JP7558658B2 - Olefin Polymerization Catalysts - Google Patents

Description

The present invention relates to an olefin polymerization catalyst, and more specifically, to an olefin polymerization catalyst that can produce olefin (co)polymers without causing fouling during polymerization.

Olefin polymerization catalysts consisting of transition metal compounds such as zirconocene and cocatalyst components such as aluminoxane (organoaluminum oxy compound) are known as catalysts used in the production of olefin (co)polymers.

In particular, when performing slurry polymerization or gas phase polymerization, it is generally known to use solid catalyst components in which a transition metal compound or aluminoxane is supported on a solid carrier such as silica gel in order to improve the powder properties of the polymer produced and to prevent fouling (adhesion to the walls of the polymerization vessel) during polymerization. (Non-Patent Document 1)

The solid support must be appropriately selected depending on the transition metal compound and manufacturing process used, and since higher polymerization activity is required to reduce costs and reduce metal residues in the polymer, numerous methods for manufacturing solid supports and solid catalyst components have been proposed. (Patent Documents 1 to 5)

JP 2002-179721 A JP 2003-327611 A JP 2004-091498 A JP 2009-001829 A International Publication No. 2014/123212 International Publication No. 2009/063084 Special table 2016/534165 publication

Chem. Rev. 2005, 105, p. 4073-4147

Among them, it has been disclosed that transition metal compounds (half metallocenes) having a cyclopentadienyl ligand and a ligand containing a Group 15 element are suitable for producing ultra-high molecular weight polyethylene (UHMWPE) having an intrinsic viscosity ([η]) of more than 5 dl/g in decalin at 135°C (Patent Documents 6 and 7). However, the inventors' investigation led to the discovery that transition metal compounds having a cyclopentadienyl ligand and a ligand containing an atom selected from Groups 15 and 16 elements are more susceptible to fouling during slurry polymerization than transition metal compounds consisting only of cyclopentadienyl ligands.

Unlike other common polyethylenes, the ultra-high molecular weight polyethylene (UHMWPE) is often used as a polymerized powder, and it is desirable for the powder to have a smaller particle size and be free of agglomerations. However, from the standpoint of fouling and powder agglomeration, the smaller the particle size, the more likely the above phenomena are to occur.

The object of the present invention is to provide an olefin polymerization catalyst that can produce olefin (co)polymers without causing fouling during polymerization.

As a result of intensive research into solving the above problems, the present inventors have found that a solid catalyst component having a transition metal compound having a cyclopentadienyl ligand and a ligand containing a Group 15 or 16 element, and a solid aluminoxane compound as a solid support, is very effective in preventing fouling, and have thus completed the present invention. That is, the gist of the present invention is as follows.
[1] An olefin polymerization catalyst comprising the following component (A) and the following solid support (S):
Component (A): A transition metal compound represented by the following general formula [1] or [2].

（一般式［１］および［２］中、Ｍは、周期表第４族遷移金属原子であり、
ｎは、Ｍの価数を満たす１～４の整数であり、
Ｘは、水素原子、ハロゲン原子、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子であり、該アニオン配位子が、ハロゲン含有基、ケイ素含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基または共役ジエン系二価誘導体基であり、ｎが２以上の場合は、複数存在するＸで示される基は互いに同一でも異なっていてもよく、互いに結合して環を形成してもよく、
Ｃｐは、置換基を有していてもよい、シクロペンタジエニル型配位子であり、相互に隣接した置換基は、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｌは、周期表第１５族および１６族元素から選ばれる原子であり、
Ｐは、リン原子であり、
実線は共有結合または配位結合であり、点線はＬが１５族元素の原子である場合に存在する共有結合であり
ｙは、Ｌが１５族元素の原子である場合は２であり、Ｌが１６族元素の原子である場合は３であり
ｚは、Ｌが１５族元素の原子である場合は３であり、Ｌが１６族元素の原子である場合４であり、
Ｒは、それぞれ独立に、水素原子、炭素数１～４０の炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基または硫黄含有基であり、それぞれ同一でも異なっていてもよく、相互に隣接したＲは、互いに結合して置換基を有していてもよい環またはビシクロ環を形成してもよい。）
固体状担体（Ｓ）：固体状アルミノキサン化合物。
［２］ 前記Ｌが、周期表１５族元素の原子であることを特徴とする［１］に記載のオレフィン重合用触媒。
［３］ 前記Ｍがチタン原子であることを特徴とする［１］に記載のオレフィン重合用触媒。
［４］ ［１］～［３］のいずれかに記載のオレフィン重合触媒の存在下にオレフィンを重合させることを特徴とするオレフィン重合体の製造方法。

(In the general formulas [1] and [2], M is a transition metal atom of Group 4 of the periodic table,
n is an integer from 1 to 4 satisfying the valence of M;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, the anionic ligand being a halogen-containing group, a silicon-containing group, an oxygen-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 divalent derivative group, when n is 2 or more, a plurality of groups represented by X may be the same or different and may be bonded to each other to form a ring,
Cp is a cyclopentadienyl ligand which may have a substituent, and adjacent substituents may be bonded to each other to form a ring which may have a substituent;
L is an atom selected from the elements of Groups 15 and 16 of the Periodic Table;
P is a phosphorus atom;
The solid lines are covalent bonds or coordinate bonds, and the dotted lines are covalent bonds that exist when L is an atom of a Group 15 element; y is 2 when L is an atom of a Group 15 element and is 3 when L is an atom of a Group 16 element; z is 3 when L is an atom of a Group 15 element and is 4 when L is an atom of a Group 16 element;
Each R is 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, and may be the same or different. Adjacent R may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.
Solid support (S): a solid aluminoxane compound.
[2] The olefin polymerization catalyst according to [1], wherein L is an atom of an element in Group 15 of the periodic table.
[3] The olefin polymerization catalyst according to [1], wherein M is a titanium atom.
[4] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [1] to [3].

The olefin polymerization catalyst of the present invention can produce olefin (co)polymers without causing fouling during polymerization.

The olefin polymerization catalyst of the present invention comprises the following component (A) and a solid support (S):
<Component (A)>
Component (A) is a transition metal compound represented by the following general formula [1] or [2] (hereinafter, also referred to as transition metal compound (A)).

前記式［１］および［２］において、Ｍは、周期表第４族遷移金属原子であり、具体的にはチタン原子、ジルコニウム原子またはハフニウム原子であり、好ましくはチタン原子である。

In the above formulas [1] and [2], M is a Group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom, and preferably a titanium atom.

n is an integer of 1 to 4 satisfying the valence of M, and is preferably 1 or 2.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-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 divalent derivative group. When n is 2 or more, the groups represented by X present in a plurality of groups may be the same or different from each other, and may be bonded to each other to form a ring.

Cp is a cyclopentadienyl ligand which may have a substituent. Among the substituents, adjacent substituents may be bonded to each other to form a ring which may have a substituent.

L is an atom selected from the elements of Groups 15 and 16 of the periodic table.
P is a phosphorus atom.
The solid lines are covalent or coordinate bonds, and the dotted lines are covalent bonds that exist when L is a Group 15 element.

y is 2 when L is an atom of a Group 15 element, and is 3 when L is an atom of a Group 16 element.
z is 3 when L is an atom of a Group 15 element, and is 4 when L is an atom of a Group 16 element.

Each R is 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, and may be the same or different. Adjacent R may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.

As described above, L is an atom selected from the group 15 and group 16 elements. Preferably, L is an atom of a group 15 element. In this case, y=2 and z=3.
In the following, examples of the component (A) will be given, particularly when L is an atom of an element in Group 15. Examples of such a component (A) include compounds represented by the following formula [3] or [4].

前記式［３］および［４］において、Ｍは周期表第４族遷移金属原子であり、具体的にはチタン原子、ジルコニウム原子、ハフニウム原子であり、好ましくはチタン原子である。

In the formulas [3] and [4], M is a Group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, and preferably a titanium atom.

In the formulas [3] and [4], n is an integer of 1 to 4 satisfying the valence of the transition metal M, and is preferably 1 or 2.
In the formulas [3] and [4], X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-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 derivative group.

X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group or a conjugated diene derivative group.
When n is 2 or more, the multiple Xs may be the same or different and may be bonded to each other to form a ring. When multiple rings are present, the rings may be the same or different.

The halogen atom includes fluorine, chlorine, bromine, iodine, etc., and is preferably chlorine or bromine.
Examples of the hydrocarbon group include:
linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl;
Linear or branched alkenyl groups or unsaturated double bond-containing groups such as vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-dien-1-yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group), buta-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3-methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, and prenyl group (3-methylbut-2-en-1-yl group);
linear or branched alkynyl groups or unsaturated triple bond-containing groups, such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl); aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups, such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-tri-isopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, and benzhydryl (diphenylmethyl);
cyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 2-adamantyl group;
Examples of aromatic substituents include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a julyl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the above hydrocarbon groups, methyl, iso-butyl, neopentyl, cyamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

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, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.
Among the above halogen-containing groups, a pentafluorophenyl group is preferred.

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, a tris(trimethylsilyl)silyl group, and a trimethylsilylmethyl group.
Among the above silicon-containing groups, a trimethylsilylmethyl group is preferred.

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

Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group).
Of the above sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferred.

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, a piperidinyl group, a morpholyl group, a pyrrolyl group, and a bistriflylimide group.
Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferred.

The phosphorus-containing group may, for example, be a hexafluorophosphate anion.
Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by _BR4 (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

The aluminum-containing group may, for example, be

で表される四員環、あるいは

or

で表される四員環
（Ｍは、前記一般式［３］または［４］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。

(M represents M in the general formula [3] or [4].)
Examples of the groups include groups represented by AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like) which can form the following formula:

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), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

Examples of neutral ligands that can be coordinated with lone pairs include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

In the formulas [3] and [4], Cp is a cyclopentadienyl ligand which may have a substituent, and the substituent may be bonded to another adjacent substituent to form a ring which may have a substituent. The cyclopentadienyl-type ligand is a substituted ligand having a five-membered carbon ring bonded to a metal by a π-type bond, and includes substituted cyclopentadienyl-type ligands such as substituted cyclopentadienyl ligands, substituted tetrahydroindenyl ligands, substituted octahydrofluorenyl ligands, substituted hydroazulenyl ligands, substituted pentahydroazulenyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenopyrrole ligands, substituted cyclopentenothiophene ligands, and substituted cyclopentenodithiophene ligands, substituted indenyl-type ligands such as substituted indenyl ligands, substituted tetrahydroindenyl ligands, substituted benzoindenyl ligands, substituted dihydroindacenyl ligands, substituted indenopyrrole ligands, substituted indenoindole ligands, and substituted indenothiophenes, and substituted fluorenyl ligands. As the cyclopentadienyl type ligand, a substituted cyclopentadienyl type ligand and a substituted indenyl type ligand are preferred, and more preferred are a substituted cyclopentadienyl ligand, a substituted dihydrocyclopentenoannulene ligand, a substituted cyclopentenothiophene ligand, a substituted cyclopentenodithiophene ligand, and a substituted indenyl ligand.

In the formulas [3] and [4], N is a nitrogen atom, and in the formula [4], P is a phosphorus atom.
R ¹ and R ² in formula [3], R ¹ to R ³ in formula [4], and the substituent of the cyclopentadienyl ligand 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. R ¹ to R ³ are preferably a hydrocarbon 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 a hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. ^{R 1} to R ³ may be the same or different.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples include the specific examples of hydrocarbon groups given as examples of X above.

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 hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include:
Methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decanyl, 1-undecanyl, 1-dodecanyl, 1-eicosanyl, isopropyl, sec-butyl, tert-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl (1,1-dimethylpropyl), cyamyl, pentan-3-yl, 2-methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl (2-methylpentan-2-yl), 3-methylpentane linear or branched alkyl groups having 1 to 40 carbon atoms, such as 2-methylpentan-2-yl, 4-methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, 3,3-dimethylbut-2-yl, hexane-3-yl, 2-methylpentan-3-yl, heptan-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, and 2,4,4-trimethylpentan-2-yl;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1 -yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en -1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en- linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, such as a 3-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group;
Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, such as butan-1-yl group, pent-4-yn-2-yl group, hex-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, 2,2-dimethyl-but-3-yn-1-yl group, hex-4-yn-1-yl group, and hex-5-yn-1-yl group;
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, 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-phenyl pentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-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-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-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)propane aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)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)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, and 2-(1-azulenyl)ethyl group;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl 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, cyclododecyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclo Hexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-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), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms;
Examples of aromatic substituents having 6 to 40 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a 3,5-di-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, pentan-3-yl, isohexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, heptane-4-yl, Preferred are yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, and 2,4,4-trimethylpentan-2-yl group, and more preferred are 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-dimethylpentan-2-yl group, and 2,4,4-trimethylpentan-2-yl group.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl groups, allyl groups, but-3-en-1-yl groups, crotyl groups, methallyl groups, pent-4-en-1-yl groups, prenyl groups, penta-1,4-dien-3-yl groups, hex-5-en-1-yl groups, 2-methylpent-4-en-2-yl groups, 2-(cyclopentadienyl)propan-2-yl groups, and 2-(cyclopentadienyl)ethyl groups are preferred, with vinyl groups, allyl groups, but-3-en-1-yl groups, pent-4-en-1-yl groups, prenyl groups, and hex-5-en-1-yl groups being more preferred.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl, prop-2-yn-1-yl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, pent-3-yn-1-yl, pent-4-yn-1-yl, 3-methyl-but-1-yn-1-yl, 3,3-dimethyl-but-1-yn-1-yl, hex-4-yn-1-yl, and hex-5-yn-1-yl groups are preferred, with prop-2-yn-1-yl, propargyl, but-2-yn-1-yl, and but-3-yn-1-yl groups being more preferred.

Among the aromatic 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, rt-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, neophyl 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-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, etc. are preferred, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, and cinnamyl group 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, 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-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cycloo Preferred are octyl, cyclooctenyl, cyclooctadienyl, cyclododecyl, 4-cyclohexyl-tert-butyl, norbornyl, 2-methylbicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.2]octan-1-yl, 1-adamantyl, 2-adamantyl, pentalenyl, indenyl, and fluorenyl groups, and more preferred are cyclopentyl, cyclopentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, cyclooctyl, cyclododecyl, and 1-adamantyl groups.

Among the aromatic substituents having 6 to 40 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, and a phenanthryl group are preferred. , anthracenyl group, ferrocenyl group, etc. are preferred, and phenyl group, tolyl 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, binaphthyl group, phenanthryl group, and anthracenyl group are more preferred.

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, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a pentafluorophenylmethyl group, a di-tert-butyl-fluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a bistrifluoromethoxyphenyl group, a trifluoromethylthiophenyl group, a bistrifluoromethylthiophenyl group, a fluorobiphenyl group, a difluoro Examples of such groups include biphenyl, trifluorobiphenyl, tetrafluorobiphenyl, pentafluorobiphenyl, di-tert-butyl-fluorobiphenyl, trifluoromethylbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxybiphenyl, bistrifluoromethoxybiphenyl, trifluoromethyldimethylsilyl, trifluoromethoxy, pentafluoroethoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy, pentafluorophenoxy, di-tert-butyl-fluorophenoxy, trifluoromethylphenoxy, bistrifluoromethylphenoxy, trifluoromethoxyphenoxy, bistrifluoromethoxyphenoxy, difluoromethylenedioxyphenyl, bistrifluoromethylphenyliminomethyl, and trifluoromethylthio groups.

Among the halogen-containing groups, preferred are fluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, pentafluorophenylmethyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethoxyphenyl, pentafluorobiphenyl, trifluoromethylbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxy, pentafluorophenoxy, bistrifluoromethylphenoxy, bistrifluoromethylphenoxy, difluoromethylenedioxyphenyl, and trifluoromethylthio groups, and more preferred are trifluoromethyl, fluorophenyl, difluorophenyl, pentafluorophenyl, pentafluorophenylmethyl, trifluoromethylphenyl, bistrifluoromethylphenyl, pentafluorobiphenyl, trifluoromethoxy, and pentafluorophenoxy groups.

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, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, and a di-n-butyl(indenyl) Examples of such groups include silyl groups, indenyldiphenylsilyl groups, fluorenyldimethylsilyl groups, di-n-butyl(fluorenyl)silyl groups, fluorenyldiphenylsilyl groups, 4-trimethylsilylphenyl groups, 4-triethylsilylphenyl groups, 4-tri-iso-propylsilylphenyl groups, 4-tert-butyldiphenylsilylphenyl groups, 4-triphenylsilylphenyl groups, 4-tris(trimethylsilyl)silylphenyl groups, and 3,5-bis(trimethylsilyl)phenyl groups.

Among the silicon-containing groups, preferred are trimethylsilyl, triethylsilyl, tri-isopropylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, 4-triphenylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups, and more preferred are trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups.

The oxygen-containing group is preferably an oxygen-containing group having 1 to 20 carbon atoms, and examples thereof 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, a methallyloxy group, a prenyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methallyloxy ... Examples of the alkyl groups include alkoxypropyl 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, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, and dibenzofuryl group.

Among the oxygen-containing groups, methoxy, ethoxy, iso-propoxy, allyloxy, n-butoxy, tert-butoxy, prenyloxy, benzyloxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, biphenyloxy, binaphthyloxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, dimethyldioxanyl, methoxyphenyl, iso-propoxyphenyl, allyloxy Phenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furyl group, benzofuryl group, dibenzofuryl group, etc. are preferred, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, 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-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group are more preferred.

The nitrogen-containing group is preferably a nitrogen-containing group having 1 to 20 carbon atoms, and examples thereof include an amino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-iso-propylamino group, a di-n-butylamino group, a di-iso-butylamino group, a dicyclopentylamino group, a dicyclohexylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, an adamantylamino group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a a phenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a piperidinylphenyl group, a morpholylphenyl group, a pyrrolylphenyl group, a pyridylphenyl group, a quinolylphenyl group, an isoquinolylphenyl group, an indolinylphenyl group, an indolylphenyl group, a carbazolylphenyl group, Examples of such groups include di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl 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, benzimidazolyl group, oxazolyl group, oxazolidinyl group, and benzoxazolyl group.

Among the nitrogen-containing groups, the amino group, the dimethylamino group, the diethylamino group, the di-n-propylamino group, the di-iso-propylamino group, the di-n-butylamino group, the di-iso-butylamino group, the dicyclopentylamino group, the dicyclohexylamino group, the allylamino group, the benzylamino group, the dibenzylamino group, the pyrrolidinyl group, the piperidinyl group, the morpholyl group, the adamantylamino group, the dimethylaminomethyl group, the benzylaminomethyl group, the pyrrolidinylmethyl group, and the dimethylaminoethyl group , pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, piperidinylphenyl group, morpholylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-te Preferred are an rt-butylcarbazolylphenyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group, and further preferably an amino group, a dimethylamino group, a diethylamino group, or a di-isopropylamino group. , dicyclopentylamino group, dicyclohexylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, piperidinylphenyl group, morpholylphenyl group, pyrrolylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group are more preferred.

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

Among the sulfur-containing groups, thienyl, methylthienyl, thienofuryl, thienothienyl, benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, thiazolyl, and benzothiazolyl groups are preferred.

R ¹ and R ² in the formula [3] may be bonded to each other to form a monocyclic or bicyclic ring which may have a substituent. In this case, the ring formed is preferably a 4-8 membered saturated or unsaturated hydrocarbon ring or heterocyclic ring which may have a substituent containing an imine carbon atom. Although not particularly limited as long as the effects of the present invention are exhibited, a 5- or 6-membered ring is preferable. In this case, examples of the structure combined with the imine carbon atom include a substituted cyclopentane ring, a substituted cyclohexane ring, a substituted cycloheptane ring, a substituted bicyclo[2.2.1]heptane ring, a substituted bicyclo[2.2.2]octane ring, a substituted pyrrolidine ring, a substituted isoindoline ring, a substituted imidazolidine ring, a substituted dihydroimidazole ring, and a substituted tetrahydropyrimidine ring. A substituted cyclopentane ring, a substituted cyclohexane ring, a substituted pyrrolidine ring, a substituted isoindoline ring, a substituted imidazolidine ring, and a substituted dihydroimidazole ring are preferable.

Adjacent substituents of R ¹ to R ³ in the formula [4] may be bonded to each other to form a monocyclic or bicyclic ring which may have a substituent. In this case, the ring formed is preferably a 4- to 8-membered saturated or unsaturated heterocyclic ring which may have a substituent containing a phosphorus atom. Although not particularly limited as long as the effects of the present invention are exhibited, a 5- or 7-membered ring is preferable. In this case, examples of the structure combined with the phosphorus atom include a substituted phosphole ring, a substituted phosphorane ring, a substituted dihydrophosphepine ring, a substituted dioxaphosphepine ring, a substituted diazaphosphepine ring, a substituted phospha-adamantane ring, and a substituted trioxaphospha-adamantane ring, and the like. A substituted dihydrophosphepine ring, a substituted dioxaphosphepine ring, a substituted diazaphosphepine ring, and a substituted trioxaphospha-adamantane ring are preferable.

Specific examples of the component (A), which is a transition metal compound represented by the above general formula [3] or [4], are shown below, but the scope of the present invention is not particularly limited thereto.
For convenience, the ligand structure of the transition metal compound component (A) excluding the portion represented by MXn (metal portion) is divided into two structures: a cyclopentadienyl-type ligand portion and an imide-type ligand portion. The abbreviation for the cyclopentadienyl-type ligand portion is α, the abbreviation for the imide-type ligand portion ^R1 , ^R2, and ^R3 substituents is β, and the abbreviation for the imide-type ligand portion cyclic structure is γ. The abbreviations for each substituent are shown in [Table 1] to [Table 3].

なお、前記［表３］中のＲ^aおよびＲ^bは、前記［表２］の略称βで示される置換基である。また、［表３］中の波線は窒素原子との結合部位を示す。

In addition, R ^a and R ^b in the above [Table 3] are the substituents represented by the abbreviation β in the above [Table 2]. In addition, the wavy line in [Table 3] indicates the bonding site with the nitrogen atom.

Specific examples of the metal moiety MXn include _TiF2 , _TiCl2 , _TiBr2 , _TiI2 , Ti(Me) ₂ , Ti(Bn) ₂ , Ti(Allyl) ₂ , Ti( _CH2 -tBu) ₂ , Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), Ti( _CH2 -Si(Me) ₃ ) ₂ , Ti(OMe) ₂ , Ti(OiPr) ₂ , Ti( _NMe2 ) ₂ , Ti(OMs) ₂ , Ti(OTs) ₂ , Ti(OTf) ₂ , ZrF ₂ , _ZrCl2 , _ZrBr2 , _ZrI2 , Zr(Me) ₂ , Zr(Bn) ₂ , Zr(Allyl) ₂ , Zr(CH2 _- tBu) ₂ , Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4- _{diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2 , Zr ( OMs ) 2 , Zr} (OTs)2, Zr(OTf) ₂ , _HfF2 , _HfCl2 , _HfBr2 , _Hfh2 , Hf(Me) ₂ , Hf(Bn) ₂ , Hf(Allyl) ₂ , Hf(CH2 _- tBu) ₂ , Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf( _CH2 -Si(Me) ₃ ) ₂ , Hf(OMe) ₂ , Hf(OiPr) ₂ , Hf( _NMe2 ) ₂ , Hf(OMs) ₂ , Hf(OTs) ₂ , Hf(OTf) 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, OMe is a methoxy group, OiPr is an isopropoxy group, _NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

When component (A) is a transition metal compound represented by the general formula [3], according to the above notation, the cyclopentadienyl ligand moiety is composed of a combination of α-7 in [Table 1], the imide ligand moiety R ¹ substituent is composed of a combination of β-51 in [Table 2], and the imide ligand moiety R ² substituent is composed of a combination of β-32 in [Table 2], and the metal moiety MXn is TiCl ₂ , the compound represented by the following formula [7] is exemplified.

In addition, when the cyclopentadienyl ligand portion is composed of a combination of α-7 in [Table 1], the imide ligand portion cyclic structure is composed of a combination of γ-9 in [Table 3], and the imide ligand portion cyclic structure R ^a substituent is composed of a combination of β-13 in [Table 2], and the metal portion MXn is _TiMe2 , the compound represented by the following formula [8] is exemplified.

In addition, when the cyclopentadienyl ligand moiety is α-1 in [Table 1], the imide ligand moiety cyclic structure is γ-10 in [Table 3], and the imide ligand moiety cyclic structure R ^a and R ^b substituents are both composed of a combination of β-9 in [Table 2], and the metal moiety MXn is _TiBn2 , the compound represented by the following formula [9] is exemplified.

In addition, when the cyclopentadienyl ligand portion is composed of α-41 in [Table 1], the imide ligand portion ^R1 and ^R2 substituents are both composed of a combination of β-9 in [Table 2], and the metal portion MXn is Ti(1,3-pentadienyl), the compound represented by the following formula [10] is exemplified.

Similarly, when component (A) is a transition metal compound represented by the general formula [4], according to the above notation, the cyclopentadienyl ligand portion is α-25 in [Table 1], the imide ligand portion R ¹ , R ² and R ³ substituents are all composed of a combination of β-9 in [Table 2], and the metal portion MXn is TiCl ₂ , the compound represented by the following formula [11] is exemplified.

In addition, when the cyclopentadienyl type ligand portion is composed of α-7 in [Table 1], the imide type ligand portion R ¹ , R ² and R ³ substituents are all composed of a combination of β-9 in [Table 2], and the metal portion MXn is TiMe ₂ , the compound represented by the following formula [12] is exemplified.

In addition, when the cyclopentadienyl type ligand portion is composed of α-18 in [Table 1], the imide type ligand portion R ¹ , R ² and R ³ substituents are all composed of a combination of β-11 in [Table 2], and the metal portion MXn is TiBn ₂ , the compound represented by the following formula [13] is exemplified.

In addition, when the cyclopentadienyl ligand portion is α-1 in [Table 1], the imide ligand portion ^R1 and ^R2 substituents are both β-9 in [Table 2], and the imide ligand portion ^R3 substituent is β-60 in [Table 2], and the metal portion MXn is Ti(1,3-pentadienyl), the compound represented by the following formula [14] is exemplified.

The compounds represented by the formula [1] or [2] can be produced using a conventionally known method, and the production method is not particularly limited. Examples of known production methods include those described in "Organometallics 1999, 18, 1116.", JP-T-2001-516776, "Organometallics 2001, 20, 4424.", "Chem. Commun. 2002, 608.", "Organometallics 2003, 22, 1937.", "J. Organomet. Chem. 2004, 689, 203.", "Organometallics 2004, 23, 1562.", and "Organometallics 2004, 23, 3309. ”, WO2005/090418 Publication, US6239061 Publication, “Oganometallics 2005, 24, 2548.”, Special Publication No. 2007-529584, “J. Organomet. Chem. 2011, 696, 2451.”, “Dal ton Trans. 2011,40,7842.", JP 2012-007171 A, JP 2012-046764 A, JP 2013-155371 A, JP 2013-510214 A, JP 2013-515120 A, US9045504 A, JP 2014-509670 A, US9035081 A, JP 2015-520276 A, JP 2016-532730 A, JP 2017-509595 A, and the like.

The compound represented by the general formula [2] is more preferable than the compound represented by the general formula [1] because it can produce a polymer with higher polymerization activity.
In the present invention, among the transition metal compounds represented by the general formula [1] or [2], one kind may be used alone, or two or more kinds of transition metal compounds having different chemical structures may be used. In addition, one kind of optical isomer having the same chemical structure may be used alone, or a mixture of optical isomers (e.g., a meso mixture or a racemic mixture) may be used.
When L is a Group 16 element, the same compounds as above except that y=3 and z=4 can be exemplified.

<Solid Carrier (S)>
The solid support (S) is a solid aluminoxane compound, and examples of the aluminoxane include at least one selected from aluminoxanes having a structure represented by the following general formula (S-a) and aluminoxanes having a structure represented by the following general formula (S-b), and aluminoxanes having a structure comprising a repeating unit represented by the following general formula (Sc) and a repeating unit represented by the following general formula (S-d).

In the general formulae (S-a) to (S-d), R ^e is each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically includes hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, and ethylphenyl groups, of which methyl, ethyl, and isobutyl groups are preferred, and methyl is particularly preferred. In addition, a portion of R ^e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R ^e . In (S-c) and (S-d), a line segment having one end not connected to an atom indicates a bond with another atom not shown.

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

The solid aluminoxane compound is different from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina or organic polymer components such as polyethylene or polystyrene, but is solidified with an alkylaluminum compound as the main component.

"Solid" means that the aluminoxane component maintains a substantially solid state in the reaction environment in which it is used. More specifically, it means that the aluminoxane component maintains a substantially solid state when the transition metal compound (A) is contacted with the aluminoxane component to prepare an olefin polymerization catalyst as described below, and when the prepared olefin polymerization catalyst is used to polymerize olefins (e.g., slurry polymerization).

Whether the aluminoxane component is in a solid state is most easily confirmed by visual inspection, but visual inspection is often difficult, for example, during polymerization. In such cases, it is possible to judge from, for example, the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and adhesion to the reactor is small, the gist of the present invention will not be deviated from even if some of the aluminoxane component is eluted in the polymerization environment. Indicators for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitativeness. The bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

The solubility 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%, and particularly preferably 0 to 10 mol%.

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

As the solid aluminoxane compound, any known solid aluminoxane can be used without restriction, and for example, the solid polyaluminoxane composition described in WO 2014/123212 can be used. Known manufacturing methods include, for example, manufacturing methods described in JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000-38410, JP-A-2000-95810, WO 2010/55652, etc.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 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 sizes of 100 or more particles, and averaging the weights. First, the particle size of each particle is determined by measuring the length of a particle image between two parallel lines in the horizontal and vertical directions, and then using the following formula:
Grain size = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound is calculated from the particle size calculated above according to the following formula.
Average particle size=Σnd ⁴ /Σnd ³
(n: number of particles, d: particle size)

The solid aluminoxane compound 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.

The particle size of the polymer particles obtained by polymerizing olefins using the olefin polymerization catalyst of the present invention is not particularly limited, but is preferably 3 to 50,000 μm. A more preferred lower limit is 5 μm, an even more preferred lower limit is 10 μm, and a particularly preferred lower limit is 20 μm. On the other hand, a more preferred upper limit is 30,000 μm, an even more preferred upper limit is 20,000 μm, and a particularly preferred upper limit is 10,000 μm. When the olefin polymerization catalyst of the present invention is used, even when an ultra-high molecular weight polymer having an intrinsic viscosity ([η]) exceeding 5 dl/g is produced, fouling and aggregation of the obtained olefin polymer particles tend not to occur, which is advantageous for efficient and stable production of the polymer particles.

The factors behind the above-mentioned advantages in terms of fouling and particle aggregation are unclear at present, but the present inventors speculate as follows.
There are two main causes of fouling and aggregation during polymerization. One is a physical cause that occurs when component (A), which becomes a polymerization active species, is liberated (leached) from the solid support (S) in the polymerization environment, resulting in the production of an amorphous polymer. The other is an electrostatic cause that occurs when frictional charging occurs between the solid catalyst component (X), which will be described later, and the produced polymer and polymerization reactor.

Many of the conventional techniques involve suppressing leaching of component (A) or precisely controlling the shape or amount of fine powder of the solid carrier (S), which can be said to have an effect against the physical factors mentioned above.

The present inventors believe that the olefin polymerization catalyst of the present invention exhibits a very effective effect in preventing fouling caused by electrostatic factors believed to be due to component (A) having a cyclopentadienyl ligand and a ligand containing an atom selected from Group 15 or Group 16 elements, by using a solid aluminoxane compound as the solid support (S). The present inventors believe that such an effect is exhibited because solid aluminoxane has a relatively flexible structure and is highly polar, and therefore exhibits not only the performance of a support and cocatalyst, but also the performance of an antistatic agent.

These effects of solid aluminoxane are not seen in transition metal compounds whose ligands consist only of cyclopentadienyl ligands, or in transition metal compounds that contain Group 15 and Group 16 elements, such as phenoxyimine ligands, and do not have cyclopentadienyl ligands, and it is difficult to infer them from conventional technology.

<Method for preparing an olefin polymerization catalyst>
As a preferred embodiment of the olefin polymerization catalyst according to the present invention, a solid catalyst component (X) prepared by adding the component (A) and the solid support (S) to an inert hydrocarbon or to a polymerization system using an inert hydrocarbon is used.

The method of contacting each component is not particularly limited as long as the effect of the present invention is achieved. For example, the method includes a method of contacting a solid or liquid component (A) by adding it all at once or in portions to a suspension consisting of a solid carrier (S) and an organic solvent, a method of contacting a suspension consisting of a solid carrier (S) and an organic solvent by adding it all at once or in portions to a suspension consisting of a solid carrier (S) and an organic solvent, and a method of contacting a solid or a solid carrier (S) suspended in an organic solvent with a component (A). From the viewpoint of making the reaction uniform, it is preferable to add the component (A) to the solid carrier (S). When two or more kinds of components (A) are used in combination, the components (A) may be added one by one or two or more kinds may be mixed and added.

In any step of the contact method, by adding component (G), fouling during the polymerization reaction can be suppressed to a higher degree and the particle properties of the resulting polymer can be further improved. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acyl amino acids being more preferred. These may be used alone or in combination of two or more.

The solvent used in the preparation of the ethylene polymerization catalyst according to the present invention may be an inert hydrocarbon solvent, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc., alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc., or mixtures thereof.

For the polymerization of olefins, the above-mentioned solid catalyst component (X) can be used as is, but by prepolymerizing an olefin on this solid catalyst component (X) to form a prepolymerized catalyst component (XP) before use, it is possible to further suppress fouling during the polymerization reaction and further improve the particle properties of the resulting polymer.

The prepolymerized catalyst component (XP) can be prepared by introducing an olefin into the presence of the solid catalyst component (X), usually in an inert hydrocarbon solvent. The reaction can be carried out in any of batch, semi-continuous and continuous modes. The reaction can be carried out under reduced pressure, normal pressure or increased pressure. This prepolymerization produces 0.2 to 500 g of polymer from the solid catalyst component sd.

The prepolymerized catalyst component (XP) prepared in an inert hydrocarbon solvent may be separated from the suspension and then suspended again in an inert hydrocarbon, and an olefin may be introduced into the resulting suspension, or the olefin may be introduced into the suspension after drying.

The prepolymerization temperature is usually −20 to 80° C., preferably 0 to 60° C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component (X) used in the prepolymerization, those already mentioned can be used without any limitation.

Furthermore, the following component (B) can be used as necessary.
Component (B): (b-1) at least one compound selected from the group consisting of organometallic compounds represented by the following general formulas [b-1-1], [b-1-2], or [b-1-3], (b-2) organoaluminum oxy compounds, and (b-3) compounds that react with component (A) and component (B) to form an ion pair.
RamAl(ORb)n Hp Xq ... [b-1-1]
(In general formula [b-1-1], R and R represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other, X represents a halogen atom, m represents a number that satisfies 0<m≦3, n represents a number that satisfies 0≦n<3, p represents a number that satisfies 0≦p<3, q represents a number that satisfies 0≦q<3, and m+n+p+q=3.)
Ma AlRa ₄ ...[b-1-2]
(In general formula [b-1-2], Ma represents Li, Na or K, and Ra represents a hydrocarbon group having 1 to 15 carbon atoms.)
RarMbRbs Xt...[b-1-3]
(In general formula [b-1-3], R and R represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other, M represents Mg, Zn or Cd, X represents a halogen atom, r represents 0<r≦2, s represents 0≦s≦1, t represents 0≦t≦1, and r+s+t=2.)

In particular, the organoaluminum compound represented by the formula [b-1-1] among the compounds (b-1) is preferably used. When the organoaluminum compound represented by the formula [b-1-1] is used as component (B), it is used in an amount of usually 0.1 to 10,000, preferably 0.5 to 5,000, in terms of the molar ratio of the aluminum atom (Al) in component (B) to the transition metal compound which is component (A) (component (B)/transition metal compound).

The concentration of the solid catalyst component (X) in the prepolymerization system is usually 1 to 1,000 g/L, preferably 10 to 500 g/L, in terms of the ratio of solid catalyst component (X)/1 liter of polymerization volume. During the prepolymerization, the component (G) can be present to suppress fouling or improve particle properties.

In addition, in order to improve the fluidity of the prepolymerized catalyst component (XP) and to suppress the occurrence of heat spots, sheeting, and polymer lumps during polymerization, the prepolymerized catalyst component (XP) that has been produced by prepolymerization may be contacted with component (G).

The temperature when component (G) is mixed and contacted is usually from -50 to 50°C, preferably from -20 to 50°C, and the contact time is from 1 to 1000 minutes, preferably from 5 to 600 minutes.
When the solid catalyst component (X) and the component (G) are mixed and contacted, the component (G) is used in an amount of usually 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight, per 100 parts by weight of the solid catalyst component (X).

The solid catalyst component (X) and component (G) can be mixed and contacted in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same solvents as those used in the preparation of the solid catalyst component (X).

The olefin polymerization catalyst according to the present invention can be used as a dried prepolymerized catalyst by drying the prepolymerized catalyst component (XP). This embodiment is particularly preferred when a gas phase polymerization method is used. Of course, it can also be used in the case of a liquid phase polymerization method.

The prepolymerized catalyst component (XP) is usually dried after removing the hydrocarbon, which is the dispersion medium, from the resulting suspension of the prepolymerized catalyst by filtration or the like.
The drying of the prepolymerized catalyst component (XP) is carried out by maintaining the prepolymerized catalyst component (XP) at a temperature of 70° C. or less, preferably in the range of 20 to 50° C., under a flow of an inert gas. The amount of volatile components in the obtained dried prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dried prepolymerized catalyst is preferably as small as possible, and there is no particular lower limit, but in practice it is 0.001% by weight. The drying time is usually 3 to 8 hours, depending on the drying temperature. If the amount of volatile components in the dried prepolymerized catalyst exceeds 2.0% by weight, the fluidity of the dried prepolymerized catalyst decreases, and it may become impossible to stably supply the dried prepolymerized catalyst to a polymerization reactor.

The amount of volatile components in the dried prepolymerized catalyst is measured, for example, by a weight loss method or a method using gas chromatography.
In the weight loss method, a dry prepolymerized catalyst is heated at 110° C. for 1 hour in an inert gas atmosphere, and the weight loss is determined and expressed as a percentage of the dry prepolymerized catalyst before heating.

In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dried prepolymerized catalyst, a calibration curve is created according to the internal standard method, and the weight percentage is calculated from the GC area.

The amount of volatile components in a dried prepolymerized catalyst is measured by a weight loss method if the amount of volatile components in the dried prepolymerized catalyst is approximately 1% by weight or more, and by gas chromatography if the amount of volatile components in the dried prepolymerized catalyst is approximately 1% by weight or less.

Examples of inert gases used to dry the prepolymerized catalyst component (XP) include nitrogen gas, argon gas, and neon gas. Such inert gases desirably have an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, and more preferably 5 ppm or less (by volume) and a moisture content of 20 ppm or less, preferably 10 ppm or less, and more preferably 5 ppm or less (by weight). If the oxygen concentration and moisture content in the inert gas exceed the above ranges, the olefin polymerization activity of the dried prepolymerized catalyst may be significantly reduced.

The above-mentioned dried prepolymerized catalyst has excellent fluidity, so it can be stably supplied to the polymerization reactor. In addition, since it is not necessary to entrain the solvent used for suspension in the gas phase polymerization system, polymerization can be carried out stably.

<Production method of olefin polymer>
According to the present invention, by polymerizing one or more α-olefins having 2 to 30 carbon atoms in the presence of an olefin polymerization catalyst comprising the above-mentioned component (A) and the solid support (S), preferably by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, it is possible to prevent fouling during polymerization and efficiently produce an olefin polymer.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method, but in the suspension polymerization method and the gas phase polymerization method, it is preferable to use the solid catalyst component (X).

Specific examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof. In addition, in liquid phase polymerization, the olefin itself can also be used as the solvent.

When polymerization is carried out using the above olefin polymerization catalyst, component (A) is used in an amount of usually 10 ^-12 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 mol, per liter of reaction volume.

The polymerization temperature using the above-mentioned solid catalyst component (X) is usually in the range of -50 to 200°C, preferably 0 to 170°C, and particularly preferably 60 to 170°C. The polymerization pressure is usually in the range of normal pressure to 100 kg/ ^cm2 , preferably normal pressure to 50 kg/ ^cm2 , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. In general, the more low molecular weight components there are, the more they adhere to the walls of the polymerization reactor and the agitator blades, which can lead to a decrease in productivity due to the burden placed on cleaning processes. Component (G) can be added during polymerization to suppress fouling or improve particle properties.

In the present invention, the olefin supplied to the polymerization reaction is, for example, one or more monomers selected from olefins having 2 to 20 carbon atoms. Specific examples of olefins having 2 to 20 carbon atoms include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

In addition, examples of monomers supplied to the polymerization reaction include styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid.

<Olefin Polymer>
One embodiment of the olefin polymer obtained by the polymerization reaction using the olefin catalyst of the present invention is an ethylene-based polymer containing ethylene-derived structural units in the range of preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and even more preferably 98 to 100 mol%. The ethylene-based polymer contains structural units derived from an α-olefin having 3 to 20 carbon atoms in a total amount of preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and even more preferably 0.2 mol%, where the sum of the content of ethylene-derived structural units and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%.

Among these polymers, ethylene homopolymer, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/propylene/1-butene copolymer, ethylene/1-octene polymer, ethylene/1-hexene polymer, ethylene/4-methyl-1-pentene polymer, ethylene/propylene/1-octene polymer, ethylene/propylene/1-hexene polymer, and ethylene/propylene/4-methyl-1-pentene polymer are preferred. Also, so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more types selected from these polymers may be used.

Although there is no particular restriction on the molecular weight of the olefin polymer produced by the olefin polymerization catalyst of the present invention, the effect of the present invention often provides favorable results in the production of polymers with high molecular weights. The intrinsic viscosity ([η]) of such an olefin polymer is preferably 5.0 dl/g or more. A more preferred lower limit is 6.0 d/g, further 8.0 d/g, and particularly (10.0) d/g. On the other hand, a preferred upper limit is (40) d/g, more preferably (35 d/g, further (30) d/g, and particularly (25) d/g. The molecular weight of the high molecular weight polymer produced by the olefin polymerization catalyst of the present invention can be determined, for example, by the ASTM-D4020 standard, and is preferably 500,000 or more, more preferably 1,000,000 or more.

Furthermore, ethylene homopolymers obtained by homopolymerization of ethylene using the olefin polymerization catalyst of the present invention may exhibit the characteristic of a high density commensurate with the molecular weight (MFR) in a relatively low molecular weight range. This is because there are few methyl and ethyl branches, and there are also few double bond structures such as vinyl and vinylidene. Specifically, ethylene homopolymers having an intrinsic viscosity ([η]) of 3.0 dl/g or less, more preferably 2.0 dl/g or less, obtained using the olefin polymerization catalyst of the present invention, have the characteristics represented by the following requirements (I) to (III).

Requirement (I): The weight average molecular weight (Mw)/number average molecular weight (Mn) measured by GPC is 2.0 to 5.0.
In the weight average molecular weight (Mw)/number average molecular weight (Mn), the lower limit is preferably 2.2, and the particularly preferred lower limit is 2.5, while the upper limit is preferably 4.8, and the particularly preferred upper limit is 4.5.
Requirement (II): The melt flow rate (MFR) and density satisfy the relationship of (density) ≧ 10.0 × log (MFR) + 958.
Requirement (III): The total number of double bonds (vinyl, vinylidene, vinylene) as measured by ¹ H-NMR is less than 0.02 per 1,000 carbon atoms.
The total amount of double bonds is preferably less than 0.01 per 1000 carbon atoms.
The methods for measuring the physical properties and characteristics of the polymer are described below.

Intrinsic viscosity [η]
According to the ASTM-D4020 standard, about 20 mg of the measurement sample is dissolved in 15 ml of decalin, and the specific viscosity η _sp is measured in an oil bath at 135° C. 5 ml of decalin solvent is added to this decalin solution to dilute it, and the specific viscosity η _sp is measured in the same manner. This dilution operation is repeated two more times, and the value of η _sp /C when the concentration (C) is extrapolated to 0 as shown in the following formula (Eq-1) is calculated as the limiting viscosity [η] (unit: dl/g).
[η]=lim(η _sp /C) (C→0) -------- (Eq-1)

Melt Flow Rate (MFR)
The measurement is performed in accordance with the ASTM D1238 standard at 190°C and a load of 2.16 kg (kgf).

Density (kg/ ^m3 )
The density is measured by heat treating the strand obtained during the MFR measurement at 120° C. for 30 minutes and then leaving it at room temperature for 1 hour, and then measuring the density by a density gradient tube method.

Weight average molecular weight (Mw), number average molecular weight (Mn)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer are determined by gel permeation chromatography (GPC). Waters "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph) The molecular weight distribution curve is calculated from the molecular weight distribution curve obtained by the following procedure:
[Equipment and conditions used]
Measurement device: Gel permeation chromatograph alliance GPC2000 (Waters)
Analysis software: Chromatography Data System Empower (trademark, Waters)
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [ODCB] (Wako Pure Chemical Industries, Ltd., special grade reagent)
Detector: Differential refractometer (built into the device)
Column temperature: 140 ° C.
Flow rate: 1.0mL/min
Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration: monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to molecular weight 20.6 million. The molecular weight distribution and various average molecular weights were calculated in terms of polyethylene molecular weight according to the general calibration procedure described in J. Polym. Sci. 1967, B5, 753. Calculate as follows.

Amount of double bonds, number of branches (per 1000 carbons)
The number of double bonds and the number of branches of the olefin polymer are determined by a nuclear magnetic resonance (NMR) spectrometer. The number of double bonds is determined by ¹ H-NMR using the following method or a method equivalent thereto.
[Equipment and conditions used]
Measurement equipment: Bruker Biospin AVANCE III cryo-500 nuclear magnetic resonance spectrometer (1H: 500MHz)
Measurement solvent: orthodichlorobenzene-d4
Sample concentration: ca. 20mg/0.6mL
Measurement temperature: 120℃
Number of accumulations: 64 to 256 Chemical shift reference: Main chain methylene peak (1.2 ppm)
The amount of double bonds per 1000 carbon atoms is calculated from the integral intensity ratio of the integral intensities of 4.8-4.9 and 5.6-5.7 ppm for vinyl groups, 4.6-4.7 ppm for vinylidene groups, and 5.1-5.2 (tri-substitution) and 5.3-5.4 (di-substitution) ppm for vinylene (internal olefin) to the integral sum of hydrogen atoms in the polymer.
The amount of branching is determined by ¹³ C-NMR using the following method or an equivalent method.
[Equipment and conditions used]
Measurement equipment: Bruker Biospin AVANCEIII cryo-500 type nuclear magnetic resonance equipment (13C: 125MHz)
Measurement solvent: orthodichlorobenzene/benzene-d6 (4/1 v/v)
Sample concentration: ca. 60mg/0.6mL
Measurement temperature: 120℃
Number of accumulations: 128 or more Chemical shift reference: Main chain methylene peak (29.7 ppm)
The number of branches per 1000 carbon atoms is calculated from the integral intensity ratio of the integral intensity of 19.9 ppm for methyl branches and 10.8 ppm for ethyl branches to the total integral of carbon (5 to 45 ppm) in the polymer.

The olefin polymer obtained by the polymerization reaction using the olefin polymerization catalyst of the present invention may contain additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as necessary, within the scope of the present invention.

The olefin polymer obtained by the polymerization reaction using the olefin polymerization catalyst of the present invention, and the resin composition containing a thermoplastic resin and additives as necessary, can be molded without restriction by any molding method suitable for ultra-high molecular weight olefin polymers. Examples include compression molding, gel sheet molding, gel spinning molding, and solid-phase stretch molding. In addition, the polymer can be molded into containers, trays, sheets, rods, films, or as a coating for various molded bodies by molding methods such as injection molding, profile extrusion molding, pipe molding, tube molding, coating molding for heterogeneous molded bodies, injection blow molding, direct blow molding, T-die sheet or film molding, inflation molding, and press molding.

In addition, ultra-high molecular weight ethylene polymers have an excellent balance of properties such as abrasion resistance, self-lubrication, impact strength, and thin-wall molding, and are therefore used in applications where these are required, such as metal coatings (laminations) for steel pipes, electric wires, and automobile sliding door rails, pressure-resistant rubber hoses, gaskets for automobile doors, gaskets for clean room doors, automobile glass run channels, automobile weather strips, and various other rubber coatings (laminations), linings for hoppers and chutes, and sliding materials such as gears, bearings, rollers, tape reels, various guide rails and elevator rail guides, and various protective liner materials.

For olefin polymers in the relatively low molecular weight range, general film molding, blow molding, injection molding, and extrusion molding are also suitable. Film molding can be obtained by extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing), etc. Stretch molding is also possible. Although the film obtained using the ethylene polymer can be used as a single layer, it can be multilayered to give it various functions. In that case, the co-extrusion method in each of the above-mentioned molding methods can be mentioned. On the other hand, lamination with paper or barrier film (aluminum foil, vapor deposition film, coating film, etc.) that is difficult to coextrude can be mentioned by lamination molding methods such as extrusion lamination molding and dry lamination. It is possible to produce high-performance products by multilayering using the co-extrusion method in blow molding, injection molding, and extrusion molding, just like film molding.

Molded articles obtained by processing the olefin polymer obtained by the polymerization reaction using the olefin polymerization catalyst of the present invention and the resin composition containing a thermoplastic resin and additives as necessary include films, blown infusion bags, blown bottles, gasoline tanks, tubes, pipes, tear-off caps, injection molded articles such as daily necessities, fibers, and large molded articles by rotational molding.

Furthermore, the olefin polymer obtained by the polymerization reaction using the olefin polymerization catalyst of the present invention, and the film obtained by processing the resin composition containing a thermoplastic resin and additives as necessary, are suitable for various packaging films such as liquid packaging bags, liquid soup bags, liquid paper containers, laminated raw material, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy-duty bags, wrap films, sugar bags, oil packaging bags, food packaging films, protective films, infusion bags, agricultural materials, etc. They can also be used as multilayer films by bonding with substrates such as nylon and polyester.

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
The transition metal compound (A) was identified using 270 MHz, ^1H -NMR (JEOL; GSH-270), gas chromatograph mass spectrometer (GC-MS) (Shimadzu Corporation; GCMS-QP5050A and Shimadzu Corporation; GCMS-QP2010Ultra), and FD-mass spectrometry (JEOL SX-102A and JMS-T100G). The Al concentration of the solid support (S) and the metal (Ti, Zr) concentrations in the supernatant during preparation of the solid catalyst component (X) were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES) (Shimadzu Corporation, ICPS-8100).

<Synthesis of Transition Metal Compound (A)>
Synthesis Example 1 Synthesis of Transition Metal Compound (A-1) (pentamethylcyclopentadienyl)Ti(N=P(t-Bu) ₃ )Cl ₂ represented by the following formula (hereinafter also referred to as “transition metal compound (A-1)”) was synthesized by the method described in Organometallics 2003, 22, 1937.

Synthesis Example 2 Synthesis of transition metal compound (A-2) (cyclopentadienyl)Ti(N=P(t-Bu) ₃ )Cl ₂ represented by the following formula (hereinafter also referred to as “transition metal compound (A-2)”) was synthesized by the method described in Organometallics 1999, 18, 1116.

Synthesis Example 3 Synthesis of transition metal compound (A-3) (indenyl)Ti(N=P(t-Bu) ₃ ) _Cl2 represented by the following formula (hereinafter also referred to as "transition metal compound (A-3)") was synthesized by the method described in J. Organomet. Chem. 2004, 689, 203.

Synthesis Example 4 Synthesis of transition metal compound (A-4) (1-(pentafluorophenylmethyl)indenyl)Ti(N=P(t-Bu)) _Cl represented by the following formula ( _hereinafter also referred to as "transition metal compound (A-4)") was synthesized by the method described in JP2015-520276A.

Synthesis Example 5 Synthesis of Transition Metal Compound (A-5) (Cyclopentadienyl)Ti(N=C(t-Bu) ₂ ) _Cl2 represented by the following formula (hereinafter also referred to as "transition metal compound (A-5)") was synthesized by the method described in J. Am. Chem. Soc. 2000, 122, 5499.

Synthesis Example 6 Synthesis of transition metal compound (A-6) (pentamethylcyclopentadienyl)Ti( _N═C (N(iPr))(2,6-F— _CH ) _{) Cl} represented by the following formula (hereinafter also referred to as “transition metal compound ₍ A-6)”) was synthesized by the method described in Chem. Commun. 2010, 46, 3339.

Synthesis Example 7 Synthesis of transition metal compound (A-7) Bis(1-butyl-3-methylcyclopentadienyl)ZrCl ₂ (hereinafter also referred to as “transition metal compound (A-7)”) represented by the following formula was synthesized by the method described in JP2015-113282A.

[Synthesis Example 8] Synthesis of transition metal compound (A-8) Bis[6-cumyl-3-methyl-2-[{(2-methylcyclohexyl)imino}methyl]phenolate] _ZrCl2 represented by the following formula (hereinafter also referred to as "transition metal compound (A-8)") was synthesized by the method described in JP2006-206768A.

Synthesis Example 9 Synthesis of transition metal compound (A-9) Bis(n-butylcyclopentadienyl)ZrCl ₂ represented by the following formula (hereinafter also referred to as “transition metal compound (A-9)”) was purchased from FUJIFILM Wako Pure Chemical Industries, Ltd. and used as it was.

Synthesis Example 10 Synthesis of transition metal compound (A-10) Di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)ZrCl ₂ represented by the following formula (hereinafter also referred to as “transition metal compound (A-10)”) was synthesized by the method described in JP-A-2004-182715.

Synthesis Example 11 Synthesis of transition metal compound (A-11) (Dimethylcyclopentadienyl)Ti(N=P(t-Bu) ₃ ) _Cl2 represented by the following formula (hereinafter also referred to as "transition metal compound (A-11)") was synthesized by the following method.

2957 mg (31.40 mmol) of 1,3-dimethylcyclopentadiene and 40 mL of hexane were added to a Schlenk flask under a nitrogen atmosphere. While cooling in an ice bath, 20.0 mL of a hexane solution (1.57 M) of nBuLi (31.40 mmol) was gradually added, and the mixture was stirred for 2 hours while returning to room temperature. The reaction liquid was filtered using a glass filter. The resulting white solid was washed with hexane and dried under reduced pressure to obtain 2.6334 g of a white solid.

Under nitrogen atmosphere, 205 mg of the white solid obtained in the previous reaction and 15 mL of THF were added to a Schlenk flask. Under nitrogen atmosphere, 741 mg of Ti(N=P(t-Bu) ₃ )Cl ₃ and 50 mL of toluene were added to another Schlenk flask. This solution was cooled in an ice bath, and the reaction solution obtained previously was added while washing with 5 mL of THF. The reaction solution was stirred for 19 hours while returning to room temperature. The reaction solvent was distilled off under reduced pressure, and extracted with dichloromethane using Celite. The filtrate was concentrated, dissolved in dichloromethane, and dropped into hexane. The obtained yellow solid was collected by filtration, washed with hexane, and dried under reduced pressure. 699.4 mg of the target product was obtained. The yield was 82%. The target transition metal compound (A-7) was identified by the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 6.10-6.02 (3H, m), 2.27 (6H, s), 1.55 (27H, d, J=13.5Hz) ppm
FD-MS: m/z=427.1 (M ⁺ )

Synthesis Example 12 Synthesis of transition metal compound (A-12) (n-butylcyclopentadienyl)Ti(N=P(t-Bu)) _Cl represented by the _following formula (hereinafter also referred to as "transition metal compound (A-12)") was synthesized by the method described in Organometallics 2003, 22, 1937.

Synthesis Example 13 Synthesis of transition metal compound (A-13) (pentafluorophenylmethylcyclopentadienyl)Ti(N=P(t- _Bu )) _Cl represented by the following formula (hereinafter also referred to as "transition metal compound (A-13)") was synthesized by the method described in JP-A No. 2006-169521.

<Preparation of solid support (S)>
Preparation Example 1 Preparation of Solid Carrier (S-1) Using a 270 L reactor equipped with a stirrer, silica gel (manufactured by Fuji Silysia Chemical Ltd., average particle size 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g) was added under a nitrogen atmosphere.
, dried at 250 ° C. for 10 hours) was suspended in 77 L of toluene, and then cooled to 0 to 5 ° C. While maintaining the temperature in the system at 0 to 5 ° C., 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was dropped into this suspension over 30 minutes. Then, after contacting each added component for 30 minutes, the temperature in the system was raised to 95 ° C. over 1.5 hours, and then contacted at 93 to 97 ° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant liquid was removed by decantation, and further washed twice with toluene to obtain a toluene slurry of the solid carrier (S-1) in a total amount of 115 L. When a part of this slurry was sampled and analyzed, the solid concentration was 123 g / L and the Al concentration was 0.62 mol / L.

[Preparation Example 2] Preparation of solid support (S-2) A solid aluminoxane compound was synthesized according to the method described in International Publication WO 2010/055652 (preliminary experiment 1 and Example 5), and used as solid support (S) (hereinafter referred to as solid support (S-2)). However, in consideration of the safety of trimethylaluminum, such as ignition, the concentration was about 1/6 of the conditions disclosed in the document.

Specifically, 100 mL of a toluene solution of trimethylaluminum adjusted to 0.5 mol/L was charged into a glass reactor equipped with a stirrer. The solution was cooled to 15°C, and 2.18 g of benzoic acid was slowly added to it at a rate that kept the temperature of the solution below 25°C. Then, heat aging was performed at 50°C for 1 hour. At this time, the molar ratio of oxygen atoms of trimethylaluminum and benzoic acid was 1.40. The reaction solution was heated at 70°C for 4 hours, then heated at 60°C for 6 hours, and then cooled to room temperature once. It was then heated at 100°C for 8 hours to precipitate solid components. After cooling the solution to 30°C or less, 100 mL of hexane was added under stirring for washing. After standing for 30 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added under stirring. After standing for 15 minutes, 150 mL of the supernatant was removed, and another 150 mL of hexane was added under stirring. Finally, after leaving it to stand for 15 minutes, 180 mL of the supernatant was removed, and hexane was added to a total amount of 14.6 mL to obtain a hexane slurry of solid carrier (S-2). A portion of the obtained slurry was sampled and analyzed, and the solid concentration was 41 g/L and the Al concentration was 0.58 mol/L. In addition, when the particles of the obtained solid carrier (S-2) were observed with a scanning electron microscope, the average particle diameter was 6.8 μm.

[Preparation Example 3] Preparation of solid carrier (S-3) A slurry of a solid aluminoxane compound was synthesized according to the method (Test Example A8) described in WO 2014/123212 pamphlet, and this was used as a solid carrier (S) (hereinafter referred to as solid carrier (S-3)). A part of the obtained slurry was sampled and analyzed, and the solid concentration was 68 g/L and the Al concentration was 0.98 mol/L. In addition, when the particles of the obtained solid carrier (S-3) were observed with a scanning electron microscope, the average particle size was 32 μm.

<Preparation of solid catalyst component (X)>
[Preparation Example 4] Preparation of solid catalyst component (X-1) In a thoroughly nitrogen-purged reactor equipped with a stirrer and having an internal volume of 200 mL, 5.12 mL of toluene and 4.88 mL of the slurry of the solid support (S-2) obtained in Preparation Example 2 (solid weight 0.20 g) were charged under a nitrogen atmosphere. Next, 5.00 mL of the toluene solution of the transition metal compound (A-1) obtained in Synthesis Example 1 (10.0 μmol as Ti) was added, and the mixture was contacted at a system temperature of 20 to 25° C. for 1 hour, after which the supernatant was removed by decantation. As a result of analyzing 10 mL of this supernatant by ICP atomic emission spectroscopy (ICP-AES), the Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L). The mixture was further washed twice with hexane. As a result, a total of 20 mL of slurry of the solid catalyst component (X-1) was prepared.

[Preparation Examples 5 to 9] Preparation of solid catalyst components (X-2) to (X-6) Slurries of solid catalyst components (X-2) to (X-6) were prepared in the same manner as in Preparation Example 4, except that the transition metal compounds (A-2) to (A-6) obtained in Synthesis Examples 2 to 6 were used instead of the transition metal compound (A-1). The Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L).

[Preparation Example 10] Preparation of solid catalyst component (X-7) In a thoroughly nitrogen-purged reactor equipped with a stirrer and having an internal volume of 200 mL, 7.06 mL of toluene and 2.94 mL of the slurry of the solid support (S-3) obtained in Preparation Example 3 (solid weight 0.20 g) were charged under a nitrogen atmosphere. Next, 5.00 mL of the toluene solution of the transition metal compound (A-1) obtained in Synthesis Example 1 (10.0 μmol as Ti) was added, and the mixture was contacted at a system temperature of 20 to 25° C. for 1 hour, after which the supernatant was removed by decantation. As a result of analyzing 10 mL of the supernatant by ICP-AES, the Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L). The mixture was further washed twice with hexane. As a result, a total of 20 mL of slurry of the solid catalyst component (X-7) was prepared.

[Preparation Example 11] Preparation of solid catalyst component (X-8) In a thoroughly nitrogen-purged reactor equipped with a stirrer and having an internal volume of 200 mL, 10.87 mL of toluene and 1.63 mL of the slurry of the solid support (S-1) obtained in Preparation Example 1 (solid weight 0.20 g) were charged under a nitrogen atmosphere. Then, 2.50 mL of the toluene solution of the transition metal compound (A-1) obtained in Synthesis Example 1 (5.0 μmol as Ti) was added, and the mixture was contacted at a system temperature of 20 to 25° C. for 1 hour, and the supernatant was removed by decantation. As a result of analyzing 10 mL of the supernatant by ICP-AES, the Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L). The mixture was further washed twice with hexane. As a result, a slurry of the solid catalyst component (X-8) having a total amount of 20 mL was prepared.

[Preparation Example 12] Preparation of solid catalyst component (X-9) A slurry of solid catalyst component (X-9) was prepared in the same manner as in Preparation Example 11, except that the transition metal compound (A-4) obtained in Synthesis Example 4 was used instead of the transition metal compound (A-1). The Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L).

[Preparation Example 13] Preparation of solid catalyst component (X-10) A slurry of solid catalyst component (X-10) was prepared in the same manner as in Preparation Example 11, except that the transition metal compound (A-6) obtained in Synthesis Example 6 was used instead of the transition metal compound (A-1). The Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L).

[Preparation Examples 14-15] Preparation of solid catalyst components (X-11)-(X-12) Slurries of solid catalyst components (X-11)-(X-12) were prepared in the same manner as in Preparation Example 11, except that the transition metal compounds (A-7)-(A-8) obtained in Synthesis Examples 7-8 were used instead of the transition metal compound (A-1). The Zr concentration in the supernatant was below the lower limit of quantification (less than 0.011 mmol/L).

[Preparation Examples 16 to 17] Preparation of solid catalyst components (X-13) to (X-14) Slurries of solid catalyst components (X-13) to (X-14) were prepared in the same manner as in Preparation Example 4, except that the transition metal compounds (A-9) to (A-10) obtained in Synthesis Examples 9 and 10 were used instead of the transition metal compound (A-1). The Zr concentration in the supernatant was below the lower limit of quantification (less than 0.011 mmol/L).

[Preparation Examples 18 to 20] Preparation of solid catalyst components (X-15) to (X-17) Slurries of solid catalyst components (X-15) to (X-17) were prepared in the same manner as in Preparation Example 4, except that the transition metal compounds (A-11) to (A-13) obtained in Synthesis Examples 11 to 13, respectively, were used instead of the transition metal compound (A-1). The Ti concentration in the supernatant was below the lower limit of quantification (less than 0.021 mmol/L).

<Evaluation of fouling in ethylene polymerization reaction>
The polymerization reaction evaluations in the following Examples, Comparative Examples and Reference Examples were carried out using a 1-liter SUS autoclave equipped with an agitating blade.
All the solvents used in this example were dehydrated solvents.

After the polymerization reaction was completed, the inside of the autoclave was cooled and depressurized, and the presence or absence of powder adhesion (fouling) to the autoclave walls and agitator blades, as well as the presence or absence of powder agglomeration, were determined. Powder adhesion refers to a state in which the powder does not come off even when a hydrocarbon solvent such as heptane or hexane is poured into it, while powder agglomeration refers to a state in which many powder particles are physically or chemically bonded together, and some powder particles will come apart when a strong force is applied after the polymerization reaction, but others will not.

In particular, in the case of a polymerization reaction in which severe fouling or aggregation occurs, the number of rotations of the stirring blades, as measured by a rotation meter, decreases with the passage of polymerization time.
The physical properties of the resulting polyethylene powder were measured by the methods described above.

[Reference Example 1]
In a 1-liter SUS autoclave that had been thoroughly purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 30 mg of the solid content of the slurry of the solid catalyst component (X-11) obtained in Preparation Example 14 were added, and the temperature and pressure were raised to 80° C. and 0.8 MPaG with ethylene, and a polymerization reaction was initiated at a rotation speed of 350 rpm.

Even after 90 minutes had passed since the start of polymerization, no decrease in the rotation speed was observed, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, no fouling or aggregation of polyethylene powder was found on the autoclave walls or stirring blades.

[Reference Example 2]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that 20 mg of the slurry of the solid catalyst component (X-12) obtained in Preparation Example 15 was added in place of the solid catalyst component (X-11) in terms of solid content.

90 minutes after the start of polymerization, no decrease in rotation speed was observed, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, no fouling or aggregation of polyethylene powder was found on the autoclave walls or stirring blades.

[Comparative Example 1]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that 20 mg of the slurry of the solid catalyst component (X-8) obtained in Preparation Example 11 was added in place of the solid catalyst component (X-11) in terms of solid content.

After a decrease in the rotation speed was confirmed 15 minutes after the start of polymerization, it was determined that normal stirring conditions were not being maintained, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was inspected, fouling on the autoclave walls and stirring blades and aggregation of polyethylene powder were found.

[Comparative Example 2]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that 10 mg of the slurry of the solid catalyst component (X-9) obtained in Preparation Example 12 was added in place of the solid catalyst component (X-11) in terms of solid content.

After a decrease in the rotation speed was confirmed 10 minutes after the start of polymerization, it was determined that normal stirring conditions were not being maintained, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, fouling on the autoclave walls and stirring blades and aggregation of polyethylene powder were found.

[Comparative Example 3]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that 50 mg of the slurry of the solid catalyst component (X-10) obtained in Preparation Example 13 was added in place of the solid catalyst component (X-11) in terms of solid content.

Because a decrease in the rotation speed was confirmed 30 minutes after the start of polymerization, it was determined that normal stirring conditions were not being maintained, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, fouling on the autoclave walls and stirring blades and aggregation of polyethylene powder were found.

The results of Reference Examples 1 and 2 and Comparative Examples 1 to 3 show that transition metal compound (A) having a cyclopentadienyl ligand and a ligand containing a Group 15 element (nitrogen) is more likely to cause fouling during polymerization than a transition metal compound containing only a cyclopentadienyl ligand.

[Examples 1 to 7]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that the slurries of the solid catalyst components (X-1) to (X-7) obtained in Preparation Examples 4 to 10, respectively, were added in the amounts shown in Table 4 as solid contents instead of the solid catalyst component (X-11).

In all cases, no decrease in rotation speed was observed 90 minutes after the start of polymerization, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, no fouling or aggregation of polyethylene powder was observed on the autoclave walls or stirring blades.

Table 4 shows the presence or absence of fouling in Examples 1 to 7, Comparative Examples 1 to 3, and Reference Examples 1 and 2, and the intrinsic viscosity [η] of the ethylene polymers obtained in Examples 1 to 7 and Comparative Examples 1 to 3. All of the ethylene polymers obtained in Examples 1 to 7 were ultra-high molecular weight polyethylenes with [η] of 10 or more.

The results of Examples 1 to 7 and Comparative Examples 1 to 3 show that when solid catalyst components (X-1) to (X-7), which are olefin polymerization catalysts of the present invention using solid aluminoxane as the solid support (S), are used, fouling and powder aggregation during polymerization are less likely to occur compared to when solid supports (X-8) to (X-10) prepared by contacting aluminoxane with silica gel are used, even under conditions generally considered unfavorable for fouling, such as a small support particle size and a large amount of contact with the transition metal compound (A).

<Polymer obtained by ethylene polymerization reaction>
[Example 8]
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 5.0 mg of the slurry of the solid catalyst component (X-1) obtained in Preparation Example 4 were added as solids, and then the temperature and pressure were raised to 75° C. and 0.65 MPaG using an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.10 vol%, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours to obtain 50.1 g of an ethylene-based polymer. The analysis results of the obtained ethylene-based polymer are shown in Table 5.

[Example 9]
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 10 mg of the solid content of the slurry of the solid catalyst component (X-2) obtained in Preparation Example 5 were added, and then the temperature and pressure were raised to 75° C. and 0.65 MPaG using an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.10 vol%, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours to obtain 34.9 g of an ethylene-based polymer. The analysis results of the obtained ethylene-based polymer are shown in Table 5.

[Example 10]
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 6.0 mg of the slurry of the solid catalyst component (X-3) obtained in Preparation Example 6 were added as solids, and then the temperature and pressure were raised to 75° C. and 0.65 MPaG using an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.10 vol%, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours to obtain 37.8 g of an ethylene-based polymer. The analysis results of the obtained ethylene-based polymer are shown in Table 5.

[Comparative Example 4]
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 6.0 mg of the slurry of the solid catalyst component (X-13) obtained in Preparation Example 16 were added as solids, and then the temperature and pressure were raised to 75° C. and 0.65 MPaG using an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.10 vol%, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours to obtain 122.5 g of an ethylene-based polymer. The analysis results of the obtained ethylene-based polymer are shown in Table 5.

[Comparative Example 5]
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mmol of triisobutylaluminum and 15 mg of the slurry of the solid catalyst component (X-14) obtained in Preparation Example 17 were added as solids, and then the temperature and pressure were raised to 75° C. and 0.65 MPaG using an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.75 vol%, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours to obtain 62.5 g of an ethylene-based polymer. The analysis results of the obtained ethylene-based polymer are shown in Table 5.

The results of Examples 8 to 10 and Comparative Examples 4 to 5 show that the ethylene homopolymer obtained by homopolymerizing ethylene using the olefin polymerization catalyst of the present invention has a higher molecular weight (MFR, [η]) and a higher molecular weight density than when a transition metal compound (A) that does not have a ligand containing an element from Group 15 or 16 of the periodic table is used. This is because there are fewer methyl and ethyl branches. In addition, there is a smaller amount of double bonds such as vinyl and vinylidene.

[Examples 11 to 13]
A polymerization reaction was initiated in the same manner as in Reference Example 1, except that the slurries of the solid catalyst components (X-15) to (X-17) obtained in Preparation Examples 18 to 20, respectively, were added in the amounts shown in Table 6 as solid contents instead of the solid catalyst component (X-11).

In all cases, no decrease in rotation speed was observed 90 minutes after the start of polymerization, and the reaction was stopped by cooling and depressurizing. When the inside of the autoclave was checked, no fouling or aggregation of polyethylene powder was observed on the autoclave walls or stirring blades.

The presence or absence of fouling in Examples 11 to 13 and the intrinsic viscosity [η] of the obtained ethylene-based polymers are shown in Table 6, along with the results of Example 1 and Comparative Examples 1 to 3. The ethylene-based polymers obtained in Examples 11 to 13 were all ultra-high molecular weight polyethylenes with [η] of 10 or more.

The results of Examples 11 to 13 and Comparative Examples 1 to 3 show that when solid catalyst components (X-15) to (X-17), which are olefin polymerization catalysts of the present invention using solid aluminoxane as the solid support (S), are used, fouling and powder aggregation during polymerization are less likely to occur, compared to when solid supports (X-8) to (X-10), which are prepared by contacting aluminoxane with silica gel, are used, even under conditions generally considered unfavorable for fouling, such as a small support particle size and a large amount of contact with the transition metal compound (A).

Claims (7)

An olefin polymerization catalyst comprising the following component (A) and the following solid support (S):
Component (A): A transition metal compound represented by the following general formula [1] or [2].
(In the general formulas [1] and [2], M is a transition metal atom of Group 4 of the periodic table,
n is an integer from 1 to 4 satisfying the valence of M;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, the anionic ligand being a halogen-containing group, a silicon-containing group, an oxygen-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 divalent derivative group, when n is 2 or more, a plurality of groups represented by X may be the same or different and may be bonded to each other to form a ring,
Cp is a cyclopentadienyl ligand which may have a substituent, and adjacent substituents may be bonded to each other to form a ring which may have a substituent;
L is an atom selected from the elements of Groups 15 and 16 of the Periodic Table;
P is a phosphorus atom;
The solid lines are covalent or coordinate bonds, and the dotted lines are covalent bonds that exist when L is an atom of a Group 15 element.
y is 2 when L is an atom of a Group 15 element, and is 3 when L is an atom of a Group 16 element;
z is 3 when L is an atom of a Group 15 element, and is 4 when L is an atom of a Group 16 element;
Each R is 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, and may be the same or different. Adjacent R may be bonded to each other to form a ring or a bicyclo ring which may have a substituent.
Solid support (S): a solid aluminoxane compound. 2. The olefin polymerization catalyst according to claim 1, wherein the solid aluminoxane compound has an average particle size of 0.01 to 50,000 μm. 2. The olefin polymerization catalyst according to claim 1, wherein the solid aluminoxane compound has an average particle size of 1 to 1000 μm. 2. The olefin polymerization catalyst according to claim 1, wherein the solid aluminoxane compound has an average particle size of 1 to 200 μm. The olefin polymerization catalyst according to claim 1, characterized in that L is an atom of an element in Group 15 of the periodic table. The olefin polymerization catalyst according to claim 1, characterized in that M is a titanium atom. A process for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 6 .