JP5269756B2 - Process for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer capable of obtaining an olefin polymer having high polymerization activity, excellent operational stability upon polymerization, high molecular weight and comparatively wide molecular weight distribution and optionally controlling the molecular weight and molecular weight distribution. <P>SOLUTION: In the method for producing the olefin polymer for polymerizing or copolymerizing an olefin in the presence of a catalyst for polymerizing olefin including a component (A): a coordination compound having a cyclopentadienyl skeleton and a component (B): an ion pair forming compound, a specified cyclopentadiene compound (C) represented by formula (1) is added upon polymerization. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an olefin polymer, and more specifically, an olefin polymer having high polymerization activity, excellent operational stability during polymerization, a high molecular weight, and a relatively wide molecular weight distribution can be obtained. The present invention relates to a method for producing an olefin polymer capable of arbitrarily controlling the molecular weight and molecular weight distribution.

  When producing an olefin polymer, particularly an ethylene polymer or an ethylene / α-olefin copolymer, it is possible to use a catalyst comprising a zirconium compound (typically a metallocene compound) and an alumoxane. No. 1 (Patent Document 1). This technique has an advantage that an ethylene-based copolymer can be produced in a high yield, but the copolymer has a drawback that the molecular weight distribution is narrow, the composition distribution is narrow, and in addition, the molecular weight is low.

  Focusing only on increasing the molecular weight of the resulting polymer, it is possible to increase the molecular weight to some extent by selecting a metallocene transition metal compound that is a component of the catalyst. For example, Japanese Patent Laid-Open No. 63-234005 (Patent Document 2) proposes to increase the molecular weight of a produced polymer by using a transition metal compound having a substituted cyclopentadienyl group.

JP-A-2-22307 (Patent Document 3) uses a hafnium compound having a ligand bonded to at least two conjugated cycloalkadienyl bridges to increase the molecular weight of the produced polymer. Proposals have been made.
However, the catalyst components as described above have a problem that the synthesis route is complicated and the operation is complicated. On the other hand, although a simple metallocene complex synthesis method has been proposed in Japanese Patent Application Laid-Open No. 09-048790 (Patent Document 4), the metallocene compound synthesis step is still necessary.

  Japanese Patent Application Laid-Open No. 08-092311 (Patent Document 5) discloses (1) a compound containing Zr, Ti, Hf, and (2) a periodic table. (5) an inorganic carrier after contacting a compound containing a group I-III element, (3) an organic cyclic compound having a conjugated double bond, and (4) a modified organoaluminum compound containing an Al—O—Al bond. And / or a method for producing a polyolefin characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst obtained by contacting a particulate polymer carrier, and by using the catalyst, the molecular weight distribution is relatively low. Polyolefins with wide, good particle properties and a narrow composition distribution for copolymerization, and high molecular weight and low tackiness can be produced. Machine, adhesion of polymer to the reactor inner wall is not observed substantially have shown very advantageous production method from the viewpoint of industrial productivity.

  JP 09-048809 (Patent Document 6) discloses (A) (a) a compound containing Zr, Ti, Hf, (b) a compound containing Group I to III elements of the periodic table, (c ) Reaction products obtained by bringing organic cyclic compounds having conjugated double bonds into contact with each other, (B) modified organoaluminum compounds containing Al—O—Al bonds, and (C) having two or more conjugated double bonds. An olefin polymerization catalyst obtained by bringing an organic cyclic compound, (D) an inorganic compound carrier and / or a particulate polymer carrier into contact with each other and a method for producing an olefin polymer have been proposed, and the polymerization activity is higher than that of conventional catalyst systems. It is described that a polymer having a high molecular weight can be produced.

  Furthermore, Japanese translations of PCT publication No. 2004-514033 (patent document 7) include (a) a bulky ligand metallocene catalyst compound, (b) a first modifier containing a Group 13 element-containing compound, and (c). An olefin polymerization catalyst containing a second modifier containing a cycloalkadiene has been proposed, and a highly active catalyst system and an olefin polymerization method using the catalyst system can be provided.

JP 2009-173896 (Patent Document 8) discloses (A) a metallocene compound, (B) a compound that reacts with an organoaluminum oxy compound and / or a transition metal compound to form an ion pair, (C) The catalyst for olefin polymerization includes a compound represented by a specific chemical formula, and the molar ratio of the metal element of the component (C) to the central metal element of the component (A) is in a specific range. An olefin polymer having excellent operational stability during polymerization, a high molecular weight, a relatively wide molecular weight distribution, good particle properties, and a narrow composition distribution for copolymerization and low tackiness. A polymerization catalyst suitable for production and a method for producing an olefin polymer using the same have been proposed.
However, even for the above-described catalysts, there is a need for a catalyst for olefin polymerization and a method for producing an olefin polymer, which are not sufficiently active and have further improved performance.

JP 58-019309 A JP 63-234005 A Japanese Patent Laid-Open No. 02-022307 JP 09-048790 A Japanese Patent Laid-Open No. 08-092311 Japanese Patent Application Laid-Open No. 09-048809 Japanese translation of PCT publication No. 2004-514033 JP 2009-173896 A

  In view of the above problems of the prior art, the present invention has high activity, excellent operational stability during polymerization, high molecular weight, relatively wide molecular weight distribution, good particle properties, and copolymerization. An object of the present invention is to produce an olefin polymer suitable for producing an olefin polymer having a narrow composition distribution and low adhesiveness. In particular, it is an object of the present invention to provide a method for producing an olefin polymer that can further improve the operational stability during polymerization and can perform, for example, highly active and long-term stable operation in continuous gas phase polymerization.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have developed a method for producing an olefin polymer in which an olefin is polymerized or copolymerized in the presence of a specific olefin polymerization catalyst. By adding a cyclopentadiene compound into the polymerization system, the operational stability during polymerization was improved, and it was found that high-activity and long-term stable operation in continuous gas phase polymerization was possible, thereby completing the present invention. .

That is, according to the first aspect of the present invention, the presence of an olefin polymerization catalyst comprising the components (A) and (B) shown below, in the process for producing an olefin polymer by polymerizing or copolymerizing an olefin, olefin the in prepolymerization, cyclopentadiene compound represented by the following formula (1) (C) relative to 1 mol of the compound represented by component (a), which comprises adding 0.5 to 5 mol A method for producing an olefin polymer is provided.
Component (A): a compound represented by L ²¹ mM ²¹ X ²¹ n, or a compound represented by (L ²² -QL ²³ ) M ²² X ²² ₂ (where M ²¹ is the fourth in the periodic table) Group element, L ²¹ represents a ligand having a cyclopentadienyl skeleton, X ²¹ represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group, and m + n is a valence of M ²¹ ; m is 1 to 3, while M ²² is an element belonging to Group 4 of the periodic table, L ²² and L ²³ are each a ligand having a cyclopentadienyl skeleton and bound by Q, Q is (The divalent hydrocarbon group or organic silicon group, X ²² represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group.)
Component (B): Ion-pair generating compound

(In the formula, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ represents either hydrogen or a substituent having 1 to 10 carbon atoms, and any two of the substituents may be cyclic. (A hydrocarbon group can be formed, but not all of R ^{11 to} R ¹⁵ become hydrogen at the same time.)

According to the second invention of the present invention, in the first invention, the cyclopentadiene compound (C) comprises an indene having a hydrocarbon group, a benzoindene having a hydrocarbon group, an unsubstituted benzoindene, a hydrocarbon. Cyclopentadiene having a group, bisindene crosslinked with a hydrocarbon group or an organosilicon group, bisindene having a hydrocarbon group or a hydrocarbon group crosslinked with an organosilicon group, a cyclopentadiene crosslinked with a hydrocarbon group or an organosilicon group And a process selected from the group consisting of cyclopentadiene having a hydrocarbon group crosslinked with a hydrocarbon group or an organosilicon group.
According to the third invention of the present invention, in the first or second invention, the cyclopentadiene compound (C) is a carbon of each of the ligands L ²¹ , L ²² and L ²³ of the component (A). There is provided a process for producing an olefin polymer characterized by having a carbon number greater than the number.
According to the fourth aspect of the present invention, in any one of the first to third aspects, the ligands L ²¹ , L ²² and L ²³ of the component (A) have 9 or less carbon atoms. A method for producing an olefin polymer is provided.
According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the olefin polymerization catalyst is supported on the inorganic compound carrier and / or the particulate polymer carrier (D). A process for producing an olefin polymer is provided.

  According to the present invention, since a specific cyclopentadiene compound is added to the polymerization system during the polymerization reaction of olefin, the activity is high, the operation stability during polymerization is excellent, the molecular weight is high, and the molecular weight distribution is relatively wide. In the case of copolymerization, an olefin polymer having a narrow composition distribution and low tackiness can be produced. That is, with the specific cyclopentadiene compound according to the present invention, it is possible to further improve the catalytic activity while maintaining the particle properties and the adhesion characteristics in the reactor, and the polymer properties and properties are further improved. Not only can an improved olefin polymer having excellent performance be obtained, but in particular, a production method with excellent operational stability during polymerization can be achieved, and high activity and long-term stable operation in continuous gas phase polymerization can be achieved. And the industrial productivity of the olefin polymer can be further improved.

  Hereinafter, the method for producing the olefin polymer of the present invention will be described in detail for each item.

The catalyst for olefin polymerization of the present invention contains the following components (A) and (B).
Component (A): a compound represented by L ²¹ mM ²¹ X ²¹ n, or a compound represented by (L ²² -QL ²³ ) M ²² X ²² ₂ (where M ²¹ is the fourth in the periodic table) Group element, L ²¹ represents a ligand having a cyclopentadienyl skeleton, X ²¹ represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group, and m + n is a valence of M ²¹ ; m is 1 to 3, while M ²² is an element belonging to Group 4 of the periodic table, L ²² and L ²³ are each a ligand having a cyclopentadienyl skeleton and bound by Q, Q is (The divalent hydrocarbon group or organic silicon group, X ²² represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group.)
Component (B): Ion-pair generating compound

1. Ingredient (A)
Component (A) of the present invention is a compound represented by L ²¹ mM ²¹ X ²¹ n, or (L ²² -QL ²³ ) M ²² X ²² ₂ , and the central metals M ²¹ and M ²² are: An element selected from Group 4 of the periodic table, specifically, Ti, Zr, and Hf, preferably Zr. The component (A) is one of the components that exhibit the basic catalytic performance of the present invention, and can determine the polymerization activity, the molecular weight of the polymer, the molecular weight distribution, the composition distribution, and the like.

The ligand L ²¹ coordinated to the central metal M ²¹ of the component (A) is a ligand having a cyclopentadienyl skeleton.
Specific examples include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group. 1,3-dimethylcyclopentadienyl group, 1,3-dipropylcyclopentadienyl group, 1-methyl-3-propylcyclopentadienyl group, 1-butyl-3-methylcyclopentadienyl group, Unsubstituted or substituted cyclopentadienyl groups such as 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilylcyclopentadienyl group; indenyl group, 2 -Methyl indenyl group, 4-methyl indenyl group, 4-phenyl indenyl group, An unsubstituted or substituted indenyl group such as a methyl-4-indenyl group; or a benzoindenyl group, a 2-methylbenzoindenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, 2, Examples thereof include 7-dimethylfluorenyl group and azulenyl group.

The ligand L ²² -QL ²³ coordinated to the central metal M ²² of the component (A) is a ligand in which L ²² and L ²³ each have a cyclopentadienyl skeleton, They are bonded by Q which is a hydrogen group or an organosilicon group.
Specific examples of L ²² and L ²³ include cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl, butylcyclopentadienyl, 1,2-dimethyl. Cyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,3-dipropylcyclopentadienyl group, 1-methyl-3-propylcyclopentadienyl group, 1-butyl-3-methylcyclo Unsubstituted or substituted cyclopentadienyl groups such as pentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilylcyclopentadienyl group Indenyl group, 2-methylindenyl group, 4-methylindenyl group, 4-phenyl Unsubstituted or substituted indenyl groups such as indenyl group and 2-methyl-4-phenyl group; or benzoindenyl group, 2-methylbenzoindenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl Group, 2,7-dimethylfluorenyl group, azulenyl group and the like.

  Q is a divalent hydrocarbon group or an organosilicon group. Specific examples thereof include a methylene group, an ethylene group, a methylmethylene group, a dimethylmethylene group, a diphenylmethylene group, a 1,2-ethylene group, and a carbon number. Examples thereof include a silylene group having 1 to 20 hydrocarbon groups or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, a silylene group, a dimethylsilylene group, and a diphenylsilylene group.

In addition, L ²² and L ²³ may be the same or different via Q. The combination of L ²² and L ^{23 in} different cases is, for example, cyclopentadienyl group-different cyclopentadienyl group, cyclopenta Dienyl group-indenyl group, cyclopentadienyl group-fluorenyl group, cyclopentadienyl group-benzoindenyl group, indenyl group-different indenyl group, indenyl group-fluorenyl group, indenyl group-benzoindenyl group, fluorenyl group -A benzoindenyl group etc. are mentioned. These ligands having a cyclopentadienyl skeleton may have a substituent.

X ²¹ and X ^{22 each} represent a halogen atom, a hydrogen atom or a hydrocarbon residue, and specific examples of the hydrocarbon group include a linear or branched hydrocarbon group having 1 to 24 carbon atoms or a cyclic hydrocarbon group. It is done. A preferable carbon number is 1-12, More preferably, it is 1-8.
Examples of such hydrocarbon groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl. Group, heptyl group, alkyl group such as octyl group; alkenyl group such as vinyl group, allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, Examples thereof include aralkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group and neophyll group. Further, hydrocarbon groups may be bonded to each other.
Examples of the halogen atom include fluorine, chlorine, bromine, or iodine.

Specific examples of compounds that can be used as the component (A) of the present invention are as follows.
For monocyclopentadienyl compounds:
(1) cyclopentadienyltrimethylzirconium,
(2) methylcyclopentadienyltrimethylzirconium,
(3) butylcyclopentadienyltrimethylzirconium,
(4) 1,2-dimethylcyclopentadienyltrimethylzirconium,
(5) 1,3-dimethylcyclopentadienyltrimethylzirconium,
(6) 1,3-dipropylcyclopentadienyltrimethylzirconium,
(7) 1-methyl-3-propylcyclopentadienyltrimethylzirconium,
(8) 1-butyl-3-methylcyclopentadienyltrimethylzirconium,
(9) 1,2,4-trimethylcyclopentadienyltrimethylzirconium,

(10) pentamethylcyclopentadienyltrimethylzirconium,
(11) cyclopentadienylmethylzirconium dichloride,
(12) cyclopentadienyldimethylzirconium monochloride,
(13) cyclopentadienylzirconium trichloride,
(14) cyclopentadienyltribenzylzirconium,
(15) indenyl zirconium trichloride,
(16) indenyltrimethylzirconium,
(17) indenyltribenzylzirconium,

For biscyclopentadienyl compounds:
(1) bis (cyclopentadienyl) zirconium dichloride,
(2) bis (methylcyclopentadienyl) zirconium dichloride,
(3) bis (butylcyclopentadienyl) zirconium dichloride,
(4) bis (1,2-dimethylcyclopentadienyl) zirconium dichloride,
(5) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(6) bis (1,3-dipropylcyclopentadienyl) zirconium dichloride,
(7) bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride,
(8) bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(9) Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride,

(10) Bis (pentamethylcyclopentadienyl) zirconium dichloride,
(11) Bis (indenyl) zirconium dichloride,
(12) Bis (2-methylindenyl) zirconium dichloride,
(13) Bis (4-methylindenyl) zirconium dichloride,
(14) Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
(15) Bis (fluorenyl) zirconium dichloride,
(16) Bis (2,7-dimethylfluorenyl) zirconium dichloride (17) [ethylenebis (1-indenyl)] zirconium dichloride,
(18) [Ethylenebis (4,5,6,7-tetrahydroindenyl)] zirconium dichloride,
(19) Dimethylmethylenebiscyclopentadienylzirconium dichloride (20) Dimethylmethylenebis (butylcyclopentadinyl) zirconium dichloride (21) Dimethylmethylenebis (butylmethylcyclopentadienyl) zirconium dichloride (22) Dimethylmethylenebisindene Nylzirconium dichloride (23) Dimethylmethylenebis (2-methylindenyl) zirconium dichloride (24) Dimethylmethylenebis (4-methylindenyl) zirconium dichloride (25) Dimethylmethylenebis (tetrahydroindenyl) zirconium dichloride (26) Dimethyl Methylenebisfluorenylzirconium dichloride (27) Dimethylmethylenebis (dimethylfluorenyl) zirconium dichloride Id (28) Dimethylmethylenebis (benzoindenyl) zirconium dichloride (29) Dimethylmethylenebis (2-methylbenzoindenyl) zirconium dichloride (30) Diphenylmethylenebiscyclopentadienylzirconium dichloride (31) Diphenylmethylenebis (butyl) Cyclopentazinyl) zirconium dichloride (32) diphenylmethylenebis (butylmethylcyclopentadienyl) zirconium dichloride (33) diphenylmethylenebisindenylzirconium dichloride (34) diphenylmethylenebis (2-methylindenyl) zirconium dichloride (35) ) Diphenylmethylenebis (4-methylindenyl) zirconium dichloride (36) Diphenylmethylenebis (tetrahydro) Loindenyl) zirconium dichloride (37) diphenylmethylenebisfluorenylzirconium dichloride (38) diphenylmethylenebis (dimethylfluorenyl) zirconium dichloride (39) diphenylmethylenebis (benzoindenyl) zirconium dichloride (40) diphenylmethylenebis (2 -Methylbenzoindenyl) zirconium dichloride (41) dimethylsilylene biscyclopentadienyl zirconium dichloride (42) dimethylsilylene bis (butylcyclopentazinyl) zirconium dichloride (43) dimethylsilylene bis (butylmethylcyclopentadienyl) zirconium Dichloride (44) Dimethylsilylene Bisindenyl Zirconium Dichloride (45) Dimethylsilylene Bis (2-methylindenyl) zirconium dichloride (46) Dimethylsilylenebis (4-methylindenyl) zirconium dichloride (47) Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride (48) Dimethylsilylenebisfluorenylzirconium dichloride ( 49) Dimethylsilylenebis (dimethylfluorenyl) zirconium dichloride (50) Dimethylsilylenebis (benzoindenyl) zirconium dichloride (51) Dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride (52) Dimethylmethylene (cyclopenta Dienyl) (butylmethylcyclopentadienyl) zirconium dichloride (53) dimethylmethylene (cyclopentadienyl) (indeni ) Zirconium dichloride (54) dimethylmethylene (cyclopentadienyl) (2-methylindenyl) zirconium dichloride (55) dimethylmethylene (cyclopentadienyl) (4-methylindenyl) zirconium dichloride (56) dimethylmethylene (cyclohexane) Pentadienyl) (tetrahydroindenyl) zirconium dichloride (57) dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (58) dimethylmethylene (cyclopentadienyl) (dimethylfluorenyl) zirconium dichloride (59) dimethyl Methylene (cyclopentadienyl) (benzoindenyl) zirconium dichloride (60) Dimethylmethylene (butylmethylcyclopentadienyl) (2-methyl Ndenyl) zirconium dichloride (61) dimethylmethylene (butylmethylcyclopentadienyl) (4-methylindenyl) zirconium dichloride (62) dimethylmethylene (butylmethylcyclopentadienyl) (fluorenyl) zirconium dichloride (63) dimethylmethylene (63) Butylmethylcyclopentadienyl) (dimethylfluorenyl) zirconium dichloride (64) Dimethylmethylene (butylmethylcyclopentadienyl) (2-methylbenzoindenyl) zirconium dichloride (65) Dimethylmethylene (indenyl) (4-methyl Indenyl) zirconium dichloride (66) dimethylmethylene (indenyl) (fluorenyl) zirconium dichloride (67) dimethylmethylene (indenyl) (Dimethylfluorenyl) zirconium dichloride (68) Dimethylmethylene (indenyl) (2-methylbenzoindenyl) zirconium dichloride (69) Diphenylmethylene (cyclopentadienyl) (butylmethylcyclopentadienyl) zirconium dichloride (70) Diphenylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride (71) Diphenylmethylene (cyclopentadienyl) (2-methylindenyl) zirconium dichloride (72) Diphenylmethylene (cyclopentadienyl) (4-methylindenyl) ) Zirconium dichloride (73) Diphenylmethylene (cyclopentadienyl) (tetrahydroindenyl) Zirconium dichloride (74) Diphenylmethylene (Sic) Pentadienyl) (fluorenyl) zirconium dichloride (75) diphenylmethylene (cyclopentadienyl) (dimethylfluorenyl) zirconium dichloride (76) diphenylmethylene (cyclopentadienyl) (benzoindenyl) zirconium dichloride (77) diphenylmethylene (77) Butylmethylcyclopentadienyl) (2-methylindenyl) zirconium dichloride (78) Diphenylmethylene (butylmethylcyclopentadienyl) (4-methylindenyl) zirconium dichloride (79) Diphenylmethylene (butylmethylcyclopentadienyl) ) (Fluorenyl) zirconium dichloride (80) diphenylmethylene (butylmethylcyclopentadienyl) (dimethylfluorenyl) zirconi Mudichloride (81) Diphenylmethylene (butylmethylcyclopentadienyl) (2-methylbenzoindenyl) zirconium dichloride (82) Diphenylmethylene (indenyl) (4-methylindenyl) zirconium dichloride (83) Diphenylmethylene (indenyl) (Fluorenyl) zirconium dichloride (84) diphenylmethylene (indenyl) (dimethylfluorenyl) zirconium dichloride (85) diphenylmethylene (indenyl) (2-methylbenzoindenyl) zirconium dichloride (86) dimethylsilylene (cyclopentadienyl) (Butylmethylcyclopentadienyl) zirconium dichloride (87) Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride Rholide (88) Dimethylsilylene (cyclopentadienyl) (2-methylindenyl) zirconium dichloride (89) Dimethylsilylene (cyclopentadienyl) (4-methylindenyl) zirconium dichloride (90) Dimethylsilylene (cyclopentadiene) Enyl) (tetrahydroindenyl) zirconium dichloride (91) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (92) dimethylsilylene (cyclopentadienyl) (dimethylfluorenyl) zirconium dichloride (93) dimethylsilylene (93) Cyclopentadienyl) (benzoindenyl) zirconium dichloride (94) dimethylsilylene (butylmethylcyclopentadienyl) (2-methylindenyl) zirconi Mudichloride (95) Dimethylsilylene (butylmethylcyclopentadienyl) (4-methylindenyl) zirconium dichloride (96) Dimethylsilylene (butylmethylcyclopentadienyl) (fluorenyl) zirconium dichloride (97) Dimethylsilylene (butylmethyl) Cyclopentadienyl) (dimethylfluorenyl) zirconium dichloride (98) dimethylsilylene (butylmethylcyclopentadienyl) (2-methylbenzoindenyl) zirconium dichloride (99) dimethylsilylene (indenyl) (4-methylindenyl) ) Zirconium dichloride (100) Dimethylsilylene (indenyl) (fluorenyl) Zirconium dichloride (101) Dimethylsilylene (indenyl) (dimethylfluoride) Reniru) zirconium dichloride (102) dimethylsilylene (indenyl) (2-methylbenzoindenyl) zirconium dichloride (103) [dimethyl bis (cyclopentadienyl) silyl] zirconium dichloride,

(104) Dimethylbis (cyclopentadienyl) zirconium,
(105) dimethylbis (methylcyclopentadienyl) zirconium,
(106) dimethylbis (butylcyclopentadienyl) zirconium,
(107) dimethylbis (1,2-dimethylcyclopentadienyl) zirconium,
(108) dimethylbis (1,3-dimethylcyclopentadienyl) zirconium,
(109) Dimethylbis (1,3-dipropylcyclopentadienyl) zirconium,
(110) dimethylbis (1-methyl-3-propylcyclopentadienyl) zirconium,
(111) dimethylbis (1-butyl-3-methylcyclopentadienyl) zirconium,
(112) dimethylbis (1,2,4-trimethylcyclopentadienyl) zirconium,
(113) Dimethylbis (pentamethylcyclopentadienyl) zirconium,
(114) Dimethylbis (indenyl) zirconium,

(115) dimethylbis (2-methylindenyl) zirconium,
(116) Dimethylbis (4-methylindenyl) zirconium,
(117) Dimethylbis (4,5,6,7-tetrahydroindenyl) zirconium,
(118) dimethylbis (fluorenyl) zirconium,
(119) Dimethyl [ethylenebis (1-indenyl)] zirconium,
(120) Dimethyl [ethylenebis (4,5,6,7-tetrahydroindenyl)] zirconium,
(121) Dimethyl [dimethylbis (cyclopentadienyl) silyl] zirconium,
(122) bis (cyclopentadienyl) methylzirconium hydride,
(123) bis (cyclopentadienyl) methylzirconium chloride,
(124) Bis (cyclopentadienyl) zirconium (chloride) (hydride),

(125) bis (cyclopentadienyl) dibenzylzirconium,
(126) bis (cyclopentadienyl) zirconacyclopentane,
(127) bis (indenyl) methylzirconium hydride,
(128) bis (indenyl) methylzirconium chloride,
(129) bis (indenyl) zirconium (chloride) (hydride),
(130) bis (indenyl) dibenzylzirconium,
(131) Bis (indenyl) zirconacyclopentane,

For triscyclopentadienyl compounds:
(1) Tris (cyclopentadienyl) zirconium chloride,
(2) Tris (methylcyclopentadienyl) zirconium chloride,
(3) Tris (butylcyclopentadienyl) zirconium chloride,
(4) Tris (trimethylsilylcyclopentadienyl) zirconium chloride,
(5) Tris (1,2-dimethylcyclopentadienyl) zirconium chloride,
(6) Tris (1,3-dimethylcyclopentadienyl) zirconium chloride,
(7) Tris (1,3-dipropylcyclopentadienyl) zirconium chloride,
(8) Tris (1-methyl-3-propylcyclopentadienyl) zirconium chloride,
(9) Tris (1-butyl-3-methylcyclopentadienyl) zirconium chloride,
(10) Tris (indenyl) zirconium chloride,
(11) Tris (benzoindenyl) zirconium chloride,
(12) Tris (4-methylindenyl) zirconium chloride,
(13) Tris (4,5,6,7-tetrahydroindenyl) zirconium chloride,
(14) Tris (cyclopentadienyl) zirconium hydride,
(15) Tris (methylcyclopentadienyl) zirconium hydride,
(16) Tris (butylcyclopentadienyl) zirconium hydride,
(17) Tris (trimethylsilylcyclopentadienyl) zirconium hydride,
(18) Tris (1,2-dimethylcyclopentadienyl) zirconium hydride,
(19) Tris (1,3-dimethylcyclopentadienyl) zirconium hydride,

(20) Tris (1,3-dipropylcyclopentadienyl) zirconium hydride,
(21) Tris (1-methyl-3-propylcyclopentadienyl) zirconium hydride,
(22) Tris (1-butyl-3-methylcyclopentadienyl) zirconium hydride,
(23) Tris (indenyl) zirconium hydride,
(24) Tris (benzoindenyl) zirconium hydride,
(25) Tris (4-methylindenyl) zirconium hydride,
(26) Tris (4,5,6,7-tetrahydroindenyl) zirconium hydride,

Other cases:
(1) bis (indenyl) (1-methyl-3-propylcyclopentadienyl) zirconium hydride,
(2) bis (indenyl) (butylcyclopentadienyl) zirconium hydride,
(3) Bis (butylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) zirconium hydride and the like.

  A specific example is a compound in which zirconium in the above compound is replaced with titanium or hafnium.

  Among the compounds described above, preferable compounds are compounds having a biscyclopentadienyl skeleton of m = 2, more preferably compounds having an unsubstituted biscyclopentadienyl skeleton, specifically, bis (cyclopenta Dienyl) zirconium dichloride, dimethylbis (cyclopentadienyl) zirconium, bis (indenyl) zirconium dichloride, dimethylbis (indenyl) zirconium and the like. When these compounds are used as the catalyst component for olefin polymerization, two or more kinds can be used.

2. Ingredient (B)
Component (B) of the present invention is an ion pair generating compound that reacts with the metallocene compound of component (A) to form an ion pair, and is a component for activating component (A) as a co-catalyst It is. Specific examples include those selected from the group consisting of organoaluminum oxy compounds, organoboron compounds, and layered silicates, preferably organoaluminum oxy compounds.

The organoaluminum oxy compound has an Al—O—Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is a product usually obtained by reacting an organoaluminum compound with water. The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.
As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any compound represented by the following formula (3) can be used, but trialkylaluminum is preferably used.
R ³¹ _h AlX ³¹ _3-h (3)
(Wherein R ³¹ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, X ³¹ represents a hydrogen atom or a halogen atom, h Represents an integer of 1 ≦ n ≦ 3.)
The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. It is particularly preferred that

Said organoaluminum compound can also be used in mixture of 2 or more types.
The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is in the range of −70 to 100 ° C., preferably −20 to 20 ° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are generally called alumoxanes, and particularly include those comprising methylalumoxane (substantially consisting of methylalumoxane (MAO)). ) Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the aforementioned organoaluminum oxy compounds may be used in combination, and a solution obtained by dispersing or dispersing the organoaluminum oxy compound in the above-described inert hydrocarbon solvent; You may use what you did.

Further, when specific examples of the organic boron compound are extracted, borane compounds and borate compounds can be mentioned.
More specifically, the borane compound is triphenylborane, tris (o-fluorophenyl) borane, tris (p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl). Borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, Examples include tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, and tris (perfluorobiphenyl), preferably tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (Perfluoronaphthyl Borane are exemplified.

When the borate compound is specifically represented, the first example is a compound represented by the following formula (4).
[L ⁴¹ −H] ⁺ [BR ⁴¹ R ⁴² X ⁴¹ X ⁴² ] ⁻ (4)
(In the formula, L ⁴¹ is a neutral Lewis base, H is a hydrogen atom, and [L ⁴¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium, etc.)
In this case, examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, and tributylammonium, and dialkylammonium such as dipropylammonium and dicyclohexylammonium.
Examples of anilium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, and N, N-2,4,6-pentamethylanilinium.
Examples of phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.
On the other hand, R ⁴¹ and R ⁴² are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group, and a halogen such as fluorine, chlorine, bromine, and iodine are preferable.
X ⁴¹ and X ⁴² are a hydride group, a halide group, a hydrocarbyl group containing 1 to 20 carbon atoms, and a substituted hydrocarbyl group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms. .

The following can be illustrated as specific examples of the borate compound represented by the above formula (4).
(1) tributylammonium tetrakis (pentafluorophenyl) borate,
(2) tributylammonium tetrakis (2,6-ditrifluoromethylphenyl) borate,
(3) tributylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate,
(4) tributylammonium tetrakis (2,6-difluorophenyl) borate,
(5) tributylammonium tetrakis (perfluoronaphthyl) borate,
(6) Dimethylanilinium tetrakis (pentafluorophenyl) borate,
(7) Dimethylanilinium tetrakis (2,6-ditrifluoromethylphenyl) borate,
(8) Dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate,
(9) Dimethylanilinium tetrakis (2,6-difluorophenyl) borate,

(10) Dimethylanilinium tetrakis (perfluoronaphthyl) borate,
(11) triphenylphosphonium tetrakis (pentafluorophenyl) borate,
(12) triphenylphosphonium tetrakis (2,6-ditrifluoromethylphenyl) borate,
(13) triphenylphosphonium tetrakis (3,5-ditrifluoromethylphenyl) borate,
(14) triphenylphosphonium tetrakis (2,6-difluorophenyl) borate,
(15) Triphenylphosphonium tetrakis (perfluoronaphthyl) borate and the like.

  Among these, tributylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (2,6-ditri) Fluoromethylphenyl) borate is particularly preferred.

A second example of the borate compound is represented by the following formula (5).
[L ⁵¹ ] ⁺ [BR ⁵¹ R ⁵² X ⁵¹ X ⁵² ] ⁻ (5)
(In the formula, L ⁵¹ represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton. R ⁵¹ and R ⁵² are the same as the definitions of R ⁴¹ and R ⁴² in the above formula (4), and X ⁵¹ and X ⁵² are X ⁴¹ and X ⁴² in the above formula (4). The same definition as

Specific examples of the borate compound include the following.
(1) trityl tetraphenyl borate,
(2) trityltetrakis (o-fluorophenyl) borate,
(3) trityltetrakis (p-fluorophenyl) borate,
(4) trityltetrakis (m-fluorophenyl) borate,
(5) trityltetrakis (pentafluorophenyl) borate,
(6) trityltetrakis (2,6-ditrifluoromethylphenyl) borate,
(7) trityltetrakis (3,5-ditrifluoromethylphenyl) borate,
(8) Trityltetrakis (perfluoronaphthyl) borate,
(9) NaBPh ₄ ,

(10) NaB (o-F-Ph) ₄ ,
(11) NaB (p-F-Ph) ₄ ,
(12) NaB (m-F-Ph) ₄ ,
(13) NaB (C ₆ F ₅ ) ₄ ,
(14) NaB (2,6- (CF ₃ ) 2-Ph) ₄ ,
(15) NaB (3,5- (CF ₃ ) 2-Ph) ₄ ,
(16) NaB (C ₁₀ F ₇ ) ₄ ,
^{_{(17) H + BPh 4 -}} · 2 diethyl ether,
_{^{(18) H + B (3,5}} -F 2 -Ph) 4 - · 2 diethyl ether,
^{_{(19) H + B (C}} 6 F 5) 4 - · 2 diethyl ether,
^{(20) H + B (2,6-} (CF 3) 2 -Ph) 4 - · 2 diethyl ether,
^{(21) H + B (3,5-} (CF 3) 2 -Ph) 4 - · 2 diethyl ether,
(22) H ⁺ B (C ₁₀ H ₇ ) ₄ ⁻ · 2 diethyl ether,

Of these, trityltetrakis (pentafluorophenyl) borate, trityltetrakis (2,6-ditrifluoromethylphenyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ — ^{_{Ph) 4, H + B (}} C 6 F 5) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 -Ph) 4 - · 2 diethyl ^ether, H + B (3,5 _{- (CF 3) 2 -Ph)} 4 - · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 - · 2 diethyl ether.

The layered silicate of the ion pair generating compound of the component (B) has a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other, and the contained ions can be exchanged. An ion-exchange layered silicate (hereinafter simply referred to as “silicate”) may be mentioned. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can. Various known silicates can be used. Specific examples include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
Montmorillonite, Sauconite, Beidellite, Nontronite, Saponite, Hectorite, Stevenite and other smectites, Vermiculite and other vermiculites, Mica, Illite, Sericite and Sea chlorite and other micas , Pyrophyllite, talc, chlorite group.

  The silicate used in the present invention may be a layered silicate in which the above mixed layer is formed. The main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. Silicates obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but are preferably subjected to chemical treatment. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.

Moreover, since these ion-exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use them after removing moisture by heat dehydration under an inert gas flow.
Moreover, in order to improve the powder property of the polymer particle obtained by superposition | polymerization, it is preferable to make the said silicate spherical. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation or the like may be used. However, in general, commercially available silicates are indefinite, and thus operations such as granulation, sizing and fractionation are often performed.
The raw material slurry liquid for spray granulation for obtaining spherical particles has a silicate concentration of 0.1 to 70%, preferably 1 to 50%, particularly preferably 2 to 30%. Although the inlet temperature of the hot air for spray granulation varies depending on the dispersion medium, it is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.
In the present invention, shape control may be performed by pulverization, granulation, or the like before chemical treatment, during treatment, or after treatment. Various known methods can be employed for granulation, and preferably, stirring granulation method and spray granulation method are exemplified.

3. Ingredient (D)
In the catalyst according to the present invention, the component (D) can be used for supporting the components (A) to (B).
Component (D) is an inorganic compound carrier and / or a particulate polymer carrier, and can be used to adjust the properties of the polymer and obtain a polymer with a high bulk density. In the present invention, when polymerization is carried out using the catalyst obtained by supporting the component (D), the effect of improving the polymerization stability is remarkably exhibited, and it is particularly suitably used for a gas phase polymerization reaction.
As the inorganic compound carrier used for component (D), a metal oxide, metal chloride, metal carbonate, carbon substance or a mixture thereof can be used, and the shape can exist as a solid during catalyst preparation and polymerization reaction. Any material may be used, such as powder, granule, flake, foil, and fiber.

Examples of the metal oxide include single oxides or double oxides of elements of Groups 1 to 14 of the periodic table. For example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, Al ₂ O ₃ .SiO ₂ , Al ₂ O ₃ .MgO.CaO, Al ₂ O ₃ .MgO.SiO ₂ , Al ₂ Examples include various natural or synthetic double oxides such as O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the double oxide used in the present invention are not particularly limited.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specific examples include MgCl ₂ and CaCl ₂ .

  As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.

  Examples of the carbon material include carbon black and activated carbon.

  Any of the above inorganic carriers can be suitably used in the present invention, but metal oxides, specifically, silica and alumina are particularly preferable.

  A layered silicate can also be used as the inorganic compound carrier of the component (D), and the same layered silicate as described in the above component (B) can be used. When layered silicate is used as the inorganic compound carrier of component (D), other ion pair generating compounds can be used in combination as component (B), but the amount used can be appropriately reduced.

These inorganic carriers are usually baked in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl group is 0.5 to 3.0 mmol / g, Preferably, it is used by adjusting to 0.8 to 2.5 mmol / g.
The properties of these inorganic carriers, is not particularly limited, usually an average particle size 5 to 200 [mu] m, preferably 10 to 100 [mu] m, a specific surface area of 100~1000m ² / g, preferably from 200 to 500 m ² / g, pore volume 0.3~2.5cm ³ / g, preferably 0.5~2.0cm ³ / g, apparent specific gravity is 0.20~0.50g / cm ^3, preferably 0.25~0.45g It is preferable to use an inorganic support in the range of / cm ³ .

  As the particulate polymer carrier used for component (D), any one of a thermoplastic resin and a thermosetting resin can be used as long as it can exist as a solid without melting at the time of catalyst preparation and polymerization reaction. The particle size is usually in the range of 5 to 2,000 μm, preferably 10 to 100 μm. The polymer used as the material for the polymer carrier can be arbitrarily selected from those having a low molecular weight to those having a very high molecular weight. Although the molecular weight of the polymer used as a raw material depends on the type, a molecular weight in the range of 1,000 to 3,000,000 is usually suitable. When specific examples of the particulate polymer carrier are extracted, various polyolefins represented by particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly 1-butene, etc. (preferably In addition to carbon number 2-12, polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic compound carrier and / or particulate polymer carrier can be used as component (D) as it is, but it can also be used as component (D) after pretreatment.
Compounds used in this pretreatment include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum, triethoxyaluminum, Al An alumoxane containing a —O—Al bond, a silane compound, or the like can be used. In particular, when an inorganic carrier is used, active hydrogen-containing compounds such as alcohol and aldehyde, fluorine-containing alcohol compounds such as trifluoromethanol and pentafluorophenol, alkoxide groups such as tetraalkoxysilicate, trialkoxyaluminum, and transition metal tetraalkoxides are contained. Compounds, fluorine-containing amine compounds such as pentafluorobutylamine, pentafluoroaniline, and the like can be used. Furthermore, fluorine-containing compounds such as hydrofluoric acid, ammonium fluoride, ammonium fluoroborate, ammonium silicofluoride, and ammonium fluorophosphate are also included as compounds used for the pretreatment. Several of these carrier pretreatments may be used in combination.

The support is pretreated in an inert atmosphere such as nitrogen or argon, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually having 6 to 12 carbon atoms), pentane, hexane, heptane, octane, decane, This is usually carried out by contacting the support and the pretreatment compound with stirring in a liquid inert hydrocarbon solvent such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as dodecane or cyclohexane. be able to. Generally, the contact temperature is in the range of −100 to 200 ° C., preferably −50 to 100 ° C., and the contact time is in the range of 30 minutes to 50 hours, preferably 1 to 24 hours.
When the carrier is pretreated in a solvent in which the pretreatment compound is soluble, that is, an aromatic hydrocarbon solvent (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, or ethylbenzene. The reaction mixture can be directly used for the preparation of the catalyst component according to the present invention without removing the solvent from the reaction mixture containing the pretreated carrier. In addition, in the reaction mixture, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or hardly soluble (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, heptane, octane, decane, dodecane) If the solid content is precipitated by further adding an aliphatic or alicyclic hydrocarbon such as cyclohexane, the pretreated component (D) can be taken out as a solid. Further, even if a part or all of the aromatic hydrocarbon solvent contained in the reaction mixture is removed, the pretreated component (D) can be taken out as a solid. The amount of the pretreatment compound used is usually 0.01 to 10,000 mmol, preferably 0.1 to 100 mmol (however, in the modified aluminum compound, the Al atom concentration) with respect to 1 g of the carrier to be subjected to the pretreatment. Selected within the range.

4). Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention can be produced by bringing the component (A), the component (B) and, if necessary, the component (D) into contact with each other. Although the contact method is not specifically limited, it can contact in the following contact sequences.
(A) The component (A) and the component (B) are contacted and then the component (D) is contacted.
(A) The component (A) and the component (D) are contacted and then the component (B) is contacted.
(C) The component (B) and the component (D) are contacted, and then the component (A) is contacted.
(D) Contact the three components simultaneously.

  The proportion of each component in the olefin polymerization catalyst is such that the above component (A) mole / component (D) gram is 0.0001 to 5, preferably 0.001 to 0.5. When the component (B) is an organoaluminum oxy compound, the mole / component (D) gram of aluminum in (B) is 0.1 to 10, preferably 1 to 5, and the aluminum / The molar ratio of component (A) is 1 to 10,000, preferably 10 to 1,000. When (B) is an organic boron compound, the boron / component (A) molar ratio of (B) is 100 to 0.1, preferably 10 to 0.5.

  Components (A), (B), and (D) are usually in an inert atmosphere such as nitrogen or argon, and each component is pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, benzene, toluene, ethylbenzene, xylene. It is preferable to make it contact in presence of inert hydrocarbon solvent, such as. The temperature condition in this case is usually in the range of −100 ° C. to 200 ° C., preferably in the range of −50 ° C. to 100 ° C., and the contact time is in the range of 5 minutes to 50 hours, preferably in the range of 10 minutes to 24 hours. In addition, when each component is contacted in an inert hydrocarbon solvent, the produced catalyst can be directly subjected to polymerization together with part or all of the solvent, and substantially contains the solvent by means such as precipitation and drying. It can also be used for the polymerization after it is once taken out as a solid catalyst in the absence. Of course, the contact reaction of each component may be performed a plurality of times.

5. Polymerization Method A method for producing the olefin polymer of the present invention will be described. The olefin referred to in the present invention includes α-olefins, cyclic olefins, dienes, trienes, and styrene analogs. The α-olefin includes those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specific examples include ethylene, propylene, butene-1, hexene-1,4-methylpentene-1, and the like. The The α-olefin can be homopolymerized using the catalyst component according to the present invention, and two or more types of α-olefin can be copolymerized. Either polymerization or block copolymerization may be used.

  For the copolymerization of α-olefin, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and 3 to 12 carbon atoms, preferably 3 carbon atoms are used. When copolymerizing with α-olefin of ˜8, like propylene and butene-1, propylene and 4-methylpentene-1, propylene and 3-methylbutene-1, propylene and hexene-1, propylene and octene-1 The case of copolymerizing propylene and an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms is included. When copolymerizing ethylene or propylene with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers. In the case of coalescence, it is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and in the case of propylene copolymer, 1 to 90 mol%, preferably 5 to 80 mol%. More preferably, it is selected in the range of 10 to 70 mol%.

  As the cyclic olefin, those having 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms, can be used in the present invention, and examples thereof include cyclopentene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, Cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2- Norbornene, 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin. In this case, the amount of the cyclic olefin is 50 mol% or less, usually 1 to 50 mol%, preferably 2 to 2 mol% of the copolymer. It is in the range of 50 mol%.

The dienes and trienes that can be used in the present invention are chain polyenes that can be represented by the general formula:
_{CH 2 CH (CH) x (} CHCH 2) y
Here, x is 1 or 2, and y is 0 to 20, preferably 2 to 20. Specifically, butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene, 2-methyl-2 , 7-octadiene, 2,7-dimethyl-2,6-octadiene, 1,5,9-decatriene and the like. The chain diene or triene is usually copolymerized with the above-mentioned α-olefin, but the content of the chain diene and / or triene in the copolymer is usually 0.1 to It is in the range of 50 mol%, preferably 0.2 to 10 mol%.

  Styrene analogs that can be used in the present invention are styrene and styrene derivatives, including t-butyl styrene, α-methyl styrene, p-methyl styrene, divinylbenzene, 1,1-diphenylethylene, N , N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and the like. The polymerization catalyst according to the present invention can also be suitably used when a homopolymer or copolymer of olefin is further reacted with a polar monomer to modify the homopolymer or copolymer. Examples of polar monomers include unsaturated carboxylic acid esters exemplified by methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, and the like. it can. The polar monomer content of the modified copolymer is usually in the range of 0.1 to 10 mol%, preferably 0.2 to 2 mol%.

As the polymerization reaction, any of slurry polymerization, solution polymerization, and gas phase polymerization can be adopted, and slurry polymerization or gas phase polymerization is particularly preferable. Therefore, typically, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic rings such as cyclohexane and methylcyclohexane, etc., in a state where oxygen and water are substantially cut off. The olefin is polymerized or copolymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like.
The polymerization conditions at this time include a temperature of 20 to 200 ° C., preferably 50 to 100 ° C., a pressure of normal pressure to 10 MPaG, preferably normal pressure to 5 MPaG, and a polymerization time of 5 minutes to 10 hours, preferably 5 minutes to 5 hours are employed. The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. it can. In addition, a component intended to remove moisture, a so-called scavenge, can be added to the polymerization reaction system. Modified organoaluminum containing alkyl can be used. A multi-stage polymerization system having two or more stages in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, polymerization temperature and the like are different from each other can also be employed without any problem in the present invention.

  In the case of gas phase polymerization, the temperature is in the range of 0 to 120 ° C., preferably 20 to 100 ° C., and the polymerization pressure is in the range of normal pressure to 10 MPaG, preferably 0.5 to 5 MPaG. Uses a continuous circulating gas stream that is circulated through the circulating gas stream of the fluidizing medium and heated in the reactor by the heat of polymerization. The heat of the circulating gas stream is removed from the recycle composition by a cooling system external to the reactor. Typically, in a gas phase fluidized bed process, a gas stream containing one or more monomers is continuously circulated through the fluidized bed under reaction conditions in the presence of a catalyst. The gas stream is withdrawn from the fluidized bed and recycled back to the reactor. At the same time, the polymer product is withdrawn from the reactor and new monomer is added to replace the polymerized monomer. In general, a gas phase reactor can produce 200 to 100,000 kg / hr.

6). Cyclopentadiene compound (C)
In the present invention, the cyclopentadiene compound (C) added during the polymerization reaction is a compound having a cyclopentadiene structure in the molecule, excluding unsubstituted cyclopentadiene, and is represented by the following formula (1). Hereinafter, the cyclopentadiene compound (C) may be simply referred to as the compound (C).

(In the formula, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ represents either hydrogen or a substituent having 1 to 10 carbon atoms, and any two of the substituents may be cyclic. (A hydrocarbon group can be formed, but R ^{11 to} R ¹⁵ do not simultaneously become hydrogen.)

The compounds represented by the formula (1) are classified as follows: substituted cyclopentadiene compounds, condensed ring cyclopentadiene compounds, and bridged cyclopentadiene compounds.
Substituted cyclopentadiene compound: As a substituent of formula (1), an alkyl group such as methyl, ethyl, propyl, butyl, t-butyl, hexyl and octyl, an aryl group such as phenyl, an alkoxy group such as methoxy, ethoxy and propoxy, An aryloxy group such as phenoxy and an aralkyl group such as benzyl are included. An organosilicon compound can also be used as a substituent.

  Fused cyclopentadiene compound: When two or more of the substituents of the formula (1) jointly form one or more cyclic hydrocarbon groups, preferred skeletons are indene, azulene and fluorene. Examples of the compound represented by the formula (1) include derivatives in which this skeleton is substituted with alkyl, aryl, aralkyl, alkoxy, or aryloxy having 1 to 10 carbon atoms. Furthermore, a benzoindene or cyclopentaphenanthrene structure in which a substituent on the condensed ring further forms a condensed ring can be used as the compound represented by the formula (1).

  Cross-linked cyclopentadiene compound: The two compounds represented by formula (1) are an alkylene group (the carbon number is usually 2 to 8, preferably 2 to 3) or an alkylidene group (the carbon number is usually 2 to 8). , Preferably 2-3), and a compound bonded (crosslinked) through a substituted silylene group is also suitably used as the compound (C) according to the present invention. In this case, the two kinds of compounds may be the same or different.

Accordingly, the organic cyclic hydrocarbon compounds that can be used as the cyclopentadiene compound (C) include the following compounds.
Substituted cyclopentadiene compounds:
Methylcyclopentadiene, ethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, isobutylcyclopentadiene, sec-butylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1, 2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,3-dipropylcyclopentadiene, 1-methyl-3-ethylcyclopentadiene, 1-ethyl-3-methylcyclopentadiene, 1-methyl-3-n -Propylcyclopentadiene, 1-butyl-3-methylcyclopentadiene, 1-ethyl-3-isopropylcyclopentadiene, 1-methyl-3-phenylcyclopentadiene 1,2,4-trimethylcyclopentadiene, 2-ethyl-3,5-dimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, trimethylsilylcyclopentadiene, trimethoxysilylcyclo Substituted cyclopentadiene such as pentadiene.

Fused cyclopentadiene compound:
Substituted indenes such as indene, 2-methylindene, 4-methylindene, 4,7-dimethylindene, 4-phenylindene, 4,5,6,7-tetrahydroindene, benzoindene, cyclopentaphenanthrene, azulene, methylazulene C7-24 cyclopolyene or substituted cyclopolyene such as ethylazulene, fluorene, methylfluorene.

Cross-linked cyclopentadiene compound:
Ethylenebiscyclopentadiene, ethylenebispropylcyclopentadiene, isopropylidenebiscyclopentadiene, isopropylidenebispropylcyclopentadiene, 1,2-bis (1-indenyl) ethane, 1,2-bis (4,5,6,7- Tetrahydro-1-indenyl) ethane, 1,3-bis (1-indenyl) propane, isopropylidenebisbenzoindene,

  Dimethylsilylylene biscyclopentadiene, dimethylsilylylene bisindene, dimethylsilylene bis 4,5,6,7-tetrahydroindene, dimethylsilylylene bispropylcyclopentadiene, dimethylsilylylene bisbutylcyclopentadiene, dimethylsilylene bisbenzoindene, Diphenylsilylene biscyclopentadiene, diphenylsilylene bisindene, diphenylsilylene bispropylcyclopentadiene, diphenylsilylene bisbutylcyclopentadiene, etc.

Asymmetric bridged cyclopentadiene compound:
(Cyclopentadienyl) (indenyl) dimethylsilane, (cyclopentadienyl) (butylcyclopentadienyl) dimethylsilane, (cyclopentadienyl) (fluorenyl) dimethylsilane, (methylcyclopentadienyl) (indenyl) Dimethylsilane, (cyclopentadienyl) (4-phenylindenyl) dimethylsilane, (indenyl) (4-methylindenyl) dimethylsilane, (cyclopentadienyl) (benzoindenyl) dimethylsilane, isopropylidene (cyclo Pentadiene) (indene), isopropylidene (cyclopentadiene) (butylcyclopentadiene), isopropylidene (cyclopentadiene) (fluorene), isopropylidene (methylcyclopentadiene) (1,3-dipropylcyclope Tajien), isopropylidene (butyl cyclopentadiene) (benzoindene), isopropylidene (cyclopentadiene), etc. (cyclopentaphenanthrene).

  Among the above compounds, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-ethyl-3-methylcyclo Pentadiene, 1-methyl-3-propylcyclopentadiene, 1-butyl-3-methylcyclopentadiene, 2-ethyl-5-isopropylcyclopentadiene, 1-methyl-3-phenylcyclopentadiene, 1,3-dipropylcyclopentadiene 1,2,4-trimethylcyclopentadiene, 4-methylindene, 4-phenylindene, 4,7-dimethylindene, bis (1-indenyl) dimethylsilane, benzoindene, cyclopenta Enanthrene, 1,2-bis (1-indenyl) ethane, (cyclopentadienyl) (indenyl) dimethylsilane, (butylcyclopentadienyl) (indenyl) dimethylsilane, (cyclopentadienyl) (4-phenylindene Nyl) dimethylsilane and the like are preferable as the cyclopentadiene compound (C) according to the present invention. Of course, two or more of the above compounds can be used in combination.

The cyclopentadiene compound (C) according to the present invention preferably has a larger number of carbon atoms than the respective ligands L ²¹ , L ²² and L ^{23 of} the component (A), and the coordination of the component (A). Those having a carbon number of 2 or more, more preferably 3 or more, and more preferably 4 or more than the number of carbon atoms of each of the children L ²¹ , L ²² and L ²³ should make the effect of the present invention remarkable. Can do.
In addition, the ligands L ²¹ , L ²² and L ²³ of the component (A) preferably have 9 or less carbon atoms. Preferred combinations of the compound (C) and the component (A) are as exemplified below.
When component (A) is a biscyclopentadienyl complex (when L ²¹ has 5 carbon atoms), the cyclopentadiene compound (C) is methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butyl Cyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-ethyl-3-methylcyclopentadiene, 1-methyl-3-propylcyclopentadiene, 1-butyl-3-methylcyclopentadiene, 2 -Ethyl-5-isopropylcyclopentadiene, 1-methyl-3-phenylcyclopentadiene, 1,3-dipropylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, pentamethylcyclopentadiene, 4-methylin Examples thereof include denene, 4-phenylindene, 4,7-dimethylindene, bis (1-indenyl) dimethylsilane, benzoindene, cyclopentaphenanthrene, 1,2-bis (1-indenyl) ethane, and the like.

When component (A) is a bisindenyl complex (when L ²¹ has 9 carbon atoms), the cyclopentadiene compound (C) is 1-butyl-3-methylcyclopentadiene, 2-ethyl-5-isopropylcyclopentadiene, 1 -Methyl-3-phenylcyclopentadiene, 1,3-dipropylcyclopentadiene, pentamethylcyclopentadiene, 4-methylindene, 4-phenylindene, 4,7-dimethylindene, bis (1-indenyl) dimethylsilane, benzoin Den, cyclopentaphenanthrene, 1,2-bis (1-indenyl) ethane, and the like can be given.

When two or more types of cyclopentadiene compounds (C) are used, the combination with component (A) is such that each carbon number of compound (C) is such that each of ligands L ²¹ , L ²² and L of component (A) ^It is sufficient if it is larger than ²³ carbon atoms.
When component (A) is a biscyclopentadienyl complex, the first compound (C) is indene, propylcyclopentadiene, butylcyclopentadiene, 1,3-dipropylcyclopentadiene, 1-methyl-3-propyl. Cyclopentadiene, 1-butyl-3-methylcyclopentadiene, the second compound (C) is dimethylcyclopentadiene, bis (1-indenyl) dimethylsilane, benzoindene, cyclopentaphenanthrene, 1,2-bis (1- Indenyl) ethane and the like are mentioned as suitable combinations.

In the present invention, the compound (C) having a cyclopentadienyl skeleton is used such that the molar ratio of compound (C) / component (A) is 0.5 to 5 with respect to component (A). To do .

The compound (C) having a cyclopentadienyl skeleton is obtained by polymerizing an olefin in the presence of an olefin polymerization catalyst obtained by bringing the components (A) and (B) and, if necessary, the component (D) into contact with each other. In the method for producing an olefin polymer to be copolymerized, it is added during the polymerization reaction.
The compound (C) makes it possible to control the performance of the olefin polymerization catalyst when the olefin is polymerized. The addition amount of the compound (C) can be selected as appropriate, but it is an equimolar amount or less with respect to the component (A) in order to improve the polymerization activity, increase the molecular weight of the polymer, and broaden the molecular weight distribution. Is preferably added. The use of the compound (C) at the time of such polymerization is effective in single-stage polymerization and further effective in multi-stage polymerization. By adjusting the amount of the compound (C) to be used, the performance of the basic metallocene catalyst can be controlled.
In addition, when there is a concern about the problem of odor due to remaining in the polymer to be produced, the amount of the compound (C) present in the polymerization system may be limited to 1000 ppm or less with respect to the amount of the olefin polymer. preferable.

Cyclopentadiene compound (C) of the present invention, when introducing the above components (A) and (B), the olefin polymerization catalyst obtained by contacting the component (D) to each other by a required reactor, catalyst It is preferable to use it so as to contact the component (A) preferentially.

  In the method for producing a polymer of the present invention, olefin may be prepolymerized in the presence of an olefin polymerization catalyst and compound (C), and then olefin polymerization may be continued.

Examples of the polymer produced by the method for producing an olefin polymer of the present invention include linear low density polyethylene, elastomer, plastomer, high density polyethylene, low density polyethylene, polypropylene and polypropylene or polyethylene copolymer. The polymer according to the present invention can be mixed with and / or coextruded with other polymers, and as the other polymer, a linear low-polymer produced using a conventional Ziegler catalyst and / or metallocene catalyst. Examples include density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, and polypropylene.
A preferred polymer according to the present invention contains 50% or more of polyethylene, and the comonomer is preferably 1-butene, 1-pentane, 1-hexane, 1-octene or the like. Density of the polymer is preferably 0.85~0.96g / cm ^3, more preferably 0.88~0.96g / cm ^3, particularly preferably a 0.90~0.96g / cm ^3.

The polymer produced by the method of the present invention can be used in a wide variety of molded articles. The polymers produced by the method of the present invention and blended compositions thereof can be molded by a molding method such as film, sheet and coextrusion molding, blow molding, injection molding, rotational molding and the like.
Films obtained from the above polymers include blown films and cast films formed by coextrusion or lamination, including shrink films, wrap films, stretch films, sealing films, oriented films, snack confectionery packaging films, high durability bags, It can be used for applications such as shopping bags, heated food or frozen food packaging films, medical packaging films, industrial liners, membranes, etc. that are in contact with or not in contact with food. Moreover, the extrusion molded product obtained from the said polymer can be used for a medical tube, a wire coating, a cable coating, a waterproof sheet, etc. Furthermore, the molded product obtained from the polymer can be used in bottles, tanks, large hollow products, containers and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, the raw material, polymerization evaluation apparatus, polymerization conditions, and physical property measurement of the polymer used in the examples are as follows.

<Catalyst raw material>
Bisindenyl zirconium dichloride or biscyclopentadienyl dichloride was used as the component (A) compound.
As the organoaluminum oxy compound of component (B), a methylalumoxane (MAO) 20% toluene solution manufactured by Albemarle Co. was used.
As the carrier for the component (D), a product obtained by baking silica C948 manufactured by Grace at 600 ° C. for 7 hours was used.

<Measurement of physical properties of polymer>
The physical properties of the polymers obtained in each Example and each Comparative Example were measured by the method described below.
The resin used for the test was prepared by adding 0.1 parts by weight of B-225 (Ciba Specialty Chemicals, Inc., Irganox (registered trademark)) as an antioxidant, and kneading at 150 ° C. for 10 minutes. Was used.
The melt flow rate (MFR) was measured according to JIS K-7210 (1999) under conditions of a temperature of 190 ° C. and a load of 21.18N.
The density was measured according to JIS K-7112 (1999).
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is measured by GPC (gel permeation chromatography), using an Alliance GPC2000 type manufactured by Waters, under the following conditions. The molecular weight and molecular weight distribution were determined.
Column: Showdex HT-G and HT-806M × 2 columns Solvent: 1,2,4-trichlorobenzene Temperature: 140 ° C.
-Flow rate: 1.0 ml / min The column was calibrated by Showa Denko monodisperse polystyrene (S-7300 S-3900 S-1950 S-1460 S-1010 S-565 S-152 S-66.0 S-28. 5 S-5.05 0.2 mg / ml solution), n-eicosane and n-tetracontane were measured, and the logarithmic values of elution time and molecular weight were approximated by a quartic equation. In addition, the following formula was used for conversion of the molecular weight of polystyrene and polyethylene.
MPE = 0.468 × MPS

[ Reference Example 1 ]
<Preparation of solid catalyst (1)>
10 g of silica was put into a 300 ml flask equipped with a magnetic induction stirrer and dried at 150 ° C. for 1 hr under reduced pressure. In a 100 ml eggplant-shaped flask, 190 mg (0.5 mmol) of bisindenylzirconium dichloride was placed, 30 ml of toluene was placed, and then 17 ml of MAO (50 mmol as Al) was placed. The solution was stirred for 30 minutes and added to silica that had been heated to 40 ° C. After stirring at 40 ° C. for 30 minutes, the solvent was distilled off under reduced pressure to recover 12 g of a powdery solid catalyst (1).
<Ethylene-butene copolymerization>
The inside of the autoclave reactor having an internal volume of 2 liters sufficiently purged with nitrogen was heated to 75 ° C., ethylene was added, and the pressure was adjusted to 0.7 MPa. 1-butene was added so that the butene / ethylene partial pressure ratio was 0.015. 0.3 mmol of triethylaluminum was added, 0.1 g (4 μmol as Zr) of the catalyst (1) and 60 mg (400 μmol) of 1,3-dipropylcyclopentadiene were added, and the mixture was stirred for 2 hours. During the polymerization, the pressure was controlled to be 0.8 MPaG at 75 ° C.
The obtained polymer was 34.7 g, and was free-flowing particles. The polymerization activity was 250 g-polymer / g-catalyst · time · MPa per 1 g of the catalyst. When the obtained copolymer was measured, the MFR was 0.2 g / 10 min, the density was 0.918 g / cm 3, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) was 3. .4. The results are shown in Table 1.

[ Reference Example 2 ]
Except for using instead 1,3-propylcyclopentadiene 15mg of 1,3-dipropyl-cyclopentadiene 60mg Reference Example 1 (400μmol) (100μmol), it was carried out in the same manner as in Reference Example 1. The results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that 1,3-dipropylcyclopentadiene of Example 1 was not added. The results are shown in Table 1.

[ Reference Example 3 ]
<Preparation of solid catalyst (2)>
10 g of silica was put into a 300 ml flask equipped with a magnetic induction stirrer and dried at 150 ° C. for 1 hr under reduced pressure. A 100 ml eggplant-shaped flask was charged with 150 mg (0.5 mmol) of biscyclopentadienylzirconium dichloride and 30 ml of toluene, and then 17 ml of MAO (50 mmol as Al). The solution was stirred for 30 minutes and added to silica that had been heated to 40 ° C. After stirring at 40 ° C. for 30 minutes, the solvent was distilled off under reduced pressure to recover 12 g of a powdery solid catalyst (2).
In a 2 L stainless steel autoclave (with stirring and temperature control) sufficiently purged with nitrogen, 900 ml of hexane, 0.2 mmol of triisobutylaluminum, 670 mg of benzoindene (4000 μmol, ie C / A = 1000), and 15 ml of hexene were added. The temperature was raised to 80 ° C. The pressure was increased to 0.2 MPaG with nitrogen, and further pressurized to 0.8 MPaG with ethylene. Thereafter, a pipe in which 100 mg of solid catalyst (2) (4 μmol as Zr) and 30 ml of hexane were enclosed was attached, and polymerization was started by pumping into the autoclave at an ethylene pressure of 0.9 MPaG. During the polymerization, ethylene was supplied so as to maintain a temperature of 80 ° C. and a pressure of 0.9 MPaG, and after 1 hr, the polymerization was stopped by cooling and depressurization.
The obtained polymer was 105 g in the form of free flowing particles. The polymerization activity was 1500 g-polymer / g-catalyst · time · MPa per 1 g of the catalyst. When the obtained copolymer was measured, the MFR was 0.8 g / 10 min, the density was 0.9275 g / cm ³ , and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 3.1. The results are shown in Table 1.

[Comparative Example 2] (Reference Example)
The same procedure as in Reference Example 3 was performed except that the amount of benzoindene in Reference Example 3 was 7 mg (40 μmol, that is, C / A = 10). The results are shown in Table 1.

[Comparative Example 3]
The same procedure as in Reference Example 3 was performed except that benzoindene in Reference Example 3 was not added (C / A = 0). The results are shown in Table 1.

[Example 1 ]
A 300 ml flask equipped with a magnetic induction stirrer was purged with nitrogen, and 5 mg (40 μmol) of n-butylcyclopentadiene and 100 ml of hexane were added. This was heated to 40 ° C., 1 g of the catalyst ( 2 ) was added, and ethylene was contacted at normal pressure. When the ethylene consumption reached 0.8 L (1 g with ethylene), the solvent was removed under reduced pressure to prepare a prepolymerized catalyst (3).
900 ml of hexane, 0.2 mmol of triisobutylaluminum, and 15 ml of hexene were placed in a 2 L stainless steel autoclave (stirring and equipped with a temperature control device) sufficiently purged with nitrogen, and the temperature was raised to 80 ° C. The pressure was increased to 0.2 MPaG with nitrogen, and further pressurized to 0.8 MPaG with ethylene. Thereafter, a pipe in which 200 mg (4 μmol as Zr) of pre-polymerization catalyst (3) and 30 ml of hexane were enclosed was attached, and the polymerization was started by pumping into the autoclave at an ethylene pressure of 0.9 MPaG. During the polymerization, ethylene was supplied so as to maintain a temperature of 80 ° C. and a pressure of 0.9 MPaG, and after 1 hr, the polymerization was stopped by cooling and depressurization.
The obtained polymer was 230 g in the form of smooth particles. The polymerization activity was 3300 g-polymer / g-catalyst · time · MPa per 1 g of the catalyst before the prepolymerization. When the obtained copolymer was measured, the MFR was 1.7 g / 10 min, the density was 0.9225 g / cm ³ , and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) was 3.1. The results are shown in Table 1.

From the results apparent Table 1, process for producing an olefin polymer of Example 1 is the present invention, by adopting the addition of prepolymerization time with a specific compound and a specific catalyst component, higher activity A polymer having a high molecular weight, a relatively wide molecular weight distribution, and good particle properties can be obtained.
On the other hand, the production method of the olefin polymer of Comparative Examples 1 to 3 (Comparative Example 2 is a reference example) has a result that the activity is low, the molecular weight is small (MFR is large), the molecular weight distribution is narrow, etc. Recognize.

  According to the present invention, an olefin having a high activity, a high molecular weight, a relatively wide molecular weight distribution, a good particle property, a narrow composition distribution characteristic of a metallocene catalyst in copolymerization, and a low tackiness. A method for producing a polymer can be provided. The present invention enables highly active and long-term stable operation in continuous gas phase polymerization, and can further improve the industrial productivity of olefin polymers, so that the industrial utility is very high.

Claims (5)

In the method for producing an olefin polymer in which an olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst containing the components (A) and (B) shown below, when the olefin is prepolymerized, the following formula (1) The manufacturing method of the olefin polymer characterized by adding 0.5-5 mol with respect to 1 mol of compounds represented by a component (A) the cyclopentadiene compound (C) shown.
Component (A): a compound represented by L ²¹ mM ²¹ X ²¹ n, or a compound represented by (L ²² -QL ²³ ) M ²² X ²² ₂ (where M ²¹ is the fourth in the periodic table) Group element, L ²¹ represents a ligand having a cyclopentadienyl skeleton, X ²¹ represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group, and m + n is a valence of M ²¹ ; m is 1 to 3, while M ²² is an element belonging to Group 4 of the periodic table, L ²² and L ²³ are each a ligand having a cyclopentadienyl skeleton and bound by Q, Q is (The divalent hydrocarbon group or organic silicon group, X ²² represents a halogen atom, a hydrogen atom, an alkoxy group or a hydrocarbon group.)
Component (B): Ion-pair generating compound

(In the formula, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ represents either hydrogen or a substituent having 1 to 10 carbon atoms, and any two of the substituents may be cyclic. (A hydrocarbon group can be formed, but not all of R ^{11 to} R ¹⁵ become hydrogen at the same time.)   The cyclopentadiene compound (C) is an indene having a hydrocarbon group, a benzoindene having a hydrocarbon group, an unsubstituted benzoindene, a cyclopentadiene having a hydrocarbon group, a bisindene crosslinked with a hydrocarbon group or an organosilicon group, Bisindene having a hydrocarbon group crosslinked with a hydrocarbon group or an organosilicon group, cyclopentadiene crosslinked with a hydrocarbon group or an organosilicon group, and cyclohexane having a hydrocarbon group crosslinked with a hydrocarbon group or an organosilicon group 2. The method for producing an olefin polymer according to claim 1, which is a compound selected from the group consisting of pentadiene. 3. The olefin polymer according to claim 1, wherein the number of carbon atoms of the cyclopentadiene compound (C) is larger than that of each of the ligands L ²¹ , L ²² and L ²³ of the component (A). Manufacturing method. Ligands ^{L 21, L 22} and ^{L 23} of the component (A), process for producing an olefin polymer according to any one of claims 1 to 3, characterized in that it has a carbon number of 9 or less. The method for producing an olefin polymer according to any one of claims 1 to 4 , wherein the olefin polymerization catalyst is supported on an inorganic compound carrier and / or a particulate polymer carrier (D).