WO2008066200A1

WO2008066200A1 - Catalyst component for olefin polymerization, and catalyst and method for producing olefin polymer using the same

Info

Publication number: WO2008066200A1
Application number: PCT/JP2007/073427
Authority: WO
Inventors: Takefumi Yano; Motoki Hosaka
Original assignee: Toho Catalyst Co., Ltd.
Priority date: 2006-11-29
Filing date: 2007-11-28
Publication date: 2008-06-05
Also published as: JP5394747B2; JPWO2008066200A1

Abstract

By using a catalyst for olefin polymerization composed of (A) a solid catalyst component containing magnesium, titanium, a halogen and an electron-donating compound, (B) an organic aluminum compound represented by the following general formula: R8pAlQ3-p, and (C) a secondary amino group-containing silacycloalkane compound, there can be obtained a polymer having high catalytic activity and high tacticity. The catalyst for olefin polymerization has good hydrogen response.

Description

(3427,,

Specification

Catalyst component for polymerization of olefins

And production method of olefin polymers using the same

The present invention is capable of maintaining a high degree of stereoregularity and catalytic activity of a polymer, and also provides an effect of obtaining a high melt flow rate by adding a small amount of hydrogen, a so-called catalyst component for polymerizing olefins having a good hydrogen response. And a catalyst, and a method for producing a polymer of olefins using the same. Background art

Conventionally, in the polymerization of olefins such as propylene, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many methods have been proposed for polymerizing or copolymerizing olefins in the presence of a catalyst for polymerizing olefins comprising the solid catalyst composition, an organoaluminum compound, and an organosilicon compound. For example, in Patent Document 1 (Japanese Patent Laid-Open No. Sho 5 7-6 3 3 10), a catalyst comprising a combination of a magnesium compound, a titanium compound, and an organosilicon compound having a Si—O—C bond is disclosed. In particular, a method for polymerizing olefins having 3 or more carbon atoms has been proposed. Among them, Patent Document 2 (Japanese Patent Laid-Open No. 5-9209) discloses that an unsaturated cyclic compound acetal compound is effective as a donor for expanding the molecular weight distribution. 3 (Patent No. 2 5 5 0 6 1) discloses that a cyclocycloalkoxy derivative is effective as a donor. 73427 ₄ « _H Recently, non-patent literature 1 (Pol ymer B ulletin 54, 3 7 7-3 8 5), among the silacyclodialkoxy derivatives, the ring substituted derivatives have the same level of performance as existing high performance donors. Have been reported. However, these methods are effective for obtaining highly stereoregular polymers with high catalytic activity, but from the viewpoint of the efficiency of controlling the molecular weight with hydrogen (hydrogen response) while maintaining these properties. However, it was not always satisfactory, and further improvement was desired.

By the way, the polymer obtained by using the catalyst as described above is used for various applications such as containers and films in addition to molded articles such as automobiles or home appliances. They melt polymer powder produced by polymerization and are molded by various molding machines. Especially when manufacturing large molded products by injection molding, the fluidity of the molten polymer (melt flow rate, MFR) In order to reduce the cost of highly functional block copolymers for automotive materials, in the copolymerization reactor, an olefin-based thermoplastic elastomer (hereinafter referred to as “TPO”) is required. ))) A method of producing as many co-polymers as necessary for production, and directly producing soot in a polymerization reactor without adding a newly synthesized copolymer after production, ie, those skilled in the art In the production of reactor-made 直 ο ο by direct weight, the melt flow rate of the final product is kept large enough to facilitate injection molding. In some cases, the flow rate is required to be 200 or more. Therefore, many studies have been made to increase the melt flow rate while maintaining high stereoregularity of the polymer.

Melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is a common practice to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. At this time, when producing a low molecular weight polymer, that is, producing a high melt flow rate polymer. Usually, a large amount of hydrogen is added in order to achieve ΡΟΤ / ϋΡ2007 / 0 '3427. However, particularly in a bulk polymerization apparatus, the pressure resistance of the reactor is limited due to its safety, and the amount of hydrogen that can be added is also limited. Further, even in the gas phase polymerization, in order to add more hydrogen, it is necessary to reduce the partial pressure of the monomer to be polymerized, and in this case, the productivity is lowered. In addition, the use of a large amount of hydrogen also causes cost problems. To solve this problem, Patent Document 4 (WO 20 04- 1 6 6

6 No. 2) uses a compound represented by S i (OR ¹ ) 3 (NR ² R ³ ) as a catalyst component for the polymerization of olefins, so that a polymer with high melt flow rate and high stereoregularity can be obtained. It is disclosed that it is manufactured, and it has given some effect. That is, the organic organocompound used as a conventional industrial catalyst component for olefin polymerization has a plurality of Si 1 OR bonds in the molecule.

(Patent Document 1) Japanese Patent Application Laid-Open No. Sho 5 7 _ 6 3 3 10 (Claims) (Patent Document 2) Japanese Patent Application Laid-Open No. Hei 5-9209 (Patents)

(Patent Document 3) Japanese Patent No. 2 5 5 7 0 6 1 (Claims)

(Patent Document 4) WO 20 04-1 6 6 6 2 (Claims) (Non-Patent Document 1)] P o lyme r B u l e ret 54, 3

7 7-3 8 5

However, these conventional techniques are not yet sufficient to fundamentally solve the problem of TPO production due to direct weight as described above, and further improvements have been desired.

Therefore, the object of the present invention is to polymerize olefins that can maintain a high degree of stereoregularity and catalytic activity of the polymer, and have a high melt flow rate by adding a small amount of hydrogen, so-called hydrogen response. It is an object of the present invention to provide a method for producing a catalyst component and catalyst for use, and an olefin polymer using the catalyst component.

Disclosure of the invention

Under such circumstances, the present inventors have conducted intensive studies, and as a result, the catalyst for polymerizing olefins formed with a specific silacycloalkane compound as an essential component, or magnesium, titanium, halogen and electron donating compounds. A catalyst formed from a solid catalyst component containing an organoaluminum compound and a silacycloalkane having an amino specific structure having a secondary amino group is more suitable as a catalyst for the polymerization of olefins than the conventional catalysts described above. As a result, the present invention has been completed.

That is, the present invention provides the following general formula (1);

(In the above formula, X is a secondary amino residue having 1 to 10 carbon atoms, a tertiary amino residue, an alkoxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group. R ¹ represents a straight or branched alkyl group having 1 to 10 carbon atoms, a cyclyl alkyl group, an aralkyl group or an aryl group, and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkyl group, an aralkyl group or an aryl group, n is an integer of 1 to 20; R ² and R ³ or R ⁴ and R ⁵ may be bonded to each other to form a ring, and ¹ to! ^ ⁵ may be the same or different.) General formula (2) below;

(In the above formula, X, R ¹ and n are the same as above, R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups, and aralkyl groups. . or indicates Ariru group, 1 ¹ Oyopi 1 ⁴ to 1 ⁶ may be made different in co -) or the following general formula (3);

(In the above formula, X, R ¹ and n are the same as above, R ⁶ and R ⁷ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group. RR ⁶ and R ⁷ may be the same or different, and provide a catalyst component for polymerizing olefins, which is represented by the following formula.

The present invention also provides an olefins polymerization catalyst formed using the olefins polymerization catalyst component as an essential component.

Further, the present invention provides (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound,

(B) The following general formula (2); R ⁷ _P A 1 Q ₃ _ _p (2) (wherein R ⁷ represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or Represents a halogen atom, p is a real number 0 <p ≤ 3. And (c) the catalyst component for polymerization of olefins, and a catalyst for polymerization of olefins formed from the following.

The present invention also provides a method for producing an olefin polymer comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization.

The catalyst for polymerizing olefins of the present invention is capable of maintaining a high degree of catalytic activity and high catalytic activity as compared with conventional catalysts, and has the effect of obtaining a high melt flow rate by adding a small amount of hydrogen (hereinafter simply “ Sometimes referred to as “hydrogen response”. Therefore, the ability to reduce the amount of hydrogen used in the polymerization, the high activity of the catalyst, and the ability to maintain the activity can provide general-purpose polyolefins at a low cost, and the weight of highly functional olefins can be reduced. Usefulness is expected in the production of coalescence. Brief Description of Drawings

FIG. 1 is a flow chart showing the steps for preparing the catalyst component and the polymerization catalyst of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The component for olefins polymerization catalyst of the present invention is a compound of the general formula (1), the general formula (2) or the general formula (3). These can be used alone or in combination of two. In the general formula (1), X is a linear or branched alkyl group having 1 to 10 carbon atoms or a secondary amino group in which a cycloalkyl group having 4 to 10 carbon atoms is bonded to an N atom, and 1 to 10 carbon atoms. A linear or branched alkyl group or an alkoxy group in which a cycloalkyl group having 4 to 10 carbon atoms is bonded to an oxygen atom, R ¹ represents 1 to A linear or branched alkyl group having 10 is preferable, and R ^{2 to} R ⁵ are each preferably a hydrogen atom, and a linear or branched alkyl group having 1 to 10 carbon atoms, and n is 2 An integer of ~ 8 is preferred. It is also preferable that R ² and R ³ or R ⁴ and R ⁵ are bonded to each other to form a ring.

The compounds represented by the general formula (1) are more specifically described as follows: 1,1 bis (alkylamino) -2, n-bis (alkyl) silacycloalkyls, 1,1 bis (alkylamino) 1 2 , N-dialkylsilacycloalkanes, 1,1 bis (alkylamino) -2, n-trialkylsilacycloalkanes, 1,1 bis (alkylamino) — 2, n-tetraalkylsilacycloalkanes, 1, 1 1 Bis (alkylamino) 1 2, n-Tetrakis (alkyl) silacycloalkanes, 1-(alkylamino) — 1 1 (alkylalkoxy) 1 2, n-dialkyl silicic alkanes, 1 — ( Alkylamino) 1 1 1 (alkoxy) 1 2, n-trialkylsilacycloalkanes, 1 1 (alkylamino) 1 1 1 (alkoxy) 1 2, n-tetraalkyl silaci Loalkanes, 1- (Cycloamino) 1 1 — (Alkoxy) Silacycloalkanes, 1 1 (Alkylamino) 1 1 1 (Phenoxy) Silacycloalkanes, 1 1 (Aralkylamino) 1 1 — (Alyloxy) Silacycloal 1- (alkylamino) 1 1- (alkoxy) dialkyl-substituted silacycloalkanes. Specific examples of particularly preferable compounds among these compounds are shown below, but are not limited thereto. In addition,

"2, n-" refers to the 2nd and nth positions, and the nth position refers to the position of the carbon atom facing the 2nd position adjacent to the key atom.

1, 1 bismethylaminosilacyclobutane, 1, 1 bis (methylamino), 1, 2, 4-dimethylsilacyclobutane, 1, 1-bis (methylamino), 1 2-methyl-1, 4-dimethylsilacyclobutane, 1, 1 One screw (Methylamino) 1 2,4-jetyl silicic acid butane, 1, 1 bis (methylamino) 1 2, 4-tetramethylsilacyclobutane, 1, 1 bis Bis (methylamino) silacyclopentane, 1, 1 1 Bis (methylamino) 1,2,5-dimethylsilicic acid pentane, 1,1 One bis (methylamino) 1,2,5-Deethylsilacyclopentane, 1,1-bis (methylamino) 1-2-methyl-5 —Ethylsilacyclopentane, 1,1 bis (methylamino) 1,2,5-tetramethylsilacyclopentane, 1,1 bis (methinoreamino) 2—Chenolere 5—Probil silicic acid pentane, 1,1 bis (methylamino) ) Silacyclohexane, 1,1-bis (methylamino) -1,6-dimethylsilacyclohexane, 1,1-bis (methylamino) 1-2,6-jetylsila Chlohexane, 1,1-bis (methinoreamino) 1-methinoleyl 6-ethinoresilacyclohexane, 1,1-bis (methylamino) -1-2-ethyloyl 6-propyl silaic hexane, 1, 1 Bis (methylamino) 1,2,6-tetramethylsilacyclohexane, 1,1 bis (methylaminosila) cycloheptane, 1,1_bis (methylamino) 2,7-dimethylsilicic heptane, 1, 1-bis (meth / reamino) 1,2,7-jeti_resilacycloheptane, 1,1 bis (methinoreamino) 1 2-methyl-7-ethinoresilacycloheptane, 1,1-bis (methylamino) ) _2-Ethyl 7-Probyl silicic heptane, 1, 1 bis (ethylamino) silacyclobutane, 1, 1 bis (ethylamino) 1, 2, 4-dityl silacyclobutane, 1, 1 Bis (ethylamino) 1-2-4-Jetylsilacyclobutane, 1, 1 Bis (methylamino) Silacyclopentane, 1, 1 Bis (ethylamino) 1, 2, 5-dimethyl silicic acid pentane, 1, 1 bis (ethylamino) 1 2,5-tetramethylsilacyclopentane, 1,1 bis (ethylamino) 1 2,5-decylsilacyclopentane, 1,1 bis (ethylamino) 2-Methyl-5-ethylsylcyclopentane, 1,1-bis (ethynoleamino) 1-2-Ethylsilacyclopentane, 1,1-bis (ethylamino) silacyclohexane, 1,1-bis (ethylamino) ) 1,6-Dimethylsilacyclohexane, 1,1 bis (ethylamino) — 2, 6-Jetylsilacyclohexane, 1,1 bis (ethylamino) 1 2-methinole 6-ethinoresila Cyclohexane, 1, 1 bis (ethynoleamino) 1 2-Ethyl 6-Probylsilacyclohexane, 1, 1-bis (ethylamino) Silacycloheptane, 1, 1 bis (ethylamino) _ 2, 7-dimethylsilacycloheptane, 1,1 bis (ethylamino) _ 2,7-jetylsilacycloheptane, 1,1-bis (ethylamino) 1-2-methyl-7-eth Noresilla cycloheptane, 1, 1 bis (ethyl amino) 1 2- ethyl 7-propyl silicic heptane,

1 1 (Methylamino) 1 1- (Methoxy) Silacyclobutane, 1 1 (Ethylamino) 1 1 1 (Methoxy) Silacyclobutane, 1 1 (Propylamino) 1 1 1 (Ethoxy) Silacyclobutane, 1 1 ( (Phenylamino) 1 1 1 (Ethoxy) Silacyclobutane, 1 1 (Methylamino)-1 1 (Methoxy) Silacyclopentane, 1 1. (Ethylamino) 1 1— (Ethoxy) Silacyclopentane, 1 1 (Propylamino) 1 1 1 (methoxy) sila cyclopentane, 1 1 (ethylamino)-1 1 (ethoxy) silacyclohexane, 1 1 (propylamino) 1 1 1 (ethoxy) silacyclohexane,

1— (Methylamino) 1 1 1 (Methoxy) 1 2-Ethylsilacyclobutane, 1— (Ethylamino) _ 1— (Methoxy) — 2— t 1-Putylsilacyclobutane, 1 — (Propylamino) 1 1 1 ( Ethoxy) 1 2-Isopropyl Silacyclobutane, 1 1 (Phenylamino) 1 1 — (Methoxy) 1 2- Ethylsilacyclobutane, 1 _ (Methylamino) 1 1 1 (Methoxy) 1 2— pCT / JP2007 / 073427 Dimethylaminosilacyclobutane, 1- (Methylamino) 1 1- (Methoxy) 1 2-Jetylaminosilacyclobutane, 1-1 (Ethylamino) 1 1 1- (Methoxy) 1 2-Putylmethyl Silacyclobutane, 1- (Methylamino) -1 1- (Methoxy) -1 2,4-Dimethylsilacyclobutane, 1- 1 (Ethylamino) -1- 1- (Methoxy) -1 2,4-Dimethylsilacyclobutane, 1- 1 (Propylamino) 1 1- (ethoxy) 1 2,4-dimethylsilacyclobutane, 1 1 (methylamino) 1 1 1 (methoxy) 1 2, 4 -jetyl silashi clobutane, 1— (ethylamino) 1 1 1 (methoxy) ) 1,2,4-Propylsilacyclobutane, 1- (Propylamino) -1- (Methoxy) -2,4-Deethylsilacyclobutane, 1-1 (dimethylamino) 1-1- (ethyl) ) 1 2-Ethyl 4-methyl silaic butane, 1 1 (Ethylamino) 1 1- (Methoxy) 1 2-Ethyl 4 4-soprovir silacyclobutane, 1 1 (Polypyramino) 1 1- (Ethoxy) 1 2- Ethyl 4-butyl silicic mouth Butane,

1 1 (Methylamino) 1 1 1 (Methoxy) 1 2 -Methylsilicic acid pentane, 1 1 (Ethylamino) 1 1-(Methoxy) 1 2 -Ethylsilicic acid pentane, 1-(Propylamino) 1 1 1 (Ethoxy ) 1-2-ethyl silaic pentane, 1- (methylamino)-1 1 (methoxy) 1 2, 5-dimethylsilacyclopentane, 1 1 (methylamino) 1 1 1 (methoxy) 2-dimethyl 5-pentapentane 1 1 (methylamino) 1 1 1 (methoxy) 1 2, 5-tetramethylsilacyclopentane, 1 1 (ethylamino) 1 1 1 (methoxy) 1 2, 5 -jetylsilacyclopentane, 1 — (Methylamino) 1 1 1 (Methoxy) 1 2, 5 — Di 1 t 1 butyl silicic-pentane, 1 1 (Ethylamino) 1 1- (Methoxy) 1 2, 5-tetraethylsilashi crope Tan, 1- (Mechiruamino) Single 1 i (ethoxy) Single 2- Echiru one 5 - methyl silacyclopentane, 1 i (Echiruamino) Single 1 i (ethoxy) FCT / JP2Q 07/073427 1-2-ethyl-5-isopropyl silicic acid pentane, 1- (propylamino) 1 1- (methoxy) 1 2-ethyl-5-butyl silicic acid pentane,

1-(Methylamino) 1 1 1 (Metoxy) 1 2 -Dimethylsilacyclohexane, 1 1 (Methylamino) 1 1- (Methoxy) 1 2-t 1-Ptylsylcyclic mouth hexane, 1- (Ethylamino) 1 1-(Methoxy) 1 2-Isobutyl Silicic Hexane, 1 1 (Propylamino) 1 1 1 (Ethoxy) 1 2-Ethyl Silicic Hexane, 1 1 (Methylamino) 1 1- (Methoxy) 1 2 — T-Butylaminosilane mouth hexane, 1 1 (ethylamino) 1 1 1 (methoxy) 1 2-isobutylaminosilane mouth hexane, 1 1 (methylamino) 1 1— (methoxy) 1 2,6-Dimethylsilacic hexane, 1 1 (Ethylamino) 1 1 1 (Methoxy) 1 2,6—Jetylsilicic hexane, 1 1 (Propylamino) 1 1 1 (Ethoxy) 1 2, 6— Dimethylsilashiku Heki Sun, 1 1 (Methylamino) _ 1— (Ethoxy) 1 2, 6 — Jetyl Silacyclohexane, 1 1 (Propylamino) 1 1 1 (Ethoxy) 1 2, 6 — Jetyl Silacyclohexane, 1 1 (Methylamino) ) 1 1 1 (Methoxy) 1 2 -Ethyl 6-Methino Resilacea Hexane, 1 1 (Ethylamino) 1 1-(Metoxy) 1 2 -Ethyl 1 6-Isoprovir Sila 1 1 (Propylamino) 1 1 _ (Etoxy) 1 2 -Ethyl 1 6-Peptinolecyl

In the above general formula (2), X is a secondary amino group in which a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms is bonded to the N atom, or 1 carbon atom Preferred is a linear or branched alkyl group having ˜10 or an alkoxy group having a C 1-4O alkyl group bonded to an oxygen atom, and a linear or branched chain having 丄 to 丄 0 carbon atoms. An alkyl group is preferable, R ^{4 to} R ^ ¾, each of which is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and n is preferably an integer of 2 to 8.

R ⁴ and R ⁵ are preferably bonded to each other to form a ring.

The compound of the general formula (2) is more specifically described as follows: 1, 1-bis (alkylamino) 1 2-alkyl, n-aza (N-alkyl) silacycloalkanes, 1, 1 bis ( Alkylamino) _ 2-dialkyl, n-aza (N-alkyl) silacycloalkanes, 1, 1 bis (alkylamino) 1 2-dialkyl, n-aza (N-cycloalkyl) silicic al 1 1 (alkylamino) 1 1 1 (alkylalkoxy) — 2 -alkyl, n-aza (N-alkyl) silicic one, 1-(alkylamino) 1 1-(alkylanoleco) Xyl) 1-dialkyl, n-aza (N-alkyl) silacycloalkanes, 1 _ (alkylamino) 1 1 1 (analkyloxy) 1 2-anolequinole, n-aza (N-cycloalkyl) sila Cycloalkanes And the like. Among these compounds, particularly preferred compounds include the following compounds 1 to 57, but are not limited thereto.

3 14 15

16 17

23 24 25 26

SI

8 ^ L 9

9 ε s ε

00Ζ990 / 800Ζ OAV

50 51

52 53 54

In the general formula (3), X is a secondary amino group having 1 to 10 carbon atoms or a straight chain or branched alkyl group having 4 to 10 carbon atoms or a quaternary alkyl group having 4 to 10 carbon atoms bonded to the N atom, A linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxy group having an alkyl group having 4 to 10 carbon atoms bonded to an oxygen atom is preferred, and R ¹ is a linear or branched chain having 1 to 10 carbon atoms. R ⁶ and R ⁷ are each preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and n is preferably an integer of 2 to 8.

The compound of general formula (3) is more specifically described as follows: 1,1-bis (alkylamino) 1, 2, n_diaza (N, N, monodialkyl) silacycloalkanes, 1,1-bis (alkylamino) 1) 2-aza (N-alkyl), n-aza (N—H) silacycloalkanes, 1,1-bis (alkylamino) 1-2-aza (N-alkyl), n-a The (N-Silk alkyl) Silacycloalkane, 1 1 (Alkylamino) 1 1- (Alkyl arco P

Xyl) 1, η-diaza (Ν Ν, -dialkyl) silacycloalkanes, 1 1 (alkylamino) 1 1- (alkylalkoxy) 1 2-aza (Ν-alkyl), η-aza (Ν — Η) Silacycloalkanes, 1- (alkylamino) 1-2-aza (Ν-alkyl), η-aza (Ν-cycloalkyl) sila cycloalkanes, Among these compounds, particularly preferred compounds are The following compounds 5 8 1 3 1 may be mentioned, but are not limited thereto. '

8T

6 9 8 9 L 9

9 9 S 9 9

ε 9 Ζ 9 Τ 9

.0 / .00Zdf / X3d 00Z990 / 800Z OAV

7 3 7 4 7 5

7 6 7 7 7 8

7 8 0 H ₃ C

8 2 8 3 8 4

8 5 8 6 8 7

8 8 8 9

93 94 95

96 9 7 9 8

99 1 00 1 0 1

02 03 04

1 05 1 0 6 107 zz

6 ΐ 8 ι τ Z ΐ

9 Τ Τ 3 Τ I

^ K ^ O / i002dP / 10d

LZ £ L0 / L00ZdT / 13d 00Z990 / 800Z OAV JP2007 / 073427

129 130 131 These compounds can be easily synthesized by a known synthesis method such as a chlorine exchange method, a method using an organolithium compound, a method using a Darrier reagent, or a combination thereof. It is.

The catalyst for olefins polymerization of the present invention is one or more silacycloalkane compounds selected from the above general formulas (1) to (3) (hereinafter sometimes referred to as “component (C)”). Preferably, in addition to component (C), solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) and organoaluminum compound (B) (hereinafter simply referred to as “component (B)”) It is formed from).

“Component (A) J of the catalyst for polymerizing olefins of the present invention contains magnesium, titanium, halogen and an electron-donating compound, and includes (a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) An electron donor compound can be obtained by contact. Examples of the component (a) may include dihalide magnesium, disimagnesium, diallyloxymagnesium, halogenated alkoxymagnesium or fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, dialkoxymagnesium is particularly preferable, and specifically, dimethoxymagnesium, diethoxymagnesium, Examples include dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like, and methoxymagnesium is particularly preferable.

These dialkoxymagnesiums may be obtained by reacting magnesium metal with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.

Furthermore, dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the resulting polymer powder during the polymerization operation is improved. Problems such as clogging of the filter in the polymer separator caused by the fine powder contained in the water are solved.

The spherical dialkoxymagnet is not necessarily spherical, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio of the major axis diameter L to the minor axis diameter W (L / W) is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. is there. _a The average particle diameter of the dialkoxymagnesium may be 1 to 200 m. Preferably, it is 5 to 1500 _μm . In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μπι, and more preferably 10 to 40 μm. As for the particle size, it is preferable to use a particle having a small particle size distribution and a small particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, the particle size distribution is expressed as D 90 / D 10 (where D 90 is the cumulative particle size at 90%, and D 10 is the cumulative particle size at 10%). Less than, preferably less than 2.

The method for producing the spherical dialkoxymagnesium as described above is disclosed in, for example, Japanese Patent Publication No. Sho 5 8-4 1 3 2, Japanese Patent Publication Sho 6 2-5 1 6 3 3, Japanese Patent Publication Hei 3 7434 1, Examples are disclosed in Japanese Patent Application Laid-Open No. Hei 4 3 6 8 3 91 and Japanese Patent Application Laid-Open No. 8-7 3 388.

The tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used in the preparation of component (A) in the present invention is represented by the general formula T i (OR ⁹ ) mX _{4 —} _m ( In the formula, R ⁹ represents an alkyl group having carbon number !! ~ 4, X represents a halogen atom, and m is an integer of 0≤m≤4.) Titanium halide or alkoxy titanium halide group represented by One or more compounds selected from the group consisting of

Specifically, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other titanium tetrahalides are used as titanium halides, and methoxytitanium trichloride and ethoxytitanium trichloride are used as alkoxytitanium halides. , Propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, di Ethoxytitanium dichloride, dipropoxytitanium dichloride, g-n-butoxytitanium dichloride, trimethoxytitanium chloride, 1, reethoxytitanium chloride, tripropoxytitanium chloride, tri

Examples include _n_butoxy titanium chloride. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

The electron-donating compound (hereinafter sometimes simply referred to as “component (c)”) used in the preparation of the solid catalyst component (A) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, isocyanates, S i—o _ c bonds or S i Organosilicon compounds containing one N—C bond. Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol monole, methyl ether, ethyl ether, propyl ether, petitnole etherenole, aminole Etherol, diphenenole etherol, 9,9_bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1, ethers such as 3-dimethoxypropane, methyl formate, ethyl acetate, butyl acetate, Propyl acetate, Otyl acetate, Cyclohexyl acetate, Ethyl propionate, Ethyl butyrate, Ethyl benzoate, Propyl benzoate, Ptyl benzoate, Octyl benzoate, Cyclohexyl benzoate, p-toluic acid Methyl, p-toluic acid ethyl, annic acid Monocarboxylic acid esters such as chill, varnished ethinole, etc. Jetyl acid, disobutinorebromoma Jetinole acid, Diisopromalonate Jetinole, Dibutinoremalonate Jetinole, Diisobutinoremalonate Jetinole, Diisopentinoremalonate Jetinole, Isopropylbutylmacrolate Jetyl, Isopropylisopentylmatonate Dimethyl, Bis (3 —Black mouth n-propyl) Jetyl malonate, Bis (3-Promo n-propyl) Jetinore malonate, Jetyl maleate, Diptyl maleate, Dimethyl adipate, Jetyl adipate, Dipropyl adipate, Dipropyl adipate Dicarboxylic acid diesters such as dibutyl adipate, disodecyl adipate, dioctyl adipate, diphthalate, phthalate diester derivatives, aceton, methinoreetizoleketone, methylbutylketone, aceto Ketones such as enone and benzophenone, acid chlorides such as phthalic acid dichloride, terephthalic acid dichloride, aldehydes such as acetate aldehyde, propion aldehyde, octyl aldehyde, benzaldehyde, methylamine, and ethylamine , Trypsylamine, piperidine, aniline, pyridine and other amines, olefinic acid amide, stearic acid amide, etc., acetonitrile, benzonitrile, trityl nitrile, etc. Nitryls, isocyanates such as methyl isocyanate, ethyl isocyanate, etc., phenolalenorecoxysilane, anoloxyalkyloxysilane, phenylalkylanolecoxysilane, cycloanolenoquinolenorecoxysilane , Cycloanolenoquinoaylalkylalkoxy Organosilicon compounds containing Si—O—C bonds such as silane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamino) dialkoxysilane, alkyl (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, An organosilicon compound containing a Si 1 N—C bond such as a cycloalkylaminotrialkoxysilane can be given.

Among the above electron donating compounds, esters, especially aromatic dicar ^ A> 1 Bonic acid diester is preferably used, and phthalic acid diester and phthalic acid diester derivatives are particularly preferred. Specific examples of these phthalic acid diesters include dimethyl phthalate, jetyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisoptyl phthalate, ethylmethyl phthalate, phthalate Methyl isopate pill, Ethyl phthalate (n-propyl), Ethyl phthalate (n-butyl), Ethyl butyl phthalate, Di-n-pentyl phthalate, Diisopentinole phthalate, Dineopentyl phthalate, Phthalic acid Dihexyl, di-n-heptyl phthalate, di_n-octyl phthalate, bis (2,2-dimethenohexynole) phthalate, bis (2-ethynolehexyl) phthalate, diphthalate 1-Nonyl, di-isodecyl phthalate, bis-phthalate (2,2-dimethylheptyl), phthalic acid n-butyl (isohexyl), phthalenolic acid n-butyl (2-ethynolehexinole), phthalate / renoic acid n-pentynole (hexyl), phthalate n-pentyl (isohexyl), isopentyl phthalate ( (Heptynole), n-pentyl phthalate (21-ethyl hexyl), n-pentyl (isononyl) phthalate, isopentyl phthalate (n-decyl), n-pentynole phthalate (undecyl), isopentyl phthalate (isohexyl) ), N-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (isonol), n-hexyl phthalate (n-decyl), n-heptinole phthalate ( 2-Ethylhexyl), n-heptyl phthalate

(Isononyl), n-heptyl phthalate (neo-decyl), phthalic acid

2-Ethylhexyl (Isonoel) is exemplified, and one or more of these phthalate esters are used.

As phthalic acid diester derivatives, one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are alkyl groups having 1 to 5 carbon atoms, or chlorine, bromine and fluorine. original

And those substituted with a halogen atom such as a child. The solid catalyst component prepared using the phthalate ester derivative as an electron-donating compound can further improve the effect of hydrogen amount on the melt flow rate, that is, the hydrogen response. Hydrogen added during polymerization Even if the amount is the same or small, the melt flow rate of the polymer can be improved. Specific examples include: 4) dineopentyl 4-methylphthalate, 4) dineopentylol, 4-ethyl phthalate, 4-5, dineopentyl dimethylphthalate, 4, 5 Di-1- _n- butyl, 4-necropentine dineopentyl phthalate, 4-dichlorobutyl phthalate, diisohexyl 4-chloro phthalate, 4-diisooctinole phthalenophthalate, 4-zetinore 4-bromophthalenoate, 4-dibromo phthalenoate di- Butinole, 4-bromophthalenoic acid dineopentinole, 4-bromophthalenoic acid disobutenole, 4-monobromophthalenoic acid disohexenole, 4-monobromophthalic acid diisooctyl, 4,5-dichlorophthalic acid diethyl, 4,5-dichlorophthalic acid di-n-butyl, 4 and 5 Hexyl Le acid diisopropyl, 4, 5-dichloro-phthalic acid Jiisookuchiru, but elevation Gerare, of which 4 _ Buromofutanore acid Jineopenchinore, 4 Buromofu Tal acid di n _ heptyl, and 4 Buromofutaru acid Jiisobuchiru is preferable arbitrariness.

In addition, it is also preferable to use a combination of two or more of the above esters. When the total number of carbon atoms of the alkyl group of the ester used is 4 or more compared to that of other esters, the esters are combined. This is desirable.

In the present invention, the above (a), (b), and (c) are brought into contact in the presence of a hydrocarbon compound (d) (hereinafter sometimes simply referred to as “component (d)”). The method of preparing component (A) by _r q Ά

Specifically, this component (d) has a boiling point such as toluene, xylene, ethylbenzene, hexane, octane, decane, cyclohexane, etc.

A hydrocarbon compound of 50 to 1500C is preferably used. These may be used alone or in combination of two or more.

A particularly preferred method for preparing component (A) in the present invention is to form a suspension from component (a), component (c), and hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A preparation method by bringing the mixed solution formed from b) and component (d) into contact with the suspension and then reacting it can be mentioned.

In the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. As a result, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer that has a siloxane bond (one S i—O bond) in the main chain, but is also referred to as silicone oil, and its viscosity at 25 ° C is 0.02 to 100 cm ² / s (2 to 1 000 centistos), liquid or viscous chain at room temperature, partially hydrogenated, cyclic or modified polysiloxane.

As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrene polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylsiloxane is used. Trisiloxane, otamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes are high-grade fats.

Examples include fatty acid group-substituted dimethylsiloxanes, epoxy group-substituted dimethylsiloxanes, and polyoxyalkylene group-substituted dimethylsiloxanes. Of these, decamethylenocyclopentasiloxane and dimethinorepolysiloxane are preferred, and decamethyl cyclopentasiloxane is particularly preferred. In the present invention, the component (a), (b), and (c), and if necessary, the component (d) or the component (e) are brought into contact with each other to form the component (A). The preparation method of component (A) is described. Specifically, the magnesium compound (a) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (b) or a hydrocarbon compound (d), and an electron-donating property such as phthalic acid diester. Examples thereof include a method of obtaining component (A) by contacting compound (c) and Z or a tetravalent titanium halogen compound (b). In this method, a spherical component having a sharp particle size distribution (A) can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, a solution or By forming particles by the so-called spray-drying method in which the suspension is sprayed and dried, the component (A) having a spherical shape and a sharp particle size distribution can be obtained.

The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture is removed. The contact temperature is the temperature at the time of contacting each component when contacting each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for denaturation treatment. When obtaining the above, a temperature range of 40 to 1300 ° C is preferable. If the temperature during the reaction is less than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if the temperature exceeds 130 ° C, the solvent used will evaporate. Is obvious

This makes it difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

A preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d). Method of preparing component (A) by reacting, or component (a) suspended in component (d), then contacting component (c) and then contacting component (b) A method for preparing the component (A) can be mentioned. Further, the component (A) thus prepared may be contacted with the component (b) or the component (b) and the component (c) again or multiple times to improve the performance of the final solid catalyst component. it can. In this case, it is desirable to carry out in the presence of the hydrocarbon compound (d).

A preferred method for preparing component (A) in the present invention is to form a suspension from component (a), component (c), and hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. ) And component (d) are brought into contact with the suspension, followed by reaction.

Preferred methods for preparing component (A) in the present invention include the following methods. A suspension is formed from the component (a), the component (c), and the hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (c) and the hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. The suspension is added to the mixed solution. Thereafter, the temperature of the obtained mixed solution is raised and the reaction process (primary reaction process) is performed. After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the washed solid substance is used as a solid product. Thereafter, the washed solid substance is further added with a component (b) and a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. — Operation at 20 to 100 ° C, raising the temperature, performing a reaction process (secondary reaction process), and washing with a liquid hydrocarbon compound at room temperature after the reaction is completed.

Component (A) can be obtained by repeating 10 times.

Based on the above, as a particularly preferred preparation method of the solid catalyst component (A) in the present invention, dialkoxymagnesium (a) is suspended in a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. Next, the tetravalent titanium halogen compound (b) is brought into contact with this suspension, followed by reaction treatment. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more of the electron donating compounds (c) such as phthalic acid diester is used. Contact at 20 to 130 ° C, and contact component (e) as necessary to carry out a reaction treatment to obtain a solid product (1). In this case, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. After washing this solid product (1) with a liquid hydrocarbon compound at room temperature (intermediate washing), the tetravalent titanium halide compound (b) is again added in the presence of the hydrocarbon compound. Contact at 0 0 ° C to carry out the reaction treatment to obtain a solid product (2). If necessary, intermediate washing and reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid catalyst component (A).

The ratio of each component used in preparing the solid catalyst component (A) varies depending on the preparation method-it cannot be roughly determined. For example, a tetravalent titanium halogen compound per mole of the magnesium compound (a). (B) Force SO. 5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.0 1 to 10 mol. , Preferably 0.001 to 1 mol, more preferably 0.02 to 0.6 mol, and hydrocarbon compound (d) force SO. 0 0 1 to 500 mol, preferably 0.00 1 to 1 0 0 mole, More preferably 0.05 to 10 monole, polysiloxane (e) force S 0.01 to; 1 00 g, preferably 0.05 to 80 g, more preferably 1 to 5 0 g.

Further, the content of titanium, magnesium, halogen atom, and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably 0.5 to 8.0% by weight of titanium, preferably 1.0 to 8.0 by weight ^_0/0, more this Masoku is 2.0 to 8.0 wt ^_0/0 magnesium 1 0-7 0% by weight, more preferably 1 0-5 0% by weight, particularly preferably 1 5-4 0 weight ^_0/0, more preferably 1 5 to 2 5% by weight, a halogen atom 20-90 wt%, more preferably 30-8 5 wt. / ₀ , particularly preferably 40 to 80% by weight, more preferably 45 to '75% by weight, and the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight. %, Particularly preferably 2 to 20% by weight in total.

As the organic aluminum Niumu compound used in forming the Orefin polymerization catalyst of the present invention (B), compounds der lever represented by the above general formula (2) is not particularly limited, as R ⁸ is And Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, p is preferably 2 or 3, and 3 is particularly preferred. Specific examples of such an organic aluminum compound (B) include triethylaluminum, jetylaluminum chloride, triisoptylaluminum, jetylalluminum promide, and jetylaluminum hydride. Two or more types can be used. Preferred are triethyl aluminum and triisobutyl aluminum.

In the presence of the catalyst for polymerizing olefins of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out. Olefins include ethylene, propylene, 1-pentene, 1-pentene, 4-methyl / _{n H} in H 1—pentene, bullcyclohexane, etc., and these olefins

These can be used alone or in combination of two or more. Above all, ethylene,

Propylene and 1-butene are preferably used. Particularly preferred is propylene

Ren. In the case of propylene, it can be copolymerized with other olefins.

You can. The olefins to be copolymerized include ethylene, 1-butene,

1-pentene, 4-methyl- 1-pentene, vinylol cyclohexane, etc.

Yes, these olefins can be used alone or in combination.

wear. In particular, ethylene and 1-pentene are preferably used. Propire

Copolymerization of ethylene with other olefins includes propylene and a small amount of ethylene.

Random copolymerization in a single step with the monomer as a comonomer,

Propylene homopolymerization in one polymerization tank), the second stage (second polymerization tank)

Copolymerization of propylene and ethylene in multiple stages (multistage polymerization tank)

A so-called propylene / ethylene block copolymer is typically used. This

In the random copolymer block copolymer, the catalyst of the present invention formed from the above component (A), component (B) and component (C) is also effective,

Good catalytic activity, stereoregularity and / or hydrogen response

In addition, the copolymerization properties and the properties of the resulting copolymer are good.

In the present invention, the above components (A), (B) and (C)

In order to further improve the catalyst performance of the catalyst formed from

(D) can be used in combination. Organosilicon compound of the above component (D)

As specific examples, di-n-propyldimethyloxysilane, diisopropyl

Mouth Pildimethoxysilane, G-n-Butyldimethoxysilane, G-n—

Butyljetoxysilane, t-Butyl (methyl) dimethoxysilane, t

1-Ptyl (Ethyl) Dimethyoxysilane, Dicyclohexyl Dimethoxy

Lan, cyclohexyl (methyl) dimethyoxysilane, dicyclopentyl

Dimethoxysilane, cyclopentyl (methyl) jetoxysilane, cycl PT / JP2007 / 073427 Mouth Pentinole (Ethinole) Dimethoxysilane, Shikuguchi Pentinole (Shikkuchi Hexyl) Dimethoxysilane, 3-Methylcyclohexyl (Cyclopentyl) Dimethoxysilane, 4-Methinorecyclohexinole (Cyclopentyl ^ /) Dimethoxysilane, 3 , 5-Dimethylcyclohexyl (pentyl) dimethoxysilane, bis (jetylamino) dimethoxysilane, bis (di-n-propylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t -Butylamino) Dimethoxysilane, Bis (dicyclopentylamino) Dimethoxysilane, Bis (Dicyclohexylamino) Dimethoxysilane, Bis (G-2-methylcyclohexamino) Dimethoxysilane, Bis (Isoxy) Reno) dimethyl Tokishishi orchid, bis (quinolinol) dimethyl Tokishishiran, bis (Echiru one _n - propyl Ruamino) dimethyl Tokishishiran, bis (E chill isopropyl § amino) dimethyl Tokishishiran, bis (Echiru n- Buchiruamino) dimethyl Tokishishiran, bis (Echiru (Isoptylamino) Dimethoxysilane, Bis (ethyl-t-butylamino) Dimethoxysilane, Bis (isobutyl-η-propylamino) Dimethoxysilane, Bis (ethyloctylpentylamino) Dimethoxysilane, Bis (ethylethylhexylamino) Dimethoxysilane, Ethyl ) Dimethyoxysilane, η-propyl (Diisopropylpyramino) Dimethyoxysilane, Isopropyl (Di-t-butylamino) Dimethoxysilane, Cyclohexyl ( Ethylamino) Dimethoxysilane, Ethyl (G-Butylamino) Dimethoxysilane, Ethyl (Perhydroisoquinolino) Dimethoxysilane, n-propyl (Perhydroisoquinolino) Dimethoxysilane, Isopropyl (Perhydroisoquinolino) Dimethoxysilane, n-Butyl (Droisoquinolino) dimethoxysilane, ethyl (perhydrodrocinolino) dimethoxysilane, n-propyl (perhydrodrocino) dimethoxysilane, isopropyl -Hydroxyquino) Dimethoxysilane, n-Butyl (Perhydroquinolino) Dimethoxysilane, Bis (Jetylamino) Diethoxysilane, Bis (Di-n-propynoleamino) Diethoxysilane, Bis (Gee n-Ptynoreamino) Dietoxysilane Bis (di-butylamino) Jetoxysilane, Bis (dicyclopentylamino) Dietoxysilane, Bis (Dicyclohexoxy-reamino) Jetoxysilane, Bis (G-methyl-2-hexylamino) Dietoxysilane, Bis (perhydroisoquinolino) diethoxy silane, bis (Pahi Dorokino Li Roh) diethoxy silane, bis (Echiru _n - Puropiruamino) diethyl Tokishishiran, bis (Echiruiso Puropiruamino) Jefferies Tokishishiran, bis (E N-Butylamino) Dietoxysilane, Bis (ethyl-isobutylamino) Jetoxysilane, Bis (ethyl-t-Butylamino) Jetoxysilane, Bis (Isobutyl-N-propylamino) Jetoxysilane, Bis (Ethylcycline Pentylamino) Jetoxysilane Bis (ethylcyclohexylamino) jetoxysilane, n-propyl (diisopropylamino) diethyloxysilane, ethyl (perhydroisoquinolino) diethoxysilane, n-propyl (perhydroisoquinolino) jetoxysilane, isopropyl (perhydroisoquinoline) ) Jetoxysilane, n_ptyl (perhydroquinoquinoline) Jetoxysilane, ethyl (perhydroquinoline) Dietoxysilane, n-propyl ( -Hydroxyquinoline) Jetoxysilane, Isopropyl (Perhydroquinoline) Jetoxysilane, n-Butyl (Perhydroquinoline) Dietoxysilane, Texyltrimethoxysilane, Jetylamino Trimethoxysilane, Di-n-propylamino Trimethoxysilane Di-n-butylaminotrimethoxysilane, di-tylaminotrimethoxysilane, dicyclopentylaminotrimethyoxysilane, dicyclohexylaminotrimethoxysilane, di-2-methyl _n „-PCT / JP2007 / 073427» «Hexylaminotrimethoxysilane, perhydroisoquinoline trimethoxysilane, perhydrodinotritrimethoxysilane, perhydrodolinotrimethoxysilane, jetinoreaminotrioxysilane, di-propylaminotriethoxysilane, Butinoreaminotriethoxysilane, ethyl-t-butylamino-triethoxysilane, ethyl-sec-butylaminotriethoxysilane, dicyclopentenoreaminotriethoxysilane, dicyclohexyleno-aminomino-trietoxysilane, di-2-methylcyclohexylaminotriethoxysilane Perhydroisoquinolino triethoxysilane, Perhydroquinoquinotriethoxysilane, Bis (t-Ptylamino) Dimethoxysilane, Bis (cyclohexa Silamino) Dimethyoxysilane, Bis (t_Butylamino) Diethoxysilane, Bis (Cyclohexylamino) Jetoxysilane, Trivinylmethylsilane, Tetravinylsilane, Methyl etherenole, Ethenoreethenore, Propinoreether, Petinoreethenore , Amyl ether, diphenyl ether, 9,9-bis (methoxymethinole) fluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and other etherols, bismethinoreaminodicyclic pentylsilane, bis Tinoleaminodioxy pentynolesilane, bismethylenodiamino hexylsilane, bisethylaminodicyclohexylsilane, bis (methylamino) bis (perhydroisoquinolino) silane, bis (ethylamino) B) Bis (perhydrobrominoquinoline) silane is preferably used, and the organosilicon compound (D) can be used alone or in combination of two or more.

In particular, in addition to the component (C) which is the catalyst component of the present invention, the component (D) described above is mixed and used, or the component (C) and the component (D) are separated in a block copolymerization multistage polymerization tank. It can also be used.

In particular, when shifting from homopolymerization of propylene to block copolymerization, , i 9 ^

In order to prevent the formation of diethyl in the final product, known electron donating compounds such as alcohols, oxygen gas or ketones can be added to the polymerization system. Specific examples of the alcohols include ethyl alcohol, isopropyl alcohol, and the like. The amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (B).

The amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, component (B) is 1 mol of titanium atom in component (A). It is used in the range of 1 to 200,000 moles, preferably 50 to 100,000 moles. Component (C) is used in the range of 0.002 to: L 0 mol, preferably 0.01 to 2 mol, particularly preferably 0.0: to 0.5 mol, per mol of component (B). . When component (D) is used in combination, 0.02 to 10 moles, preferably 0.01 to 2 moles, particularly preferably 0.01 to 0.5 moles per mole of component (B) In addition, it is used in a range of 0.001 to 10 mol, preferably 0.01 to 10 mol, particularly preferably 0.01 to 2 mol, per mol of component (C).

The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged in the polymerization system, and then the component (C) represented by the general formula (1) is contacted or mixed in advance. It is desirable to bring the solid catalyst component (A) into contact by contacting the component (C) with the component (D), or with the component (C) and the component (D) in any order. Alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are brought into contact with each other in advance. It is also a preferred embodiment that component (A) and component (C) or component (C) and component (D) are charged into the polymerization system to form a contact catalyst. In this way, by subjecting the component (A) and the component (B) or the component (C) and the component (D) to the contact treatment in advance, the hydrogen response of the catalyst and the crystallinity of the polymer produced can be improved. This can be further improved.

The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and an olefin monomer such as propylene can be used for polymerization in any state of gas and liquid. The polymerization temperature is 20 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 1 OMPa or lower, preferably 6 MPa or lower. Both continuous polymerization and patch polymerization are possible. Furthermore, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

Furthermore, in polymerizing olefins using a catalyst formed from the component (A), the component (B) and the component (C) in the present invention (also referred to as “main polymerization”), catalytic activity, stereoregularity In order to further improve the particle properties and the like to be generated, it is desirable to perform preliminary polymerization prior to the main polymerization. In the prepolymerization, the same olefins or monomers such as styrene as in the main polymerization can be used. Specifically, component (A;), component (B) and / or component (C) are contacted in the presence of olefins, and 0.1 to 100 g of polyolefin per 1 g of component (A) is reserved. Then, polymerization is carried out, and then component (B) and / or component (C) is contacted to form a catalyst. When component (D) is used in combination, component (A), component (B) and component (D) are brought into contact with each other in the presence of olefins during the preliminary polymerization, and component (C) is used in the main polymerization. You can also.

In performing the prepolymerization, the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set in an inert gas atmosphere or a gas atmosphere in which propylene is polymerized. Then, after contacting component (C) and Z or component (D) and then contacting component (A), olefins such as propylene and Z or one or more other olefins Contact The prepolymerization temperature is arbitrary, , «»

ϋΡώυυν / υνό 27 Although there is no particular limitation, it is preferably in the range of 1 ° C to 7 ° C, more preferably in the range of 0 ° C to 50 ° C.

When olefins are polymerized in the presence of the olefins polymerization catalyst of the present invention, high stereoregularity is maintained and hydrogen response is improved as compared with the case where conventional catalysts are used. In addition, the structure of component (C) improves the catalytic activity and stereoregularity compared to the case where a conventional catalyst is used. That is, when the catalyst of the present invention is used for the polymerization of olefins, the structure of component (C) maintains high stereoregularity, improves hydrogen response, and improves catalytic activity and stereoregularity. Was confirmed.

Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

(Example 1)

1,1,1-bis (ethylamino) 1,2,6-dimethylsilacyclohexane synthesis>

According to the synthesis method described in Polymer Bulletin 54, 377- 385 (2005), 0.2 mol of 1,1-bis (methoxy) -1,6-dimethylsilacyclohexane was synthesized. did. Using this part, the following synthesis was advanced. Separately, 0.1 mol of a monolithium salt of ethylamine was prepared by a reaction between a hexane solution of butyllithium and a THF solution of ethylamine. 1, 1 bis (methoxy) 1, 2, 6-dimethyl silaic hexane Take 0.05 ml of toluene solution containing 0.5 mol of toluene and replace with nitrogen gas, cool to o ° c, Using a syringe, 0.1 mol slurry of the prepared lithium salt of ethylamine was gradually added under a nitrogen stream. After the addition was completed, the reaction temperature was gradually raised, and the reaction was carried out at 60 ° C for 3 hours. After completion of the reaction, the reaction mixture is separated into a solid and a solution by centrifugation. The solvent was distilled off by distillation, and the temperature was raised to fractionate a 1,1,1-bis (ethylamino) -1,6-dimethylsilacyclohexane fraction. Elemental analysis of C, H, N of the obtained fraction was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 59. 9 1% (5 9. 93%), H; 1 2. 07% (1 2. 07%), N; 1 3. 99% (1 3. 98%)

(Example 2)

The same method as in Example 1 except that the THF solution of methylamine was used instead of the THF solution of ethylamine and that the reaction was performed at 60 ° C for 2 hours instead of the reaction at 60 ° C for 3 hours. To obtain a fraction of 1,1 bis (methylamino) -1,2,6-dimethylsilacyclohexane. Elemental analysis of C, H, and N of the obtained fraction was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 58. 0 1% (58. 00%), H; 1 1. 92% (1 1. 90%), N; 1 5. 00% (1 5. 03%)

(Example 3)

<1, 1 Monobis (methylamino) 1 2-Methyl-5-aza (N-methyl) Silacyclopentane synthesis>

Commercially available 1-methyl-1-trimethoxysilyl-3-methylaminopropan was purified by distillation, dehydrated while being kept in a molecular sieve (3A) under a nitrogen stream, and dried. Prepare a toluene solution containing 0.1 mol of 1-methyl-1-trimethoxysilyl-3-methylolaminopropane in a nitrogen gas stream, cool to _10 ° C, and add commercially available butyllithium hexane solution. 0.1 mol was slowly poured into a nitrogen atmosphere using a dropping funnel. Thereafter, the temperature was gradually raised and reacted at 40 ° C for 2 hours. After the reaction, the solid and the solution were separated by centrifugation under a nitrogen stream. The solvent is then removed under reduced pressure PGIJP2Q 07/073427 Distilled off and purified by distillation under reduced pressure at elevated temperature to obtain multiple components. By controlling the temperature, the product was purified by distillation under reduced pressure, yielding the desired 1,1,1-bis (methoxy) -1,2-methyl-1,5-aza (N-methyl) silacyclopentane component in a yield of 20 Obtained in%. Elemental analysis of the obtained fractions C, H, and N was performed, and the following results were obtained. Figures in parentheses are theoretical values. C ； 47. 94% (4

7.96%), H; 9.74% (9.77%), N; 7.97% (7.

99%)

Then, separately, by a conventional method, a methyllithium monolithium salt is obtained by reacting a hexane solution of butyllithium with a THF solution of methylamine.

02 moles were prepared. 1. Prepare a toluene solution containing 1,1 bis (methoxy) _2 methinoleol 5-aza (N-methinole) silacyclopentane 0.01 mole synthesized above, and fully replace with nitrogen gas The flask was taken up and cooled to o ° C under a nitrogen atmosphere. To this cooling liquid, 0.02 mol of methylamine monolithium salt was gradually added. After the addition was completed, the temperature was gradually raised and the reaction was carried out at 70 ° C for 3 hours. After the reaction, the solvent was distilled off under reduced pressure under a nitrogen stream, and the target 1,1-bis (methylamino) -2-methyl-5-aza (N-methyl) silicic acid pentane was purified by distillation under reduced pressure. Elemental analysis of the obtained fractions C, H, and N was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 48. 52% (48.5 1%), H; 1 1. 02% (1 1. 05%) _s N; 24. 23% (24. 24%) (Example 4)

<1, 1 Bis (methylamino) 1, 2, 6-Diaza (N, N, monodimethyl) Synthesis of Silacic Hexane>

1, 3 _bis (methylamino) monopropane A THF solution containing 0.1 mol of 10 Oml was placed in a flask thoroughly substituted with nitrogen gas under a nitrogen atmosphere. Cooled to C. Then 0.2 mol of commercially available butyl lithium The hexane solution contained was gradually added dropwise using a dropping funnel. After completion of the dropwise addition, the temperature was gradually raised and reacted at 30 ° C. for 2 hours to prepare a 0.1 mol slurry of lithium salt of 1,3-bis (methylamino) monopropane. Next, a toluene 20 Oml solution containing 0.05 mole of tetramethoxysilane that had been sufficiently dehydrated and dried under a nitrogen stream was fractionated into a flask that had been sufficiently replaced with nitrogen gas, and this was cooled to 0 ° C. . To this cooled solution, 0.1 mol of the above-mentioned N, N, dimethy / reethylenediamine amine lithium salt was gradually added under a nitrogen stream using a syringe. The temperature was gradually raised and reacted at room temperature for 2 hours and at 30 ° C for 3 hours. By making the reaction system sufficiently diluted, polymer formation was avoided. After completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure, the temperature was raised, and the product was separated and purified by distillation under reduced pressure. The elemental analysis values of C, H and N fractions of the obtained 1,1_bis (methoxy) -1,2,6-diaza (N, N, monodimethyl) silacyclohexane fraction were as follows. Figures in parentheses are theoretical values. C; 44. 1 6% (44. 18%), H; 9.5 1% (9.5 3%), N; 1 4. 70% (1 4. 7 2%)

Separately, 0.1 mol of methylamine monolithium salt was prepared by a reaction between a hexane solution of butyllithium and a THF solution of methylamine. 70 ml of toluene solution containing 0.02 mol of synthesized 1,1-bis (methoxy) -1,2,6-diaza (N, N, -dimethyl) siloxane hexane was sufficiently substituted with nitrogen gas Take to flask and cool to 0 ° C. To this cooling liquid, 0.04 mol of methylamine monolithium salt slurry was gradually added dropwise under a nitrogen gas atmosphere using a syringe. After completion of the dropwise addition, the temperature was gradually raised and reacted at 40 ° C for 3 hours. Next, the solid components are separated by centrifugation under a nitrogen gas atmosphere, the solvent is distilled off from the solution portion under reduced pressure, the temperature is raised, and the desired 1, 1-bis (methylamino) C) 1,2,6-Diaza (N, N, monodimethyl) silacyclohexane was purified by distillation under reduced pressure. Elemental analysis of C, H, and N of the obtained fraction was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 44. 6 2% (44. 64%), H; 1 0.7.70% (1 0. 70%), N; 2 9. 7 3% (2 9. 75%)

(Example 5)

1 1 (Ethylamino) 1 1- (Ethoxy) 1 2,5-Detylsilicic Synthesis of Pentane>

According to the synthesis method described in the literature of Polymer Bulletin 54, 3 7 7- 3 8 5 (200 5), 1, 1 bis (ethoxy) 1, 2, 5-jetinoresilacyclopentane 0 . 2 Monore synthesized. Using this part, the following synthesis was advanced. Separately, 0.05 mol of a monolithium salt of ethylamine was prepared by a reaction between a hexane solution of butyllithium and a THF solution of ethylamine. 1, 1 bis (ethoxy) 1, 2, 5- ethinoresilacyclopentane 0.05 Take a toluene solution containing monole in a flask thoroughly purged with nitrogen gas, cool to o ° c, then syringe Then, 0.05 mol slurry of the prepared lithium salt of ethylamine was gradually added under a nitrogen stream. After the addition was completed, the reaction temperature was gradually raised, and the reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, the reaction mixture was separated into a solid and a solution by centrifugation, and the solvent was distilled off by distillation under reduced pressure under a nitrogen atmosphere, and the temperature was raised. 1 1 (Ethylamino) 1 1 1 A fraction of (ethoxy) -1,2,5-jetyl silicic pentane was collected. Elemental analysis of the obtained fractions C, H, and N was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 6 2. 80% (6 2. 82%), H; 1 1. 85% (1 1. 86%), N; 6.1 2% (6.1 0%) (Example 6)

<1-(Ethylamino)-1 1 (Ethoxy) 1 2 _Methyl _ 5—Laza (N-methinole) silacyclopentane synthesis>

Synthesized in the same manner as in Example 3 except that 1-methyl-1-trimethoxysilyl-3-methylaminopropane was used instead of 1-methyl-1-trimethoxysilyl-3-methylaminopropane. (Ethoxy) 1-2-Methyl-5-aza (N-methyl) silacyclopentane 0.05 Prepare a 5-molar toluene solution, take it into a flask that has been thoroughly replaced with nitrogen gas, and place it in a nitrogen atmosphere at 0 ° Cooled to C. Separately, a 0.05 mol slurry of monolithium salt of ethylamine was prepared by a reaction between a hexane solution of butyl lithium and a THF solution of ethylamine. To the above cooled solution, 0.05 mole slurry of ethyl salt of ethylamine was gradually added under a nitrogen atmosphere using a syringe. After the addition, the temperature was gradually raised and reacted at 40 ° C for 3 hours. After completion of the reaction, the solid was separated from the solution by centrifugation under a nitrogen stream, and the solution part was separated. Next, the solvent was distilled off from the solution under reduced pressure, and the target compound 1 1 (ethylamino) _ 1 1 (ethoxy) 1 2 -methyl 1 5 -aza (N-methyl) sila cyclopentane was distilled under reduced pressure. And purified. Elemental analysis of the obtained fractions C, H and N was carried out, and the following results were obtained. Figures in parentheses are theoretical values. C; 53. 40% (53. 42%), H; 1 0.95% (1 0. 96%), N; 1 3.82% (1 3.84%)

(Example 7)

1- (Methylamino) 1 1 1 (Methoxy) _ 2, 6-Diaza (N, N, 1-dimethyl) Silacic Hexane Synthesis>

A toluene solution containing 0.02 mol of 1,1 bis (methoxy) _2,6-diaza (N, N, -dimethyl) silacyclohexane synthesized as in Example 4 was cooled to 0 ° C. did. Then, as in Example 4, Methylamine monolithium salt slurry (0.02 mol) was prepared and gradually added to the above toluene solution with stirring. After the addition was completed, the temperature was gradually raised and the reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, the solid was separated from the solution by centrifugal separation under a nitrogen stream, and the solution part was separated. Next, the solvent was distilled off under reduced pressure, and the target compound, 1- (methylamino) 1-1- (methoxy) 1-2,6-diaza (N, N, monodimethyl) silacyclohexane, was reduced in pressure. Purified by distillation. Elemental analysis of the obtained fractions C, H, and N was performed, and the following results were obtained. Figures in parentheses are theoretical values. C; 44. 40% (44. 41%), H; 10. 1 1% (1 0. 1 2%), N; 22. 1 7% (2 2. 1 9%)

(Example 8)

Preparation of solid catalyst components>

A round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas and having a volume of 200 Oml was charged with 150 g of methoxymagnesium and 750 ml of toluene to form a suspended state. The suspension was then added to a solution of 450 ml toluene and 300 ml titanium tetrachloride pre-loaded in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. did. The suspension was then reacted for 1 hour at 5 ° C. Thereafter, 21.5 ml of di-n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by reaction treatment with stirring for 2 hours. After completion of the reaction, the product was washed 4 times with 1300 ml of 80 ° C toluene, and 100 ml of toluene and 300 ml of titanium tetrachloride were newly added and stirred at 110 ° C. The reaction was carried out for 2 hours. The intermediate wash and the second treatment were repeated once more. The product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid component was measured and found to be 3.1% by weight. <Formation and polymerization of polymerization catalyst>

In an autoclave with an internal volume of 2.0 liters and completely replaced with nitrogen gas, triethylaluminum 1.32 mm o 1, 1, 1 bis (ethylamino) 1 obtained in Example 1, 2, A polymerization catalyst was formed by charging 0.13 mm o 1 of 6-dimethylsilacyclopentane and 0.0026 mm o l of the solid catalyst component as titanium atoms. Thereafter, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C for 5 minutes, then heated, and polymerized at 70 ° C for 1 hour. The obtained polymer, catalytic activity, bulk density (BD, g / m 1), heptane-insoluble portion (HI, wt ^_0/0), the melt flow rate in accordance with AS TM Merutoi Ndettasu (MI, g- PP / 1 0 min). The molecular weight distribution was measured as necessary. The results are shown in Table 1.

The catalytic activity is indicated by the amount of polymer produced per hour (g) of the polymerization time per 1 g of the solid catalyst component. Calculated by the following formula.

Catalytic activity = polymer produced (F) g / solid catalyst component g / 1 hour

Further, after drying this polymer, Gg was purified, and after continuous extraction with boiling n-heptane for 6 hours, the polymer (Hg) insoluble in n-heptane was dried and weighed. The percentage of boiling insoluble heptane insoluble matter (HI, weight. / ₀ )) was calculated from the following equation.

HI (weight%) = (H) g / (G) gxl The value of the melt index (Ml) indicating the melt flow rate of the OO polymer was measured in accordance with A STEM D 1 238 and JISK 72 10. The molecular weight distribution of the polymer is the ratio of the weight average molecular weight Mw and the number average molecular weight Μη determined by cross-fraction chromatography (CFC) (Mitsubishi Chemical Corporation CF CT-1 50 Β) under the following conditions: MwZMn Evaluated by.

Solvent: o-dichlorobenzene (ODCB)

Temperature: 140 ° C (S E C)

Column: Sho d e x GP C UT— 8 06M

Sample concentration: 4 gZ l i ter -ODCB (200 mg / 5 0 m 1 -OD C B)

Injection volume: 0.5ml

Flow rate: 1.0 m 1 / m i n

Measuring range: 0 ° C ~ 1 40 ° C

(Example 9)

1, 1-bis (ethylamino) 1, 2, 6-dimethyl silicic acid hexane Instead of 1, 1, 1-bis (methylamino) 1, 2, 6-dimethyl silicic acid hexane synthesized in Example 2 was used. The experiment was performed in the same manner as in Example 8 except that. The results obtained are shown in Table 1.

(Example 10)

1, 1-bis (ethylamino) -2,6-dimethyl 1,1-bis (methylamino) -1,2-methyl-5-aza (Ν—) synthesized in Example 3 instead of dimethylsiloxane Methyl) An experiment was conducted in the same manner as in Example 8 except that silacic mouth pentane was used. The results obtained are shown in Table 1.

(Example 1 1)

1,1-bis (ethylamino)-1,6-bis (methylamino) -1,2,6-diaza (Ν, N'-dimethyl) synthesized in Example 4 instead of 2,6-dimethylsilassic hexane ) The experiment was performed in the same manner as in Example 8 except that silacyclohexane was used. The results obtained are shown in Table 1.

(Example 1 2)

1, 1, 1 Bis (ethylamino) 1, 2, 6-dimethyl silicic acid 1- (Ethylamino) synthesized in Example 5 instead of hexane 7073427 The experiment was conducted in the same manner as in Example 8 except that 2,5-jetylsilacyclopentane was used. The results obtained are shown in Table 1.

(Example 1 3)

1, 1-bis (ethylamino) 1, 2, 6-dimethylsilacyclohexane 1 1 (ethylamino) 1 1 1 (ethoxy) 1 2-methyl-5-aza (N- Methyl) An experiment was conducted in the same manner as in Example 8 except that silacous-mouthed pentane was used, and the results obtained are shown in Table 1.

(Example 14)

1, 1 bis (ethylamino) 1 2, 6-dimethyl silicic acid Hexane instead of 1 1 (methylamino) 1 1 1 (methoxy) 1 2, 6-diaza (N , N, -dimethyl) An experiment was conducted in the same manner as in Example 8 using silacyclohexane. The results obtained are shown in Table 1. ■

(Example 15)

A 500 ml round bottom flask equipped with a stirrer and thoroughly replaced with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol. And reacted at 30 ° C for 2 hours to obtain a homogeneous solution. Next, 1.1 g of phthalic anhydride was added to the homogeneous solution and reacted at 1300C for 1 hour. The solution was then charged into 200 ml of titanium tetrachloride equipped with a stirrer and fully charged with nitrogen gas, charged in a 500 ml round bottom flask and maintained at 20 ° C. The whole amount was dropped over 1 hour. Next, the mixed solution was heated to 110 ° C. over 4 hours, and 2.68 ml of diisobutyl phthalate was added thereto and reacted for 2 hours. After completion of the reaction, the liquid part is removed by filtration, and the remaining solid component is washed at 110 ° C until no free titanium compound is detected with decane and hexane, filtered and dried to obtain a powdery solid Catalyst formation Got the minute. When the titanium content in this solid catalyst component was measured, 3.

1% by weight.

A polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The results obtained are shown in Table 1.

(Example 16)

Preparation of solid catalyst components>

A round bottom flask having a capacity of 100 Om 1 and equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 3 2 g of ground magnesium for Grignard. Next, a mixed solution of 120 g of butyl chloride and 500 ml of dibutyl ether was added dropwise to the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature, and the solid content was removed by filtration to obtain a magnesium compound solution. Next, a round bottom flask having a capacity of 5 O Oml, equipped with a stirrer and sufficiently substituted with nitrogen gas, was added 240 ml of hexane, 5.4 g of tetrabutoxytitanium and tetraethoxysilane 61.4. To the place where g was charged to obtain a homogeneous solution, the magnesium compound solution 15 Om 1 was added dropwise at 5 ° C. over 4 hours to react, and then stirred at room temperature for 1 hour. Next, the reaction solution was filtered at room temperature to remove the liquid portion, and then the remaining solid was washed with hexane 240 ml 8 times and dried under reduced pressure to obtain a solid product. Next, 8.6 g of the solid product was charged into a round bottom flask equipped with a stirrer and fully substituted with nitrogen gas and having a volume of 10 Oml, and further toluene 48 8 ml and phthalic acid. Disobutyl 5.8 ml was added and reacted at 95 ° C. for 1 hour. Thereafter, the liquid part was removed by filtration, and the remaining solid part was washed 8 times with 85 ml of toluene. After completion of washing, add 21 ml of toluene, 0.48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride to the flask, and 8 hours at 95 ° C. It was made to react between. After completion of the reaction, solid-liquid separation was performed at 95 ° C, and the solid content was washed twice with 48 ml of toluene.Then, treatment with the above-mentioned mixture of disobutyl phthalate and titanium tetrachloride was performed again under the same conditions, and The product was washed 8 times with 8 ml of xanane, filtered and dried to obtain a powdery solid catalyst component. The titanium content in this solid catalyst component was measured and found to be 2.1% by weight.

Formation of polymerization catalyst and polymerization>

Example No. Polymerization activity H I B D M I M w / M g -PP / g -cat. g / ml g / lOmin n Example 8 49, 100 97. 9 0. 44 150 4.3 Example 9 50, 800 97., 7 0. 44 91 5.1 Example 10 46, 000 98. 0 0 44 90 4.9 Example 11 42, 800 85. 0 0. 44 280 4.5 Example 12 49, 500 97. 1 0. 44 78 5. 0 Example 13 39, 800 97. 5 0. 44 75 5.1 Example 14 38, 000 98. 0 0. 44 58 4. 7 Example 15 32, 000 96. 6 0. 44 170 4. 6 Example 16 40, 100 97. 2 0. 44 140 5 . 1

From the above results, it can be seen that when a silacic mouth compound derivative containing a secondary amino group is used, a polymer with high stereoregularity can be obtained in good yield and the hydrogen response is good. PGT / JP 2007/073427 Industrial Applicability

The olefin-based polymerization catalyst of the present invention is able to maintain the high degree of catalytic activity of the polymer and the hydrogen response better than conventional catalysts. Therefore, the ability to reduce the amount of hydrogen used in the polymerization, the high activity of the catalyst, and the ability to maintain the activity can provide general-purpose polyolefins at a low cost, and the weight of highly functional olefins can be reduced. Usefulness is expected in the production of coalescence.

Claims

PGTJP2Q07 / 073427 Claims The following general formula (1)

(In the above formula, X is a secondary amino residue having 1 to 10 carbon atoms, a tertiary amino residue, an alkoxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group. R ¹ represents a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aralkyl group, or an aryl group, and R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, n is an integer of 1 to 20, R ² and R ³ or R ⁴ and R ⁵ may be bonded to each other to form a ring, and R ¹ ! ^ ⁵ may be the same or different.) General formula (2) below;

(In the above formula, X, R ¹ and n are the same as described above, R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, linear or branched alkyl groups having from ι to 20 carbon atoms, cycloalkyl groups, and aralkyl groups. Or R ¹ and R ^{4 to} R ⁶ may be the same or different.) Or the following general formula (3); PGT.JP2Q07 / 073427

(3)

(In the above formula, X, R ¹ and n are the same as above, R ⁶ and R ⁷ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group. ¹ , R ⁶ and R ⁷ may be the same or different.) A catalyst component for polymerizing olefins, which is represented by the following formula:

2. A catalyst for polymerizing olefins, characterized in that the catalyst component for polymerizing olefins according to claim 1 is formed as an essential component.

3. (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound,

(B) The following general formula (4); RA 1 Q ₃ _ p (4)

(In the formula, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 and p 3.) , and

(C) A catalyst for polymerizing olefins according to claim 1, which is formed from the catalyst component for polymerizing olefins according to claim 1.

4. The solid catalyst component is prepared by bringing a magnesium compound (A), a tetravalent titanium halogen compound (B), and an electron donating compound (C) into contact with each other. Catalyst for polymerizing olefins.

5. An olefin polymer comprising polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 2 to 4.

Manufacturing method.

6. The method for producing an olefin polymer according to claim 5, wherein the olefin polymer is a propylene polymer.