In Comparative Example 1, Al ⁱ Bu ₂ (OEt) was used instead of Al ⁱ Bu ₃ , and a polymerization catalyst 6 was obtained in the same manner as the polymerization catalyst 1 except that triethoxyboron was not used. In Comparative Example 2, a polymerization catalyst 7 was obtained in the same manner as the polymerization catalyst 1 except that triisopropoxyaluminum was used instead of triethoxyboron. Ethylene / acrylic acid ester copolymerization was carried out in the same manner as in Example 1. In Comparative Example 1, the amount of catalyst was 260 mg, and in Comparative Example 2, the amount of catalyst was 130 mg.

From Table 6, by comparing Examples 1 to 5 and Comparative Examples 1 and 2, the polymerization catalyst of the present invention can obtain a polymer having high copolymerizability, relatively high polymerization activity, and a good particle state. It turns out that it can be done. In Comparative Example 1 using an aluminum compound having an alkoxy group, sufficient activity could not be obtained. In Comparative Example 2 in which the boron compound was not used, the content of butyl acrylate as a comonomer was reduced.

(2) Ethylene homopolymerization [Examples 6 and 7]
A hexane solution of dry hexane (1 L) and tri-n-octyl aluminum (0.01 mL, 1 mL) was introduced into an induction stirring autoclave having an internal volume of 2 L. After raising the temperature of the autoclave to 70 ° C. with stirring, ethylene was supplied to the autoclave at 3.0 MPa. After completion of the adjustment, a hexane slurry of a polymerization catalyst was supplied to start the polymerization. After polymerizing for 1 hour, the unreacted gas was removed, and then the autoclave was opened, and filtration, solvent washing, and heat drying were performed to obtain a polymer.
The activity represents the polymer yield (g) per 1 g of the polymerization catalyst used for the polymerization and the polymerization time per hour. The bulk density (BD) is the apparent density when the powder is placed in a container having a known volume in the loosest state. The GPC measurement results for the obtained polymer are also shown in Table 7.

[Comparative Example 3]
In Comparative Example 3, a polymerization catalyst was prepared in the same manner as in the polymerization catalyst 2 except that the boron compound was not used, and ethylene homopolymerization was carried out in the same manner as in Example 6. The amount of catalyst used was as shown in Table 7.

As is clear from Table 7, by comparing Examples 6 to 7 with Comparative Example 3, the polymerization catalyst of the present invention having both aluminum and boron is highly polymerizable even in ethylene homopolymerization and is in a particle state. It can be seen that a good polymer can be obtained.

By using the catalyst of the present invention, it is possible to produce a highly active and particulate olefin (co) polymer without using a large amount of expensive co-catalyst, so that the olefin (co) polymer can be inexpensively produced. Can be manufactured. Therefore, the present invention is industrially extremely valuable.

Claims (12)

The compound represented by M ¹ R ^c ₃ and the compound represented by B (OR ^b ) _n R ^c _3-n (where M ¹ represents aluminum or boron, and R ^b and R ^c are independent of each other. A solid support (1) contacted with a hydrocarbon group having 1 to 20 carbon atoms and n representing an integer of 1 to 3), and
OR ⁸ , CO ₂ R ⁸ , CO ₂ M', C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , SO ₃ R ⁸ , P (O) (OR ⁸ ) _2-y (R ⁹ ) _y , P (OR ⁹ ) _3-x (R ⁹ ) _x , NHR ⁸ , N (R ⁸ ) ₂ , Si (OR ⁸ ) _3-x (R ⁸ ) _x , OSi (OR ⁸ ) _{3 ^{-x (R 8) x, SO}} 3 M ', PO 3 M' 2, PO 3 M ", P (O) (oR 9) 2 M ' and epoxy-containing group (wherein, ^{R 8} is a hydrogen atom or R ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms, M'represents an alkali metal, ammonium, quaternary ammonium or phosphonium, and M'represents alkaline soil. Represents a class metal, x represents an integer of 0 to 3, y represents an integer of 0 to 2), and has ^a reactive group R ^a selected from the group consisting of the following general formula (A) or (B). ):

[In the formula, E ¹ is phosphorus, arsenic or antimony, X ¹ is oxygen or sulfur, and R ² and R ³ may independently contain heteroatoms 1 to 1 carbon atoms. A hydrocarbon group having 30 hydrocarbon groups or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom and contains ^a group −Q—R ^a (where Q is a carbon which may contain a heteroatom). Represents a divalent hydrocarbon group of numbers 1-20, where ^Ra is as defined above), or R ² and R ³ are bonded together to form a ring with E ^1. R ⁴ , R ⁵ and R ⁶ may each independently contain a hydrocarbon atom, a halogen atom, or a heteroatom, which may contain a hydrocarbon group having 1 to 30 carbon atoms, a cyano group, a nitro group, or a group. -Q-R ^a , where R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, but of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ . At least one of them is ^a substituent containing the group -Q-R ^a ]
An olefin polymerization catalyst containing a metal catalyst component (2) containing a transition metal compound (C) containing a transition metal M which is nickel or palladium . The metal catalyst component (2) has the following general formula (D):

[In the formula, E ¹ , X ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in claim 1 , where M is nickel or palladium and L ¹ is. , M is a ligand capable of coordinating, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom].
In comprising a metal complex represented, olefin polymerization catalyst according to claim 1. The olefin polymerization catalyst according to claim 1 or 2 , wherein the solid carrier (1) is an inorganic oxide or polymer carrier. R ^a is OR ⁸ , CO ₂ R ⁸ , C (O) N (R ⁸ ) ₂ , C (O) R ⁸ , SR ⁸ , NHR ⁸ , N (R ⁸ ) ₂ or Si (OR ⁸ ) _{3- x} (R ⁸ ) _x (where R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms and R ⁹ is a hydrocarbon group having 1 to 10 carbon atoms). The olefin polymerization catalyst according to any one of 1 to 3 . The step of treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , and treating the treated solid carrier (1) with the metal catalyst component (2). The method for producing an olefin polymerization catalyst according to any one of claims 1 to 4 , which comprises a step. The step of treating the solid carrier (1) with M ¹ R ^c ₃ and B (OR ^b ) _n R ^c _3-n , the treated solid carrier (1) is represented by the general formula (A) or (B). The olefin polymerization catalyst according to any one of claims 1 to 4 , which comprises a step of contacting the compounds to prepare a mixture and a step of contacting the obtained mixture with the transition metal compound (C). Manufacturing method. The method for producing an olefin polymerization catalyst according to claim 5 or 6 , which comprises a step of treating the solid carrier (1) with M ¹ R ^c ₃ and then further treating with B (OR ^b ) _n R ^c _3-n . Further, a method for producing an olefin prepolymerization catalyst, which comprises a step of prepolymerizing the olefin polymerization catalyst obtained by the method according to any one of claims 5 to 7 with an α-olefin. The method for producing an olefin prepolymerization catalyst according to claim 8 , wherein the prepolymerization is carried out in the presence of a Lewis base. The method for producing an olefin prepolymerization catalyst according to claim 8 or 9 , wherein the α-olefin is ethylene or propylene. In the presence of the olefin polymerization catalyst according to any one of claims 1 to 4 or the olefin polymerization catalyst or olefin prepolymerization catalyst obtained by the method according to any one of claims 5 to 10 , the olefin is homopolymerized or A method for producing an olefin polymer, which comprises a step of copolymerizing. In the presence of the olefin polymerization catalyst according to any one of claims 1 to 4 or the olefin polymerization catalyst or olefin prepolymerization catalyst obtained by the method according to any one of claims 5 to 10 , the olefin and (meth) A method for producing an α-olefin / (meth) acrylic acid ester copolymer, which comprises a step of copolymerizing an acrylic acid ester.