JP5649812B2 - A novel triarylphosphine or triarylarsine compound, an α-olefin polymerization catalyst using them, and a method for producing an α-olefin copolymer. - Google Patents

Description

  The present invention relates to a novel triarylphosphine or triarylarsine compound, an α-olefin polymerization catalyst using the same, and a method for producing an α-olefin copolymer, and in particular, α using these novel compounds. It relates to a method for producing an α-olefin / (meth) acrylic acid copolymer having both a high molecular weight and a comonomer content by an olefin polymerization catalyst.

  Conventionally, copolymers of ethylene and polar group-containing vinyl monomers such as vinyl acetate, (meth) acrylic acid or esters have been produced using a high-pressure radical method, but a copolymer is obtained by a method other than the high-pressure method. This is difficult, and when a Ziegler catalyst or a metallocene catalyst is used, catalyst deactivation cannot be avoided.

Since the 1990s, polar group-containing comonomer copolymerization by late transition metal complex catalysts has been intensively studied. For example, (α-diimine) palladium complex reported by Brookhart et al. (Salicylamidinate) nickel catalyst, a so-called SHOP-based catalyst ((phosphanylphenolate)) nickel catalyst is known. In these catalysts, in order to suppress frequent occurrence of chain transfer, the polymerization temperature is set to be low, the copolymer productivity is generally low, and the molecular weight is also low (see, for example, Non-Patent Document 1). ).
In 2002, Pugh et al. Reported that when a phosphine sulfonate ligand was used in combination with a palladium compound as a catalyst component, copolymerization was possible even at high temperatures (80 ° C.) (Patent Document 1 and Non-Patent Document 2). This technology was highly productive and had a relatively high content of comonomer (meth) acrylate.
However, since the upper limit of the molecular weight (Mw) of the copolymer is about several tens of thousands, industrial uses are also limited.
This phosphine sulfonate ligand is expected to be chelating or potentially chelating, for example, it has been reported that it forms a chelated metal complex by complexing with palladium (see Non-Patent Document 3). . In the case of a phosphine carboxylate ligand having a —CO ₂ H group, it has been reported that it forms a chelate metal complex by complexing with nickel (see Non-Patent Document 4).

Nozaki et al. Isolated a (phosphine sulfonate) palladium (methyl) lutidine complex as a catalytically active component and reported its usefulness as a catalyst (see Patent Document 2 and Non-Patent Document 3). In this case, although the catalyst activity was greatly improved, the molecular weight still remained low.
Jordan et al. Have reported the production of ethylene polymerization and ethylene / 1-hexene copolymer using an isolated (phosphine sulfonate) palladium (methyl) lutidine complex (Non-patent Document 6). This catalyst is reported to copolymerize with a small amount of hexene when it is polymerized at ethylene pressure (3 MPa), but does not incorporate 1-hexene, but at low ethylene pressure (0.5 MPa). (See Non-Patent Document 6).
Furthermore, Goodall et al. Improved a phosphine sulfonate ligand and developed a phosphine sulfonate ligand having a biphenyl structure (see, for example, Patent Documents 3 to 8 and Non-Patent Document 5). It is disclosed that a copolymer having a molecular weight (Mw) of 100,000 or more can be produced by using this as a copolymerization catalyst of ethylene and acrylic acid ester. However, according to the evaluation of the present inventor, it has been found that there is a drawback that the comonomer content decreases.

  Therefore, in the field of copolymerization of ethylene with polar group-containing vinyl monomers such as vinyl acetate, (meth) acrylic acid or esters, development of a polymerization catalyst capable of achieving both high copolymerization and high molecular weight (Mw) has been developed. It was sought after.

Special table 2002-521534 gazette JP 2007-46032 A JP 2007-63280 A JP 2007-77395 A JP 2007-117991 A JP 2008-214628 A JP 2007-214629 A JP 2007-214630 A

S. Mecking et al. , J .; Am. Chem. Soc. 1998, 120, 888. E. Drent et al. , Chem. Commun. 2002, 744. K. Nozaki et al. Dalton TRANSACTIONS, 2006, 25. W. Keim, Stud. Surf. Sci. Catal. 1986, 25, 201. J. et al. P. Claverie et al. , Macromolecular Rapid Communications 2007, 28, 2033-2038. R. F. Jordan et al. , Organometallics 2007, 26, 6624-35.

  In light of the above-described situation of the background art, the present invention has a high molecular weight, a high comonomer content, an industrially useful α-olefin / (meth) acrylic acid copolymer, and two different types. A catalyst component capable of producing a copolymer of an α-olefin and (meth) acrylic acid or an ester, and a production method using the same are developed.

  In order to solve the above-described problems of the present invention, the present inventors provide a polymerization catalyst capable of realizing the production of an α-olefin / (meth) acrylic acid copolymer having a high molecular weight and a high comonomer content. In search of various ligand compounds in late-period transition metal complex catalysts, new triarylphosphine and triarylarsine compounds having specific structures are exceptionally used as components of the above-mentioned polymerization catalyst. It has been found that it functions, and the present invention has been realized.

・・・（１）

（一般式（１）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３Ｈ又はＣＯ_２Ｈである。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、二級もしくは三級のアルキル基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。） The triarylphosphine and triarylarsine compound having the specific structure are novel compounds constituting the first invention of the present invention, that is, a novel triarylphosphine represented by the following general formula (1) Or a triarylarsine compound. (The “present invention” means an invention group consisting of the invention units of the following first to fifteenth inventions.)

... (1)

(In General Formula (1), Y is phosphorus or arsenic, and Z is —SO ₃ H or CO ₂ H. R ^{1 to} R ⁴ are each independently a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms Wherein at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1; Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms 30 aryloxy groups or hydrocarbon groups having 1 to 30 carbon atoms Indicates a substituted silyl group.)

As a second invention of the present invention, in the general formula (1), at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a secondary or tertiary alkyl group. Characteristic novel triarylphosphine or triarylarsine compounds are provided.

・・・（２）
（一般式（２）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３Ｈ又はＣＯ_２Ｈである。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、芳香環に直接結合している炭素と、Ｏ又はＮより選ばれる元素との単結合を含む置換基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。） The third invention of the present invention is a triarylphosphine and triarylarsine compound having a specific structure, that is, a novel triarylphosphine or triarylarsine compound represented by the following general formula (2). is there.

... (2)
(In General Formula (2), Y is phosphorus or arsenic, and Z is —SO ₃ H or CO ₂ H. R ^{1 to} R ⁴ are each independently a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms And at least one of R ^{1 to} R ⁴ is a substituent containing a single bond between carbon directly bonded to the aromatic ring and an element selected from O and N. R ⁵ to R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon atom having 1 to 30 carbon atoms having a hetero atom. Hydrocarbon group, an alkoxy group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms (A silyl group substituted with an aryloxy group or a hydrocarbon group having 1 to 30 carbon atoms is shown.)

  As a fourth invention of the present invention, there is provided an α-olefin polymerization catalyst obtained by reacting any one of the compounds of the first to third inventions with a group 8-10 transition metal.

  As a fifth invention of the present invention, there is provided an α-olefin polymerization catalyst comprising any one of the compounds of the first to third inventions, a group 8-10 transition metal and a fine particle support.

  As a sixth aspect of the present invention, there is provided an α-olefin polymerization catalyst comprising a reaction product of any one of the compounds of the first to third aspects and a group 8-10 transition metal and a fine particle carrier.

・・・（３）
（一般式（３）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３−又はＣＯ_２−である。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、二級もしくは三級のアルキル基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。Ｍは、８〜１０族の遷移金属からなる群より選択された金属原子を示し、Ａは、水素原子、ハロゲン原子、ヘテロ原子を有していてもよい炭素数１〜３０のアルキル基又はヘテロ原子を有していてもよい炭素数６〜３０のアリール基を示す。Ｂは、Ｍに配位した任意のリガンドを示す。また、ＡとＢは互いに結合して環を形成していてもよい。）
As a seventh aspect of the present invention, there is provided a metal complex represented by the following general formula (3).

... (3)
(In General Formula (3), Y is phosphorus or arsenic, and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms Wherein at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1; Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms 30 aryloxy groups or hydrocarbon groups having 1 to 30 carbon atoms Represents a substituted silyl group, M represents a metal atom selected from the group consisting of Group 8-10 transition metals, and A represents a carbon atom which may have a hydrogen atom, a halogen atom or a hetero atom. 1 represents an alkyl group of 1 to 30 or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B represents an arbitrary ligand coordinated to M. A and B are bonded to each other. And may form a ring.)

As an eighth invention of the present invention, in the general formula (3), at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a secondary or tertiary alkyl group. A featured metal complex is provided.

・・・（４）
（一般式（４）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３−又はＣＯ_２−である。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、芳香環に直接結合している炭素と、Ｏ又はＮより選ばれる元素との単結合を含む置換基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。Ｍは、８〜１０族の遷移金属からなる群より選択された金属原子を示し、Ａは、水素原子、ハロゲン原子、ヘテロ原子を有していてもよい炭素数１〜３０のアルキル基又はヘテロ原子を有していてもよい炭素数６〜３０のアリール基を示す。Ｂは、Ｍに配位した任意のリガンドを示す。また、ＡとＢは互いに結合して環を形成していてもよい。） As a ninth aspect of the present invention, there is provided a metal complex represented by the following general formula (4).

... (4)
(In General Formula (4), Y is phosphorus or arsenic, and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms And at least one of R ^{1 to} R ⁴ is a substituent containing a single bond between carbon directly bonded to the aromatic ring and an element selected from O and N. R ⁵ to R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon atom having 1 to 30 carbon atoms having a hetero atom. Hydrocarbon group, an alkoxy group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms An aryloxy group or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms, M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom , A halogen atom, an alkyl group having 1 to 30 carbon atoms which may have a hetero atom, or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B is coordinated to M An arbitrary ligand is shown, and A and B may be bonded to each other to form a ring.)

  As a tenth aspect of the present invention, there is provided an α-olefin polymerization catalyst comprising the metal complex of any one of the seventh to ninth aspects.

  As an eleventh aspect of the present invention, there is provided an α-olefin polymerization catalyst comprising the metal complex according to any one of the seventh to ninth aspects and a fine particle carrier.

  According to a twelfth aspect of the present invention, there is provided the α-olefin polymerization catalyst according to any of the fifth, sixth or eleventh aspects, wherein the fine particle carrier is an ion-exchange layered silicate. Is done.

  As the thirteenth invention of the present invention, there is provided an α-olefin polymerization catalyst characterized in that the ion-exchange layered silicate of the twelfth invention is a smectite group.

  As the fourteenth invention of the present invention, in the presence of the α-olefin polymerization catalyst of any one of the fourth to sixth and tenth to thirteenth inventions, an α-olefin and (meth) acrylic acid or ester And a method for producing an α-olefin / (meth) acrylic acid-based copolymer.

  In the fifteenth aspect of the present invention, in the presence of the α-olefin polymerization catalyst according to the fourth to sixth and tenth to thirteenth aspects, two different α-olefins, (meth) acrylic acid or esters There is provided a method for producing an α-olefin / (meth) acrylic acid copolymer, characterized by copolymerizing these three components.

  By copolymerizing an α-olefin and (meth) acrylic acid or ester in the presence of the polymerization catalyst according to the present invention, the α-olefin has a high molecular weight and a high comonomer content, and is industrially useful.・ (Meth) acrylic acid copolymers can be produced. Such a remarkable effect is demonstrated by the data of each example of the present invention described later and the comparison between each example and each comparative example.

In the above copolymerization, the properties of the polymer produced can be improved by supporting the catalyst component on the fine particle carrier. This can improve the adaptability to a polymer production process that requires the formation of polymer particles, such as slurry polymerization or gas phase polymerization. This olefin copolymer is excellent in mechanical and thermal properties, and can be applied as a useful molded product. Specifically, the copolymer of the present invention has paintability, printability, antistatic properties, Using various properties such as films, sheets, adhesive resins, binders, compatibilizers, etc. by utilizing the good properties in inorganic filler dispersibility, adhesiveness with other resins, compatibilizing with other resins, etc. Applicable.

The present invention relates to novel triarylphosphine and triarylarsine compounds having specific structures, catalysts in which these novel compounds are coordinated to specific metal elements, and α-olefin / (meth) acrylic acid systems using them. The present invention relates to the production of a copolymer and two different types of α-olefin and a (meth) acrylic acid copolymer.
In the following, these novel compounds, polymerization catalysts, polymer components (monomer components), polymerization methods, and the like will be described in detail.

・・・（１）
（一般式（１）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３Ｈ又はＣＯ_２Ｈである。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、二級もしくは三級のアルキル基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。） 1-1. Triarylphosphine and triarylarsine compound In the polymerization catalyst of the present invention, a novel triarylphosphine or triarylarsine compound serving as a ligand for a specific metal element is represented by the following general formula (1).

... (1)
(In General Formula (1), Y is phosphorus or arsenic, and Z is —SO ₃ H or CO ₂ H. R ^{1 to} R ⁴ are each independently a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms Wherein at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1; Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms 30 aryloxy groups or hydrocarbon groups having 1 to 30 carbon atoms Indicates a substituted silyl group.)

Y is phosphorus or arsenic, preferably phosphorus. Z is —SO ₃ H or CO ₂ H, preferably —SO ₃ H.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a C ^{1 to} 30 carbon atom having a hetero atom. A hydrocarbon group, an alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms is shown, and at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group. R ^{1 to} R ⁴ are in the ortho position as viewed from the central group 15 atom (phosphorus or arsenic), that is, the triarylphosphine compound of the present invention has at least one sterically bulky substitution in the molecule (in the ortho position). One of the characteristics is that it has a group, and this steric effect is considered to affect the improvement of the catalyst performance.

Preferred secondary or tertiary alkyl groups as R ^{1 to} R ⁴ are each independently a hydrocarbon group having 3 to 30 carbon atoms, more preferably a hydrocarbon having 3 to 18 carbon atoms which is a secondary alkyl group. A hydrocarbon group having 3 to 12 carbon atoms, which is a secondary alkyl group. Preferred examples are tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group. 1-phenyl-2-propyl group, tertiary butyl group, isobutyl group, 1,1-dimethylbutyl group, 2-isopentyl group, 3-isopentyl group, 2-isohexyl group, 3-isohexyl group, 2-ethylhexyl group 2-isoheptyl group, 3-isoheptyl group, 4-isoheptyl group, 2-propylheptyl group, 2-isooctyl group, 3-isononyl group, 1-adamantyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group Cyclohexyl group, methylcyclohexyl group, cycloheptyl group, A looctyl group, a cyclododecyl group, an exo-norbornyl group, an endo-norbornyl group, a 2-bicyclo [2.2.2] octyl group, a 2-adamantyl group, a nopinyl group, a menthyl group, a neomenthyl group, and a neopentyl group, Particularly preferred are isopropyl group and cyclohexyl group.

Further, R ^{1 to} R ⁴ which are secondary or tertiary alkyl groups may contain a hetero atom in the partial structure. Here, introduction of an electron donating group resulting from a heteroatom can increase the electron density of the central metal that is spatially close, and is effective in improving the catalytic activity. A heteroatom refers to a nonmetallic atom other than a carbon atom, a hydrogen atom, or a group 17 or 18 atom in a broad sense, but is preferably a nonmetallic atom having a second period or a third period, more preferably an oxygen atom or A nitrogen atom, particularly preferably an oxygen atom.

This heteroatom-containing secondary or tertiary alkyl group is a secondary alkyl group having 4 to 30 carbon atoms each independently containing an oxygen atom, and more preferably a secondary alkyl group containing 4 to 15 carbon atoms containing an oxygen atom. A secondary alkyl group, particularly preferably a secondary alkyl group having 4 to 7 carbon atoms and containing an oxygen atom. Preferred specific examples are 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- (phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group , Examples thereof include a di (methoxymethyl) methyl group, a di (ethoxymethyl) methyl group, and a di (phenoxymethyl) methyl group. Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (phenoxymethyl) ethyl group.

When R ^{1 to} R ⁴ are not secondary or tertiary alkyl groups, they are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom. , A hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms.
Preferred hydrocarbon groups having 1 to 30 carbon atoms as R ^{1 to} R ⁴ are alkyl groups having 1 to 6 carbon atoms, and preferred specific examples are methyl group, ethyl group, normal propyl group, normal butyl group, and normal hexyl. Group, particularly preferably a methyl group.
Hydrocarbon group R ¹ to R have been C1-30 substituted with preferred halogen atoms as ⁴ is an alkyl group having 1 to 6 carbon atoms which is substituted with one halogen atom. The halogen to be substituted is preferably fluorine, and preferred specific examples are fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 6-fluorohexyl group. It is.
Hydrocarbon group having 1 to 30 carbon atoms having a preferred heteroatom as R ¹ to R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms having an oxygen atom, preferred examples include methoxymethyl group, ethoxymethyl group It is.
An alkoxy group preferably having 1 to 30 carbon atoms as R ¹ to R ⁴ is an alkoxy group having 1 to 6 carbon atoms, preferred examples are methoxy group, an ethoxy group.
A preferable aryloxy group having 6 to 30 carbon atoms as R ^{1 to} R ⁴ is an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples are a phenoxy group and a 2-methylphenoxy group.
Among the specific examples of the substituent group in which R ^{1 to} R ⁴ are not a secondary or tertiary alkyl group, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number having a hetero atom. It is a silyl group substituted by a 1-30 hydrocarbon group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, or a C1-C30 hydrocarbon group. Since these substituents are substituents that are relatively distant from the central metal at the time of complex formation, any substituent that does not adversely affect the complex formation of the phosphorus sulfonic acid ligand may be used. Compared to the steric effects of these substituents, the electronic effect is considered to affect the catalyst performance, and electron donating substituents are preferred. These substituents may be the same or different.

Preferred halogen atoms as R ^{5 to} R ¹⁴ include fluorine, chlorine, bromine and the like.
Preferred examples of the hydrocarbon group having 1 to 30 carbon atoms as R ^{5 to} R ¹⁴ include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group.
Here, examples of the alkyl group and the cycloalkyl group include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1 -Nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2- Ethylhexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cycl Pentyl group, cyclopropyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, Examples include 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, and 5-decyl group. Among these, preferred substituents are isopropyl group, isobutyl group, and 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 anthracenyl group, and a fluorenyl group. Examples of the substituent 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 group. Group, phenylbutenyl group, tolyl group, xylyl group, p-ethylphenyl group and the like. Among these, a preferred substituent is a phenyl group.

The hydrocarbon group having 1 to 30 carbon atoms that is substituted with a halogen atom that is preferable as R ^{5 to} R ¹⁴ is a substitution in which the hydrocarbon group having 1 to 30 carbon atoms is substituted with a halogen atom such as fluorine, chlorine, or bromine. It is a group.
The R ⁵ to R ¹⁴ Preferred hetero atom which may be contained in the hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, more preferably, an oxygen atom and a nitrogen atom. As specifically is a hydrocarbon group having 1 to 30 carbon atoms having a hetero _{^{atom, OR 15, CO 2 R 15}} , CO 2 M', C (O) N (R 15) 2, C (O) R 15 , SO ₂ R ¹⁵ , SOR ¹⁵ , OSO ₂ R ¹⁵ , P (O) (OR ¹⁵ ) _2-y (R ¹⁶ ) _y , CN, NHR ¹⁵ , N (R ¹⁵ ) ₂ , NO ₂ , SO ₃ M ′ , PO ₃ M ′ ₂ , P (O) (OR ¹⁵ ) ₂ M ′, or a hydrocarbon group having a substituent containing a hetero atom such as an epoxy group. Here, M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. R ¹⁵ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms. Of the above heteroatom-containing substituents, OR ¹⁵ and N (R ¹⁵ ) ₂ are preferable, and OR ¹⁵ is particularly preferable.

An alkoxy group preferably having 1 to 30 carbon atoms as R ⁵ to R ¹⁴ is an alkoxy group having 1 to 6 carbon atoms, preferred examples are methoxy group, an ethoxy group.
Preferred aryloxy group having 6 to 30 carbon atoms as R ⁵ to R ¹⁴ is an aryloxy group having 6 to 12 carbon atoms, preferred examples are phenoxy group, a 2-methylphenoxy group.
The silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms, which is preferable as R ^{5 to} R ¹⁴ , is a silyl group having 3 to 18 carbon atoms. A phenylsilyl group and a triphenylsilyl group.

・・・（２）（一般式（２）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３Ｈ又はＣＯ_２Ｈである。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、芳香環に直接結合している炭素と、Ｏ又はＮより選ばれる元素との単結合を含む置換基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。） 1-2. Triarylphosphine and triarylarsine compound In the polymerization catalyst of the present invention, another novel triarylphosphine or triarylarsine compound serving as a ligand for a specific metal element is represented by the following general formula (2). .

In (2) (formula (2), Y is phosphorus or arsenic, Z is, ^.R 1 to R ⁴ is -SO ₃ H or CO ₂ H are each independently a hydrogen atom , A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, Or an aryloxy group having 6 to 30 carbon atoms, wherein at least one of R ^{1 to} R ⁴ includes a single bond between a carbon directly bonded to an aromatic ring and an element selected from O and N R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a hetero atom. The hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms, carbon A silyl group substituted with an aryloxy group having 6 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms is shown.)

Y is phosphorus or arsenic, preferably phosphorus. Z is —SO ₃ H or CO ₂ H, preferably —SO ₃ H.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a C ^{1 to} 30 carbon atom having a hetero atom. A hydrocarbon group, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, wherein at least one of R ^{1 to} R ⁴ is a carbon directly bonded to an aromatic ring, O or A substituent containing a single bond with an element selected from N. R ^{1 to} R ⁴ are in the ortho position as viewed from the central group 15 atom (phosphorus or arsenic), that is, the triarylphosphine compound of the present invention has at least one sterically bulky substitution in the molecule (in the ortho position). One of the characteristics is that it has a group, and this steric effect is considered to affect the improvement of the catalyst performance. Therefore, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a substitution that includes a single bond between carbon directly bonded to the aromatic ring and an element selected from O or N What is group is preferable.

A carbon bonded directly to the aromatic ring, the substituent containing a single bond between the element selected from O or N, 1 or alkoxyalkyl group or cyclic ethers composed of carbon C and one oxygen O, and Pyrrolidines or pyrroles consisting of one carbon C and one nitrogen N, acetals consisting of two oxygen Os, morpholines or oxazoles consisting of one oxygen O and one nitrogen N, two And imidazolidines or imidazoles composed of nitrogen N. These substituents containing two or more C, O, and N may be linked to form a ring. Among these, A Turkey alkoxyalkyl group, cyclic ethers are preferred, and particularly preferred is Te tiger tetrahydrofuryl groups as described below.

When R ^{1 to} R ⁴ are not a substituent containing a single bond between carbon directly bonded to an aromatic ring and an element selected from O or N, each independently a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms Group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms It is a group.

Preferred hydrocarbon groups having 1 to 30 carbon atoms as R ^{1 to} R ⁴ are alkyl groups having 1 to 6 carbon atoms, and preferred specific examples are methyl group, ethyl group, normal propyl group, normal butyl group, and normal hexyl. Group, preferably a methyl group.
Hydrocarbon group R ¹ to R have been C1-30 substituted with preferred halogen atoms as ⁴ is an alkyl group having 1 to 6 carbon atoms which is substituted with one halogen atom. The halogen to be substituted is preferably fluorine, and preferred specific examples are fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 6-fluorohexyl group. It is.
Hydrocarbon group having 1 to 30 carbon atoms having a preferred heteroatom as R ¹ to R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms having an oxygen atom, preferred examples include methoxymethyl group, ethoxymethyl group It is.
An alkoxy group preferably having 1 to 30 carbon atoms as R ¹ to R ⁴ is an alkoxy group having 1 to 6 carbon atoms, preferred examples are methoxy group, an ethoxy group.
A preferable aryloxy group having 6 to 30 carbon atoms as R ^{1 to} R ⁴ is an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples are a phenoxy group and a 2-methylphenoxy group.
Of the specific examples in the case where these R ^{1 to} R ⁴ are not a substituent containing a single bond between carbon directly bonded to an aromatic ring and an element selected from O or N, more preferably a hydrogen atom, A methyl group and an ethyl group, particularly preferably a hydrogen atom.

R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number having a hetero atom. It is a silyl group substituted by a 1-30 hydrocarbon group, a C1-C30 alkoxy group, a C6-C30 aryloxy group, or a C1-C30 hydrocarbon group.
The specific contents are the same as the substituents in the triarylphosphine or triarylarsine compound represented by the general formula (1).

2. Synthesis of Triarylphosphine and Triarylarsine Compound The synthesis of the triarylphosphine compound as the first invention is performed by the following route. In other words, there are several known synthesis routes for compounds, and as a specific example, an aryl group to be introduced into phosphorus trichloride as a raw material is reacted at an appropriate molar ratio. Route. After the reaction, the target product can be obtained by extraction under acidic conditions and washing. The synthesis of the triarylarsine compound is similarly performed.

3. Complexation The ligands of the present invention are expected to be chelating or potentially chelating. For example, it has been reported that a ligand having a —SO ₃ H group is complexed with palladium to form a chelate metal complex (Non-patent Document 3), and a ligand having a —CO ₂ H group is nickel and It has been reported that a chelate metal complex is formed by complex formation (Non-patent Document 4).

4). Synthesis of polymerization catalyst

The polymerization catalyst of the present invention is an α-olefin polymerization catalyst obtained by reacting a novel triarylphosphine or triarylarsine compound represented by the general formula (1) with a group 8-10 transition metal compound. .

The synthesis of the catalyst composition is generally carried out by contacting a group 8-10 transition metal compound and a ligand in a solution or slurry.
The transition metal compound is preferably a Group 10 transition metal compound, and is bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, palladium sulfate, palladium acetate, bis (allyl palladium chloride), palladium chloride, bromide. Palladium, (cyclooctadiene) palladium (methyl) chloride, dimethyl (tetramethylethylenediamine) palladium, bis (cyclooctadiene) nickel, nickel chloride, nickel bromide, (tetramethylethylenediamine) nickel (methyl) chloride, dimethyl (tetra It is synthesized using (methylethylenediamine) nickel, (cyclooctadiene) nickel (methyl) chloride, or the like.

The complexing reaction may be performed in a reactor used for copolymerization with an α-olefin, or may be performed in a container separate from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation. Furthermore, it can be carried out in the presence of a porous carrier described later.
One type of the catalyst composition of the present invention may be used alone, or a plurality of types of catalyst compositions may be used in combination. Particularly, for the purpose of widening the molecular weight distribution and the comonomer content distribution, the combined use of such a plurality of catalyst compositions is useful.

・・・（３）
（一般式（３）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３−又はＣＯ_２−である。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、二級もしくは三級のアルキル基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。Ｍは、８〜１０族の遷移金属からなる群より選択された金属原子を示し、Ａは、水素原子、ハロゲン原子、ヘテロ原子を有していてもよい炭素数１〜３０のアルキル基又はヘテロ原子を有していてもよい炭素数６〜３０のアリール基を示す。Ｂは、Ｍに配位した任意のリガンドを示す。また、ＡとＢは互いに結合して環を形成していてもよい。）
4-1. A metal complex formed by reacting a triarylphosphine or triarylarsine compound represented by the general formula (1) with a triarylphosphine or triarylarsine metal complex and a group 8-10 transition metal compound has the following general formula ( It may be represented by 3).

... (3)
(In General Formula (3), Y is phosphorus or arsenic, and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms Wherein at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1; Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms 30 aryloxy groups or hydrocarbon groups having 1 to 30 carbon atoms Represents a substituted silyl group, M represents a metal atom selected from the group consisting of Group 8-10 transition metals, and A represents a carbon atom which may have a hydrogen atom, a halogen atom or a hetero atom. 1 represents an alkyl group of 1 to 30 or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B represents an arbitrary ligand coordinated to M. A and B are bonded to each other. And may form a ring.)

Here, Y, Z, and R ^{1 to} R ¹⁴ are the same as the substituents in the triarylphosphine or triarylarsine compound represented by the general formula (1).
M represents a Group 8-10 transition metal, preferably Fe, Co, Ni, Pd, Pt and lanthanide, and more preferably Ni, Pd.
A represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms which may contain a hetero atom, or an aryl group having 6 to 30 carbon atoms which may contain a hetero atom. Here, the hetero atom is preferably an oxygen atom, a nitrogen atom, a silicon atom or a halogen atom, more preferably an oxygen atom.

  The alkyl group having 1 to 30 carbon atoms which may contain a hetero atom which is preferable as A is more preferably an alkyl group having 1 to 6 carbon atoms, and preferred specific examples include a methyl group, an ethyl group, and trifluoromethyl. Group, acyl group, and acetoxy group. Further, the aryl group having 6 to 30 carbon atoms which may contain a hetero atom which is preferable as A is more preferably an aryl group having 6 to 13 carbon atoms. Preferred examples include a phenyl group, a tolyl group, and xylyl. Group, phenacyl group and pentafluorophenyl group. Of the specific examples of these substituents, particularly preferred substituents are a hydrogen atom, a methyl group and a phenyl group.

  B is any ligand coordinated to M. Such a ligand is a hydrocarbon compound having 1 to 20 carbon atoms having oxygen, nitrogen, phosphorus, and sulfur as atoms capable of coordination bonding. More preferably, phosphines, pyridine derivatives, piperidine derivatives, alkyl ether derivatives, aryl ether derivatives, alkyl aryl ether derivatives, ketones, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters. , Aromatic esters, amines and the like. More preferred are ketones, cyclic ethers, phosphines, and pyridine derivatives, and preferred specific examples include acetone, tetrahydrofuran, pyridine, lutidine, and triphenylphosphine. Particularly preferred is pyridine or lutidine.

・・・（４）
（一般式（４）中、Ｙは、リン又は砒素であり、Ｚは、−ＳＯ_３−又はＣＯ_２−である。Ｒ^１〜Ｒ^４は、各々独立して水素原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、又は炭素数６〜３０のアリールオキシ基を示し、Ｒ^１〜Ｒ^４の少なくとも一つは、芳香環に直接結合している炭素と、Ｏ又はＮより選ばれる元素との単結合を含む置換基である。Ｒ^５〜Ｒ^１４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基、ハロゲン原子で置換された炭素数１〜３０の炭化水素基、ヘテロ原子を有する炭素数１〜３０の炭化水素基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、又は炭素数１〜３０の炭化水素基で置換されたシリル基を示す。Ｍは、８〜１０族の遷移金属からなる群より選択された金属原子を示し、Ａは、水素原子、ハロゲン原子、ヘテロ原子を有していてもよい炭素数１〜３０のアルキル基又はヘテロ原子を有していてもよい炭素数６〜３０のアリール基を示す。Ｂは、Ｍに配位した任意のリガンドを示す。また、ＡとＢは互いに結合して環を形成していてもよい。）
ここで、Ｙ、Ｚ、Ｒ^１〜Ｒ^１４は、前述の一般式（２）で表されるトリアリールホスフィン又はトリアリールアルシン化合物における置換基と同様である。
また、Ｍ、Ａ、Ｂの具体的内容は、前述の一般式（３）において前述した記載と同様である。
4-2. A metal complex formed by reacting a triarylphosphine or triarylarsine compound represented by the general formula (2) with a triarylphosphine or triarylarsine metal complex and a group 8-10 transition metal compound has the following general formula ( It may be represented by 4).

... (4)
(In General Formula (4), Y is phosphorus or arsenic, and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 30. Hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms And at least one of R ^{1 to} R ⁴ is a substituent containing a single bond between carbon directly bonded to the aromatic ring and an element selected from O and N. R ⁵ to R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon atom having 1 to 30 carbon atoms having a hetero atom. Hydrocarbon group, an alkoxy group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms An aryloxy group or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms, M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom , A halogen atom, an alkyl group having 1 to 30 carbon atoms which may have a hetero atom, or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B is coordinated to M An arbitrary ligand is shown, and A and B may be bonded to each other to form a ring.)
Here, Y, Z, and R ^{1 to} R ¹⁴ are the same as the substituents in the triarylphosphine or triarylarsine compound represented by the general formula (2).
The specific contents of M, A, and B are the same as those described in the general formula (3).

5. Fine particle carrier As the fine particle carrier used in the present invention, any fine particle 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 include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, and SiO ₂ —Al ₂ O _3. , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₃ and other mixed oxides can also be used, and inorganic silicates, polyethylene, polypropylene, polystyrene, Carriers such as polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polyester, polyamide, and polyimide can also be used.
Among these carriers, a carrier made of an inorganic oxide is preferably used, and an ion-exchange layered silicate is more preferably used. Even more preferably, the smectite group is used.

As the ion-exchange layered silicate, clay, clay mineral, zeolite, diatomaceous earth, or the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, sericite and sea chlorite and other mica minerals, attapulgite, sepiolite, pigolite, bentonite, wood Examples include knot clay, gyrome clay, hysingelite, pyrophyllite, and ryokdee stones. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

  Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Examples include smectites, such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Smectite such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, Adult saponite, synthetic taeniolite.

These fine particle carriers may be used as they are, but acid treatment with hydrochloric acid, nitric acid, sulfuric acid and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti Salt treatment such as (SO ₄ ) 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 produce a salt in the reaction system, and the treatment may be performed, or shape control such as pulverization and granulation and drying treatment may be performed.
There are no particular restrictions on the particle size of these fine particle carriers, and any particle can be used, but the average particle size is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm.

  The fine particle carrier can be used after being treated with an organoaluminum compound. The organoaluminum compound used here has a substituent selected from an alkyl group having 1 to 20 carbon atoms, a halogen, hydrogen, an alkoxy group, or an amino group. Among these substituents, a C1-C20 alkyl group, hydrogen, and a C1-C20 alkoxy group are preferable, More preferably, it is a C1-C20 alkyl group. A plurality of substituents may be the same or different, and the organoaluminum compound may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride are preferable. More preferably, it is a trialkylaluminum having 1 to 8 carbon atoms.

6). Use Mode of Polymerization Catalyst The triarylphosphine or triarylarsine compound, the group 8-10 transition metal compound, and the particulate carrier can be contacted in any order. When contacting, each component may be brought into contact with a solid, or may be brought into contact with a solvent slurry or a uniform solution. The contact order of each component is, for example, as follows.
(1) A method in which a triarylphosphine or a triarylarsine compound and a Group 8-10 transition metal compound are brought into contact with each other, and then a fine particle carrier is brought into contact therewith.
(2) A method of contacting a group 8-10 transition metal compound after contacting a triarylphosphine or triarylarsine compound with a fine particle carrier.
(3) A method in which a triarylphosphine or a triarylarsine compound is contacted after contacting a Group 8-10 transition metal compound and a fine particle carrier.
Among these contact methods, (1) is preferable. Further, after bringing the fine particle carrier into contact with another catalyst component, it can be washed with a solvent that is not reactive with the catalyst component. As the solvent, hydrocarbon solvents and halogenated hydrocarbons are preferable.

The triarylphosphine or triarylarsine compound is usually used in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol, with respect to 1 g of the fine particle carrier.
The temperature at which each component is brought into contact may be any temperature as long as it is not higher than the boiling point of the solvent, but is preferably from room temperature to not higher than the boiling point of the solvent.
The contacted catalyst component can be used for polymerization evaluation as it is, but can also be dried and stored in a solid state. Furthermore, prepolymerization described below can also be performed.

The contacted catalyst component may be prepolymerized in the presence of an olefin in the polymerization tank or outside the polymerization tank. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Preferred are olefins having 2 or 3 carbon atoms.
The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

7). Monomers used Examples of the monomers used for the production of the copolymer include α-olefins, (meth) acrylic acid or esters, and other olefins described below.
(A) α-Olefin One of the monomers used in the present invention is an α-olefin represented by the general formula CH ₂ ═CHR ¹⁷ (hereinafter sometimes referred to as “component (a)”). Here, R ¹⁷ is hydrogen or an alkyl group having 1 to 20 carbon atoms.
Of these, preferred component (a) include α- olefins having ^{R 17} having 1 to 10 carbon atoms. More preferable component (a) includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene. It is done. In addition, a single component (a) may be used, or a plurality of components (a) may be used in combination.

(B) (Meth) acrylic acid or ester Another one of the monomers used in the present invention is represented by (meth) acrylic acid or the general formula CH ₂ ═C (R ¹⁸ ) CO ₂ (R ¹⁹ ). (Meth) acrylic acid ester (hereinafter sometimes referred to as “component (b)”). Here, R ¹⁸ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R ¹⁹ is hydrogen or an alkyl group having 1 to 30 carbon atoms. Further, it may contain a hetero atom at any position within R ¹⁹ .

Preferable (b) component includes (meth) acrylic acid ester having 1 to 5 carbon atoms R ¹⁸ and (meth) acrylic acid. More preferable component (b) includes methacrylic acid ester in which R ¹⁸ is a methyl group, acrylic acid ester in which R ¹⁸ is hydrogen, and (meth) acrylic acid. As more preferable component (b), methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate , Cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, acrylic acid Etc. In addition, a single component (b) may be used, or a plurality of components (b) may be used in combination.

(C) Other olefins Another monomer used in the present invention is other olefins (hereinafter sometimes referred to as “component (c)”).
Preferred examples of the component (c) include cyclic olefin monomers such as cyclopentene, cyclohexene, norbornene and ethylidene norbornene, and styrene monomers such as p-methylstyrene. These skeletons include a hydroxyl group, an alkoxide group and a carboxylic acid group , May contain an ester group or an aldehyde group.

Norbornene-based olefins can be made by the Diels-Alder reaction ([4 + 2] cycloaddition) using cyclopentadiene. The dienophile used is, for example, diethyl azodicarboxylate, aldehyde, maleic anhydride, dihydrofuran, vinyl pyridine, alkyl acrylate or the above substituted olefins (TL Gilchrist, “Heterocyclic Chemistry”, 1985, 4. See chapter 3.3). These monomers can be represented by the formulas (9a) to (9f). Here, R ²⁰ is a hydrocarbon group having 1 to 30 carbon atoms and may have a branch, a ring, or an unsaturated bond.
Moreover, as a monomer prescribed | regulated by (a) component, the monomer containing hydroxyl groups, such as (3-butene) -1-ol, the monomer containing ether groups, such as methyl vinyl ether, and carboxylic acid groups, such as acrylic acid, It may be a monomer containing an ester group such as methyl acrylate, a monomer containing an aldehyde group such as acrolein, etc. In addition, a diene derivative, maleic anhydride, vinyl acetate, or the like can also be used.

8). Copolymerization Reaction The copolymerization reaction in the present invention may be carried out by using a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, a liquid such as a liquefied α-olefin, In the presence or absence of polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. Is called. Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent is more preferable.

  In the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor or an additive having an action of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of alkoxide of tetravalent titanium and BHT, etc. Can be used. Further, as an additive, inorganic and / or organic fillers may be used and polymerization may be performed in the presence of these fillers.

In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in the vaporized monomer, or a polymer produced in the monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used.
Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain shunting agent (CSA) may be used in combination to perform chain shunting reaction or coordinative chain transfer polymerization (CCTP).

  Unreacted monomers and media may be separated from the produced copolymer and recycled. In recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used to separate the produced copolymer from the unreacted monomer and medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0.00. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.
In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, nitrogen and argon can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

  There are no particular restrictions on the supply of catalyst and monomer to the copolymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a method in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously can be employed.

  Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a control of the ligand structure in the transition metal complex. For example, controlling the molecular weight.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used. In addition, when the component (b) or (c) itself becomes a kind of chain transfer agent, the molecular weight can be adjusted by controlling the concentration of the component (b) or (c) and the ratio to the component (a). Is possible. When the molecular weight is adjusted by controlling the ligand structure in the transition metal complex, bulky substituents are arranged around the metal M, or electron donation such as aryl groups and heteroatom-containing substituents is provided on the metal M. Generally, the tendency to increase the molecular weight can be utilized by arranging the sex groups so that they can interact with each other or introducing heteroatoms into R ^{18 to} R ²⁰ described above.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples, and the rationality and significance of the configuration of the present invention and the prior art based on the data of each preferred example and the comparison between each example and each comparative example. Demonstrate excellence. The ligand structures used in Examples and Comparative Examples are shown in Table 1.

In the examples, the following abbreviations were used.
Pd (dba) 2: bis (dibenzylideneacetone) palladium
Ni (cod) 2: bis (cyclooctadiene) nickel
MA: Methyl acrylate
EA: Ethyl acrylate
tBA: Tertiary butyl acrylate
MMA: Methyl methacrylate
AA: Acrylic acid
VA: Vinyl acetate
LUA: Lauryl acrylate
HEA: 2-hydroxyethyl acrylate
EUA: Ethyl undecylate
NBMOH: (5-norbornene) -2-methanol
NBYA: (5-norbornene) -2-yl acetate
ATMS: Allyltriethoxysilane
BTOH: (3-butene) -1-ol
TPB: Triphenylborane
Cray: sulfuric acid / lithium sulfate treated montmorillonite

1. Evaluation method (1) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
(Measurement conditions) Model used: 150C manufactured by Waters Inc. Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M manufactured by Showa Denko KK / S (3) Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Preparation of sample) A sample was prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)) at 140 ° C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the conversion from the retention capacity to the molecular weight was performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrene used is a brand (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation.
A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. The calibration curve used was a cubic equation obtained by approximation by the least square method. The following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(2) Melting point (Tm)
Using a DSC6200 differential scanning calorimeter manufactured by Seiko Instruments Inc., the sheet-like sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and held for 5 minutes. Thereafter, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final temperature increase step performed to obtain the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.

(3) Comonomer (α-olefin and polar group-containing vinyl monomer) content The measurement was carried out by the following two methods.
a) Measurement of α-olefin and polar group-containing vinyl monomer content by ¹³ C-NMR (sample preparation)
About 250 mg of a sample formed into a film having a thickness of about 100 μm was weighed into a sample tube having an outer diameter of 10 mm, and 1.84 ml of ortho-dichlorobenzene and 0.46 ML of deuterated bromobenzene were added. After replacing the upper part of the sample tube with nitrogen, the sample tube was covered and heated and dissolved in a high-temperature bath at 130 ° C. until the sample became uniform.
( ^13C -NMR measurement)
The measurement was carried out under conditions without NOE by gated proton decoupling using a Bruker BioSpin (AVANCE III · 400) NMR measuring apparatus equipped with a cryoprobe. The flip angle of the excitation pulse was 90 °, the pulse interval was 16.33 seconds, the measurement temperature was 120 ° C., the number of integration was 500 times or more, and the spectrum observation width was 24,038.5 Hz. Assignment of 13C-NMR spectrum was performed with reference to various documents.

(Determining α-olefin content and polar group-containing vinyl monomer content)
From the obtained ¹³ C-NMR spectrum, the amount TE proportional to the number of moles of ethylene units, the amount Tα-O proportional to the number of moles of α-olefin units, and the number of moles TF of the polar group-containing vinyl monomer unit were determined. From O / (TE + Tα-O + TF) × 100, α-olefin content (unit: mol%), TF / (TE + Tα-O + TF) × 100, polar group-containing vinyl monomer content ( Unit: mol%).
When the α-olefin was propylene and 1-hexene, when the polar group-containing vinyl monomer unit was methyl acrylate and ethyl acrylate, Tα-O and TF were determined as follows.

(When α-olefin is propylene)
When the α-olefin is propylene, among the nuclear magnetic resonance peaks generated by copolymerization of propylene and insertion into the chain, 1/2 and 33.2 of the integrated intensity of the peak derived from α methylene carbon near 37.6 ppm The average value with the integrated intensity of the peak derived from methine carbon in the vicinity of ppm was determined as an amount Tα-O proportional to the number of moles of propylene units. Tα-O = (I37.6 / 2 + I33.2) / 2. Here, for example, I37.6 is an integrated intensity of a peak derived from α-methylene carbon generated in the vicinity of 37.6 ppm.

(When α-olefin is 1-hexene)
As in the case of propylene, using the characteristic peak generated by 1-hexene, the amount Tα-O proportional to the number of moles of hexene units was determined using the following formula. Tα-O = (I27.3 / 2 + I34.2 + I34.6 / 2) / 3. Here, I27.3 is the integrated intensity of the peak due to the resonance of β-methylene generated near 27.3 ppm by copolymerization of 1-hexene, and I34.2 is 4 counted from the branch end of the butyl branch generated by copolymerization of 1-hexene. The integrated intensity of the resonance peak due to the 2nd carbon, I34.6 is the integrated intensity of the peak due to the resonance of α methylene.

(When polar group-containing vinyl monomer is methyl acrylate)
Of the nuclear magnetic resonance signals generated by copolymerization of methyl acrylate, half of the integral intensity of β-methylene carbon near 27.8 ppm, half of the integral intensity of α-methylene carbon near 32.8 ppm, and methine carbon integral near 46.0 ppm The average value of strength was taken as an amount (TF) proportional to the number of moles of methyl acrylate units. TF = (I27.8 / 2 + I32.8 / 2 + I46.0) / 3.

(When the polar group-containing vinyl monomer is ethyl acrylate)
As in the case of methyl acrylate, among the nuclear magnetic resonance signals generated by copolymerization of ethyl acrylate, half of the integral intensity of β methylene carbon near 27.8 ppm, half of the integral intensity of α methylene carbon near 32.8 ppm, And the average value of the methine carbon integrated intensity around 46.0 ppm was taken as the amount (TF) proportional to the number of moles of ethyl acrylate units. TF = (I27.8 / 2 + I32.8 / 2 + I46.0) / 3.
The amount TE proportional to the number of moles of ethylene units is the integral intensity of the main peak containing γ methylene near 30 ppm, half the integrated intensity of all α methylene carbon peaks generated by each of the above-mentioned comonomers, and all β methylene carbons. The value obtained by multiplying the sum of the peak integrated intensities by 1/2 was obtained. TE = (I30 + Iα / 2 + Iβ) / 2. Where I30 is the integrated intensity of the main peak containing γ-methylene near 30 ppm, Iα is I37.6 + I32.8 if the comonomer is propylene and methyl acrylate, and 1-hexene and ethyl acrylate I34.6 + I32.8.

(Total amount of branching other than branched structure derived from copolymerized α-olefin and polar group-containing vinyl monomer)
Performed 13C-NMR spectrum analysis with reference to Macromolecules 32 (5) 1620 (1999) to identify branched structures other than branched structures derived from copolymerized α-olefins and polar group-containing vinyl monomers, and well-known The amount of those branches per 1,000 carbons and the sum of them were obtained by the above method.

b) As a sample for measurement and analysis of polar group-containing vinyl monomer content by IR, a press plate of about 0.5 mm was prepared, and an infrared absorption spectrum was obtained using Shimadzu Corporation FTIR-8300 type. Comonomer content, and harmonic absorption of the carbonyl group in the vicinity of 3450 cm ^-1, was calculated based on the infrared absorption intensity ratio of olefin absorption around 4250cm ^-1. In the calculation, a calibration curve prepared by the ¹³ C-NMR measurement was used.

In the present invention, the above two methods are employed. The analysis method by IR is a simple method, but the analysis accuracy is relatively lower than that by ¹³ C-NMR. In the Example of this invention, when there exist both analysis values, the analysis value by < ¹³ > C-NMR is employ | adopted.

2. Ligand synthesis The ligands obtained in the following synthesis examples were used. Unless otherwise specified in the following synthesis examples, the operation was performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated.

(Synthesis Example 1) Synthesis of Ligand (I) To a solution of anhydrous benzenesulfonic acid (400 mg, 2.5 mmol) in tetrahydrofuran (20 mL), normal butyllithium hexane solution (2.5 M, 2 mL, 5 mmol) was added at 0 ° C. The solution was slowly added dropwise and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −70 ° C., phosphorus trichloride (340 mg, 2.5 mmol) was added, and the mixture was stirred for 2 hours while raising the temperature to room temperature (reaction solution A).
To a solution of 1-bromo-2-isopropylbenzene (1 g, 5 mmol) in diethyl ether (20 mL), normal butyllithium hexane solution (2.5 M, 2 mL, 5 mmol) is slowly added dropwise at −30 ° C., and the temperature is raised to room temperature. The mixture was stirred for 3 hours while being raised. This solution was added dropwise to the previous reaction solution A at room temperature and stirred overnight. After the reaction, water (20 mL) was added, extracted with ether (20 mL × 2), washed with 1N hydrochloric acid (20 mL × 2), and then the solvent was distilled off. Washing with methanol (5 mL) gave 100 mg of the white target product.
1H NMR (CDCl3, ppm / d): 8.35 (ddd, J = 0.8, 4.8, 7.6 Hz, 1 H), 7.74 (tt, J = 1.4,7.6 Hz, 1 H), 7.65 (t, J = 7.6 Hz , 2 H), 7.53 (t, J = 6.4 Hz, 2 H), 7.42 (ddt, J = 1.2, 2.8, 7.6 Hz, 1 H), 7.26 (ddt, J = 0.8, 4.8, 8.0 Hz, 2 H ), 7.05 (dd, J = 0.8, 7.6 Hz, 1 H), 6.98 (dd, J = 0.8, 5.2 Hz, 2 H), 3.00 (m, 2 H), 1.15 (d, J = 6.8 Hz, 6 H), 1.09 (d, J = 6.0 Hz, 6 H). 31P NMR (CDCl3, ppm / d): 9.5.

(Synthesis Example 2) Synthesis of Ligand (II) To a solution of benzenesulfonic anhydride (400 mg, 2.5 mmol) in tetrahydrofuran (10 mL), a normal butyllithium hexane solution (2.5 M, 1.9 mL, 4.8 mmol). Was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (0.2 mL, 2.4 mmol) was added, and the mixture was stirred for 2 hours (reaction solution B).
A solution of 1-bromo-2- (1′-methyl-2′-methoxy) ethylbenzene (1 g, 4.8 mmol) in tetrahydrofuran (10 mL) was added to a normal butyl lithium hexane solution (2.5 M, 1.9 mL, 4.8 mmol). ) Was added dropwise at 0 ° C., and the mixture was stirred for 1 hour while raising the temperature to room temperature. This solution was added dropwise to the previous reaction solution B at 0 ° C. and stirred at room temperature for 3 hours. After the solvent was distilled off, water (100 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Recrystallization from a mixed solvent of ethyl acetate / diethyl ether (1/10) gave a white target product.
1H NMR (CDCl3, ppm / d): 8.30 (br, 1 H), 7.60 (br, 3 H), 7.50 (br, 2 H), 7.40 (br, 1 H), 7.27 (br, 2 H), 7.04 (br, 3 H), 3.0 (br, 12 H), 1.1 (br, 6 H) .31P NMR (CDCl3, ppm / d): -8.5.

(Synthesis Example 3) Synthesis of Ligand (III) To a solution of benzenesulfonic anhydride (3.4 g, 21.8 mmol) in tetrahydrofuran (200 mL) was added a normal butyl lithium hexane solution (2.5 M, 17.4 mL, 43. 6 mmol) was slowly added dropwise at 0 ° C., and the mixture was stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.9 mL, 21.8 mmol) was added, and the mixture was stirred for 2 hours (reaction solution C).
To a solution of 1-bromo-2-isopropyl-4-methoxybenzene (10 g, 43.6 mmol) in tetrahydrofuran (200 mL) was added t-butyllithium hexane solution (1.6 M, 54.5 mL, 87.2 mmol) at -78 ° C. The solution was slowly added dropwise and stirred for 1 hour. This solution was added dropwise to the previous reaction solution C at −78 ° C. and stirred overnight at room temperature. After the solvent was distilled off, water (200 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. By recrystallization from methanol, 0.3 g of a white target product was obtained.
1H NMR (CDCl3, ppm / d): 8.34 (dd, J = 5.2, 7.6 Hz, 1 H), 7.71 (t, J = 7.6 Hz, 1 H), 7.40 (m, 1 H), 7.1-7.0 ( m, 3 H), 6.91 (dd, J = 8.8, 14.4 Hz, 2 H), 6.75 (d, J = 8.4 Hz, 2 H), 3.80 (s, 6 H), 2.97 (m, 2 H), 1.15 (d, J = 6.8 Hz, 6 H), 1.08 (br, 6 H). 31P NMR (CDCl3, ppm / d): -10.7.

(Synthesis Example 4) Synthesis of Ligand (IV) To a solution of benzenesulfonic anhydride (2 g, 12.6 mmol) in tetrahydrofuran (50 mL) was added a normal butyl lithium hexane solution (2.5 M, 10 mL, 25.3 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution D).
To a solution of 1-bromo-2-cyclohexylbenzene (6 g, 25.3 mmol) in tetrahydrofuran (50 mL), a tbutyllithium hexane solution (1.6 M, 31.6 mL, 50.6 mmol) was slowly added dropwise at 0 ° C., Stir for 1 hour. This solution was added dropwise to the previous reaction solution D at −78 ° C. and stirred overnight at room temperature. LC-MS purity 50% / water (200 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Purification by silica gel column chromatography (dichloromethane / methanol = 50/1) gave 1.0 g of a white target product.
1H NMR (CDCl3, ppm / d): 7.86 (m, 1 H), 7.30 (dt, J = 1.2, 7.6 Hz, 1 H), 7.24-7.15 (m, 5 H), 6.96 (m, 2 H) , 6.83 (m, 1 H), 6.57 (m, 2 H), 3.21 (br, 2 H), 1.55 (br, 8 H), 1.31 (br, 4 H), 1.14 (br, 8 H). NMR (CDCl3, ppm / d): -28.7.

(Synthesis Example 5) Synthesis of Ligand (V) To a solution of benzenesulfonic anhydride (0.9 g, 5.8 mmol) in tetrahydrofuran (20 mL), a normal butyl lithium hexane solution (2.5 M, 4.6 mL, 11. 5 mmol) was slowly added dropwise at 0 ° C., and the mixture was stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (0.5 mL, 5.8 mmol) was added, and the mixture was stirred at 0 ° C. for 2 hours (reaction solution E).
To a solution of 1-bromo-2-hydrofurylbenzene (2.6 g, 11.5 mmol) in tetrahydrofuran (50 mL), a t-butyllithium hexane solution (1.5 M, 15.4 mL, 23 mmol) was added dropwise at 0 ° C. And stirred for 1 hour. This solution was added dropwise to the previous reaction solution E at −50 ° C. and stirred overnight at room temperature. After the solvent was distilled off, water (100 mL) was added, washed with MTBE (100 mL × 3), and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Washing with methanol gave 1.0 g of the white target product.
1H NMR (DMSO, ppm / d): 7.88 (m, 3 H), 7.42 (m, 2 H), 7.37-7.29 (m, 3 H), 7.22 (t, J = 7.4 Hz, 1 H), 7.11 (t, J = 7.4 Hz, 2 H), 6.72 (m, 1 H), 6.63 (m, 2 H), 5.27 (br, 2 H), 3.94 (m, 2 H), 3.67 (m, 2 H ), 2.0-1.1 (br, 8 H). 31P NMR (CDCl3, ppm / d): -30.4.

(Synthesis Example 6) Synthesis of Ligand (VI) To a solution of benzenesulfonic anhydride (2.3 g, 14.5 mmol) in tetrahydrofuran (100 mL), a normal butyl lithium hexane solution (2.5 M, 11.6 mL, 29 mmol). Was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.26 mL, 14.5 mmol) was added, and the mixture was stirred for 2 hours (reaction solution F).
To a solution of 1-bromo-2-t-butylbenzene (6.2 g, 29 mmol) in diethyl ether (100 mL), a normal butyllithium hexane solution (1.6 M, 11.6 mL, 29 mmol) was added dropwise at 0 ° C. Stir for hours. This solution was added dropwise to the previous reaction solution F at −78 ° C. and stirred overnight at room temperature. After the solvent was distilled off, water (100 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Recrystallization from methanol gave 3.5 g of the white target product.
1H NMR (CDCl3, ppm / d): 8.33 (dd, J = 5.2, 7.6 Hz, 1 H), 7.7 (m, 3 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.55 (t, J = 7.6 Hz, 1 H), 7.38 (m, 1 H), 7.25 (t, J = 7.6 Hz, 1 H), 7.2-7.1 (m, 3 H), 6.90 (dd, J = 8.0, 14.0 Hz , 1 H), 1.37
(s, 9 H), 1.34 (s, 9 H). 31P NMR (CDCl3, ppm / d): 4.5.

Synthesis Example 7 Synthesis of Ligand (VII) A solution of 1-bromo-2-isopropylbenzene (2.34 g, 11.8 mmol) in diethyl ether (10 mL) was added to a normal butyl lithium hexane solution (2.5 M, 4 7 mL, 11.8 mmol) was slowly added dropwise at −30 ° C., and the mixture was stirred for 2 hours while raising the temperature to room temperature. The reaction solution was added dropwise at −78 ° C. to a tetrahydrofuran solution of phosphorus trichloride (0.81 g, 5.88 mmol), and stirred at the same temperature for 2 hours (Reaction solution G).
To a solution of 1-bromo-2-sulfonic acid isopropyl ester-4-methoxybenzene (1.5 g, 4.7 mmol) in tetrahydrofuran (12 mL) was added t-butyllithium hexane solution (1.6 M, 5.9 mL, 9.4 mmol). ) Was slowly added dropwise at -78 ° C and stirred for 4 hours. This solution was added dropwise to the previous reaction solution G at −78 ° C. and stirred overnight at room temperature. Water (20 mL) was added and acidified with hydrochloric acid (PH <2). Methylene chloride was extracted (50 mL × 3) and washed with an aqueous sodium chloride solution. After drying with sodium sulfate, the solvent was distilled off (yield 1.2 g). This product was dissolved in methanol (8 mL), aqueous sodium hydroxide solution (1M, 4 mL, 4 mmol) and tetrahydrofuran (8 mL) were added, and the mixture was stirred at 50 ° C. for 4 hr. 2N hydrochloric acid (20 mL) was added, followed by extraction with methylene chloride (50 mL × 3), drying over sodium sulfate, and then the solvent was distilled off. By washing with a small amount of diethyl ether, a white target product was obtained (yield 0.3 g).
1H NMR (CDCl3, ppm / d): 7.94 (br, 1 H), 7.68 (m, 2 H), 7.59 (m, 2 H), 7.31 (m, 2 H), 7.04 (m, 2 H), 6.94 (d, J = 2.8 Hz, 2 H), 3.95 (s, 3 H), 3.06 (m, 2 H), 1.19 (m, 12 H). 31P NMR (CDCl3, ppm / d): -10.4.

(Synthesis Example 8) Synthesis of Ligand (VIII) A normal butyl lithium hexane solution (2.5 M, 5 mL, 12.6 mmol) was added to a tetrahydrofuran (20 mL) solution of benzenesulfonic anhydride (1 g, 6.3 mmol). The solution was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (0.54 mL, 6.3 mmol) was added, and the mixture was stirred for 2 hours (reaction solution H).
To a solution of 1-bromo-2- (1′-methyl-2′-phenoxy) ethylbenzene (3.8 g, 12.6 mmol) in diethyl ether (20 mL), a normal lithium hexane solution (2.5 M, 5.0 mL, 12 .6 mmol) was slowly added dropwise at 0 ° C. and stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution H at room temperature and stirred overnight at room temperature. LC-MS purity 22% and water were added, and hydrochloric acid was added to acidify (PH <3). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Purification by silica gel column chromatography (dichloromethane / methanol = 70/1) gave 2.0 g of the white target product.
1H NMR (DMSO, ppm / d): 8.34 (t, J = 6.0 Hz, 1 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.40 (m, 1 H), 7.4-7.0 (m, 10 H), 6.9-6.5 (m, 9 H), 4.0 (m, 2 H), 3.7 (m, 4 H), 1.1 (m, 3 H), 0.8 (m, 3 H). 31P NMR (CDCl3 , ppm / d): -29.9.

(Synthesis Example 9) Synthesis of Ligand (IX) To a solution of anhydrous benzenesulfonic acid (0.6 g, 3.8 mmol) in tetrahydrofuran (10 mL), a normal butyl lithium hexane solution (2.5 M, 3 mL, 7.6 mmol). Was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (0.33 mL, 3.8 mmol) was added, and the mixture was stirred for 2 hours (reaction solution I).
To a solution of 1-bromo-2-isopropyl-3-hexylbenzene (2.2 g, 7.6 mmol) in diethyl ether (20 mL) was added a normal butyl lithium hexane solution (2.5 M, 3.0 mL, 7.6 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred at room temperature for 3 hours. This solution was added dropwise to the previous reaction solution I at −78 ° C. and stirred overnight at room temperature. LC-MS purity 51%. Water was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (50 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Purification by silica gel column chromatography (dichloromethane / methanol = 70/1) gave 0.8 g of a white target product.
1H NMR (CDCl3, ppm / d): 8.34 (d, J = 6.0 Hz, 1 H), 7.70 (d, J = 7.6 Hz, 1 H), 7.40 (m, 1 H), 7.29 (d, J = 4.4 Hz, 2 H), 7.04 (m, 3 H), 6.85 (dd, J = 7.6, 14.8 Hz, 2 H), 2.97 (m, 2 H), 2.60 (t, J = 7.6 Hz, 4 H) , 1.54 (m, 4 H), 1.25 (s, 12 H), 1.2-1.0 (m, 12 H), 0.82 (br, 6 H). 31P NMR (CDCl3, ppm / d): -9.9.

(Synthesis Example 10) Synthesis of Ligand (X) To a solution of benzenesulfonic anhydride (2 g, 12.6 mmol) in tetrahydrofuran (20 mL) was added a normal butyl lithium hexane solution (2.5 M, 10 mL, 25.3 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution J1).
Magnesium was dispersed in tetrahydrofuran (20 mL), 1-bromo-2-methoxybenzene (2.3 g, 12.6 mmol) was added, and the mixture was stirred at room temperature for 3 hours. This solution was added dropwise to the previous reaction liquid J1 at −78 ° C. and stirred for 1 hour (reaction liquid J2).
To a solution of 1-bromo-2-isopropylbenzene (2.5 g, 12.6 mmol) in diethyl ether (20 mL), slowly add normal butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) at −30 ° C. And stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution J2 at −78 ° C. and stirred overnight at room temperature. LC-MS purity 60% / water (50 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL) and drying with sodium sulfate, the solvent was distilled off. By recrystallization from methanol, 1.1 g of a white target product was obtained.
1H NMR (CDCl3, ppm / d): 8.34 (t, J = 6.0 Hz, 1 H), 7.7-7.6 (m, 3 H), 7.50 (t, J = 6.4 Hz, 1 H), 7.39 (m, 1 H), 7.23 (m, 1 H), 7.1-6.9 (m, 5 H), 3.75 (s, 3 H), 3.05 (m, 1 H), 1.15 (d, J = 6.8 Hz, 3 H) , 1.04 (d, J = 6.4 Hz, 3 H). 31P NMR (CDCl3, ppm / d): -10.5.

(Synthesis Example 11) Synthesis of Ligand (XI) To a solution of benzenesulfonic anhydride (3.0 g, 19 mmol) in tetrahydrofuran (40 mL) was added a normal butyllithium hexane solution (2.5 M, 15.2 mL, 38 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.7 mL, 19 mmol) was added, and the mixture was stirred for 2 hours (reaction solution K1).
To a solution of 1-iodo-2,6-dimethoxybenzene (5.0 g, 19 mmol) in tetrahydrofuran (40 mL), isopropylmagnesium chloride (2.0 M, 9.5 mL, 19 mmol) is slowly added dropwise at −40 ° C. For 2 hours. This solution was added dropwise to the previous reaction solution K1 at −78 ° C. and stirred at room temperature for 1 hour (reaction solution K2).
To a solution of 1-bromo-2-isopropylbenzene (3.8 g, 19.0 mmol) in diethyl ether (30 mL), slowly add a normal butyl lithium hexane solution (2.5 M, 7.6 mL, 19.0 mmol) at −30 ° C. And stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution K2 at −78 ° C. and stirred overnight at room temperature. LC-MS purity 39% / water (60 mL) was added and acidified with hydrochloric acid (PH <1). After extraction with methylene chloride (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. By recrystallization from methanol, 4.4 g of a white target product was obtained.
1H NMR (CDCl3, ppm / d): 9.67 (d, J = 290.2 Hz, 1 H), 8.34 (m, 1 H), 7.7-7.5 (m, 3 H), 7.50 (m, 1 H), 7.41 (m, 1 H), 7.33-7.26 (m, 3 H), 6.67 (dd, J = 5.2, 8.8 Hz, 2 H), 3.65 (s, 6 H), 2.97 (m, 1 H), 1.14 ( d, J = 6.8 Hz, 3 H), 1.05 (d, J = 6.4 Hz, 3 H). 31P NMR (CDCl3, ppm / d): -19.1.

Synthesis Example 12 Synthesis of Complex (XII) To a solution of ligand (I) (0.62 g, 1.45 mmol) in methylene chloride (40 mL) was added sodium carbonate (0.19 g, 1.75 mmol) at room temperature. For 4 hours. The reaction solution was cooled to −20 ° C., Ni (PPh ₃ ) ₂ (Ph) Cl complex (1.0 g, 1.46 mmol) was added, and the mixture was stirred overnight at room temperature. After distilling off the solvent, extraction with diethyl ether (10 mL × 3) was followed by recrystallization to obtain 0.9 g of the target complex.
1H NMR (CDCl3, ppm / d): 8.45-7.07 (m, 32 H), 2.29 (m, 2 H), 1.24 (m, 12 H). 31P NMR (CDCl3, ppm / d): -9.5.

(Synthesis Example 13) Synthesis of Ligand (XIII) To a solution of anhydrous benzenesulfonic acid (5.2 g, 32.9 mmol) in tetrahydrofuran (60 mL) was added a normal butyl lithium hexane solution (2.5 M, 25 mL, 62 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred for 20 hours while raising the temperature to room temperature. To this reaction solution, a solution of bis (2-methoxyphenyl) methoxyphosphine (9.1 g, 32.9 mmol) in tetrahydrofuran (20 mL) was added dropwise and stirred for 16 hours. After adding ammonium chloride (3.4 g, 62 mmol), the solvent was distilled off and water (100 mL) was added. After washing with MTBE (40 mL × 2), the mixture was acidified with hydrochloric acid (PH <3). Extraction with methylene chloride (60 mL × 2), drying with sodium sulfate, and recrystallization at −35 ° C. gave 3.7 g of the white target product.
1H NMR (C2D2Cl4, ppm / d): 6.7-8.2 (m, 12H), 3.79 (s, 6H). 31P NMR (C2D2Cl4, ppm / d): -9.8.

(Synthesis Example 14) Synthesis of Ligand (XIV) To a tetrahydrofuran (20 mL) solution of benzenesulfonic anhydride (0.74 g, 4.7 mmol), a normal butyl lithium hexane solution (2.5 M, 3.8 mL, 9. 4 mmol) was slowly added dropwise at 0 ° C., and the mixture was stirred for 2 hours while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (0.41 mL, 4.7 mmol) was added, and the mixture was stirred at room temperature for 2 hours (reaction solution L).
To a solution of 1-bromo-2- (2 ′, 6′-dimethoxyphenyl) benzene (2.8 g, 9.4 mmol) in tetrahydrofuran (25 mL) was added t-butyllithium hexane solution (1.5 M, 12.5 mL, 18 .8 mmol) was slowly added dropwise at 0 ° C. and stirred for 30 minutes. This solution was added dropwise to the previous reaction liquid L at −50 ° C. and stirred overnight at room temperature. After the solvent was distilled off, water (200 mL) was added and acidified with hydrochloric acid (PH <3). After MTBE extraction (100 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Washing with THF (5 mL) gave a white target product. 0.5g.
1H NMR (CDCl3, ppm / d): 8.08 (m, 1 H), 7.61 (m, 3 H), 7.42-7.12 (m, 10 H), 6.68-6.22 (br, 4 H), 3.84-3.31 ( br, 9 H), 2.96 (br, 3 H). 31P NMR (CDCl3, ppm / d): -2.4.

3. Preparation of chemically treated montmorillonite (treatment example 1) Preparation of sulfuric acid / lithium sulfate treated montmorillonite Into a 500 mL round three-necked flask equipped with a stirring blade and a reflux apparatus, 170 g of distilled water was added and 50 g of 98% sulfuric acid was added dropwise. The temperature was 90 ° C. There, 30 g of Benclay SL (manufactured by Mizusawa Chemical Co., Ltd.) was added and stirred. Thereafter, the reaction was carried out at 90 ° C. for 3.5 hours. The slurry was poured into 150 mL of distilled water to stop the reaction, filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 75 mL of distilled water. The obtained cake was dispersed in 300 mL of distilled water, filtered after stirring. This operation was repeated three times.
The recovered cake was added to an aqueous solution in which 17 g of zinc sulfate heptahydrate was dissolved in 135 mL of pure water in a 1 L beaker and reacted at room temperature for 2 hours. This slurry was filtered through a device in which an aspirator was connected to Nutsche and a suction bottle, and washed with 75 mL of distilled water. The obtained cake was dispersed in 300 mL of distilled water, filtered after stirring. This operation was repeated three times.
The collected cake was dried at 120 ° C. overnight. As a result, 22 g of a chemically treated product was obtained. This chemically treated montmorillonite was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C., and after the generation of gas had ceased, it was further dried under reduced pressure for 2 hours. After drying, it was stored in a nitrogen atmosphere, and when used for polymerization evaluation, it was slurried with methylene chloride or toluene (40 mg-montmorillonite / ml-solvent) and added.

(Treatment Example 2) Organic Aluminum Treatment of Chemically Treated Montmorillonite 1 g of the chemically treated montmorillonite dried in the above (Treatment Example 1) was weighed into a flask with an internal volume of 200 mL, and 3.6 mL of heptane and a heptane solution of triisobutylaluminum 6. 4 mL (2.5 mmol) was added and stirred at room temperature for 1 hour. Thereafter, the residue was washed with methylene chloride or toluene to a residual liquid ratio of 1/100, and the same solvent as that used for the last washing was used to make the slurry volume 25 mL.

4). Polymerization 4-1. (Example 1-1)
100 μmoles of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand are weighed in a 30 mL flask thoroughly purged with nitrogen, and after adding dehydrated toluene (10 mL), this is treated with an ultrasonic vibrator for 10 minutes. A catalyst slurry was prepared. Next, the inside of the induction-stirring stainless steel autoclave with an internal volume of 1 L is replaced with purified nitrogen, and purified toluene (617 mL) and methyl acrylate (72 mL, adjusted so that the concentration during polymerization is 1 mol / L) are in a purified nitrogen atmosphere The autoclave was introduced below. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was kept at 80 ° C., and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 3 MPa.
After the polymerization, ethylene was purged, the autoclave was cooled to room temperature, and when the obtained polymer was a toluene-insoluble solid, the polymer and the solvent were separated by filtration. When separation was insufficient by filtration, the polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. Each polymerization result is shown in Table 2.

4-2. (Example 2-1)
After adding 100 μmol of nickel complex (VII) and dehydrated toluene (10 mL) to a 30 mL flask sufficiently purged with nitrogen, this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry. Next, the inside of the induction-stirring stainless steel autoclave with an internal volume of 1 L is replaced with purified nitrogen, and purified toluene (617 mL) and methyl acrylate (72 mL, adjusted so that the concentration during polymerization is 1 mol / L) are in a purified nitrogen atmosphere The autoclave was introduced below. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was kept at room temperature, and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 3 MPa. After 15 minutes, ethylene was purged and concentrated with an evaporator. 1N hydrochloric acid (20 ml) was added thereto and stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to recover the product. 0.3 g, Mw: 36,000, Mw / Mn: 6.72, Tm: 120.1 ° C.

(Comparative Example 2-1)
Add 1,000 μmol of (biscyclooctadiene) nickel and phosphorous sulfonic acid ligand (VIII) to a 30 mL flask thoroughly purged with nitrogen, add dehydrated toluene (10 mL), and then use an ultrasonic vibrator. A catalyst slurry was prepared by treatment for 10 minutes. Next, the inside of the induction stirring type stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and purified toluene (708 mL) and methyl acrylate (1 mol / L) were introduced into the autoclave under a purified nitrogen atmosphere. The catalyst slurry was added, and the polymerization was started at room temperature at an ethylene pressure of 3 MPa. During the reaction, the temperature was kept at room temperature, and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 3 MPa. After 15 minutes, ethylene was purged and concentrated with an evaporator. When 1N hydrochloric acid (20 mL) was added thereto and stirred for 60 minutes, no polymer was obtained.

4-3. (Examples 3 and 4)
(Bisdibenzylideneacetone) A slurry of palladium and a phosphorus sulfonic acid ligand is prepared separately, treated with an ultrasonic vibrator, then mixed and stirred at room temperature for 15 minutes, so that 0.0025-0. A catalyst slurry of 002 mol / L was prepared. The inside of an induction stirring stainless steel autoclave having an internal volume of 10 mL was replaced with purified nitrogen, and purified toluene and a predetermined amount of comonomer were introduced. After raising the temperature and pressurizing with ethylene to 2 MPa, a predetermined amount of the previously prepared catalyst slurry was added to initiate polymerization. In addition, it prepared so that the liquid total amount at the time of superposition | polymerization might be 5 mL. During the reaction, the temperature was kept constant, and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 2 MPa. After 60 minutes, unreacted ethylene was purged, the autoclave was cooled to room temperature, and the resulting polymer was collected by filtration and dried under reduced pressure at 40 ° C. for 6 hours. Detailed polymerization conditions and polymerization results are shown in Tables 3 and 4.

4-4. (Examples 5, 6, and 7)
The inside of an induction stirring stainless steel autoclave having an internal volume of 10 mL was replaced with purified nitrogen, and purified toluene and a predetermined amount of comonomer were introduced. After raising the temperature, the pressure was increased with ethylene to 2 MPa. Prepare a solution of (biscyclooctadiene) nickel and phosphorous sulfonic acid ligand in toluene separately. Started. Moreover, when using 3rd components, such as aniline, it added after adding (biscyclooctadiene) nickel and before adding a phosphorus sulfonic acid ligand. In addition, it prepared so that the liquid total amount at the time of superposition | polymerization might be 5 mL. During the reaction, the temperature was kept constant, and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 2 MPa. After 60 minutes, unreacted ethylene was purged, the autoclave was cooled to room temperature, and the solvent was distilled off. The polymer was washed with a small amount of acetone, collected by filtration, and dried under reduced pressure at 40 ° C. for 6 hours. The polymerization conditions and polymerization results are shown in Tables 5, 6 and 7.

4-5. (Examples 8 and 9)

(Bisdibenzylideneacetone) A methylene chloride solution or slurry of palladium and a phosphorus sulfonic acid ligand is separately prepared, mixed at room temperature, and then stirred for 30 minutes with an ultrasonic vibrator. A catalyst slurry of 002 mol / L was prepared. Then, a predetermined amount of methylene chloride slurry (40 mg-cray / ml-toluene) of chemically treated montmorillonite obtained in Treatment Example 1 or Treatment Example 2 was added, and further stirred with a stirrer at room temperature for 30 minutes to obtain a supported catalyst slurry. It was. The evaluation of the polymerization was carried out when the supported catalyst slurry obtained here was used as it was for the evaluation of polymerization and when it was washed with methylene chloride to a residual liquid ratio of 1/100.
The inside of an induction stirring stainless steel autoclave having an internal volume of 10 mL was replaced with purified nitrogen, and purified toluene and a predetermined amount of comonomer were introduced. After raising the temperature and pressurizing with ethylene to 2 MPa, a predetermined amount of the previously prepared supported catalyst slurry was added to initiate polymerization. In addition, it prepared so that the liquid total amount at the time of superposition | polymerization might be 5 mL. During the reaction, the temperature was maintained at 80 ° C., and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 2 MPa. After 60 minutes, unreacted ethylene was purged, the autoclave was cooled to room temperature, and the resulting polymer was collected by filtration and dried under reduced pressure at 40 ° C. for 6 hours. The polymerization conditions and polymerization results are shown in Table 8.

4-6. (Examples 10 and 11, Comparative Example 11)

A toluene solution or slurry of (biscyclooctadiene) nickel and a phosphorus sulfonic acid ligand was prepared separately. A catalyst slurry of 0.0025 to 0.002 mol / L was prepared by stirring for 30 minutes at room temperature using an ultrasonic vibrator. Then, a predetermined amount of the toluene slurry (40 mg-cray / ml-toluene) of the chemically treated clay obtained in Treatment Example 1 or Treatment Example 2 of chemically treated montmorillonite was added, and further stirred at room temperature for 30 minutes with a stirrer. A catalyst slurry was obtained. The evaluation of the polymerization was carried out when the obtained supported catalyst slurry was used for the evaluation of the polymerization as it was, and when the residual liquid ratio was washed to 1/100 with toluene.
The inside of an induction stirring stainless steel autoclave having an internal volume of 10 mL was replaced with purified nitrogen, and purified toluene and a predetermined amount of comonomer were introduced. After raising the temperature and pressurizing with ethylene to 2 MPa, a predetermined amount of the previously prepared supported catalyst slurry was added to initiate polymerization. In addition, it prepared so that the liquid total amount at the time of superposition | polymerization might be 5 mL. During the reaction, the temperature was maintained at 80 ° C., and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 2 MPa. After 60 minutes, unreacted ethylene was purged, the autoclave was cooled to room temperature, and the resulting polymer was collected by filtration and dried under reduced pressure at 40 ° C. for 6 hours. The polymerization conditions and polymerization results are shown in Table 9.

4-7. (Example-12: Copolymerization of ethylene / 1-hexene / ethyl acrylate) Into a 30-mL flask sufficiently purged with nitrogen, 200 μmol of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed and dehydrated toluene ( 10 mL) was added, and then this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry. Next, the inside of the induction stirring stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and purified toluene (170 mL), 1-hexene (279 mL), and ethyl acrylate (245 mL) were introduced into the autoclave under a purified nitrogen atmosphere. . The whole amount of the catalyst slurry prepared previously was added, and ethylene was pressurized at a pressure of 3 MPa to initiate polymerization. During the reaction, the temperature was maintained at 80 ° C., and ethylene was continuously supplied so that the pressure was maintained at 3 MPa. After 180 minutes, ethylene was purged, the autoclave was cooled to room temperature, the polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer.
74 g of ethylene / 1-hexene / ethyl acrylate copolymer was obtained. Catalytic activity is 1.2E + 05 g / mol / h, Mw by GPC is 92,000, Mw / Mn: 2.1, melting point is 102.9 ° C., monomer composition by ¹³ CNMR is ethylene content is 96.3 mol %, 1-hexene content was 1.1 mol%, and ethyl acrylate content was 2.6 mol%. Polymerization conditions and polymerization results are shown in Tables 10 and 11.

4-8. (Examples 13-22: Copolymerization of ethylene / 1-hexene / ethyl acrylate) Into a 30-mL flask sufficiently purged with nitrogen, predetermined amounts of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I ) Was weighed, dehydrated toluene (10 mL) was added, and this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry.
Next, the inside of a stainless steel autoclave with an induction stirrer with an internal volume of 2.4 L was replaced with purified nitrogen, and a predetermined amount of purified toluene shown in Table 10 (Example 22 uses hexane instead of toluene), ethyl acrylate 1-hexene was introduced into the autoclave.
After controlling the inside of the autoclave to a predetermined temperature, the pressure in the autoclave was increased to 0.1 MPa with nitrogen, and the ethylene partial pressure was further increased (total pressure = ethylene partial pressure + 0.1). After the temperature in the autoclave was stabilized, the previously prepared catalyst slurry was pressed into the autoclave with a small amount of nitrogen to initiate polymerization. During the reaction, the temperature was maintained at a predetermined temperature, and ethylene was continuously supplied so that the pressure was maintained at the predetermined pressure.
After polymerization for a predetermined time, the polymerization was stopped by purging ethylene and cooling the autoclave to room temperature. The produced polymer was washed by adding the reaction solution to 1 L of acetone, and then separated by filtration. The separated polymer was further washed twice with acetone and filtered twice and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. Each polymerization result is shown in Table 11.

4-9. (Example-23: Copolymerization of ethylene / propylene / methyl acrylate) 100 μmol of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed into a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL). Then, this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry.
Next, the inside of the induction-stirring stainless steel autoclave with an internal volume of 1 L is replaced with purified nitrogen, and purified toluene (617 mL) and methyl acrylate (72 mL, adjusted so that the concentration during polymerization is 1 mol / L) are in a purified nitrogen atmosphere The autoclave was introduced below. The whole amount of the catalyst slurry prepared above was added and polymerization was performed by pressurizing an ethylene / propylene mixed gas (gas composition ratio: 7/3) that had been adjusted at 80 ° C. in advance using another autoclave at a pressure of 1.0 MPa. Started. During the reaction, the temperature was kept at 80 ° C., and the mixed gas was continuously supplied so that the pressure was kept at 1.0 MPa. After 60 minutes, the mixed gas was purged, the autoclave was cooled to room temperature, the polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover 7.0 g of an ethylene / propylene / ethyl acrylate copolymer. The catalytic activity was 6.6E + 04 g / mol / h. The obtained copolymer had a molecular weight Mw of 65,000, Mw / Mn of 1.9, a melting point of 92.1 ° C., a methyl acrylate content of 3.7 mol%, and a propylene content of 2.4 mol%. The polymerization results are shown in Table 12.

4-10. (Example-24: Copolymerization of ethylene / propylene / methyl acrylate) Into a 30-mL flask sufficiently purged with nitrogen, 264 μmoles of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed and dehydrated toluene (20 mL). Then, this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry.
Next, another 2 L induction stirring autoclave was prepared in advance as a buffer tank for ethylene / propylene mixed gas. The tank was charged with liquefied propylene (150 mL) and ethylene (2.5 MPa) at 20 ° C., and then stirred until it was sufficiently mixed, and the temperature was raised to 50 ° C.

Subsequently, the inside of the induction-stirring stainless steel autoclave having an internal volume of 2 L used for the polymerization is replaced with purified nitrogen, and purified toluene (500 mL), methyl acrylate (37.5 mL), and the total amount of the catalyst slurry prepared above are purified in a nitrogen atmosphere. The autoclave was introduced below. Introduce propylene (100 mL) into the autoclave at 20 ° C, increase the pressure to 1.2 MPa by introducing the adjusted mixed gas, raise the temperature to 70 ° C, and mix so that the total pressure becomes 2.0 MPa Added gas. During the polymerization, a mixed gas was appropriately introduced so as to maintain the total pressure. After 10 minutes, ethanol (25 ml) was charged and the unreacted gas was purged to terminate the polymerization. Ethanol (1,000 mL) was added to the recovered toluene suspension and allowed to stand overnight, and then the mixture was filtered. Acetone (500 mL) was added to the precipitate, and the mixture was stirred at 20 ° C. for 20 minutes, followed by filtration. This washing was performed twice more. After washing, it was dried under reduced pressure at 70 ° C. for 3 hours to obtain 23.2 g (catalytic activity: 5.3E + 05 (g / mol / h)) of an ethylene-propylene-methyl acrylate copolymer. The obtained copolymer had a melting point of 107.2 ° C. by DSC, Mw by GPC of 80,000, Mw / Mn of 1.7, methyl acrylate content of 1.0 mol%, and propylene content of 3.0 mol%. there were. The polymerization results are shown in Table 12.

4-11. (Example-25: Copolymerization of ethylene / propylene / methyl acrylate) Into a 100 mL flask sufficiently substituted with nitrogen, 580 μmol of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed and dehydrated toluene (50 mL). Then, this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry.
Next, another 2 L induction stirring autoclave was prepared in advance as a buffer tank for ethylene / propylene mixed gas. The tank was charged with liquefied propylene (150 mL) and ethylene (2.5 MPa) at 20 ° C., and then stirred until it was sufficiently mixed, and the temperature was raised to 50 ° C.

Subsequently, the inside of the induction-stirring stainless steel autoclave having an internal volume of 2 L used for the polymerization is replaced with purified nitrogen, and purified toluene (500 mL), methyl acrylate (37.5 mL), and the total amount of the catalyst slurry prepared above are purified in a nitrogen atmosphere. The autoclave was introduced below. Introduce propylene (100 mL) into the autoclave at 20 ° C, increase the pressure to 1.2 MPa by introducing the adjusted mixed gas, raise the temperature to 55 ° C, and mix so that the total pressure becomes 2.0 MPa Added gas. During the polymerization, a mixed gas was appropriately introduced so as to maintain the total pressure. After 25 minutes, ethanol (25 ml) was charged and the unreacted gas was purged to terminate the polymerization. Ethanol (1,000 mL) was added to the recovered toluene suspension and allowed to stand overnight, and then the mixture was filtered. Acetone (500 mL) was added to the precipitate, and the mixture was stirred at 20 ° C. for 20 minutes, followed by filtration. This washing was performed twice more. After washing, drying under reduced pressure was performed at 70 ° C. for 3 hours to obtain 19.6 g of an ethylene-propylene-methyl acrylate copolymer (catalytic activity was 8.1E + 04 (g / mol / h)). The melting point of the obtained copolymer by DSC was 113.6 ° C., the Gw Mw was 58,000, the Mw / Mn was 1.6, the methyl acrylate content was 0.6 mol%, and the propylene content was 2.4 mol%. there were. The polymerization results are shown in Table 12.

4-12. (Example-26: Copolymerization of ethylene / propylene / methyl acrylate) Palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) were weighed in an amount of 256 μmol each in a 50 mL flask sufficiently substituted with nitrogen, and dehydrated toluene (20 mL). Then, this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry.
Next, another 2 L induction stirring autoclave was prepared in advance as a buffer tank for ethylene / propylene mixed gas. The tank was charged with liquefied propylene (150 mL) and ethylene (2.5 MPa) at 20 ° C., and then stirred until it was sufficiently mixed, and the temperature was raised to 50 ° C.

Subsequently, the inside of the induction-stirring stainless steel autoclave having an internal volume of 2 L used for polymerization is replaced with purified nitrogen, and purified toluene (500 mL), methyl acrylate (46.9 mL), and the total amount of the catalyst slurry prepared above are purified to a nitrogen atmosphere. The autoclave was introduced below. Introduce propylene (100 mL) into the autoclave at 20 ° C, increase the pressure to 1.2 MPa by introducing the adjusted mixed gas, raise the temperature to 55 ° C, and mix so that the total pressure becomes 2.0 MPa Added gas. During the polymerization, a mixed gas was appropriately introduced so as to maintain the total pressure. After 30 minutes, ethanol (25 ml) was charged and the unreacted gas was purged to terminate the polymerization. Ethanol (1,000 mL) was added to the recovered toluene suspension and allowed to stand overnight, and then the mixture was filtered. Toluene (100 mL) and 35% hydrochloric acid (0.5 mL) were added to the resulting precipitate, stirred at 70 ° C. for 30 minutes, and filtered again. Acetone (500 mL) was added to the precipitate, and the mixture was stirred at 20 ° C. for 20 minutes, followed by filtration. This washing was performed twice more. After washing, drying under reduced pressure was performed at 70 ° C. for 3 hours to obtain 1.87 g of ethylene-propylene-methyl acrylate copolymer (catalytic activity was 1.5E + 04 (g / mol / h)). The melting point of the obtained copolymer by DSC was 120.1 ° C., Mw by GPC was 55,000, Mw / Mn was 1.9, the methyl acrylate content was 0.6 mol%, and the propylene content was 1.0 mol%. there were. The polymerization results are shown in Table 12.

4-13. (Examples 27 to 29: ethylene homopolymerization) Using a phosphorus sulfonic acid ligand shown in Table 13 in a fully nitrogen-substituted 30 mL flask, palladium bisdibenzylideneacetone and a phosphorus sulfonic acid ligand (I ) Were weighed 25 μmol each, dehydrated toluene (10 mL) was added, and then this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry. Next, the inside of the induction-stirring stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and purified toluene (790 mL) was introduced into the autoclave under a purified nitrogen atmosphere. The whole amount of the catalyst slurry prepared previously was added, the temperature was raised to 80 ° C., and the polymerization was started by pressurizing at an ethylene pressure of 3.0 MPa. During the reaction, the temperature was kept at 80 ° C., and the mixed gas was continuously supplied so that the pressure was kept at 3.0 MPa. After 60 minutes, the ethylene gas was purged, the autoclave was cooled to room temperature, and the precipitated polymer was filtered. Furthermore, the obtained polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the ethylene homopolymer. The polymerization results are shown in Table 13.
As a result of measuring ¹³ C-NMR of the polyethylene homopolymer of Example 27, short chain branching such as methyl and ethyl was not confirmed, and it was confirmed that the polyethylene was below the detection limit and very short chain branching.

4-14. (Examples 30 and 31: Copolymerization of ethylene-ethyl acrylate) Into a 30-mL flask sufficiently purged with nitrogen, the predetermined amounts of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) shown in Table 14 were weighed. After adding dehydrated toluene (10 mL), this was treated with an ultrasonic vibrator for 10 minutes to prepare a catalyst slurry. Next, the inside of the induction stirring stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and predetermined amounts of purified toluene and methyl acrylate shown in Table 14 were introduced into the autoclave under a purified nitrogen atmosphere. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was maintained at 80 ° C., and ethylene was continuously supplied for a predetermined time so that the partial pressure of ethylene was maintained at 3 MPa.
After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, and when the obtained polymer was a toluene-insoluble solid, the polymer and the solvent were separated by filtration. When separation was insufficient by filtration, the polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. The respective polymerization results are shown in Table 14.
As a result of confirmation by ¹³ C-NMR, ethyl acrylate was inserted into the main chain, and short chain branching such as methyl and ethyl could not be confirmed.

4-15. (Examples-32 and 33: ethylene-1-hexene copolymerization)
A predetermined amount of palladium bisdibenzylideneacetone and phosphorus sulfonic acid ligand (I) shown in Table 15 were weighed into a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) was added thereto. The catalyst slurry was prepared by processing for 10 minutes with a vibrator. Next, the inside of the induction-stirring stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and predetermined amounts of purified toluene and 1-hexene shown in Table 14 were introduced into the autoclave under a purified nitrogen atmosphere. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was maintained at 80 ° C., and ethylene was continuously supplied for a predetermined time so that the partial pressure of ethylene was maintained at 3 MPa.

After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, and when the obtained polymer was a toluene-insoluble solid, the polymer and the solvent were separated by filtration. When separation was insufficient by filtration, the polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. The respective polymerization results are shown in Table 15.

4-16. (Example-34: ethylene / propylene copolymerization) The same procedure as in Example-23 was carried out except that methyl acrylate was not used and 700 mL of purified toluene was used. As a result, 36 g of ethylene / propylene copolymer was recovered. The catalyst activity was 4.3E + 05 g / mol / h. The obtained copolymer had a molecular weight Mw of 23,000, Mw / Mn of 2.3, a melting point of 90.2 ° C., and a propylene content of 16.9 mol%.

5. Consideration of results of Examples and Comparative Examples

Each example that satisfies the requirements of each claim of the present application has the following good results when compared with each comparative example.
In Example 1, it was clarified that by using the catalyst composition according to the present invention, both comonomer content and molecular weight can be expressed in a balanced manner with a relatively high activity as compared with the comparative example which is a known technique.

In Example 2, it was shown that the copolymer can be produced by using the nickel complex according to the present invention as a catalyst, in contrast to the known technique in which an ethylene-acrylate copolymer was not obtained.

In Example 3, it was clarified that by using the catalyst composition according to the present invention, both comonomer content and molecular weight can be expressed with a relatively high activity in a balanced manner as compared with the comparative example which is a known technique.

In Example 4, it was clarified that various comonomer can be applied by using the catalyst composition according to the present invention.

In Example 5, it was shown that an ethylene / polar group-containing olefin copolymer can be produced by using a phosphorus sulfonic acid ligand according to the present invention in combination with nickel in a catalyst composition.

In Example 6, the phosphorous sulfonic acid ligand according to the present invention was used in a catalyst composition in combination with nickel, and even if aniline, MMA, clay, triphenylborane was added as a third component, ethylene / polar group contained It was shown that olefin copolymers can be produced.

In Example 7, it was shown that an ethylene homopolymer can be produced with high activity by using the phosphorus sulfonic acid ligand according to the present invention in combination with nickel in the catalyst composition.

In Examples 8 and 9, it was shown that an ethylene polymer and an ethylene-acrylate copolymer can be obtained even by using a catalyst carrying a phosphorus sulfonic acid ligand and palladium according to the present invention.
In Examples 10 and 11, it was shown that an ethylene polymer can be obtained with higher activity than the comparative example, which is a known technique, even when the catalyst carrying the phosphorus sulfonic acid ligand and nickel according to the present invention is used. It was also shown that an ethylene-acrylate copolymer was obtained.
In Examples 12 to 22, the reaction product of the phosphorus sulfonic acid ligand and the palladium compound, which is the catalyst composition of the present invention, has a narrow molecular weight distribution and a relatively high molecular weight of ethylene-1-hexene-ethyl acrylate ternary. The copolymer was shown to be manufacturable.
Furthermore, in Examples 24-26, it was shown that an ethylene-propylene-methyl acrylate terpolymer can also be produced.
In Examples 27 to 29, a highly active ethylene homopolymer can be produced by the reaction product of the phosphorus sulfonic acid ligand and the palladium compound, which is the catalyst composition of the present invention. It was shown that a polymer with a narrow molecular weight distribution and a small branching difference can be produced.
In Examples 30 to 33, ethylene and acrylate, ethylene and 1 were used in the same manner as in Example 1 and Example 4, depending on the reaction product of the phosphorus sulfonic acid ligand and the palladium compound, which is the catalyst composition of the present invention. -It was confirmed that hexene copolymerization was in progress.
In Example 34, it was confirmed by ¹³ C-NMR that the copolymerization of ethylene and propylene had progressed by the reaction product of the phosphorus sulfonic acid ligand, which is the catalyst composition of the present invention, and a palladium compound.

The significance and rationality of the configuration of the present invention (invention specific matter) and the superiority over the prior art are clarified by the good results of each of the above examples and the comparison with each comparative example.

  By copolymerizing an α-olefin and an acrylic monomer in the presence of the catalyst composition of the present invention, an industrially useful copolymer having a high comonomer content and a high molecular weight can be produced. Became. This copolymer has excellent mechanical and thermal properties and can be applied as a useful molded product. Specifically, the copolymer of the present invention is utilized by utilizing good properties such as paintability, printability, antistatic properties, inorganic filler dispersibility, adhesiveness with other resins, and compatibilizing ability with other resins. Can be used in various applications such as films, sheets, adhesive resins, binders, compatibilizers and the like.

Claims (12)

An α-olefin polymerization catalyst obtained by reacting a triarylphosphine compound represented by the following general formula (1) with a group 8-10 transition metal compound .

... (1)
(In General Formula (1), Y is phosphorus and Z is —SO ₃ H or CO ₂ H. R ^{1 to} R ⁴ are each independently a hydrogen atom or a carbon atom having 1 to 30 carbon atoms. A hydrogen group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms Represents an oxy group, and at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 30; Hydrocarbon group substituted with a halogen atom, a C1-C30 hydrocarbon group having a hetero atom, a C1-C30 alkoxy group, a C6-C30 carbon group Substituted with an aryloxy group or a hydrocarbon group having 1 to 30 carbon atoms Silyl group.) The general formula (1), wherein at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a secondary or tertiary alkyl group. Α-olefin polymerization catalyst . An α-olefin polymerization catalyst obtained by reacting a triarylphosphine compound represented by the following general formula (2) with a group 8-10 transition metal compound .

... (2)
(In General Formula (2), Y is phosphorus and Z is —SO ₃ H or CO ₂ H. R ^{1 to} R ⁴ are each independently a hydrogen atom, carbon atoms having 1 to 30 carbon atoms. A hydrogen group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms Represents an oxy group, and at least one of R ^{1 to} R ⁴ is a substituent containing a single bond between carbon directly bonded to the aromatic ring and an element selected from O or N. R ^{5 to} R ¹⁴ Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon atom having 1 to 30 carbon atoms having a hetero atom. Hydrogen group, C1-C30 alkoxy group, C6-C30 aryl An oxy group or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms is shown.) The α-olefin polymerization catalyst according to claim 1, further comprising a fine particle carrier. The alpha olefin polymerization catalyst containing the metal complex characterized by being represented by following General formula (3).

... (3)
(In General Formula (3), Y is phosphorus and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ are each independently a hydrogen atom or carbon atom having 1 to 30 carbon atoms. A hydrogen group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms Represents an oxy group, and at least one of R ^{1 to} R ⁴ is a secondary or tertiary alkyl group, and R ^{5 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 30; Hydrocarbon group substituted with a halogen atom, a C1-C30 hydrocarbon group having a hetero atom, a C1-C30 alkoxy group, a C6-C30 carbon group Substituted with an aryloxy group or a hydrocarbon group having 1 to 30 carbon atoms M represents a metal atom selected from the group consisting of a transition metal of group 8 to 10, and A represents a hydrogen atom, a halogen atom, or a hetero atom having 1 to 1 carbon atoms. 30 represents an alkyl group having 30 or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B represents an arbitrary ligand coordinated to M. A and B are bonded to each other to form a ring. May be formed.) In the general formula (3), at least one of R ^1, R ^2, and wherein at least one of R ^3, R ⁴ is a secondary or tertiary alkyl groups, according to claim 5 Α-olefin polymerization catalyst . The alpha olefin polymerization catalyst containing the metal complex characterized by being represented by following General formula (4).

... (4)
(In General Formula (4), Y is phosphorus and Z is —SO ₃ — or CO ₂ —. R ^{1 to} R ⁴ are each independently a hydrogen atom or carbon atom having 1 to 30 carbon atoms. A hydrogen group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms having a hetero atom, an alkoxy group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms Represents an oxy group, and at least one of R ^{1 to} R ⁴ is a substituent containing a single bond between carbon directly bonded to the aromatic ring and an element selected from O or N. R ^{5 to} R ¹⁴ Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon atom having 1 to 30 carbon atoms having a hetero atom. Hydrogen group, C1-C30 alkoxy group, C6-C30 aryl An oxy group or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms, M represents a metal atom selected from the group consisting of group 8-10 transition metals, A represents a hydrogen atom, A halogen atom, an alkyl group having 1 to 30 carbon atoms which may have a hetero atom, or an aryl group having 6 to 30 carbon atoms which may have a hetero atom, B is an arbitrary coordinated to M And A and B may be bonded to each other to form a ring.) The α-olefin polymerization catalyst according to claim 5, further comprising a fine particle carrier. The α-olefin polymerization catalyst according to claim 3 , wherein the fine particle carrier is an ion-exchange layered silicate. The α-olefin polymerization catalyst according to claim 9, wherein the ion-exchange layered silicate is a smectite group. An α-olefin and a (meth) acrylic acid or ester are copolymerized in the presence of the α-olefin polymerization catalyst according to any one of claims 1 to 10. ) A method for producing an acrylic acid copolymer. In the presence of the α-olefin polymerization catalyst according to any one of claims 1 to 10 , two types of different α-olefin, (meth) acrylic acid or ester are copolymerized, and α -Method for producing an olefin / (meth) acrylic acid copolymer.