JPH11147905A - Production of ethylene polymer and ethylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which can give a polymer being nonproblematic in particle break and the formation of fine powder and having a high bulk density and to obtain a polymer. SOLUTION: There is provided a process for producing an ethylene polymer which comprises polymerizing ethylene or copolymerizing ethylene with an α-olefin in the substantial absence of a solvent in the presence of a catalyst comprising a metallocene transition metal compound and layered silicate particles comprising a smectite group layered silicate and a mica group layered silicate and containing 0.1-50 wt.% smectite group layered silicate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an ethylene polymer and the polymer. More specifically, the present invention relates to a method for stably producing an ethylene polymer having excellent powder properties under gas-phase polymerization conditions, and a polyethylene obtained by the method.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, a method using a catalyst comprising (1) a metallocene compound and (2) an aluminoxane has been proposed (Japanese Patent Application Laid-Open No. 58-119309, JP-A-2-167307). A polymerization method using these catalysts is based on a conventional Ziegler-based compound comprising a titanium compound or a vanadium compound and an organoaluminum compound.
As compared with the method using a Natta catalyst, a polymer having a very high polymerization activity per transition metal and a sharp molecular weight distribution and a sharp composition distribution can be obtained.

However, a large amount of aluminoxane is required in order to industrially obtain sufficient polymerization activity using these catalysts. Therefore, the polymerization activity per aluminum is low, which is not only uneconomical, but also produces a heavy polymer. It was necessary to remove the catalyst residue from the coalescence. On the other hand, a method has been proposed in which olefin polymerization is carried out using a catalyst in which one or both of the above metallocene complex and aluminoxane are supported on an inorganic oxide such as silica or alumina (Japanese Patent Application Laid-Open No. 61-1986).
Nos. 108610, 60-135408, 61-296008, JP-A-3-74412, and 3-74415. Further, a method of polymerizing an olefin using a catalyst in which one or both of a metallocene compound and an aluminum compound are supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-1-101303, JP-A-1-101303). −20730
No. 3, JP-A-3-234709 and JP-T-Hei 3-50.
No. 1869). Furthermore, a method of pre-polymerizing these supported catalysts has also been proposed (Japanese Patent Laid-Open No. 3-234710).
No.).

[0004] However, even in these proposed methods, the polymerization activity per aluminum was still not sufficient, and the amount of catalyst residue in the product was not negligible. As a solution to these problems,
A catalyst comprising an ion-exchange layered silicate or inorganic silicate, an organoaluminum and a metallocene compound and a catalyst obtained by prepolymerizing the same have been proposed (JP-A-5-252).
No. 95022).

[0005] Although these catalysts have sufficient polymerization activity per transition metal or aluminum, in the actual polymerization reaction, depending on the polymerization conditions, crushing of particles or generation of fine powder may occur, resulting in a bulk density of the polymerized powder. , And the flowability is deteriorated in the gas phase polymerization. Alternatively, in some cases, the generation of fine powder may cause adhesion to the reactor, sheeting, etc., or may cause troubles such as blockage of pipes and heat exchangers. .

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for crushing particles,
An object of the present invention is to provide a catalyst and an ethylene polymer capable of obtaining an ethylene polymer having a high bulk density without generating fine powder. It is another object of the present invention to provide a catalyst capable of stably polymerizing ethylene without adhesion or blockage to a catalyst supply line or adhesion or blockage in an inner wall or piping of a polymerization reactor or heat exchange.

[0007]

The present inventors have conducted various studies on an ethylene polymerization catalyst comprising a metallocene-based transition metal compound and layered silicate particles and on the production of an ethylene polymer using the same. By using silicate particles, it has been found that a polymer excellent in particle shape can be obtained without particle crushing and fine powder generation in the polymerization step, and the present invention has been achieved.

That is, in the present invention, the polymerization of ethylene or the copolymerization of ethylene and an α-olefin is carried out in the substantially absence of a solvent in the presence of a catalyst comprising the following components (A) and (B). It is intended to provide a method for producing an ethylene polymer characterized by the above, and an ethylene polymer obtained by using the method. Component (A): Metallocene-based transition metal compound Component (B): Layered silicate composed of smectite group silicate and mica group silicate, containing 0.1 to 50% by weight of smectite group silicate particle

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [Ethylene Polymerization Catalyst] The polymerization catalyst according to the present invention comprises component (A) and component (B). <Component (A)> This component (A) is a metallocene transition metal compound. This metallocene transition metal compound is
Preferably, one or two cyclopentadienyl-based ligands which may be substituted, that is, one or two cyclopentadienyl ring-containing ligands which may combine with each other to form a condensed ring An organometallic compound comprising a ligand and a transition metal belonging to Group 3, 4, 5, or 6 of the long period table, or a cationic complex thereof. (Here, the periodicity of atoms is based on the group 18 system recommended by IUPAC in 1989.) Preferred examples of such a metallocene transition metal compound include the following general formula [1] or [2] ] It is a compound represented by these.

[0010]

## STR1 ## ^{_{(CpR 1 a H 5-a}} ) p (CpR 2 b H 5-b) q MR 3 r ... [1] [(CpR 1 a H 5-a) p (CpR 2 b H 5-b ^{_{) q MR 3 r L m]}} n + [R 4] n- ... [2]

(Where CpR ¹ _a H _5-a and CpR
² _b H _5-b represents a cyclopentadienyl (Cp) group or a derivative thereof, that is, an R ¹ or R ² substituent of cyclopentadienyl. R ¹ and R ² each may be a hydrocarbon group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or an oxygen-containing hydrocarbon group which may have 1 to 30 carbon atoms and may be substituted; And each may be the same or different. )

A and b are each an integer of 0-5. P, q and r are each 0 or a positive integer satisfying p + q + r = V when the valence of M is V and the metallocene-based transition metal compound is represented by the formula [1]; When the transition metal compound has the formula [2], p + q + r = 0 or a positive integer satisfying Vn. Usually, p and q are integers of 0 to 3, preferably 0 or 1. r is an integer of 0 to 3, preferably 1 or 2. n is an integer satisfying 0 ≦ n ≦ V. R ¹
When and / or R ² is substituted, the substituent is preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or halogen.

Specific examples of R ¹ and R ² include (a)
A hydrocarbon group, for example, (i) an alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group; Pentyl group, isopentyl group,
(Ii) C6-C30, preferably C6-C3, such as hexyl, heptyl, octyl, nonyl, and decyl groups.
20, halo substituents of the above hydrocarbons such as phenyl, p-tolyl, o-tolyl, m-tolyl, etc., for example, fluoromethyl, fluoroethyl, fluorophenyl, Chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc .;
0, preferably a silicon-containing hydrocarbon group having 1 to 10 carbon atoms, for example, a trimethylsilyl group, a triethylsilyl group,
(D) phosphorus-containing hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, such as triphenylsilyl group, for example, dimethylphosphino group, diethylphosphino group, diphenylphosphino group, etc .; A nitrogen-containing hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, such as a dimethylamino group, a diethylamino group, and a diisopropylamino group; , An oxygen-containing hydrocarbon group such as (i) an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group,
(ii) aryloxy groups such as tert-butoxy group and the like, for example, phenoxy, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group, m-tolyloxy group, o-
And a tolyloxy group.

Of these, particularly preferred are alkyl groups having 1 to 4 carbon atoms, especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
-Alkyl group (preferably having 1 to 4 carbon atoms) substituted silicon-containing group such as -butyl group, especially trimethylsilyl group, alkoxy group having 1 to 4 carbon atoms, particularly methoxy group, aryloxy group, especially phenoxy group And so on.

Further, two cyclopentadienyl (C
The p) groups may be linked to each other via a bridging group. Specific examples of such a cross-linking group include (a) carbon numbers 1 to 3.
0, preferably 1 to 20, alkylene groups such as methylene group, ethylene group, (ii) alkylidene group having 1 to 20 carbon atoms, such as ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, diphenylmethylidene Groups, (c) a silicon-containing crosslinking group having 1 to 20 carbon atoms,
For example, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, (d) carbon number 1-20 germanium-containing cross-linking groups, such as dimethylgermylene groups,
Such as diethylgermylene group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t-butylgermylene group, and the like ( E) Nitrogen-containing groups such as amino groups and (f) boron-containing groups such as phosphinyl groups.

When a plurality of R ¹ are present in the same cyclopentadienyl (Cp) group, or when a plurality of R ² are present, R ¹ or R ² may have the same ω.
One end may be bonded to each other to form a ring. Specifically, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, an octahydrofluorenyl group and the like are preferable, and these may be substituted. As the substituent in this case, for example, a methyl group, an ethyl group and an indenyl group are preferable.

R ³ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent,
It is an alkoxy group, an aryloxy group, an amide group, or a thioalkoxy group. Specifically, (a) alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, (Ii) aryl group such as nonyl group and decyl group,
For example, phenyl, p-tolyl, o-tolyl, m-
(C) halo-substituted hydrocarbons such as tolyl group, for example, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group , Iodophenyl group, etc.
(D) halogen, for example, fluorine, chlorine, bromine, iodine, etc., (e) silicon-containing group, for example, trimethylsilyl group,
(E) triethylsilyl group, triphenylsilyl group, etc.
(G) aryloxy groups such as alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and t-butoxy group, such as phenoxy, methylphenoxy, pentamethylphenoxy group, and p-tolyloxy Group, m-tolyloxy group, o
A (thi) amide group such as a tolyloxy group, for example, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, an ethyl-t-butylamide group,
(Ri) thioalkoxy groups such as bis (trimethylsilyl) amide group, for example, methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butylthioalkoxy group, t-butylthioalkoxy group, phenylthioalkoxy group, and ( G) Hydrogen.
Among these, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl, halogen such as chlorine, methoxy, ethoxy, propoxy, isopropoxy, dimethylamide, A methylthioalkoxy group is mentioned, and hydrogen, a methyl group and chlorine are particularly preferred.

This R ³ may be bonded to R ^1, R ² or Cp. As a specific example of such a ligand, CpH ₄ (CH ₂ ) _n O- (1 ≦ n ≦
5), CpMe ₄ (CH ₂ ) _n O- (1 ≦ n ≦ 5), C
pH ₄ (Me ₂ Si) (t-Bu) N-, CpMe
₄ (Me ₂ Si) (t-Bu) N—, etc. (Cp indicates cyclopentadienyl group, Me methyl, Bu indicates butyl group)
Is raised. Further, when there are a plurality of R ³ ,
Two of them may combine with each other to form a bidentate ligand. Specific examples of such R ³ include —OCH _{2
O -, - OCH 2 CH 2} O -, - O (o-C 6 H 4) O
-And the like.

M is a transition metal atom belonging to Group 3, 4, 5, or 6 of the periodic table, and specifically, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.
Of these, titanium, zirconium, and hafnium of Group 4 are preferably used. These may be used as a mixture.

L is an electrically neutral ligand, and m is an integer of 0 or more by the number of the ligand. Specifically, ethers such as diethyl ether, tetrahydrofuran and dioxane, and nitriles such as acetonitrile Amides such as dimethylformamide, phosphines such as trimethylphosphine, and amines such as trimethylamine. Preferred are tetrahydrofuran, trimethylphosphine and trimethylamine.

[R ⁴ ] ^n- is one or more anions that neutralize the cation, and specifically, tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, dicarbaun Examples include decaborate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, hexafluorophosphate, and the like. Preferred are tetraphenylborate, tetra (p-tolyl) borate, tetrafluoroborate and hexafluorophosphate.

The above-mentioned metallocene transition metal compound, specifically, taking zirconium as an example, those corresponding to the formula [1] include (1) bis (methylcyclopentadienyl) zirconium dichloride and ( 2) bis (ethylcyclopentadienyl) zirconium dichloride,
(3) bis (methylcyclopentadienyl) zirconium dimethyl, (4) bis (ethylcyclopentadienyl) zirconium dimethyl, (5) bis (methylcyclopentadienyl) zirconium dihydride, (6) bis (ethyl) (Cyclopentadienyl) zirconium dihydride, (7) bis (dimethylcyclopentadienyl) zirconium dichloride, (8) bis (trimethylcyclopentadienyl) zirconium dichloride, (9) bis (tetramethylcyclopentadienyl) Zirconium dichloride, (10) bis (ethyltetramethylcyclopentadienyl) zirconium dichloride, (1
1) bis (indenyl) zirconium dichloride,
(12) bis (dimethylcyclopentadienyl) zirconium dimethyl, (13) bis (trimethylcyclopentadienyl) zirconium dimethyl, (14) bis (tetramethylcyclopentadienyl) zirconium dimethyl, (15) bis (ethyltetra Methylcyclopentadienyl) zirconium dimethyl, (16) bis (indenyl) zirconium dimethyl, (17) bis (dimethylcyclopentadienyl) zirconium dihydride, (1
8) bis (trimethylcyclopentadienyl) zirconium dihydride, (19) bis (ethyltetramethylcyclopentadienyl) zirconium dihydride, (2
0) bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, (21) bis (trimethylsilylcyclopentadienyl) zirconium dihydride, (2
2) Bis (trifluoromethylcyclopentadienyl)
Zirconium dichloride, (23) bis (trifluoromethylcyclopentadienyl) zirconium dimethyl, (24) bis (trifluoromethylcyclopentadienyl) zirconium dihydride, (25) isopropylidene-bis (indenyl) zirconium dichloride, (26) isopropylidene-bis (indenyl) zirconium dimethyl, (27) isopropylidene-bis (indenyl) zirconium dihydride, (28) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (29) penta Methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (30) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, (31) ethyltet Cyclopentadienyl (cyclopentadienyl) zirconium dihydride,
(32) isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, (33)
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, (34) dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dimethyl, (35) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dihydride,
(36) bis (cyclopentadienyl) zirconium dichloride, (37) bis (cyclopentadienyl) zirconium dimethyl, (38) bis (cyclopentadienyl) zirconium diethyl, (39) bis (cyclopentadienyl) zirconium Dipropyl, (40) bis (cyclopentadienyl) zirconium diphenyl,
(41) methylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (42) ethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (43) methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl ,
(44) ethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (45) methylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, (46) ethylcyclopentadienyl (cyclopentadienyl) Zirconium dihydride, (4
7) Dimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (48) trimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (49) tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride (50) bis (pentamethylcyclopentadienyl) zirconium dichloride, (51) tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (52) indenyl (cyclopentadienyl) zirconium dichloride, (53)
Dimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (54) trimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (55) tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, ( 5
6) bis (pentamethylcyclopentadienyl) zirconium dimethyl, (57) ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (58) indenyl (cyclopentadienyl)
Zirconium dimethyl, (59) dimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, (60) trimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, (61)
Bis (pentamethylcyclopentadienyl) zirconium dihydride, (62) indenyl (cyclopentadienyl) zirconium dihydride, (63) trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (64) trimethylsilyl Cyclopentadienyl (cyclopentadienyl) zirconium dihydride, (65) trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (66) trifluoromethylcyclopentadienyl (cyclopentadienyl) Zirconium dimethyl,
(67) trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, (6
8) bis (cyclopentadienyl) (trimethylsilyl) (methyl) zirconium, (69) bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, (70) bis (cyclopentadienyl) [tris ( Trimethylsilyl) silyl] (methyl) zirconium, (71) bis (cyclopentadienyl) [bis (methylsilyl) silyl] (methyl) zirconium,
(72) bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, (7
3) bis (cyclopentadienyl) (trimethylsilyl) (benzyl) zirconium, (74) methylene-bis (cyclopentadienyl) zirconium dichloride, (75) ethylene-bis (cyclopentadienyl)
Zirconium dichloride, (76) isopropylidene-bis (cyclopentadienyl) zirconium dichloride, (77) dimethylsilyl-bis (cyclopentadienyl) zirconium dichloride, (78) methylene-bis (cyclopentadienyl) zirconium dimethyl, (79) Ethylene-bis (cyclopentadienyl)
Zirconium dimethyl, (80) isopropylidene-bis (cyclopentadienyl) zirconium dimethyl,
(81) dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, (82) methylene-bis (cyclopentadienyl) zirconium dihydride,
(83) ethylene-bis (cyclopentadienyl) zirconium dihydride, (84) isopropylidene-bis (cyclopentadienyl) zirconium dihydride,
(85) dimethylsilyl-bis (cyclopentadienyl) zirconium dihydride, (86) bis (cyclopentadienyl) zirconiumbis (methanesulfonato), (87) bis (cyclopentadienyl) zirconiumbis (p -Toluenesulfonato), (88) bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), (89) bis (cyclopentadienyl) zirconium trifluoromethanesulfonatochloride, (90) bis (cyclopentadiene) (Enyl) zirconium bis (benzenesulfonato), (91) bis (cyclopentadienyl) zirconium bis (pentafluorobenzenesulfonato), (92) bis (cyclopentadienyl) zirconium benzenesulfonatochloride, (93) bis (Shiku Pentadienyl) zirconium (ethoxy) trifluoromethanesulfonate, (9
4) bis (tetramethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), (9
5) Bis (indenyl) zirconium bis (trifluoromethanesulfonate), (96) ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate), (97) isopropylidene-bis (indenyl)
Zirconium bis (trifluoromethanesulfonate),
(98) (Tertiary butylamido) dimethyl (tetramethylcyclopentadienyl) silane dibenzyl zirconium (tertiary butylamido) dimethyl (2,3,4,5-
Tetramethylcyclopentadienyl) silanedibenzyl zirconium, (99) indenyl zirconium tris (dimethylamide), (100) indenyl zirconium tris (diethylamide), (101) indenyl zirconium tris (di-n-propylamide) , (10
2) cyclopentadienyl zirconium tris (dimethylamide), (103) methylcyclopentadienyl zirconium tris (dimethylamide), (104) (tertiary butylamide) (tetramethylcyclopentadienyl) -1,2- Ethanediylzirconium dichloride, (105) (methylamido)-(tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (106) (ethylamido) (tetramethylcyclopentadienyl) methylenezirconium dichloride, (107) ) (Tertiary butylamido) dimethyl- (tetramethylcyclopentadienyl) silane zirconium dichloride, (108) (benzylamide)
Dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (109) (phenylphosphide) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (110) (phenylamido) dimethyl (tetramethylcyclopentadienyl) ) Silane zirconium dichloride, (111)
(2-methoxyphenylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (112) (4-fluorophenylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (113) ((2, 6-di (1
-Methylethyl) phenyl) amido) dimethyl (tetramethylcyclopentadienyl) amido zirconium dichloride.

(114) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, (115)
Bis (1-ethyl-3-methylcyclopentadienyl)
Zirconium dichloride, (116) bis (1-n-propyl-3-methylcyclopentadienyl) zirconium dichloride, (117) bis (1-i-propyl-3)
-Methylcyclopentadienyl) zirconium dichloride, (118) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, (11
9) bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride, (120) bis (1
-Cyclohexyl-3-methylcyclopentadienyl)
Zirconium dichloride, (121) bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
(122) bis (1-ethyl-3-methylcyclopentadienyl) zirconium dimethyl, (123) bis (1
-N-propyl-3-methylcyclopentadienyl) zirconium dimethyl, (124) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dimethyl, (125) bis (1,3-dimethylcyclopenta Dienyl) zirconium dibis (diethylamide),
(126) bis (1-ethyl-3-methylcyclopentadienyl) zirconium bis (diethylamide), (1
27) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium bis (diethylamide)

The compounds corresponding to the general formula [2] include (1) bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, and (2) bis (ethylcyclopentadienyl). ) Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (3) bis (methylcyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
(4) bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (5) bis (methylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (6) bis (Ethylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (7) bis (dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (8) bis (trimethylcyclopenta (Dienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (9) bis (tetramethylcyclopentadienyl) zirconium (chloride) (tetraphenyl Rate) tetrahydrofuran complex, (10) bis (ethyltetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (11) bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, 12) bis (dimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (13) bis (trimethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (14) bis (tetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (15)
Bis (ethyltetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (16) bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (17) bis (dimethylcyclopentadiene) (Enyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (18) bis (trimethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (19) bis (ethyltetramethylcyclopentadienyl) Zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (20) bis (trimethylsilylcyclopentadienyl) zirconium (methyl) (tetraf Nylborate) tetrahydrofuran complex, (21) bis (trimethylsilylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (22) bis (trifluoromethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) Tetrahydrofuran complex, (23) bis (trifluoromethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (24) isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (25) isopropylidene-bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (26) Propylidene - bis (indenyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (2
7) Pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (28) ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) ) Tetrahydrofuran complex, (29) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (30) ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) ) (Tetraphenylborate) tetrahydrofuran complex, (31) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
(32) ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (3
3) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (34) isopropylidene (cyclopentadienyl) (fluorenyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (35) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (36) bis (cyclopentadienyl) zirconium ( Chloride) (tetraphenyl borate)
Tetrahydrofuran complex, (37) bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (38) bis (cyclopentadienyl) (ethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (39) Bis (cyclopentadienyl) (propyl) zirconium (tetraphenylborate) tetrahydrofuran complex,
(40) bis (cyclopentadienyl) (phenyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (41) methylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (4)
2) Ethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (43) bis (ethylcyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(44) methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (45) ethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran Complex, (46) methylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (47)
Ethylcyclopentadienyl (cyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, (48) dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (49) trimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(50) tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (51) bis (pentamethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex (52) indenyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (53) dimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, 54) Trimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
(55) tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex; (56) bis (pentamethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex (57) cyclopentadienyl (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (58) dimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, 59) Trimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
(60) bis (pentamethylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (61) indenyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (62) trimethylsilyl Cyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (63) trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (64 ) Trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, 5) bis (cyclopentadienyl)
(Trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (66) bis (cyclopentadienyl) (triphenylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (67) bis (cyclopentadienyl) [tris (trimethylsilyl) ) Silyl] zirconium (tetraphenylborate) tetrahydrofuran complex, (68) bis (cyclopentadienyl) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (69) bis (cyclopentadienyl) (benzyl) zirconium ( Tetraphenyl borate) tetrahydrofuran complex, (70) methylene-bis (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(71) ethylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (72) isopropylidene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, 73) dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (74) methylene-
Bis (cyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
(75) ethylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (76) isopropylidene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, 7
7) Dimethylsilyl-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (78) methylene-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (79) ) Ethylene-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (80) isopropylidene-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (81) Dimethylsilyl-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (82) bis (cyclopentadienyl) zirconium (meth (Sulfonato) (tetraphenylborate) tetrahydrofuran complex, (83) bis (cyclopentadienyl) zirconium (p-toluenesulfonato) (tetraphenylborate) tetrahydrofuran complex, (84) bis (cyclopentadienyl) zirconium (trifluoromethane) Sulfonato) (tetraphenylborate) tetrahydrofuran complex, (85)
Bis (cyclopentadienyl) zirconium (benzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, (86) bis (cyclopentadienyl) zirconium (pentafluorobenzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, (8)
7) bis (tetramethylcyclopentadienyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, (88) bis (indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, (89) ) Ethylenebis (indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, (90) isopropylidene-bis (indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate)
And tetrahydrofuran complexes. In addition, the same compounds as those described above for other Group 3, 4, 5, and 6 metal compounds such as titanium compounds and hafnium compounds can also be used. Further, a mixture of these compounds may be used.

<Component (B)><GeneralDescription> The component (B) layered silicate particles according to the present invention are a mixture of a smectite group phyllosilicate and a mica group phyllosilicate. Is contained in an amount of 0.1 to 50% by weight. Here, the term “consisting of” means a layer consisting only of the smectite group silicate and the mica group silicate, that is, 0.1 to 50% by weight of the smectite group silicate and the mica group silicate. In addition to those of 50 to 99.9% by weight, other than the smectite group phyllosilicate and mica group phyllosilicate, a component which is purposely or inevitably present may be present in a small amount, for example, of the above-mentioned two groups. 0.1 of layered silicate
About 30% by weight.

And the layered silicate particles according to the present invention are:
In addition to the above, it is preferable that the following specific conditions (a) to (c) are simultaneously satisfied. Conditions Condition (a): The average particle size is 20 μm or more and 1000 μm or less, and the number of particles having a particle size of 10 μm or less is 20% or less of the total number of particles. Condition (B): Measured with a micro compression tester The crushing strength of the obtained particles is 0.5 MPa or more. Condition (c): The bulk density of the particles is 0.6 g / cm ³ or more.

Here, the condition (a) relates to the average particle diameter and the existence ratio of the layered silicate particles according to the present invention of 10 μm or less, and specifically, the average particle diameter of 20 μm or more. 1000 μm or less and a particle size of 10 μm
m or less than 20% of all particles. In the present invention, those having an average particle diameter of 20 μm or more and 500 μm or less, particularly preferably 20 μm or more and 100 μm or less are preferable.
Those having 5% or less, particularly less than 10%, are preferred. Therefore, it is preferable in the present invention that the condition (a) satisfies both the above-mentioned preferable conditions regarding the average particle diameter and the abundance of particles having a particle diameter of less than 10 μm.

Here, the measurement of the particles is specifically carried out by
Particle size distribution analyzer (“LMS-24”, laser diffraction method by Seishin Enterprise, light source: semiconductor laser (wavelength 6
70 nm)). The measurement was performed using ethanol as a dispersion medium, with a refractive index of 1.33,
The particle size distribution and the average particle size were calculated as the shape factor of 1.0.

The condition (b) relates to the strength of the layered silicate particles according to the present invention, and specifically, the condition that the crushing strength of the particles measured by a micro compression tester is 0.5 MPa or more. It is. A preferable condition (b) in the present invention is that the crushing strength is 1.0 MPa or more. The upper limit is about 40 MPa. Here, the crushing strength is, specifically, using a micro-compression tester “MCTM-500” manufactured by Shimadzu Corporation, the compressive strength of any 10 or more particles is measured, and the average value is used as the crushing strength. It is when I asked. The condition (c) relates to the bulk density of the layered silicate particles according to the present invention, and specifically, the value is 0.6 g / cm ³ or more, preferably 0.7 g / cm ³ or more. That is. The upper limit is about 1.5 g / cm ³ .

<Smectite Group Layered Silicate> The smectite group layered silicate used to obtain the layered silicate particles according to the present invention is defined as a smectite group silicate having a 2: 1 type layer structure. It refers to the layered silicate to which it belongs. The typical ones are generally montmorillonite, beidellite, saponite, nontronite,
Hectorite, sauconite and the like. In the present invention, either natural products or synthetic products can be used. "Kunipia", "Smecton" (all manufactured by Kunimine Industries),
Commercial products such as "Montmorillonite K10" (manufactured by Aldrich and Jute Chemie) and "K-Catalysts series" (manufactured by Jute Chemie) can also be used. In the practice of the present invention, these may be used alone, or two or more may be arbitrarily mixed and used.

Such a smectite group phyllosilicate can be pulverized if necessary. When the desired layered silicate particles according to the present invention are obtained, for example, by a method of producing a slurry state (details described later), the layered silicate of the smectite group is converted into a slurry dispersion medium by subjecting to such a pulverization treatment. It can be highly dispersed. Therefore, in the case of producing by the above method, it is preferable that the smectite group layered silicate is subjected to a pulverizing treatment. The pulverization method at this time is not particularly limited, but the method of pulverization by collision of particles by a high-speed air flow or collision of particles with the wall of a pulverizer is one of methods that can be easily performed on an industrial scale. One. Specific devices that can be used include a jet mill and a single track mill. The size of the particles after grinding is
Preferably 0.01 to 50 μm, particularly preferably 0.0
1 to 30 μm. Needless to say, the diameter and the particle size distribution of the smectite group phyllosilicate particles after the pulverization treatment satisfy the above-mentioned condition (a) when they are used as the phyllosilicate phyllosilicate particles according to the present invention. .

<Mica Group Layered Silicate> The mica group layered silicate used for obtaining the layered silicate particles according to the present invention is a layered silicate belonging to the mica group having a 2: 1 type layer structure. Things. Representative examples include muscovite, paragonite, phlogopite, biotite, and lepidolite.
In the present invention, either natural products or synthetic products can be used. Commercially available "synthetic mica somasif" (Corp Chemical Co., Ltd.), "fluorphlogopite mica", "fluorine tetrasilicon mica",
"Teniolite" (all manufactured by Topy Industries, Ltd.) and the like are typical examples of those particularly preferred in the present invention. In the present invention, these can be used alone or in combination of two or more.

<Specific Description> The layered silicate particles according to the present invention are a mixture of the above mica grouped silicate and smectite grouped silicate. The content of the smectite group layered silicate is 0.1 to 50% by weight, preferably 1 to 3%.
0% by weight. When the content of the smectite group layered silicate is too small, the crushing strength or bulk density is reduced.On the other hand, when the content is too large, the viscosity of the water slurry is reduced when the layered silicate particles are produced by spray granulation. Is too high, causing nozzle clogging, etc. Conversely, lowering the concentration to obtain an appropriate slurry viscosity reduces the average particle size,
There arises a problem that the condition (a) is not satisfied.

In the present invention, both the smectite group silicate and the mica group silicate are preferably ion-exchangeable (or swellable). here,
"Ion exchangeability" means that interlayer cations of the layered silicate are exchangeable. The term "swelling" means that when the layered silicate coexists with water, water molecules are taken into the interlayer region to increase the distance between the bottom surfaces. The ratio of the bottom surface interval expansion is at least 1.2 times, preferably 1.5 times or more. The term “layered” means having a layered structure.

In general, natural products are often non-ion-exchangeable (non-swellable). In such a case, in order to have a favorable ion-exchangeability (or swellability), the ion-exchangeability (or swellability) is preferable. (Swelling property) is preferably performed. Among such treatments, particularly preferred are the following chemical treatments. That is, it is preferable that both of these silicates have been subjected to a chemical treatment. Here, the chemical treatment can be any of a surface treatment for removing impurities attached to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate. Specifically, (a) acid treatment, (b)
Alkali treatment, (c) salt treatment, and (d) organic substance treatment. These treatments remove surface impurities, exchange cations between layers, and have a crystalline structure of Al, S
Cations such as i and Mg are eluted, and as a result, an ion complex, a molecular complex, an organic complex and the like are formed, and the surface area, interlayer distance, solid acidity and the like can be changed. These processes may be performed independently, or two or more processes may be combined. In addition, as a result of this "chemical treatment",
When one or both of the silicates are given or improved in the ion exchange property (or swelling property), the “chemical treatment” is the “treatment for imparting the ion exchange property (or swelling property)”. It can also be considered as These chemical treatments may be performed on the smectite group phyllosilicate and the mica group phyllosilicate either before or after mixing them, or may be performed simultaneously on both after mixing. Good.

As the (a) acid used in the chemical treatment,
Suitable inorganic or organic acids, preferably, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like,
(B) Examples of the alkali include NaOH, KOH, and NH ₃ . (C) As the salts, at least one selected from the group consisting of a cation containing at least one atom selected from the group consisting of Group 2 to Group 14 atoms and a halogen atom or an anion derived from an inorganic acid or an organic acid. And a kind of anion are preferred. More preferred are Al, Mg, Ti, Zr, Hf, Cr, Zn,
Those having ions derived from Sn, Cu, Ni, Fe, Nb or Ta as cations, Cl, SO ₄ NO ₃ , OH,
Ions derived from C ₂ H ₄ and PO ₄ as anions. (D) As organic substances, alcohols (aliphatic alcohols having 1 to 4 carbon atoms, preferably, for example, methanol, ethanol, propanol, ethylene glycol, glycerin, aromatic alcohols having 6 to 8 carbon atoms, preferably, for example, phenol), higher alcohols Hydrocarbons (carbon number 5
10 to 10, preferably 5 to 8, preferably hexane, heptane and the like. Preferred examples include formamide, hydrazine, dimethyl sulfoxide, N-methylformamide, N, N-dimethylaniline and the like. Here, the periodic rule of the atom was
It is based on the group 18 system recommended by the PAC.

The layered silicate particles satisfy the above conditions (a) to (d).
In order to make it more preferable even when (c) is not simultaneously satisfied, or when it is simultaneously satisfied, in the present invention, the properties of the particles are controlled by, for example, granulation, sizing, and sorting. can do. The method can be of any suitable purpose. In particular, for the granulation method, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method , An emulsion granulation method and a submerged granulation method. Particularly preferred granulation methods are spray granulation, tumbling granulation and compression granulation among the above.

When such particle properties are controlled, a mixture of smectite group phyllosilicate particles and mica group phyllosilicate is prepared in advance in a form suitable for the control method. I can do it. For example, when the spray granulation method is adopted as a method for controlling the particle properties, the mixture can be dispersed in a dispersion medium to be in a slurry state, which is preferable.

As a dispersion medium used in spray granulation, water or an organic substance (for example, methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene) alone or in a mixed solution is preferable. Particularly preferred among these is water. The slurry concentration is 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight. The optimum slurry concentration is appropriately selected in consideration of the slurry viscosity. Specifically, 6000 cps or less, preferably 10 to
5000 cps, particularly preferably 1000 to 3000 c
ps.

In the present invention, the slurry viscosity means a value measured by a B-type viscometer at a temperature of 30 ° C. and 6 rpm. If the viscosity is more than 6000 cps, it is difficult to feed the liquid to the spray nozzle, and the nozzle tends to be clogged. Conversely, if the slurry concentration is reduced to lower the viscosity, a granulated product having a small particle shape is obtained. Tend to be obtained only.
Although the particle size of the granulated particles depends on the spraying speed, it is difficult to obtain particles of 10 μm or more when the slurry concentration is less than 5%. When spraying, disk type or pressure nozzle type,
A general spray drying method such as a two-fluid nozzle method can be applied. In any case, the inlet temperature of hot air during spraying is 150 ° C
It can be set in a wide temperature range from about 300 ° C to about 300 ° C. Also,
The exhaust temperature is defined by the spray flow rate from the nozzle and the like, but is preferably about 100 ° C.

Therefore, as one of typical, simple and economical methods for producing the layered silicate particles according to the present invention, a mixed powder of a mica grouped silicate and a smectite grouped silicate is prepared by ion exchange. A method comprising subjecting the resultant to a treatment, dispersing the obtained ion exchanger in a dispersion medium to form a slurry, and then subjecting the slurry to a spray granulation treatment. In this case, the content of the smectite group layered silicate is 0.1 to 50% by weight, preferably 0.5 to 4% by weight.
It is preferable to add and mix 0% by weight, particularly preferably 1 to 30% by weight.

As another typical, simple and economical structural method, a layered silicate of mica group subjected to an ion exchange treatment is dispersed in a dispersion medium to form a slurry, and the ion exchange treatment is not performed here. A method of adding and mixing a slurry of a smectite group layered silicate and subjecting the mixed slurry to spray granulation treatment may be mentioned. The combination of the component (A) metallocene-based transition metal compound and the component (B) layered silicate particles generally shows olefin polymerization activity as it is. By further combining an organoaluminum compound as), a more suitable olefin polymerization catalyst can be obtained. Therefore, the present invention also relates to an ethylene polymerization catalyst obtained by combining such a metallocene transition metal compound and an organoaluminum compound with the above-mentioned layered silicate particles. Here, the term “combined” includes a combination with a suitable other than the above three components.

<Component (C)> Organoaluminum Compound The organoaluminum compound used in the present invention is:
It is considered that the decrease in the catalytic activity due to water and the like present in the polymerization system is suppressed, and this addition also contributes to the improvement in the catalytic activity. Therefore, the addition of the organoaluminum compound is one of the desirable embodiments. Examples of the organoaluminum compound used in the present invention include:

[0044]

Embedded image AlR ⁶ _j X _3-j

(Wherein, R ⁶ represents a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, X represents hydrogen, a halogen or an alkoxy group, and j represents a number of 0 <j ≦ 3) It is shown by. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and diethylaluminum chloride And alkylaluminum alkoxides such as diethyl aluminum methoxide and diisobutylaluminum methoxide, and alkylaluminum amides such as diethylaluminum (diethylamide) and diisobutylaluminum (diethylamide). Among them, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-
Trialkyl aluminum such as hexyl aluminum is preferred.

Component (A) a metallocene transition metal compound,
In order to obtain a polymerization catalyst from the component (B) layered silicate particles and, if necessary, the component (C) the organoaluminum compound, these components are usually brought into contact with each other. The method of contacting each component is not particularly limited, but the components can be contacted in the following contact order. The components (A) and (B) are brought into contact. After contacting the components (A) and (B), the component (C) is added. After contacting the component (A) with the component (C), the component (B) is added. After contacting the component (B) with the component (C), the component (A) is added. The three components are contacted simultaneously.

The contact may be carried out in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact temperature is -20
C. to the boiling point of the solvent, preferably from room temperature to the boiling point of the solvent. The amount of the catalyst component used is such that the component (A) per 1 g of the layered silicate particles of the component (B) is
01 to 10 mmol, preferably 0.001 to 5 mmol
When the component (C) organoaluminum compound used as needed is used, its amount is 10
000 mmol or less, preferably 0.0001 to 100
00 mmol, more preferably 0.1-100 mmol
It is.

In the present invention, it is also suitably employed that the contact product obtained as described above is brought into contact with an α-olefin or an aromatic vinyl monomer in advance and then subjected to preliminary polymerization. The prepolymerization is usually carried out with ethylene, but if necessary, other olefins, for example, propylene, 1-butene, 4-methyl-1-pentene, α-olefins such as 3-methyl-1-pentene, styrene, α-
An aromatic vinyl monomer such as methylstyrene or a mixture thereof can be used. The amount of the polymer produced by the prepolymerization is 0.00 per g of the component (B).
The range is 1 to 1000 g, preferably 0.01 to 300 g, and more preferably 0.1 to 300 g.

The prepolymerization method is not particularly limited, but is usually carried out by slurry polymerization in an inert hydrocarbon solvent.
The inert hydrocarbon solvent used at this time is appropriately selected. For example, the hydrocarbon solvent used at the time of the above-mentioned contact is suitably used. The temperature of the prepolymerization is not particularly limited, but it is preferable to carry out the temperature between -20 ° C and 150 ° C. It is also desirable to add a part of the component (C) organoaluminum compound during the prepolymerization.

When the prepolymerization is carried out using ethylene, the weight average molecular weight of the polyethylene is preferably 30,000 or more, particularly preferably 50,000 or more.
If the molecular weight is too small, the effect of improving the particle properties and the effect of preventing particle crushing may not be sufficiently exhibited. The pre-polymerization catalyst may be used as it is after the completion of the pre-polymerization, or may be used after washing if necessary. Moreover, you may use what dried and made the powder. At this time, the drying conditions are not particularly limited, but preferably the drying is performed at 0 ° C. to 100 ° C. under reduced pressure or under a flow of a dry inert gas.

At the time of prepolymerization or after drying, a solid such as a polymer such as polyethylene or polypropylene or an inorganic oxide such as silica or alumina may coexist or be brought into contact. According to the present invention, particularly when applied to gas phase polymerization, a polymer having a high bulk density and a good particle shape can be obtained, and its characteristics can be exhibited. The gas phase polymerization of the present invention is carried out in a gaseous monomer substantially free of a solvent or the like. The apparatus used for the gas phase polymerization is not particularly limited, but a known apparatus such as a fluidized bed, a stirred bed, and a stirred fluidized bed equipped with a stirrer / mixer well known in the art can be used.

In the present invention, the polymerization of ethylene is carried out.
Includes homopolymerization of ethylene and copolymerization of ethylene with other α-olefins. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 1
-Hexene, 1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like. In the case of copolymerization of ethylene and α-olefin, α-olefin
The olefin can be copolymerized up to 50% by weight, preferably 20% by weight, based on ethylene. The gas phase polymerization temperature is from 30C to 150C, preferably from 50C to 100C. The polymerization pressure is usually in the range of 1 to 50 kg / cm ² G. In the polymerization, the operation is carried out at a hydrogen concentration (H ₂ / ethylene) in the monomer of 10 ppm to 10000 ppm.

[0053]

According to the present invention, an olefin can be polymerized with high polymerization activity, and a polymer having excellent particle properties without particle crushing or generation of fine powder can be stably produced by gas phase polymerization. be able to.

[0054]

The following examples are provided to illustrate the present invention. Therefore, the present invention is not limited by these embodiments unless departing from the gist thereof. In addition, although a flowchart for assisting understanding of the technical contents included in the present invention has been described, the present invention is not limited by the flowchart unless departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated and purified with molecular sieve 4A.

Example 1 (1) [Preparation of Layered Silicate Particles] 400 g of commercially available swellable synthetic mica (“Somasif ME-100”, manufactured by Corp Chemical Co., average particle size 7 μm) and commercially available hydrophilic smectite (“SWN”, manufactured by Corp Chemical Co., average particle size: 5 μm) and mixed with 100 g.
The resultant was dispersed in 2.8 L of a 0 wt% chromium nitrate aqueous solution and stirred at room temperature for 2 hours. This was filtered and washed with deionized water.
Water was added to the obtained solid part to prepare a 20.0% by weight slurry, and spray drying was performed. 450 g of spherical particles having an average particle size of 54 μm were obtained. The number of particles having a particle size of 10 μm or less was 4% of all the particles, the crushing strength was 2.0 MPa, and the bulk density was 0.75 g / cc.

(2) [Preparation of Catalyst] In a 10 L reactor equipped with a stirrer, 4.4 L of normal heptane, 150 g of the layered silicate particles obtained in the above (1), which had been dried under reduced pressure at 200 ° C. for 2 hours in advance. And 6 more
12.0 mmol of bis (normalbutylcyclopentadienyl) zirconium dichloride dissolved in 00 ml was added, and the mixture was stirred at room temperature for 10 minutes. (3) [Preliminary polymerization] Triethyl aluminum 24 m
mol was added and the temperature of the system was brought to 60 ° C. Here, ethylene gas was introduced and the reaction was continued for 2 hours. The polyethylene produced during this period weighed 1050 g.

(4) [Ethylene-butene gas phase copolymerization] Induction stirring previously dried at 100 ° C for 30 minutes under a nitrogen flow.
Stainless steel, 1.0 L autoclave with stirrer
100 g of dry sodium chloride, and dry nitrogen
Minutes replaced. Triethyl aluminum 2.0m
mol of ethylene-butene mixed gas (butane).
Ten / ethylene = 6 mol%) with a total pressure of 20 kg / cm^Two
I stuck it to G. Then heat the system to 80 ° C
Then, 50 mg of the solid catalyst obtained in the above (3)
Press-fit)
The polymerization was started. While maintaining the polymerization temperature constant,
Polymerization for 1 hour by continuously supplying a mixed gas of n-butene
Continued. At this time, H _TwoLimit concentration to 50ppm
did. Thereafter, unreacted gas was purged to stop the polymerization.
The content is separated from sodium chloride, and 42 g of polymerized powder is obtained.
Obtained. The polymer powder thus obtained is spherical and has a bulk density
0.34 g / cc, fine powder of 106 μm or less is 0.1 weight
%Met. The MFR of the polymer is 1.2 and the density is 0.92
It was 0 g / cc.

Example 2 (1) [Preparation of Layered Silicate Particles] 200 g of commercially available swellable synthetic mica (“Na-teniolite”, manufactured by Topy Industries Co., Ltd.) was added to 1.0 L of a 4.0% by weight aqueous solution of chromium nitrate. And stirred at room temperature for 2 hours. This was filtered and washed with deionized water. Water was added to the obtained solid part to prepare a 30.0% by weight water slurry. 400 ml of a 1.5% by weight water slurry of a commercially available hydrophilic smectite ("SWN", manufactured by Corp Chemical) was added to the slurry and spray-dried. At this time, the content of hydrophilic smectite was 3% by weight. As a result, the average particle size was 65 μm.
150 g of m spherical particles were obtained. The number of particles having a particle size of 10 μm or less is 0.0%, the crushing strength is 3.5 MPa,
The bulk density was 0.88 g / cc.

(2) [Preparation of catalyst] A catalyst was prepared in the same manner as in Example 1 (2) except that the layered silicate particles obtained in the above (1) were used. (3) [Preliminary polymerization] Preliminary polymerization was carried out in the same manner as in Example 1 (3) using the catalyst component obtained in the above (2). (4) [Ethylene-butene copolymerization] Using the prepolymerized catalyst obtained in (3) above, ethylene-butene copolymerization was carried out in the same manner as in Example 1 (4) to obtain 33 g of a polymer powder. . The bulk density of this polymer powder is 0.32 g / cc, 10
The percentage of fine particles having a size of 6 μm or less was 0.6%.

Example 3 [Ethylene-butene Gas Phase Continuous Copolymerization] A solid gas was fed into a continuous gas phase polymerization reactor in which a mixed gas of ethylene and butene (1-butene / ethylene = 6.0 mol%) was circulated. 1349 mg of the prepolymerized catalyst obtained in Example 1 (3) as a catalyst component
/ H, 628 mg / h of triethylaluminum was intermittently supplied. The conditions of the polymerization reaction were 88 ° C., ethylene pressure 18 kg / cm ² G, average residence time 5.5 hours,
The average polymerization rate of the produced polyethylene was 8.6 kg / h. The resulting polymers are all spherical and have a bulk density of 0.3.
Fine particles having a particle size of 4 g / cc and 106 μm or less were 0.2%.

Comparative Example 1 (1) [Preparation of Layered Silicate Particles] 2.0 g of 500 g of commercially available swellable synthetic mica (“Somasif ME-100”, manufactured by Corp Chemical Co., average particle size 7 μm) was used. It was dispersed in 2.5 L of chromium nitrate aqueous solution and stirred at room temperature for 2 hours. This was filtered and washed with deionized water. Water was added to the obtained solid portion to prepare a 20.0% by weight water slurry, and spray drying was performed. As a result, particles having an average particle size of 60 μm
0 g was obtained. The number of particles having a particle size of 10 μm or less is 10%, the crushing strength is 0.1 MPa, and the bulk density is 0.55 g / c.
c.

(2) [Preparation of catalyst] A catalyst was prepared in the same manner as in Example 1 (2) except that the layered silicate particles obtained in the above (1) were used. (3) [Preliminary polymerization] Preliminary polymerization was carried out in the same manner as in Example 1 (3) using the catalyst component obtained in the above (2). (4) [Ethylene-butene copolymerization] Using the prepolymerized catalyst obtained in the above (3), ethylene-butene copolymerization was carried out in the same manner as in Example 1 (4). As a result, 43 g of a polymer powder was obtained. The polymer powder had many irregular shaped particles, the bulk density was 0.13 g / cc, and the fine powder having a particle size of 106 μm or less was 7.5%.

Comparative Example 2 (1) [Preparation of Layered Silicate Particles] 200 g of commercially available swellable synthetic mica (“Na-teniolite”, manufactured by Topy Industries, Ltd.)
Was dispersed in 1.0 L of a 4.0% by weight aqueous solution of chromium nitrate and stirred at room temperature for 2 hours. This was filtered and washed with deionized water. Water was added to the obtained solid portion, and 30.0% by weight was added.
A water slurry was prepared and spray dried. As a result, 180 g of particles having an average particle size of 70 μm were obtained. The number of particles having a particle size of 10 μm or less was 10%, the crushing strength was 0.2 MPa, and the bulk density was 0.40 g / cc.

(2) [Preparation of catalyst] A catalyst was prepared in the same manner as in Example 1 (2) except that the layered silicate particles obtained in the above (1) were used. (3) [Preliminary polymerization] Preliminary polymerization was carried out in the same manner as in Example 1 (3) using the catalyst component obtained in the above (2). (4) [Ethylene-butene copolymerization] Using the prepolymerized catalyst obtained in the above (3), ethylene-butene copolymerization was carried out in the same manner as in Example 1 (4). As a result, 35 g of a polymer powder was obtained. The polymer powder has many scaly or irregular particles, bulk density is 0.11 g / cc, and 106 μm
The following fine powder was 5.0%.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (7)

[Claims] 1. Polymerization of ethylene or ethylene and α-α in the presence of a catalyst comprising the following components (A) and (B):
A method for producing an ethylene polymer, wherein copolymerization with an olefin is carried out substantially in the absence of a solvent. Component (A): Metallocene-based transition metal compound Component (B): Layered silicate composed of smectite group silicate and mica group silicate, containing 0.1 to 50% by weight of smectite group silicate particle 2. The method for producing an ethylene polymer according to claim 1, wherein a catalyst obtained by further combining the following component (C) with the component (A) and the component (B) is used. Component (C): Organoaluminum compound 3. The method for producing an ethylene polymer according to claim 1, wherein the layered silicate particles of the component (B) simultaneously satisfy the following conditions (a) to (c). Condition (A): Average particle diameter is 20 μm or more and 1000 μm or less, and the number of particles having a particle diameter of 10 μm or less is 20% or less of the total number of particles. Condition (B): Measured by a micro compression tester. The crushing strength of the particles is 0.5 MPa or more. Condition (c): The bulk density of the particles is 0.6 g / cm ³ or more. 4. The layered silicate particles of the component (B) wherein at least 30% of mica group exchangeable cations are exchanged for cations of Group 2 to Group 14 of the periodic table or H ^+. The method for producing an ethylene polymer according to any one of claims 1 to 3, wherein 5. The layered silicate particles of the component (B) contain at least 30% of their exchangeable cations from the second group of the periodic table.
The method for producing an ethylene polymer according to any one of claims 1 to 4, wherein the ethylene polymer has been exchanged for a Group 4 cation or H ⁺ . 6. An ethylene polymer obtained by the method according to claim 1. 7. The ethylene polymer according to claim 6, wherein the polymerization of ethylene or the copolymerization of ethylene and α-olefin is carried out by a gas phase polymerization method.