JP2021066772A - Olefinic polymer and polyolefin resin - Google Patents

Abstract

To provide an olefinic polymer which has wide molecular weight distribution and in particular has wider molecular weight distribution on a higher molecular weight side.SOLUTION: An olefinic polymer is provided which includes a repeating unit derived from olefin having 2 to 10 carbon atoms, and in which (α) intrinsic viscosity [η] measured at 135°C in decalin is 0.1 to 13 dl/g, and (β) a ratio Mz/Mw value (Z) of a Z-average molecular weight (Mz) measured by gel permeation chromatography to a weight average molecular weight (Mw), and a ratio Mw/Mn value (Q) of the weight average molecular weight (Mw) to a number average molecular weight (Mn) satisfy at least one condition of (β1) and (β2). (β1)10≥Z/Q≥1.1.(β2)10≥Z/Q≥0.55 and 13.0≥Q≥8.0.SELECTED DRAWING: None

Description

The present invention relates to an olefin polymer and a polyolefin resin containing the same.

Conventionally, as a catalyst for producing an olefin-based polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium compound and an organoaluminum compound are used as a catalyst. Vanadium-based catalysts are known.

Further, as a catalyst capable of producing an olefin-based polymer with high polymerization activity, a metallocene-based catalyst composed of a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) is known.

On the other hand, the applicant has proposed a catalyst for olefin polymerization containing a transition metal compound having a salicylaldoimine ligand (see, for example, Patent Document 1). The catalyst for olefin polymerization containing the transition metal compound represented by the general formula (I) of Patent Document 1 is known to exhibit high olefin polymerization activity, but further improvement of the polymerization activity is required. Further, although the catalyst for olefin polymerization containing the transition metal compound can copolymerize two or more kinds of olefins, further improvement in polymerization activity and copolymerizability has been required.

Further, the applicant has proposed a transition metal compound represented by the general formula (I) of Patent Document 2 and a transition metal compound represented by the general formula (I) of Patent Document 3. The olefin polymerization catalyst containing the transition metal compound exhibits superior olefin polymerization activity when homopolymerizing the olefin, as compared with the catalyst containing the transition metal compound represented by the general formula (I) of Patent Document 1. It has also been found that the polymerization activity and copolymerizability when copolymerizing two or more kinds of olefins are improved.

The polymer obtained by using the above catalyst often has a narrower molecular weight distribution than the polymer obtained by the Ziegler-Natta catalyst. Polymers with a narrow molecular weight distribution tend to exhibit excellent performance as, for example, impact resistance modifiers, while they have "low melt fluidity", "low melt tension", and "molding". It is known that there is a tendency such as "inferior in sex" and "slightly low in rigidity".

In the product market, various high-speed molding technologies such as high-speed stretching technology aimed at improving the productivity of stretched films are evolving from the viewpoint of productivity improvement, cost reduction, etc., but they are relatively narrow as described above. When a polymer having a molecular weight distribution is to be stretched at high speed, for example, neck-in and fluttering of the film become more prominent due to insufficient melt tension, which may make it difficult to improve productivity. Therefore, there is a demand from the market for a polymer having a higher melt tension.
In order to solve such a problem, there are many reports such as a method of producing polymers having different molecular weights by multistage polymerization to widen the molecular weight distribution of the polymers (Patent Document 4).

On the other hand, Non-Patent Documents 1 and 2 report dinuclear Group 10 metal compounds having salicylaldoimine ligands and examples of using them as olefin polymerization catalysts, and mononuclear metal compounds were used. It has been shown that the molecular weight distribution of the obtained polyolefin is wider than in the case, but no example of a Group 4 metal compound is shown.

Further, Patent Document 5 reports a dinuclear Group 4 metal compound having a salicylaldoimine ligand and an example in which they are used as an olefin polymerization catalyst, but there is no description regarding the molecular weight distribution of the polymer. ..

Further, Non-Patent Document 3 reports a dinuclear Group 9 metal compound having a salicylaldoimine ligand and an example in which they are used as a catalyst for stereoselective ring-opening polymerization of an epoxide. Examples of Group 4 metal compounds are not shown, and the molecular weight distribution of the obtained polymer is not wide.

Japanese Unexamined Patent Publication No. 11-315109 Japanese Unexamined Patent Publication No. 2011-016789 Japanese Unexamined Patent Publication No. 2014-224053 Japanese Unexamined Patent Publication No. 5-170843 China National Intellectual Property Office Public CN104211726 Pamphlet

Organometallics 2005, 24, 2628. J. Mol. Catal. Chem. 2006, 253, 155. J. Am. Chem. Soc. 2008, 130, 17658.

The present invention has been made in view of the above-mentioned problems in the prior art, and an olefin-based polymer having a wide molecular weight distribution, particularly a wider molecular weight distribution toward the higher molecular weight side, and such an olefin-based polymer. An object of the present invention is to provide a polyolefin resin containing the mixture.

The present inventors have conducted diligent research to solve the above problems. The present invention was completed by finding that the polymer obtained by using the transition metal compound obtained by converting into a dinuclear Group 4 metal compound as a polymerization catalyst is a polymer capable of solving the above problems.

The polymer of the present invention has a molecular weight distribution that tends to be different from the conventional one. That is, it tends to have a wide molecular weight distribution that spreads toward the high molecular weight side.
The gist of the present invention is as follows.

[1]
(Α) The ultimate viscosity [η] measured at 135 ° C. in decalin was 0.1 to 13 dl / g.
(Β) The ratio Mz / Mw value (Z) of the Z average molecular weight (Mz) and the weight average molecular weight (Mw) measured by gel permeation chromatography, and the weight average molecular weight (Mw) and the number average molecular weight (Mn). A olefin polymer containing a repeating unit derived from an olefin having 2 to 10 carbon atoms, wherein the ratio Mw / Mn value (Q) of the above satisfies at least one of the following (β1) and (β2). ..
(Β1) 10 ≧ Z / Q ≧ 1.1
(Β2) 10 ≧ Z / Q ≧ 0.55 and 13.0 ≧ Q ≧ 8.0

[2]
The olefin-based polymer of the above [1], wherein the olefin is an olefin having 2 to 6 carbon atoms.

[3]
The olefin-based polymer of the above [1], wherein the olefin is an olefin having 2 to 4 carbon atoms.

[4]
A polyolefin resin containing the olefin polymer according to any one of [1] to [3].

The olefin-based polymer of the present invention has a wide molecular weight distribution, and particularly, the higher the molecular weight side, the wider the molecular weight distribution. Further, the polymer of the present invention is also a polymer that can be preferably obtained by single-stage polymerization, and it can be expected that the high molecular weight portion contained therein is well dispersed. It can be expected that it will be difficult to get out.

Therefore, the olefin-based polymer of the present invention can be suitably applied to high-speed molding of stretched films, can suppress neck-in and fluttering of the films, and is useful for improving productivity. Since the polyolefin resin of the present invention also contains the olefin polymer, it can be suitably applied to high-speed molding of stretched films, can suppress neck-in and fluttering of films, and is expected to be useful for improving productivity. Will be done.

[Olefin-based polymer]
The olefin-based polymer of the present invention has a wide molecular weight distribution, and particularly, the higher the molecular weight side, the wider the molecular weight distribution.

Specifically, the olefin polymer of the present invention satisfies the following requirements (α) and (β).
(Α) The ultimate viscosity [η] measured at 135 ° C. in decalin is 0.1 to 13 dl / g.
The lower limit of the ultimate viscosity [η] is preferably 0.5 dl / g, and more preferably 0.7 dl / g. On the other hand, the upper limit of the ultimate viscosity [η] is preferably 11.0, more preferably 10.0 dl / g, and further preferably 9.0 dl / g.
(Β) The ratio Mz / Mw value (Z) of the Z average molecular weight (Mz) and the weight average molecular weight (Mw) measured by gel permeation chromatography, and the weight average molecular weight (Mw) and the number average molecular weight (Mn). The ratio Mw / Mn value (Q) of is satisfied with at least one of the following (β1) and (β2).
(Β1) 10 ≧ Z / Q ≧ 1.1
(Β2) 10 ≧ Z / Q ≧ 0.55 and 13.0 ≧ Q ≧ 8.0

The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) described above are determined by the gel permeation chromatograph and measurement conditions described in the column of Examples below.

Generally, a large Mw / Mn value (Q) means that the molecular weight distribution of the olefin polymer is wide. On the other hand, a large Mz / Mw value (Z) means that the distribution of the molecular weight tends to spread toward the high molecular weight side. When the Mz / Mw value is large and the Mz / Mw value is larger than the Mw / Mn value, especially when the Z / Q is 1.1 or more, the molecular weight distribution is wide, and the molecular weight distribution is particularly wide toward the high molecular weight side. Can be thought of. Further, even if the Z / Q is in the range of 0.55 or more, if the Mw / Mn value (Q) is 8.0 or more and 13.0 or less, it is within the range of the present invention.

Regarding the above condition (β1), the preferable lower limit of the Z / Q ≧ value of the olefin polymer is 1.2, more preferably 1.3. On the other hand, the preferable upper limit value is 8, more preferably 6, and even more preferably 5. At this time, the lower limit of Mw / Mn (Q) of the olefin polymer of the present invention is preferably 2, more preferably 2.5, and even more preferably 3. On the other hand, the upper limit of the Mw / Mn value (Q) is preferably 25, more preferably 20.

Regarding the above condition (β2), the preferable lower limit value of Q of the olefin polymer is 8.5. On the other hand, the upper limit is 13.0, preferably 12.7, more preferably 12.0, still more preferably 11.0, and particularly preferably 10.0. Moreover, the preferable lower limit value of Z / Q is 0.56, the preferable upper limit value is 8, more preferably 6, and further preferably 5. Of course, the present invention also includes olefin-based polymers that satisfy the requirements of both (β1) and (β2). Among them, among the specifications of (β1) and (β2), a polymer satisfying the specification of (β1) is preferable.

A polymer satisfying the above range is considered to be a polymer having excellent moldability and impact resistance because it is a polymer having a wide molecular weight distribution having a relatively wide spread in the high molecular weight portion.
The olefin-based polymer of the present invention has a Mz / Mw value of preferably 7.0 or more, more preferably 7.1 or more, still more preferably 7.2 or more. The upper limit of the Mz / Mw value is preferably 30 and more preferably 20.

Olefin polymer of the present invention, for example, in the case of the ethylene-based polymer, the density is preferably 875kg / m ³ or more 965 kg / m ³ or less, more preferably 885kg / m ³ or more 945 kg / m ³ or less.

The olefin-based polymer of the present invention contains a repeating unit derived from an olefin having 2 to 10 carbon atoms.
Examples of the olefin having 2 to 10 carbon atoms include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Cyclic olefins such as cyclopentene, cycloheptene, norbornene, and 5-methyl-2-norbornene can be mentioned.

The olefin is preferably an olefin having 2 to 6 carbon atoms, and more preferably an olefin having 2 to 4 carbon atoms.
Examples of the olefin-based polymer include ethylene homopolymers, propylene homopolymers, and copolymers of ethylene and propylene with α-olefins having 3 or more and 20 or less carbon atoms.

The olefin-based polymer of the present invention further comprises a small amount of styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, etc., as long as the effects of the present invention are not impaired. It may contain repeating units derived from polar monomers such as methyl methacrylate, ethyl methacrylate, and methacrylic acid.
The olefin-based polymer of the present invention (eg, ethylene-based polymer) may be pelletized.

The molecular weight of the olefin polymer of the present invention measured by the above [η] or GPC is the value of the solvent-soluble component (excluding the solvent-free substance). As the solvent, known solvents can be used, and among them, hydrocarbon solvents are preferable, aliphatic hydrocarbons such as hexane, heptane and decane, alicyclic hydrocarbons such as cyclohexane and decalin, and fragrances such as benzene and toluene. Group hydrocarbons can be mentioned. In addition, halogen-containing hydrocarbons such as chloroform and chlorobenzene are also suitable examples.

As a preferred embodiment of the present invention, a polyolefin resin containing the olefin polymer can be mentioned. Examples of the polyolefin resin include polyethylene resin and polypropylene resin.

Moreover, as a preferable embodiment of the present invention, an olefin polymer resin composition containing the olefin polymer can be mentioned. Examples of the olefin polymer composition include an ethylene polymer composition and a propylene polymer composition. Assuming that the total composition of the olefin polymer and the other resin is 100 parts, the amount of the olefin polymer is preferably 50 parts or less, more preferably 30 parts or less, still more preferably 20 parts or less. included. On the other hand, the preferable lower limit value is 1 part, more preferably 2 parts, and further preferably 3 parts.

The olefin polymer composition may contain a polymer other than the olefin polymer of the present invention as long as the object of the present invention is not impaired, and is a weather resistance stabilizer, a heat stabilizer, an antistatic agent, and an anti-slip agent. , Anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants and other additives may be included. The content of such an additive is preferably 2 parts or less, more preferably 1 part or less, still more preferably 0.6 part or less, based on 100 parts of the entire composition.

The olefin polymer of the present invention can be made into a molded product by using a conventionally known molding method. For example, using known methods such as extrusion molding, blow molding, inflation molding, press molding, injection molding, and vacuum forming, the olefin polymer of the present invention can be used as a container for films, sheets, bottles, and the like. Various structural members and the like can be manufactured.

The olefin-based polymer according to the present invention is not particularly limited in its production method, but is preferably produced by using, for example, a catalyst for olefin polymerization containing a transition metal compound [A] represented by the following general formula [1]. can do.

(In the general formula [1], M is a Group 4 transition metal atom in the periodic table.
n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based derivative group. May be combined with each other to form a ring,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , and R ^1' , R ^2' , R ^3' , R ^4' , ^{R 5 ', R 6',} R 7 ', R 8', R 9 ', R 10' and R ^{11 'are} each independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, A silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,
Adjacent substituents together of R ¹ to R ^11, and R ^{1 '~R 11'} may be bonded to each other to form a ring. )
Hereinafter, the transition metal compound and the like will be described in more detail.

[Transition metal compound [A]]
The transition metal compound [A] (hereinafter, may be referred to as “component (A)”) is represented by the following general formula [1].

<< M, n, X >>
In the general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a titanium atom.

n is an integer of 1 to 4, preferably 2 or 3, in which the transition metal compound [A] is selected to be electrically neutral.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based derivative group. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group or an oxygen-containing hydrocarbon group, and more preferably an isolated electron pair on the halogen atom or the oxygen atom. It is a neutral ligand that is located.

When n is 2 or more, a plurality of Xs may be the same or different from each other, or may be combined with each other to form a ring. When a plurality of the rings are present, the rings may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine or bromine.
Examples of the hydrocarbon group include
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2- Il group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3) -Methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamil group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 , 3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 4,4-dimethylpentyl group and other linear or branched alkyl groups;
Vinyl group, allyl group, propenyl group (propa-1-ene-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-diene-1) -Il group), porcine-3-ene-1-yl group, crotyl group (but-2-en-1-yl group), porcine-3-en-2-yl group, metalyl group (2-methylallyl group) , Buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbuta-3-ene-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) A linear or branched alkenyl group such as group) or an unsaturated double bond-containing group;
Linear or branched alkynyl groups such as ethynyl group, propa-2-in-1-yl group, propargyl group (propa-1-in-1-yl group) or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group (4-iso-propylbenzyl group), 2,4,6 -Aroma-containing linear chain such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group) Or branched alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, trill group (methylphenyl group), xsilyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3) 5,6-Tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Examples thereof include aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group and ferrosenyl group.

Among the above-mentioned hydrocarbon groups, a methyl group, an iso-butyl group, a neopentyl group, a siamil group, a benzyl group, a phenyl group, a trill group, a xsilyl group, a mesityl group and a cumenyl group are preferable.

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, and a trifluorophenyl group. , Tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion.
Among the halogen-containing groups, a pentafluorophenyl group is preferable.

Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, and a tris (tris). Trimethylsilyl) silyl group, trimethylsilylmethyl group and the like can be mentioned.
Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.

Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, and a benzyloxy group. Group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group , 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, periodate anion.
Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.

Examples of the sulfur-containing group include a mesyl group (methanesulphonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), a nonaflate group (nonaflatebutanesulfonyl group), and the like. Examples thereof include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonaflatebutanesulfonate group).
Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferable.

Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group and a piperidinyl. Examples thereof include a group, a morpholic group, a pyrrolyl group, and a bistrifurylimide group.

Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.
Examples of the phosphorus-containing group include hexafluorophosphate anion.

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, and (benzyl) (tris (pentafluorophenyl)). ) Borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is an aryl group or halogen atom which may independently have a hydrogen, an alkyl group, a substituent, etc. The group represented by) is mentioned.

で表される四員環、あるいは

で表される四員環
（Ｍは、前記一般式（１）中のＭを表す。）
を形成可能な、ＡｌＲ₄（Ｒは水素、アルキル基、置換基を有してもよいアリール基またはハロゲン原子等を示す）で表される基が挙げられる。 Examples of the aluminum-containing group include

Four-membered ring represented by, or

Four-membered ring represented by (M represents M in the general formula (1))
_{Examples thereof include a group represented by AlR 4} (R represents an aryl group or a halogen atom which may have a hydrogen, an alkyl group, a substituent and the like) capable of forming the above.

Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), and a 2,4-hexadienyl group. , 1,4-Diphenyl-1,3-pentadienyl group, cyclopentadienyl group and the like, metallocyclopentene groups can be mentioned.

Examples of the neutral ligand capable of coordinating with a lone electron pair include ethers such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, pyridine, picolin and lutidine. Heterocyclic compounds such as oxazoline, oxazole, thiazole, imidazole and thiophene, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine are preferred, preferably tetrahydrofuran.

"R ¹ ~R ^11, and R ¹ '~R ^11'"
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , and R ^1' , R ^2' , ^{R 3 ', R 4',} R 5 ', R 6', R 7 ', R 8', R 9 ', R 10' and R ^{11 'each} independently represent a hydrogen atom, the number 1 to 40 carbon It is a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. R ¹ to R ^11, and R ^{1 'to} R ^11' is at least one substituent is preferably a substituent other than hydrogen atom.

Examples of the hydrocarbon group having 1 to 40 carbon atoms as R ¹ to R ^11, and R ^{1 '~R 11',} there are mentioned hydrocarbon group having 1 to 20 carbon atoms, as a more specific example, Specific examples of the hydrocarbon groups mentioned above as examples of X can be mentioned.

The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include, for example.
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-decanyl group, 1-undecanyl group , 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group , Tert-Pentyl group (1,1-dimethylpropyl group), sheamil group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (1,1-dimethylbutyl group) 2-Methylpentan-2-yl group), 3-methylpentane-2-yl group, 4-methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 -Dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, heptane-4 -Il group, 2,4-dimethylpentane-2-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane-4-yl group, 4-propylheptan-4 A linear or branched alkyl group having 1 to 40 carbon atoms, such as a −yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group. ;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, porcine-3-en-1-yl group, crotyl group, porcine-3-en-2-yl group, methylyl group, porcine-1,3 -Dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-ene- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-ene-1-yl group, penta-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1 , 4-diene-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5- En-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-ene- 1-yl group, 3-methyl-penta-4-ene-1-yl group, 2-methyl-penta-4-ene-1-yl group, hexa-5-en-2-yl group, 4-methyl- Penta-3-ene-1-yl group, 3-methyl-3-pent-3-ene-1-yl group, 2,3-dimethyl-but-2-ene-1-yl group, 2-methylpenta-4-ene -2-yl group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1 , 3-Diene-1-yl group, 2,3-dimethyl-buta-1,3-diene-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadi) A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as an enyl) propan-2-yl group and a 2- (cyclopentadienyl) ethyl group;
Ethynyl group, propa-2-in-1-yl group, propargyl group, porcine-1-in-1-yl group, porcine-2-in-1-yl group, porcine-3-in-1-yl group, Penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta- 1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4-in-2-yl group, hexa-1- In-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, 2,2-dimethyl-but-3-in A linear or branched alkynyl group or unsaturated triplet having 2 to 40 carbon atoms such as a -1-yl group, a hexa-4-in-1-yl group, and a hexa-5-in-1-yl group. Bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2- (4-methylphenyl) ) Propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2-yl group, 2- (3,5-di) -Tert-Butylphenyl) Propan-2-yl group, 3-phenylpentane-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-2 -Il group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-3-ene-1-yl group, 1,1,2-triphenylethyl group, trityl group (Triphenylmethyl group), tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2- (2-methylphenyl) ethyl group, 2- (4-) Methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) Ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropi Lu group, cinnamyl group (3-phenylallyl group), neofil group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutane-2-yl group , Cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) ) Propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, (1- Benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azulenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- Aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms such as (1-azulenyl) ethyl groups and unsaturated double bond-containing groups;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill group, xsilyl group, mesityl group, cumenyl group, juryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl Group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl group , Plenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group, etc. Examples thereof include aromatic substituents having 6 to 40 carbon atoms.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 1-heptyl group. Group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl Group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, heptan-4-yl group, 2,4-dimethylpentane-2-yl group, 3-Ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentane-2-yl Groups are preferred, such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentane. A -2-yl group and a 2,4,4-trimethylpentane-2-yl group are more preferable.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, buta-3-ene-1-yl group, crotyl group and metallicl Group, penta-4-ene-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-ene-1-yl group, 2-methylpenta-4-en-2- Il group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group and the like are preferable, and vinyl group, allyl group, buta-3-ene-1-yl group and penta. A -4-en-1-yl group, a prenyl group, and a hexa-5-ene-1-yl group are more preferable.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, propa-2-in-1-yl group, propargyl group, buta-2-in -1-yl group, buta-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-but-1-in-1 -Il group, 3,3-dimethyl-buta-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group and the like are preferable, and propa-2- More preferred are an in-1-yl group, a propargyl group, a buta-2-in-1-yl group and a buta-3-in-1-yl group.

Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4 , 6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl Group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group , 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3) , 5-Di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neofil group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9- Fluolenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group and the like are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group and 3-phenylpropyl group are preferable. , Synamyl groups are more preferred.

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group and 1-allylcyclopentyl Group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcyclo Heptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [2.2 .1] Heptan-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like are preferable, and cyclopentyl group, cyclopentyl group, etc. More preferably, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group.

Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xsilyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group , Binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl group and the like are preferable, and phenyl group, trill group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group preferable.

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, and a 3,3,3-tri. Fluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl Group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl Group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethyl Biphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, Di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, tri Fluoromethylthio groups, etc. may be mentioned.

Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-tri Fluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, Trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, trifluoromethylthio group are preferable. More preferably, a methyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group.

Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, and a tris (tris). Trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, di-n-butyl (indenyl) silyl Group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri- Examples thereof include an iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris (trimethylsilyl) silylphenyl group, and a 3,5-bis (trimethylsilyl) phenyl group.

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-Triphenylsilylphenyl group, 3,5-bis (trimethylsilyl) phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4 -Tri-iso-propylsilylphenyl group and 3,5-bis (trimethylsilyl) phenyl group are more preferable.

Examples of the oxygen-containing group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group and metallyloxy group. , Plenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxy Phenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl Group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl Group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, Methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydro Examples thereof include pyranyl group, flofuryl group, benzofuryl group and dibenzofuryl group.

Among the oxygen-containing groups, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, and a tert. -Butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, Allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldi Oxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group ,, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert- Butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, etc. Phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert- A butyl-4-methoxyphenyl group, a frill group, a methyl frill group, a benzofuryl group, and a dibenzofuryl group are more preferable.

Examples of the nitrogen-containing group include amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, molyphoryl group and azepinyl group. Didimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidini Ruvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl -4-Dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, Kinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolill group, phenylpyrrolill group, pyridyl Group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, Examples thereof include a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

Among the nitrogen-containing groups, an amino group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, and a dibenzylamino group. Group, pyrrolidinyl group, piperidinyl group, morpholic group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethyl Aminoallyl group, pyrrolidinyl allyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl Group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group , Iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, Oxazoridinyl group, benzoxazolyl group and the like are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso -Propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferable.

Examples of the sulfur-containing group include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group and benzylthioethyl group. Group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, Methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl Group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl Examples include a group, a benzothiazolyl group, a thiazolidinyl group and the like.

Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofryl group, a thienotienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Adjacent substituents together of R ¹ to R ^11, and R ^{1 '~R 11'} are bonded to each other to form a ring which may have a substituent.
R ¹ to R ^11, and each other substituents adjacent of R ^{1 '~R 11'} (Example: R ¹ and R ^2, R ² and R ^3, R ³ and R ^4, R ⁴ and R ^5, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ and R ¹⁰ and R ¹¹ , as well as R ^1'and R ^2' , R ^2'and R ^3' , R ^3'and R ^4' , R ^4'and R ^5' , R ^5'and R ^6' , R ^6'and R ^7' , R ^8'and R ^9' , R ^9'and R ^10'and R ^10'and R ^{11 As the} ring formed by bonding') to each other, a saturated hydrocarbon (the hydrocarbon of the aromatic ring portion of the mother nucleus) which may have a substituent which is condensed in the aromatic ring portion of the mother nucleus is used. ) Or a 5-8 membered ring composed of unsaturated hydrocarbons is preferred. When a plurality of rings are present, they may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring, and in this case, the structure in which the ring and the aromatic ring portion of the mother nucleus are combined is, for example, a substituent. Naphthalene ring (hereinafter referred to as "substituted naphthalene ring"; the same applies to other rings), substituted tetrahydronaphthalene ring, substituted phenanthrene ring, substituted indan ring, substituted kumaran ring, substituted benzodio. Examples thereof include a xol ring, and a substituted naphthalene ring and a substituted tetrahydronaphthalene ring are preferable. Incidentally, R ¹ and R ² together, R ⁶ and R ⁷ together or R ⁸ and R ⁹ together, and between ^{'R 2 and'} R ^1, R ^{6 'and} R ^7' together or R ^{8 'and} R ^{9,, '} They may bond to each other to form a ring that may have a substituent.

Examples of the ring R ⁷ and R ⁸ together and R ^{7 'and} R ^8' together, and R ¹ and R ¹ biphenol skeleton ^'to each other are bonded to each other to form, include four carbon atoms biphenyl portion of the mother nucleus An annular structure is a preferred example. Such a cyclic structure is preferably a 5- to 10-membered ring structure composed of a saturated hydrocarbon (excluding the hydrocarbon in the aromatic ring portion of the mother nucleus) or an unsaturated hydrocarbon. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 9- or 10-membered ring. Examples thereof include a xonine ring and a substituted dibenzodioxesin ring.

R ³ , R ⁵ , R ⁷ , R ⁸ and R ¹⁰ , and R ^3' , R ^5' , R ^7' , R ^8'and R ^10'are preferably hydrogen atoms.
R ¹ , R ² , R ⁴ , R ⁶ , R ⁹ and R ¹¹ , and R ^1' , R ^2' , R ^4' , R ^6' , R ^9'and R 11'are independent and preferably ^{R 11', respectively.} A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, more preferably carbon atoms. 1 to 10 hydrocarbon groups.
Furthermore, R ⁹ and R ^11, as well as R ^{9 'and} R ^11', independently, is preferably a hydrocarbon group having 1 to 10 carbon atoms.

<< Preferred Embodiment of Transition Metal Compound [A] >>
A preferred embodiment of the transition metal compound [A] is
In the general formula [1],
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing group, or an oxygen-containing group.
R ³ , R ⁵ , R ⁷ , R ⁸ and R ¹⁰ , and R ^3' , R ^5' , R ^7' , R ^8'and R ^10'are hydrogen atoms.
^{R 1, R 2, R 4} , R 6, R 9 and R ^11, and ^{R 1 ', R 2',} R 4 ', R 6', is R ^{9 'and} R ^11', each independently, a hydrogen atom , A hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.
R ¹ and R ² together, with the substituents of the combination selected ^'and R ^2' R 1 from each other ^`` may be bonded to each other to form a transition may form a ring which may have a substituent group metal compound [ A-1] can be mentioned.

As a more preferable embodiment of the transition metal compound [A-1],
In the general formula [1],
R ⁹ and R ^11, as well as R ^{9 'and} R ^11', independently, include transition metal compounds are hydrocarbon groups having 1 to 10 carbon atoms [A-2].

As a more preferable embodiment of the transition metal compound [A-2],
In the general formula [1], M is a titanium atom.
n is 2 or 3
Examples thereof include a transition metal compound [A-3] in which X is a neutral ligand coordinated with a lone electron pair on a halogen atom or an oxygen atom.

<< Example of Transition Metal Compound [A] >>
Specific examples of the transition metal compound [A] are shown below. Here, for the purpose of simplification ^{, an example is given for the case where R n} and R ^{n'have the} same structure (that is, a symmetrical structure). (The n is a natural number of 1 to 11).
For convenience, the ligand structure of the transition metal compound [A] excluding the portion represented by MXn (metal moiety) is aniline-derived ring moiety, aniline ring ortho-bonded phenol ring moiety, biphenol-derived moiety, R ^{1 to} R ¹¹ Divide into 4 substituents.

The abbreviation of the aniline-derived ring portion is α, the abbreviation of the aniline ring ortho-bonded phenol ring portion is β, the abbreviation of the biphenol-derived moiety is γ, the abbreviation of the R ^{1 to} R ¹¹ substituents is δ, and the abbreviation of each substituent is [ It is shown in Table 1] to [Table 4].

The wavy line in the above [Table 1] indicates the binding site with the aniline ring ortho-bonded phenol ring portion β.

The wavy line in [Table 2] indicates the binding site with the aniline-derived ring portion α.

Note that the R ^a of Table 3 in gamma-2 shows the R ¹ to R ¹¹ the same substituents in the following Table 4. For asymmetric structure, R n ^'also shows the R ¹ to R ¹¹ the same substituents in the following Table 4.

^{The R 1 to} R ¹¹ and ^Ra substituents in the above [Table 4] may be the same or different from each other in the combination.

Specific examples of the metal portion MXn _{is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2, Ti (1,3-butadienyl), Ti (1,3-pentadienyl), Ti (2,4-hexadienyl), Ti _{(1,4-diphenyl-1,3-pentadienyl), Ti (CH 2 -Si (} Me ) ₃ ) ₂ , Ti (ОMe) ₂ , Ti (ОiPr) ₂ , Ti (NMe ₂ ) ₂ , Ti (ОMs) ₂ , Ti (ОTs) ₂ , Ti (ОTf) ₂ , ZrF ₂ , ZrCl ₂ , ZrBr _{2 , ZrI 2, Zr (Me)} 2, Zr (Bn) 2, Zr (Allyl) 2, Zr (CH 2 -tBu) 2, Zr (1,3- butadienyl), Zr (1,3-pentadienyl), Zr (2,4-hexadienyl), Zr _{(1,4-diphenyl-1,3-pentadienyl), Zr (CH 2 -Si (} Me) 3) 2, Zr (ОMe) 2, Zr (ОiPr) 2, Zr ( _{NMe 2) 2, Zr (ОMs} ) 2, Zr (ОTs) 2, Zr (ОTf) 2, HfF 2, HfCl 2, HfBr 2, HfI 2, Hf (Me) 2, Hf (Bn) 2, Hf (Allyl ) ₂ , Hf (CH _2- tBu) ₂ , Hf (1,3-butadienyl), Hf (1,3-pentadienyl), Hf (2,4-hexadienyl), Hf (1,4-diphenyl-1,3) -Pentadienyl), Hf (CH _2- Si (Me) ₃ ) ₂ , Hf (ОMe) ₂ , Hf (ОiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf ( ОTf) _{2 and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and ОMs is a methanesulfonate. The group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

According to the above notation, the aniline-derived ring moiety is α-1, and the aniline-derived ring moiety R ⁴ and R ⁶ substituents are all δ-22, R ⁵ and R in [Table 4]. ⁷ Substituents are all δ-1 in [Table 4], aniline ring ortho-linked phenol ring moiety is β-1, aniline ring ortho-linked phenol ring moiety R ⁸ and R ¹⁰ substituents in [Table 2]. However, the δ-1 and R ⁹ substituents in [Table 4] are δ-15 in [Table 4], the R ¹¹ substituents are δ-12 in [Table 4], and the biphenol-derived portion is [Table 3]. ], The γ-1, biphenol-derived moiety R ¹ , R ² and R ³ substituents are all composed of the combination of δ-1 in [Table 4], _{and when the MXn of the metal moiety is TiCl 2} , the following The compound represented by the formula [2] is illustrated.

The aniline-derived ring moiety is α-2 in [Table 1], the aniline-derived ring moiety R ⁴ and R ⁵ substituents are all δ-1 in [Table 4], and the aniline ring ortho-bonded phenol ring moiety is. Β-2 in [Table 2], aniline ring ortho-bonded phenol ring moiety R ¹⁰ substituent is δ-1 in [Table 4], R ¹¹ substituent is δ-35 in [Table 4], derived from biphenol When the moiety is composed of a combination of γ-3 in [Table 3] and the biphenol-derived moiety R ³ substituent is δ-1 in [Table 4], and the MXn of the metal moiety is TiBn ₂ , the following formula [3] ] Is illustrated.

Also, alpha-1 in the aniline from the ring portion [Table 1], the aniline-derived ring moiety R ^4, R ^5, R ⁶ and R ⁷ both substituents in Table 4] [delta]-1, aniline ring ortho The position-bonded phenol ring moiety is β-1 in [Table 2], the aniline ring ortho-linked phenol ring moiety R ⁸ and R ¹⁰ substituents are in [Table 4], and the δ-1, R ⁹ substituents are in [Table 4]. ], The δ-11 and R ¹¹ substituents are δ-21 in [Table 4], the biphenol-derived moiety is γ-1 in [Table 3], and the biphenol-derived moiety R ¹ substituent is in [Table 4]. When the δ-2, R ² and R ³ substituents are all composed of the combination of δ-1 in [Table 4] and the MXn of the metal portion is Time ₂ , the compound represented by the following formula [4] Is illustrated.

In addition, the aniline-derived ring moiety is α-1, and the aniline-derived ring moiety R ⁴ substituent is [Table 4], and the δ-19, R ⁵ , R ⁶ and R ⁷ substituents are all [ Δ-1 in [Table 4], β-1, aniline ring ortho-linked phenol ring moiety in [Table 2], and R ^{8 and R 10} substituents are all [Table 4]. The δ-1, R ⁹ substituents in [Table 4] are δ-14 in [Table 4], the R ¹¹ substituents are δ-13 in [Table 4], and the biphenol-derived moiety is γ-1, in [Table 3]. The biphenol-derived moiety R ¹ substituent is composed of a combination of δ-40 in [Table 4], the R ² and R ³ substituents are a combination of δ-1 in [Table 4], and the MXn of the metal moiety is Ti (1, In the case of 3-pentadienyl), the compound represented by the following formula [5] is exemplified.

Further, the transition metal compound [A] has two types of structures represented by the following general formulas [6a] or [6b] centered on the bond axis between the aniline-derived ring portion and the aniline ring ortho-bonded phenol ring portion. Isomers may be present.

Similarly, there may be two types of structural isomers represented by the following general formulas [7a] or [7b] centered on the bond axis of the biphenol-derived moiety.

Purification, preparative production, or selective production of structural isomers of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. As a known production method, a production method using an optically active material as a raw material can be mentioned.

Within the range of the transition metal compound [A], one type of transition metal compound may be used alone, two or more types may be used in combination, a mixture of structural isomers may be used, and structural isomers may be used. May be used alone, or a mixture of two or more structural isomers may be used.

<< Production method of transition metal compound [A] >>
The transition metal compound [A] can be produced by using a conventionally known method, and the production method is not particularly limited. Examples of typical synthetic routes include the following production methods [Formula 1] disclosed in JP-A-2011-016789, JP-A-2014-224053, and the like. Here, for the purpose of simplification ^{, an example is given for the case where R n} and R ^n` have the same structure (that is, a symmetrical structure). (The n is a natural number of 1 to 11).

In the above [Formula 1], PG represents a hydroxyl protecting group such as a methoxymethyl group or a tetrahydropyranyl group, X represents a halogen atom, B is a boronic acid, a boronic acid ester, an alkylboran or a tetrafluoroborate salt and the like. Shows the boron functional group of.

As a method for synthesizing the substituted 3,3'-bisformylbiphenol compound <Y>, which is a precursor compound of the transition metal compound [A] precursor compound (ligand), "Tetrahedron: Asymmetry 2006, 17, 2328." Examples thereof include a production method using a substituted 2,2'-biphenol compound as a starting material disclosed in the above. As a method for protecting the hydroxyl group, a corresponding protected substance can be produced by a known method such as chloromethyl methyl ether treatment in the presence of a base or dihydropyran treatment in the presence of an acid catalyst, and the production method is particularly limited. Not done. A hydroxyl-protecting group ortho-position formylation reaction can be carried out by a regioselective lithiolysis reaction at the hydroxyl-protecting group ortho position followed by a reaction with N, N-dimethylformamide, and substitution by an acid-catalyzed deprotection reaction 3 , 3'-Bisformylbiphenol compound <Y> can be produced, but the production method is not particularly limited.

For the production of the coupling product <Z>, the corresponding coupling body <Z> can be produced by a known method such as the Suzuki-Miyaura coupling reaction with a boron compound, and the production method is particularly limited. is not it.

The substituted 2,2'-biphenol compound may have structural isomers similar to those represented by the general formula [7a] or [7b] via the 1,1'-position bond axis. A mixture of these isomers may be used.

[Catalyst for olefin polymerization]
A preferred example of the catalyst for olefin polymerization used in the production of the olefin polymer of the present invention is an embodiment containing the transition metal compound [A].
A typical example of the catalyst for olefin polymerization is a catalyst for ethylene polymerization.

(Compound [B])
The catalyst for olefin polymerization is preferably further [B-1] an organometallic compound, preferably an organometallic compound represented by the following general formulas (B-1a), (B-1b) or (B-1c) (B-1c). Hereinafter, it is also referred to as "ingredient (B-1)"),
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In the general formula (B-1a), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, where X represents a halogen atom and m is 0. <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ... (B}} -1b)
[In the general formula (B-1b), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t … (B-1c)
[In the general formula (B-1c), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, and M ^b is derived from Mg, Zn and Cd. Selected, X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
[B-2] an organoaluminum oxy compound (hereinafter, also referred to as “component (B-2)”) and a compound that reacts with [B-3] transition metal compound (A) to form an ion pair (hereinafter, “component”). (B-3) "
It contains at least one compound [B] (hereinafter, may be referred to as “component (B)”) selected from the group consisting of.

As the organometallic compound [B-1], the compound disclosed in JP-A-11-315109 and EP0874005A by the applicant can be used without limitation.
The organic metal compound [B-1] is preferably represented by the general formula (B-1a), and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, and tri. Trialkylaluminum such as octylaluminum, tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkylaluminum sesquihalide such as aluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalide such as ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride , Dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum Examples thereof include alkylaluminum hydride such as hydride, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and dialkylaluminum alcoxyside such as diisobutylaluminum ethoxide.
These may be used alone or in combination of two or more.

As the organoaluminum oxy compound [B-2], aluminoxane prepared from trialkylaluminum and tricycloalkylaluminum is preferable, and an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminum oxy compounds may be used alone or in combination of two or more.

Examples of the compound [B-3] that reacts with the transition metal compound (A) to form an ion pair include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179005. , JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. Furthermore, heteropoly compounds and isopoly compounds can be used without limitation.

In the catalyst for olefin polymerization, when an organoaluminum oxy compound [B-2] such as methylaluminoxane is used in combination as a co-catalyst component, not only the catalytic activity is very high for olefins such as ethylene, but also in a solid carrier. Since the solid carrier component containing the co-catalyst component can be easily prepared by reacting with the active hydrogen of the above, it is preferable to use the organoaluminum oxy compound [B-2] as the component (B).

(Solid support [S])
The catalyst for olefin polymerization preferably contains a solid support [S] (hereinafter, may be referred to as “carrier [S]” or “component (S)”).

The solid support [S] is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2, and the} like, or a composite or mixture containing these. It can also be used, for example natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TIO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TiO _2- MgO or the like can be used. Of these, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , Mg _{CO 3} , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Although the properties of the porous oxide differ depending on the type and manufacturing method, the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m ^2. It is in the range of / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of ^{0.3 to 3.0 cm 3 / g.} Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane having a structure represented by the following general formula (Sa) or (Sb), a repeating unit represented by the following general formula (Sc), and the following general formula ( Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit represented by Sd) as a structure.

In the general formulas (S-a) to (S-d), R ^e is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group and an ethyl group. Group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group , Octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, trill group, ethylphenyl group and other hydrocarbon groups can be exemplified, and methyl group, ethyl group and isobutyl group are preferable, and methyl group is particularly preferable. preferable. A part of R ^e is chlorine, substituted with a halogen atom such as bromine, and halogen content may be not more than 40 wt%, based on the R ^e. A straight line in (Sc) and (Sd) in which one is not connected to an atom indicates a bond with another atom (not shown).

In the general formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, and particularly preferably in the range of 10 to 100. In the general formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane can remain substantially solid in the reaction environment in which it is used.

Unlike the conventionally known carrier for an olefin polymerization catalyst, the solid aluminoxane compound does not contain an inorganic solid component such as silica or alumina or an organic polymer component such as polyethylene or polystyrene, and is solidified with an alkylaluminum compound as a main component. It is a thing. "Solid" means that the aluminoxane component remains substantially solid in the reaction environment in which it is used. More specifically, as described later, when the transition metal compound [A] is brought into contact with the aluminoxane component to prepare a catalyst for olefin polymerization (eg, a catalyst for ethylene polymerization), and the prepared catalyst for olefin polymerization When the polymerization of an olefin (eg, ethylene) (for example, suspension polymerization) is carried out using the above, the aluminoxane component maintains a substantially solid state.

The simplest method is to visually confirm whether or not the aluminoxane component is in a solid state, but it is often difficult to visually confirm, for example, during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after the polymerization and the state of adhesion to the reactor. On the contrary, if the properties of the polymer powder are good and the adhesion to the reactor is small, the gist of the present invention will not be deviated even if a part of the aluminoxane component is eluted in the polymerization environment. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of abundance of the amorphous polymer, but the polymer bulk density is preferable from the viewpoint of quantitativeness. The bulk density is usually 0.01 to 0.9, preferably in the range of 0.05 to 0.6, more preferably 0.1 to 0.5.

The dissolution ratio of the solid aluminoxane compound in n-hexane maintained at a temperature of 25 ° C. is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%. ..

The dissolution ratio was determined by adding 2 g of a solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25 ° C., stirring for 2 hours, and then separating the solution portion using a G-4 glass filter. , Obtained by measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane compound, known solid aluminoxane can be used endlessly, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. As known manufacturing methods, for example, JP-A-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. Examples thereof include the production methods described in JP-A-2000-95810, WO2010 / 55652, and the like.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. First, the particle size of each particle is calculated by the following formula after measuring the length of the particle image with two parallel lines in each of the horizontal and vertical directions.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound is calculated by the following formula using the particle size obtained above.
Average particle size = Σnd ⁴ / Σnd ³
(N; number of particles, d; particle size)

The solid aluminoxane compound preferably has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The obtained inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it into fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, an ionic crystalline compound having a layered crystal structure such _{as hexagonal fine packing type, antimony type, CdCl 2} type and CdI _{2 type can be exemplified.}

Furthermore, as clays and clay minerals, kaolin, bentonite, wood knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, dicite, etc. Halloy site etc.
The ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples thereof include crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ and H _{2 O.}

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method and having a radius of 20 Å or more. Is particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.
When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

It is also preferable to chemically treat the clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as _{TiCl 4} , ZrCl _4, and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions And so on. These compounds are used alone or in combination of two or more. Further, when these compounds are intercalated _{, metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , and Ge (OR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as _{SiO 2 can coexist.} In addition, examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after being subjected to a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, one type may be used alone, or two or more types may be used in combination.

Of these, preferred are clays or clay minerals, with particular preference being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound that can be used as the carrier [S] include granular or fine particle solids having a particle size in the range of 1 to 300 μm. Specifically, a polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. The polymers produced as, and their variants can be exemplified.

<Usage and order of addition of each component>
The catalyst for olefin polymerization can be prepared by mixing and contacting the component (A), optionally the component (S), and optionally the component (B) in an inert hydrocarbon.

As a method of contacting each component, paying attention to the order of contact, for example,
(I) Method of contacting component (B) with component (A) (ii) Method of contacting component (A) with component (S) (iii) Contacting component (S) with component (B), then component Method of contacting (A) (iv) Method of contacting component (B) with component (A) and then contacting component (S) (v) Contacting component (S) with component (B), then component A method of contacting a mixture of (A) and component (B),
(Vi) Examples thereof include a method in which the component (B) is brought into contact with the component (S), the component (B) is further brought into contact with the component (S), and then a mixture of the component (A) and the component (B) is brought into contact with the component (S). When a plurality of types of the component (B) are used, the components (B) may be the same or different from each other. Of the above methods, (i), (ii), (iii) and (iv) are preferable.

In each of the methods showing the contact sequence form, in the step including the contact between the component (S) and the component (B) and the step including the contact between the component (S) and the component (A), the component (G) is used. By coexisting with the above, fouling during the polymerization reaction is suppressed, and the particle properties of the produced polymer are improved. As the component (G), a compound having a polar functional group can be used, a nonionic (nonionic) surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, and a polyalkylene oxide alkyl ether are used. , Alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, N-acylamino acid are more preferable. These may be used alone or in combination of two or more.

Examples of the solvent used for preparing the olefin polymerization catalyst include inert hydrocarbon solvents. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. , Cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, ethylene chloride, chlorbenzene, dichloromethane and other halogenated hydrocarbons or mixtures thereof. Depending on the type of olefin to be polymerized, the olefin itself can be used as a solvent.

In the contact between the component (B) and the component (S), the reaction site in the component (B) and the reaction site in the component (S) are chemically bonded to each other, and the component (B) and the component (S) are chemically bonded. ) Is formed. The contact time between the component (B) and the component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually −50 to 200 ° C., preferably -20 to 120 ° C. It is done in. When the initial contact between the component (B) and the component (S) is abruptly performed, the component (S) collapses due to the reaction heat generation and the reaction energy, and the morphology of the obtained solid catalyst component deteriorates, which is used for polymerization. If so, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between the component (B) and the component (S), the reaction is brought into contact at a lower temperature for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled to react at a speed at which the initial contact temperature can be maintained. Is preferable. The same applies to the case where the component (B) and the component (S) are brought into contact with each other and the component (B) is further brought into contact with each other. The contact weight ratio between the component (B) and the component (S) (weight of the component (B) / weight of the component (S)) can be arbitrarily selected, but the higher the contact weight ratio, the more components (A). ) Can be brought into contact with each other, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of the component (B) to the component (S) [= weight of the component (B) / weight of the component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2. It is 0.0.
When the contact material between the component (B) and the component (S) and the component (A) are brought into contact with each other, the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature. Is usually in the range of −50 to 200 ° C., preferably −50 to 100 ° C.

The molar ratio [(B-1) / M] of the component (B-1) to all the transition metal atoms (M) in the component (A) is usually 0.01 to 100, It is used in an amount such that it is 000, preferably 0.05 to 50,000.

Component (B-2) usually has a molar ratio [(B-2) / M] of component (B-2) (aluminum atom equivalent) to all transition metal atoms (M) in component (A) of 10. It is used in an amount of up to 500,000, preferably 200,000 to 100,000.

The molar ratio [(B-3) / M] of the component (B-3) to all the transition metal atoms (M) in the component (A) is usually 1 to 10, preferably 1. It is used in an amount such that it becomes 1 to 5.
The ratio of the component (B) to all the transition metal atoms (M) in the component (A) can be determined by inductively coupled plasma emission spectrometry (ICP analysis).

The catalyst for olefin polymerization can be used as it is for olefin polymerization, but it can also be used after prepolymerizing an olefin with the catalyst for olefin polymerization to form a prepolymerized solid catalyst component.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin (eg, ethylene) in an inert hydrocarbon solvent in the presence of the olefin polymerization catalyst, and is of a batch type or a semi-continuous type. , It can be carried out by any of the continuous methods, and it can be carried out under reduced pressure, normal pressure or pressurized. Further, it is desirable that the prepolymerized solid catalyst component is produced in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid catalyst component.

The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent is separated from the suspension, then suspended again in the inert hydrocarbon, and an olefin (eg, ethylene) is introduced into the obtained suspension. Alternatively, an olefin (eg, ethylene) may be introduced after drying.

The prepolymerization temperature is -20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. The prepolymerization temperature is preferably lower than the polymerization temperature in the method for producing an olefin polymer described later. More preferably, it is 10 ° C. or more lower than the polymerization temperature in the method for producing an olefin polymer. The olefin used for the prepolymerization may be the same as or different from the olefin used in the method for producing the olefin polymerization described later, but it is usually preferable that the olefin is the same. For example, in the method for producing an ethylene polymer, it is preferable that an olefin containing ethylene as a main component is used for prepolymerization.

As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. Further, the component (B) is used as needed, and the organoaluminum compound [B-1a] represented by the general formula (B-1a) is particularly preferably used. When the component (B) is used, the component (B) is the molar ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the transition metal compound [A]. ) Is used in an amount of 0.1 to 10000, preferably 0.5 to 5000.

The concentration of the olefin polymerization catalyst in the prepolymerization system is usually 1 to 1000 g / liter, more preferably 10 to 500 g / liter in terms of the olefin polymerization catalyst / polymerization volume ratio. At the time of prepolymerization, the above-mentioned component (G) may coexist for the purpose of suppressing fouling or improving the particle properties.

Further, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot seating during polymerization, and suppressing the generation of polymer lumps, the component (G) is brought into contact with the prepolymerized solid catalyst component once generated by prepolymerization. May be good.

The temperature at which the component (G) is brought into contact is usually −50 to 50 ° C., preferably -20 to 50 ° C., and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. ..
When the olefin polymerization catalyst according to the present invention is brought into contact with the component (G), the component (G) is 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst according to the present invention. It is used in an amount of 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.
The mixed contact between the olefin polymerization catalyst and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same as described above.

In the method for producing an olefin polymer, a dried prepolymerized solid catalyst component (hereinafter, also referred to as “dry prepolymerized catalyst”) can be used as the catalyst for olefin polymerization. The prepolymerized solid catalyst component is usually dried after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

The prepolymerized solid catalyst component is dried by keeping the prepolymerized solid catalyst component at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of an inert gas. The amount of the volatile component of the obtained dry prepolymerization catalyst is preferably 2.0% by weight or less, preferably 1.0% by weight or less. The smaller the amount of the volatile component of the dry prepolymerization catalyst, the better, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 1 to 48 hours, although it depends on the drying temperature.

Since the dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dry prepolymerization catalyst is used, stable polymerization can be performed because it is not necessary to accompany the solvent used for suspension in the gas phase polymerization system.

[Method for producing olefin polymer]
Examples of the method for producing an olefin-based polymer of the present invention include a method for polymerizing an olefin in the presence of the catalyst for olefin polymerization.

A preferred embodiment of the method for producing an olefin-based polymer of the present invention is a step of polymerizing an α-olefin having 2 or more and 10 or less carbon atoms in the presence of the olefin polymerization catalyst, for example, ethylene homopolymerization and propylene. Examples thereof include a method for producing an olefin polymer including homopolymerization or a step of copolymerizing ethylene with an α-olefin having 3 or more and 10 or less carbon atoms.

Examples of the polymerization method include a liquid phase polymerization method such as solution polymerization and suspension polymerization and a vapor phase polymerization method, and a solution polymerization method and a suspension polymerization method are preferable.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, or mixtures thereof.

When polymerizing an olefin (eg, ethylene) using the catalyst for olefin polymerization, the component (A) is usually 1 × 10 ^-12 to 1 × 10 ^-1 mol, preferably 1 ×, per 1 liter of the reaction volume. It is used in an amount such that it is 10 ^-8 to 1 × 10 ^{-2 mol.} Further, the component (B) is used, and preferably the compound represented by the general formula (B-1a) or the component (B-2) is used.

When polymerizing an olefin (eg, ethylene), the lower limit of the polymerization temperature is 0 ° C., preferably 20 ° C., particularly preferably 40 ° C. The higher the temperature, the more advantageous in terms of heat removal and the like in production on an industrial scale. The upper limit is usually 200 ° C., preferably 170 ° C., the polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2.

The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.
The molecular weight of the olefin-based polymer obtained by the method for producing the olefin-based polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the above-mentioned component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

When the method for producing the olefin polymer is the method for producing an ethylene polymer, the monomer supplied to the polymerization reaction is ethylene alone or ethylene and an olefin having 3 or more and 20 or less carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-. Α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8 -Dimethano-1,2,3,4,4a, 5,8,8a-Cyclic olefins such as octahydronaphthalene can be mentioned.

Further, a small amount of styrene, vinylcyclohexane, diene or acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc., as long as the effects of the present invention are not impaired. A polar monomer such as methacrylic acid may be supplied.

By using the transition metal compound, the olefin can be polymerized with high activity. Further, even at a relatively high polymerization temperature, an olefin polymer can be obtained while maintaining a relatively high activity. The reason for this is not clear at this time, but the present inventors speculate as follows.

Since the transition metal compound is a dinuclear transition metal compound and has two active sites serving as catalytic reaction fields in the molecule, it is probably due to the effect derived from the three-dimensional structure of the ligand including its substituent. It is speculated that a stable active point can be formed even by polymerization under high temperature conditions, and a polymer having a high molecular weight can be obtained with excellent polymerization activity. We also consider the possibility that the olefin-based polymer produced as described later moves between active sites. In any case, this point is an advantageous feature for stable production of high molecular weight polymers.

Further, the transition metal compound can produce a resin having a molecular weight distribution having a spread on the high molecular weight side. In other words, there is a tendency to produce a resin having a relatively high Z average molecular weight (Mz). Specifically, the relationship between the Mz / Mw value and the Mw / Mn value tends to be relatively high with respect to the Mw / Mn value as compared with the resin of a normal olefin polymer. This also has two active sites as described above, so that the polymer (macromonomer) having a terminal olefin produced at one active site is not copolymerized at the other active site. I'm guessing. In addition, the polymer chain grown at one active site may have moved to another active site, and the polymerization reaction may be further progressing.

Since it is unlikely that such steps will occur continuously, relatively high molecular weight components, relatively low molecular weight polymer components, and medium molecular weight polymer components are good at the molecular level. It can also be expected to form a dispersed state.

Relatively high molecular weight components may be difficult to melt and may be said to be the core of fisheye. With the above mechanism, it is less likely that relatively high molecular weight components will aggregate, so it can be expected that they tend to melt easily.

Further, based on this speculation, if the transition metal compound has an asymmetric structure (the above-mentioned Rn and Rn'are different substituents), a block copolymer can be produced in one step under olefin copolymerization conditions. There is a possibility that it can be done.

Such a phenomenon can be explained by the following hypothesis.
The ligand of the transition metal compound may approach the very vicinity at two active sites due to the rotation of the bond axis, and the growing polymer chain may move between the active sites at the time of the closest approach. Will increase. Then, since the polymerization reaction proceeds again based on the performance of the moved active site, it can be inferred that the proportion of the high molecular weight compound may increase or a block copolymer may be provided.

Block copolymers may be produced in one step by using a catalyst system in which a zinc compound is used in combination, but in the present invention, the block copolymer does not require other components such as the above-mentioned zinc compound and can be produced in one step. There is a possibility that it can be manufactured. Further, when the olefin is copolymerized, the copolymerization reactivity is good, which is considered to be advantageous for the stable production of the copolymer for the following reasons. The reason for these effects is unknown at this time, but the present inventors speculate as follows.

When the olefin copolymer is carried out by, for example, continuous polymerization, the unreacted olefin may be recovered and reused for the polymerization. In this case, the copolymerization of ethylene and propylene is taken as an example, but if the copolymerization reactivity of ethylene and propylene is almost equal, the composition of the mixture of unreacted olefins is almost the same as the composition of the olefin to be fed. Can be expected to be. Therefore, it is less necessary to adjust the composition of the olefin when reusing the unreacted gas, or even if it is done, a steady state can be realized with a slight adjustment. On the other hand, it is generally known that ethylene is often considerably more reactive than α-olefins having 3 or more carbon atoms such as propylene. The characteristic of the transition metal compound can be said to be an excellent function from that point of view.

Structurally, the transition metal compound is expected to have a wide configuration space even if it is a dinuclear complex. It is speculated that such a specific structure may form a stable reaction field for copolymerization. Since such a special environment can be formed, the transition metal compound of the present invention exhibits high polymerization reactivity even with the α-olefin, which is bulkier than ethylene, and provides a catalyst having good copolymerizability. It is thought that it can be formed.

Of course, the olefin-based polymer of the present invention may be a catalyst other than the above, or one obtained by using a different production method. Further, the polymer of the present invention is preferably soluble in the above-mentioned hydrocarbon solvent. On the other hand, a solvent-insoluble component may be contained as long as the object of the present invention is not impaired. The preferable content of the solvent-insoluble component is 5 parts or less, more preferably 2 parts or less, still more preferably 1 part or less, particularly preferably 0.5 part or less, and particularly preferably 0, based on 100 parts of the entire polymer. .3 copies or less.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
The structures of the compounds obtained in the synthetic examples and the examples ^{used were 270 MHz 1} H NMR (using JEOL GSH-270 type equipment), FD-mass spectrometry (using JEOL SX-102A type equipment), and the like. It was measured and determined according to a conventional method.

[Measurement of various physical properties]
The method for measuring the physical characteristics of the olefin polymer is shown below.
<Melting point (Tm .; ° C)>
Using an RDC220 differential scanning calorimeter manufactured by SII, a sample of about 10 mg was heated to 30 to 200 ° C. at a heating rate of 50 ° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a heating rate of 10 ° C./min. The endothermic peak observed during the second temperature rise was defined as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm.).

<Ultimate viscosity [η]>
About 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity η _sp was measured in the same manner. _{This dilution operation was repeated twice more, and the value of η sp} / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) as shown in the following formula.
[Η] = lim (η _sp / C) (C → 0)

<Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)>
The measurement was performed as follows using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent.

Two Agilent PLgel Olexis are used for the analysis column, a differential refractometer and a 3-capillary viscometer are used for the detector, the column temperature is 145 ° C., o-dichlorobenzene is used as the mobile phase, and the flow velocity is 1.0 ml. The sample concentration was 0.1% by weight. As the standard polystyrene, one manufactured by Tosoh Co., Ltd. was used. In the molecular weight calculation, the measured viscosity is calculated from a viscometer and a refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz) are calculated from the measured universal calibration. / Mw) was calculated.

<Comonomer content>
The content of the copolymer comonomer obtained in the examples was measured by IR (FT / IR-4200 manufactured by JASCO Corporation).

For IR, the copolymer obtained in the example was melted and stretched by a hot press heated to 180 ° C., and then the film obtained by pressurizing and cooling at room temperature was used as a measurement sample, and the light source wavelength was 5000 cm-1. Measured between ~ 400 cm-1. The propylene content is based on propylene-based C-CH3 skeleton vibration (1150 cm-1) as a key band, and the absorbance of the key band (D1150) and the internal standard band (4320 cm-1: CH expansion and contraction vibration and methylene and methyl variable angle vibration). It was determined by the ratio [D1150 / D4320] of the binding sound) to the absorbance (D4320). The hexene content is based on hexene-based C-CH3 skeletal vibration (1378 cm-1) as a key band, and the absorbance of the key band (D1378) and the internal standard band (4320 cm-1: CH expansion and contraction vibration and methylene and methyl eccentric vibration). It was determined by the ratio [D1378 / D4320] of the binding sound) to the absorbance (D4320).

It should be noted that such a method for measuring the comonomer content by IR is known. This determination method is a calibration curve showing the relationship between the above-mentioned absorbance ratio and the comonomer oil content, which is obtained by measuring a plurality of types of polymers whose comonomer content has ^{been determined in advance by a method such as 13 C NMR by the above-mentioned IR method.} It is due to the line.

<Synthesis of transition metal compound (A)>
[Synthesis Example 1]
In a fully dried, nitrogen-substituted 100 mL reactor, Tetrahedron: Asymmetry 2006, 17, 2328. (S) -2,2'-dihydroxy- [1,1'-binaphthalene] -3,3'-dicarboxyaldehyde 0.69 g (2.00 mmol) synthesized by the method described, JP-A-2014-224053. 1.25 g (4.21 mmol) of 2'-amino-3,5-di-tert-butyl-2-hydroxy-1,1'-biphenyl synthesized by the method described, a small amount of p-toluenesulfonic acid, 20 mL of toluene. Was charged and stirred for 4 hours under heating and reflux. The residue obtained by distilling off the solvent was purified by washing with methanol to obtain 1.18 g (yield) of the target product (hereinafter referred to as compound (A-1L)) represented by the following formula (A-1L). 65%) obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 11.49 (2H, br-s, -OH), 8.63 (2H, s, -CH = N-), 7.92 (2H, br-s, Ar) -H), 7.82 (2H, dd, J = 7.1 and 1.8Hz, Ar-H), 7.46 (4H, dt, J = 7.6and 1.6Hz, Ar-H), 7.36 ( 2H, dt, J = 7.3and1.3Hz, Ar-H), 7.32-7.11 (8H, m, Ar-H), 7.06 (2H, dd, J = 7.7and1.6Hz, Ar-H), 6.99 (2H, d, J = 1.6Hz, Ar-H), 5.45 (2H, br-s, -OH), 1.26 (18H, s, -C (CH) ₃ ) ₃ ), 1.15 (18H, s, -C (CH ₃ ) ₃ ) ppm

[Example 1A]
0.45 g (0.50 mmol) of the compound (A-1L) obtained in Synthesis Example 1 and 15 mL of a toluene solution were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. This solution was cooled to −78 ° C., and 1.00 mL (1.00 M, 1.00 mmol) of a toluene solution of titanium tetrachloride was added dropwise. After completion of the dropping, stirring was continued for 20 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 15 mL of n-hexane was added to the obtained solid and irradiated with ultrasonic waves to prepare a suspension. The insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.55 g (yield 97) of a brown powder compound represented by the following formula (A-1) (hereinafter referred to as titanium compound (A-1)). %)Obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 8.66-8.60 (2H, m, -CH = N-), 8.33 (1H, d, J = 1.6 Hz, Ar-H), 8. 29 (1H, s, Ar-H), 8.00 (2H, t, J = 8.4Hz, Ar-H), 7.68-6.94 (18H, m, Ar-H), 1.42 -1.22 (36H, m, -C (CH ₃ ) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 1134

[Synthesis Example 2]
Tetrahedron 1994, 50, 11827. Synthesized by the method described in (S) -3-formyl-2-hydroxy-2'-phenyl-1,1'-binaphthyl 1.13 g (3.02 mmol), JP-A-2014-224053. Add 0.94 g (3.15 mmol) of 2'-amino-3,5-di-tert-butyl-2-hydroxy-1,1'-biphenyl, a small amount of p-toluenesulfonic acid, and 15 mL of toluene, and heat and reflux. Below, it was stirred for 2 hours. When the residue obtained by distilling off the solvent was purified by silica gel column chromatography, the target product represented by the following formula (A-2L) (hereinafter referred to as compound (A-2L)) was quantitatively obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 11.51 (1 H, s, -OH), 8.62 (1 H, s, -CH = N-), 7.98 (1 H, d, J = 8.4 Hz) , Ar-H), 7.92 (1H, d, J = 8.2Hz, Ar-H), 7.79 (1H, s, Ar-H), 7.72-7.64 (1H, m, Ar-H), 7.60 (1H, d, J = 8.4Hz, Ar-H), 7.53-7.28 (5H, m, Ar-H), 7.28-7.10 (6H) , M, Ar-H), 7.07-6.90 (5H, m, Ar-H), 5.22 (1H, s, -OH), 1.27 (9H, s, -C (CH ₃₎ ) ₃ ), 1.13 (9H, s, -C (CH ₃ ) ₃ ) ppm

[Comparative Example 1A]
0.33 g (0.50 mmol) of the compound (A-2L) obtained in Synthesis Example 2 and 15 mL of a toluene solution were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. This solution was cooled to −78 ° C., and 0.50 mL (1.00 M, 0.50 mmol) of a toluene solution of titanium tetrachloride was added dropwise. After completion of the dropping, stirring was continued for 17 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 2.0 mL of toluene and 12 mL of n-hexane were added to the obtained solid, and the mixture was irradiated with ultrasonic waves to prepare a suspension. The insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.30 g (yield 77) of a brown powder compound represented by the following formula (A-2) (hereinafter referred to as titanium compound (A-2)). %)Obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 8.40 (1H, s, -CH = N-), 8.13-8.04 (2H, m, Ar-H), 7.99 (1H, d, J = 8.2Hz, Ar-H), 7.94-7.87 (1H, m, Ar-H), 7.73 (1H, d, J = 8.4Hz, Ar-H), 7.54 -7.34 (9H, m, Ar-H), 7.20-7.00 (7H, m, Ar-H), 6.95 (1H, d, J = 8.5Hz, Ar-H), 1.26 (9H, s, -C (CH ₃ ) ₃ ), 0.93 (9H, s, -C (CH ₃ ) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 769

[Example 1]
<Manufacturing of polyethylene>
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with 100 liters / hr of ethylene. Then, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the titanium compound (A-1) obtained in Example 1A, and 0 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). Polymerization was started by adding .006 mmol. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.53 g of polyethylene (PE). The polymerization activity was 2,550 g / mmol-Cat. The melting point (Tm.) Of the obtained polyethylene was 132 ° C., the ultimate viscosity [η] was 8.29 dL / g, and the weight average molecular weight (Mw) in terms of polystyrene was 1,678, 200, the number average molecular weight (Mn) is 192,600, the Z average molecular weight (Mz) is 13,212,100, the molecular weight distribution (Mw / Mn) is 8.71, and (Mz / Mw) is 7.87. there were. The results are shown in Tables 5 and 6.

[Example 2]
<Manufacturing of polyethylene>
When ethylene polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was set to 50 ° C., 0.62 g of polyethylene was obtained. The polymerization activity was 2,990 g / mmol-Cat. The melting point (Tm.) Of the obtained polyethylene was 131 ° C., the ultimate viscosity [η] was 5.26 dL / g, and the weight average molecular weight (Mw) in terms of polystyrene was 937,300. The number average molecular weight (Mn) was 74,900, the Z average molecular weight (Mz) was 6,834,600, the molecular weight distribution (Mw / Mn) was 12.52, and (Mz / Mw) was 7.29. .. The results are shown in Tables 5 and 6.

[Example 3]
<Manufacturing of polyethylene>
When ethylene polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 75 ° C., 0.81 g of polyethylene was obtained. The polymerization activity was 3,910 g / mmol-Cat. -Hr, the melting point (Tm.) Of the obtained polyethylene was 130 ° C., the ultimate viscosity [η] was 3.01 dL / g, and the weight average molecular weight (Mw) in terms of polystyrene was 471,300. The number average molecular weight (Mn) was 56,200, the Z average molecular weight (Mz) was 5,905,400, the molecular weight distribution (Mw / Mn) was 8.39, and (Mz / Mw) was 12.53. .. The results are shown in Tables 5 and 6.

[Example 4]
<Manufacturing of ethylene / propylene copolymer>
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with a mixed gas of 100 liters / hr of ethylene and 100 liters / hr of propylene. Then, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the titanium compound (A-1) obtained in Example 1A, and 0 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). Copolymerization was started by adding .006 mmol. Ethylene was continuously supplied at 100 liters / hr and propylene at 100 liters / hr, and polymerization was carried out at 50 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, and the mixture was shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation a total of 3 times, the solvent was distilled off under reduced pressure, and the mixture was further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) weighed 2.66 g. The polymerization activity was 6,390 g / mmol-Cat. -Hr, the propylene (C3 ") content measured by IR was 41.3 mol%, the ultimate viscosity [η] was 2.07 dL / g, and the polystyrene-equivalent weight average molecular weight (Mw) was 115, 900, the number average molecular weight (Mn) is 36,200, the Z average molecular weight (Mz) is 1,009,900, the molecular weight distribution (Mw / Mn) is 3.20, and (Mz / Mw) is 8.71. The results are shown in Tables 5 and 6.

[Example 5]
<Manufacturing of polypropylene>
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with 100 liters / hr of propylene. Then, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the titanium compound (A-1) obtained in Example 1A, and 0 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). Polymerization was started by adding .006 mmol. Propylene was continuously supplied at 100 liters / hr, and the polymerization was carried out at 50 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.67 g of polypropylene (PP). The polymerization activity was 1,610 g / mmol-Cat. -Hr, the ultimate viscosity [η] of the obtained polypropylene was 2.05 dL / g, the polystyrene-equivalent weight average molecular weight (Mw) was 500,000, and the number average molecular weight (Mn) was 111,800. The Z average molecular weight (Mz) was 9,020,100, the molecular weight distribution (Mw / Mn) was 4.47, and (Mz / Mw) was 18.04. The results are shown in Tables 5 and 6.

[Comparative Example 1]
<Manufacturing of polyethylene>
Instead of the titanium compound (A-1), 0.0025 mmol of the titanium compound (A-2) obtained in Comparative Example 1A and 0.003 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were used. When ethylene polymerization was carried out in the same manner as in Example 1 except for the above, 0.86 g of polyethylene was obtained. The polymerization activity was 4,120 g / mmol-Cat. -Hr, and the ultimate viscosity [η] of the obtained polyethylene was 4.30 dL / g. The results are shown in Tables 5 and 6.

[Comparative Example 2]
<Manufacturing of polyethylene>
0.250 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of titanium compound (A-2) obtained in Comparative Example 1A instead of titanium compound (A-1), triphenylcarbenium tetrakis (pentafluorophenyl) Ethylene polymerization was carried out in the same manner as in Example 2 except that 0.003 mmol of borate (TrB) was used, and 0.59 g of polyethylene was obtained. The polymerization activity was 2,810 g / mmol-Cat. The melting point (Tm.) Of the obtained polyethylene was 134 ° C., the ultimate viscosity [η] was 1.54 dL / g, and the weight average molecular weight (Mw) in terms of polystyrene was 92,300. The number average molecular weight (Mn) was 47,700, the Z average molecular weight (Mz) was 164,700, the molecular weight distribution (Mw / Mn) was 1.94, and (Mz / Mw) was 1.78. The results are shown in Tables 5 and 6.

[Comparative Example 3]
<Manufacturing of polyethylene>
Instead of the titanium compound (A-1), 0.0025 mmol of the titanium compound (A-2) obtained in Comparative Example 1A and 0.003 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were used. When ethylene polymerization was carried out in the same manner as in Example 3 except for the above, 0.66 g of polyethylene was obtained. The polymerization activity was 3,170 g / mmol-Cat. -Hr, and the ultimate viscosity [η] of the obtained polyethylene was 1.03 dL / g. The results are shown in Tables 5 and 6.

[Comparative Example 4]
<Manufacturing of ethylene / propylene copolymer>
Instead of the titanium compound (A-1), 0.0025 mmol of the titanium compound (A-2) obtained in Comparative Example 1A and 0.003 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were used. When ethylene / propylene copolymer was carried out in the same manner as in Example 4 except for the above, 4.36 g of ethylene / propylene copolymer (EPR) was obtained. The polymerization activity was 10,470 g / mmol-Cat. -Hr, the propylene content measured by IR is 45.2 mol%, the ultimate viscosity [η] is 1.89 dL / g, the polystyrene-equivalent weight average molecular weight (Mw) is 267,100, and the number average. The molecular weight (Mn) was 137,400, the Z average molecular weight (Mz) was 503,700, the molecular weight distribution (Mw / Mn) was 1.94, and (Mz / Mw) was 1.89. The results are shown in Tables 5 and 6.

[Comparative Example 5]
<Manufacturing of polypropylene>
0.250 mmol of triisobutylaluminum (TIBA), 0.0010 mmol of titanium compound (A-2) obtained in Comparative Example 1A instead of titanium compound (A-1), triphenylcarbenium tetrakis (pentafluorophenyl) Propylene polymerization was carried out in the same manner as in Example 5 except that 0.0012 mmol of borate (TrB) was used, and 0.60 g of polypropylene was obtained. The polymerization activity was 3,580 g / mmol-Cat. -Hr, the ultimate viscosity [η] of the obtained polypropylene was 2.70 dL / g, the polystyrene-equivalent weight average molecular weight (Mw) was 581,800, and the number average molecular weight (Mn) was 278,900. The Z average molecular weight (Mz) was 1,026,800, the molecular weight distribution (Mw / Mn) was 2.09, and (Mz / Mw) was 1.76. The results are shown in Tables 5 and 6.

[Example 6]
After dissolving 5 parts of the polymer of Example 1 and 95 parts of Hi-Zex R3300F manufactured by Prime Polymer Co., Ltd. in heated toluene, the solution was added little by little to a large amount of methanol to precipitate a polymer composition.

The polymers of Examples 1 and 2 described above have a Z / Q value in the range of 0.55 to 10, and a weight having a peculiar molecular weight distribution in which Q satisfies the range of 8.0 to 13.0. It is a coalescence.
On the other hand, Examples 3 to 5 described above are polymers having a peculiar molecular weight distribution in which the Mz / Mw value of Z / Q of 1.1 to 10 is higher than the Mw / Mn value.

Since both polymers are obtained by a polymerization reaction using the above-mentioned special transition metal compound catalyst, it is estimated from the polymerization mechanism that a polymer having a relatively high molecular weight is extremely finely dispersed. Conceivable. Therefore, it is expected that fish eyes and the like are unlikely to occur even if a component having a high molecular weight is contained.

Claims (4)

(Α) The ultimate viscosity [η] measured at 135 ° C. in decalin was 0.1 to 13 dl / g.
(Β) The ratio Mz / Mw value (Z) of the Z average molecular weight (Mz) and the weight average molecular weight (Mw) measured by gel permeation chromatography, and the weight average molecular weight (Mw) and the number average molecular weight (Mn). A olefin polymer containing a repeating unit derived from an olefin having 2 to 10 carbon atoms, wherein the ratio Mw / Mn value (Q) of the above satisfies at least one of the following (β1) and (β2). ..
(Β1) 10 ≧ Z / Q ≧ 1.1
(Β2) 10 ≧ Z / Q ≧ 0.55 and 13.0 ≧ Q ≧ 8.0 The olefin-based polymer according to claim 1, wherein the olefin is an olefin having 2 to 6 carbon atoms. The olefin-based polymer according to claim 1, wherein the olefin is an olefin having 2 to 4 carbon atoms. A polyolefin resin containing the olefin polymer according to any one of claims 1 to 3.