JPS63222177A - Bis(disubstituted cyclopentadienyl)zirconium dihalide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is substituent group on the cyclopentadienyl ring and 1-5C alkyl; R2<1>-C5H3 is disubstituted cyclopentadienyl; X is halogen) or formula II. EXAMPLE:Bis(1,2-dimethylcyclopentadienyl)zirconium dichloride. USE:A highly active catalyst component for polymerization of olefins used together with an aluminoxane expressed by formula III (R<2> is CH3, C2H5, C3H7 or C4H9; n is 4-20) or formula IV for homopolymerization of an alpha-olefin or copolymerization thereof with dienes, such as butadiene, or cyclic olefins, such as norbornene. PREPARATION:A disubstituted cyclopentadiene expressed by formula V is lithiated with a compound formula VI to provide a compound expressed by formula VII, which is then heated with a compound expressed by formula VIII in a solvent, such as tetrahydrofuran, at -20-100 deg.C to afford the compound expressed by formula I or temperature within 3 days or in a short period by heating.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to bis(2!!-substituted cyclopentadienyl) zirconium cybaride. be.

[Conventional technology and its problems]

Since it was discovered that a catalyst consisting of bis(cyclopentagenyl)zirconium dichloride and methylaluminoxane can polymerize olefins with high activity (Japanese Patent Application Laid-Open No. 1983-1989)
-19309 Publication, Makroho o1゜Chsm,
Rapid Co-un, Volume 4, 41
7 (1983)), various zirconium compounds have been investigated as catalyst components for olefin polymerization.

Examples of such zirconium compounds having a substituent on the cyclopentagenyl ring include bis(methylcyclopentagenyl)zirconium dichloride (J
, Cham, Soc, 0alton Trans.

805 pages (H2O2)), bis(pentamethylcyclopentadienyl)zirconium dichloride (J, A layer or.

Chem, Joc, vol. 100, p. 3078 (1978
)), (pentamethylcyclopentagenyl) (cyclopentagenyl) zirconium dichloride (J, Ame
r, Cbs'm.

Sec., Vol. 10Et, p. 8355 (1984)). However, a zirconium compound having two ligands having a disubstituted cyclopentadienyl group has not been synthesized so far.

Also, JP-A-80-35006, JP-A-80-3
5007, JP-A-80-35008, and JP-A-81-298008, the general formula (Os
R2) pRs(CsR2)N@Q3-p and Rs(C
There is a description of using a compound called 5Rs)2Ns6 as a catalyst, but regarding the synthesis method and physical properties of this compound,
There is no description at all.

(Object of the Invention) The present inventors conducted research to synthesize a zirconium compound having two of the above-mentioned 2-substituted cyclopentadienyl groups as ligands as a new compound useful as a catalyst component for olefin polymerization. We succeeded in obtaining this new compound using the synthetic routes of formulas (1) and (2) described below, and also confirmed through polymerization experiments that this compound is useful as a catalyst component for olefin polymerization.

As is clear from the above description, an object of the present invention is to provide a novel and useful compound and uses thereof.

[Structure of the invention]

The zirconium compound of the present invention has the following general formula: X represents a halogen atom) The compound of the present invention [■,] is a 2M-substituted cyclopentadienyl group ligand, and the following CI) and [II
] can take any of the following structures.

(However, R1, R2-C5H3 and (III
), RI is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ee-butyl group, tert
- A hydrocarbon group such as a butyl group or a pentyl group, preferably a methyl group or an ethyl group. Further, X is a halogen atom such as fluorine, chlorine, bromine, or iodine, and preferably chlorine.

The synthetic route of the compound (m) of the present invention can be abbreviated as follows.

R2-C3H5+ n-BuLi-(R2-C5H
3) + n -Butane --- (1),
1 2Ll (R2-C5H3) +ZrL-+(R2
-CsH3)2ZrX2+2LiX ・-(2)(
However, R', R2-C5H3 and X have the same meanings as above. ) For disubstituted cyclopentadiene, 1.2-R2CsHs
There are two types, both of which are included. Note that the method for producing this type of compound is known as follows. Namely, Bull, Soa, Chis.

Ft,, 21381 pages (11170), J, Cbam
, Soc, p. 1127 (1852).

Dingetrahedron, Volume 19, Page 19311 (1
9H), 1bid, vol. 21, p. 2313 (1985
) and lOrg, chem, vol. 38, 3111
7B (1971).

Such disubstituted cyclopentadiene can be lithiated with an alkyllithium and used in the next reaction as disubstituted cyclopentadienyllithium. Also, 28
! It can also be used as substituted cyclopentadienyl potassium or disubstituted cyclopentadienyl sodium.

For example, the ZrX4-Li(R2-CaB6) reaction is carried out using an ether, preferably tetrahydrofuran (OF) or 1,2-dimethoxyethane as a reaction solvent,
It can be implemented.

The reaction is carried out when the molar ratio of Li(R2-CaB6)/ZrX4 is between 1.11 and 3.0, especially between 2. The reaction temperature is preferably carried out in the range of Q to 2.4, -20 to 100
C, particularly preferably in the range of 0 to 30 C. The reaction is completed within 3 days if carried out at room temperature, but one reaction can be completed in a short period of time by heating. The produced compound (m) can be purified by recrystallization or sublimation.

The zirconium compound (m) according to the present invention exhibits excellent olefin polymerization activity in the presence of aluminoxane, and is a compound useful as a polymerization catalyst component. The aluminoxane used in the polymerization is generally.

RzAl-+0AJl+f-OAIRz (however, n is 4
-20, and R2 is a methyl group, an ethyl group, a propyl group, a butyl group, preferably a methyl group. ) and a cyclic aluminoxane represented by the general formula (where n and R2 have the same meanings as above). Methods for producing compounds of this type are known. It is important that the linear and cyclic aluminoxanes have a degree of polymerization of at least 6, particularly preferably 10 or more.

The olefins used in the polymerization reaction include ethylene,
Propylene, 1-butene, 4-methyl-1-pentene,
! -Hexene! - α-olefins such as octene can be mentioned, and two or more of these components can also be mixed and subjected to polymerization. The zirconium compound according to the present invention can be used in the polymerization of the above-mentioned α-olefins. In addition, it is also effective in copolymerizing the α-olefin with dienes such as butadiene, 1,7-octadiene, 1,4-hexadiene, etc., or cyclic olefins such as norbornene, dicyclopentadiene, etc. .

As the polymerization method, any of suspension polymerization, solution polymerization, and gas phase polymerization is possible. Polymerization solvents for liquid phase polymerization include aliphatic hydrocarbons such as pentane, hexane, octane, decane, and dodecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane, benzene, toluene, Aromatic hydrocarbons such as xylene, petroleum fractions such as gasoline, kerosene, and light oil are used. Among these, aromatic hydrocarbons are preferred.

The olefin pressure in the reaction system is normal pressure to 50 kg/c layer 2G, and the polymerization temperature is -50°C to 230°C, preferably -20°C.
Molecular weight adjustment during polymerization in the range of 0°C to 200°C can be carried out by known means such as temperature selection or hydrogen introduction.

There are no particular restrictions on the concentration and molar ratio of both the zirconium compound and aluminoxane components in the polymerization system according to the present invention, but preferably the Zr concentration is between 10-4 and 10-4.
The molar ratio of AI/Zr is preferably in the range of 100 or more, particularly 1000 or more.

〔Effect of the invention〕

According to the method of the present invention, a novel zirconium compound having two 2M-substituted dicyclopentadienyl group ligands can be obtained. If these zirconium compounds are used as catalyst components for olefin polymerization in olefin polymerization, excellent polymerization performance can be obtained.

〔Example〕

Next, the present invention will be specifically explained using examples.

Example 1 [Bis(1,2-dimethylcyclopentadienyl)zirconium dichloride J] All reactions were performed under an inert gas atmosphere. Moreover, the reaction solvent used was one that had been dried in advance. 1,2-dimethylcyclopentadiene 2.0% in a 500 Somi glass reaction vessel. (21 mmol) was diluted with 150 layers of tetrahydrofuran, and a 15% solution of n-butyllithium/hexane 181 was added dropwise at 0<0>C. After stirring at room temperature for 1 hour, the resulting solution of 1,2-dimethylcyclopentadienyllithium was cooled to 0° C., and 2.4 g (10 mmol) of zirconium tetrachloride was added in 5 portions.

The reaction solution was slowly warmed to room temperature and stirred for 12 hours. After removing the solvent from the yellow solution containing the white precipitate (LiC1) under reduced pressure, the product was sublimed (120 ~ b1 msHg).
Purified by drying to give white crystals of the desired product 0.25
g (yield 7%) was obtained. The physical properties of this compound are shown below; the IR spectrum was obtained by the KBr method, and the 1-NMRM spectrum was obtained by the CDCJ13 method (100NH2).

Melting point: 252-254℃ Elemental analysis value:
(C+J+sCu 2Zr) Calculated value (%): c;
48.2B, H, 5, 21 actual value (%): C, 4
8,10,)I; ! li, oeIR spectrum: Shown in FIG.

NNR spectrum: shown in Figure 2. Example 2 [Polymerization] 450 ml of purified toluene was placed in a SUS autoclave with an internal volume of 1.51 that was sufficiently purged with nitrogen, and methylaluminoxane (molecular weight 90!1) manufactured by Toyo Stouffer Φ Chemical ■ was added.
) 8.3 mmol and 0.02 mmol of bis(1,2-dimethylcyclopentadienyl)zirconium dichloride were sequentially added, and the temperature was raised to 50°C. Next, propylene was added to the mixture at a total pressure of 8 kg/cm2G. The polymerization was carried out for 4 hours by continuously introducing the polymer so as to maintain the same temperature. As a result, 300 g of atactic polypropylene was obtained. Catalytic activity was 164 kg/g Zr.

Example 3 [Bis(l,3-dimethylcyclopentadienyl)zirconium dichloride] All reactions were performed under an inert gas atmosphere. Moreover, the reaction solvent used was one that had been dried in advance. 500m
In a Jl glass reaction vessel, 4 g (38 mmol) of 1,3-dimethylcyclopentadiene L was diluted with 150 l of tetrahydrofuran, and 24 layers of a 15% solution of butyllithium/hexane were added dropwise at 0°C.

After stirring at room temperature for 1 hour, the resulting solution of 1,3-dimethylcyclopentadienyllithium was cooled to 0°C and
Zirconium chloride 3.5. (15 mmol) was added in 5 portions.

The reaction solution was slowly warmed to room temperature and stirred for 48 hours. The solvent was distilled off under reduced pressure from the yellow solution containing the white precipitate (LiC1), followed by extraction with methylene chloride 3001 and filtration. Concentrate the yellow filtrate, add pentane and cool to -30°C,
1.7 g of white crystals were obtained. The desired product (130-b 22%) was obtained from the crystals. The physical property values of this compound are shown below.The IR spectrum was determined by the KBr method, and the H-NNR spectrum was determined by the Croc13 method (100NH2).

Melting point: 175-176℃ Elemental analysis value:
(C+4HtslC1zZr) Calculated value (%): C;
4B, 2B, H; 5.21 Actual value (%): C;
48.45. H; 5.08 IR spectrum: 3rd
As shown in the figure.

Nl'lR spectrum: shown in FIG.

Example 4 [Polymerization] In a SUS autoclave with an internal volume of 1.51 which was sufficiently purged with nitrogen, 450 ml of purified toluene was added, and methylaluminoxane (molecular weight 909, manufactured by Toyo Stouffer Chemical) was added.
) 8.3 mmol and bis(l,3-dimethylcyclopentadienyl)zirconium dichloride 0.02
Millimoles were added one after another and the temperature was raised to 50°C.

Next, propylene was added to this at a total pressure of 8 Kg/c layer 2G.
The polymerization was carried out for 4 hours by continuously introducing the polymer so as to maintain the same amount of water. As a result, 450 g of atactic polypropylene was obtained. Catalytic activity was 248 Kg/g Zr.

[Brief explanation of the drawing]

Figures 1 and 3 show the following compounds! The R spectrum and FIGS. 2 and 4 show the NNR spectra of the following compounds. Figures 1 and 2: Bis(l,2-dimethylcyclopentagenyl) zirconium dichloride Figures 3 and 4: Bis(1,3-dimethylcyclopentagenyl) zirconium dichloride Procedural amendment 1. Display of the case 1985 Patent Application No. 54.367 2, Name of the invention Bis (disubstituted cyclopentadienyl) Zirconium cybaride 3, Person making the amendment Relationship to the case Patent applicant representative Sadao Nogi ( (1 other person) 4. Agent θ. The number of inventions will not increase due to the amendment. 7. Each column of the claims and detailed description of the invention of the specification to be amended, as well as the drawings. 8.Amendment details A and detail 4 will be corrected as shown. ■Correct the full text of the claims as shown in Attachment 1. ■9 The detailed explanation of the invention is corrected as follows. (1) Add "→" next to r n-BuLiJ on the second line from the bottom of page 5. (2) r 1,2-R2C3H4J on page 6, line 5
1.2-R2-cs H4, ie, corrected to ``. (3) After “and” on the 7th line of the same page, r 1,3-R2
-C5H4, ie, add ". (Delete rl, 3-R2-CsH4J on the 8th line of the same page. (5) r on the 2nd line of page 7, page 31178)
Corrected to page 9. (8) Delete "for example" in line 10 of the same page. (7) rH-NMRJ on page 12, line 10
Corrected to IIRJ. (8) Insert "sublimation" after "the crystal" on page 14, lines 7-8. (8) rH-NNRJ on the 10th line of the same page to rH-NNR
” is corrected. 80 Drawing will be corrected as follows. The entirety of Figures 1 and 3 is corrected as shown in Attachment 2. 3. Attached document (Full text of claims) 1 General rule Paper
(Figure 1.3) At least one separate copy (full text of claims) (1) Substituent of the following formula (I) or (n) (wherein R is on the cyclopentadienyl ring) an alkyl group having 1 to 5 carbon atoms, R2-C3H5 is 2
Bis(21-substituted cyclopentadienyl) zirconium cybaride represented by a substituted cyclopentadienyl group, X represents a halogen atom.

Claims (1)

[Claims] (1) The following formula [I] or [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (Tazushi, R ^1-C_5H_3 is a value substituent on the cyclopentadienyl ring, an alkyl group having 1 to 5 carbon atoms, R
^1_2 is a bis(2-substituted cyclopentadienyl) zirconium dihalide represented by a 2-substituted cyclopentadienyl group, and X represents a halogen atom.