JPS60130604A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin in good efficiency, by polymerizing an olefin in the presence of a catalyst comprising a specified transition metal compound, an aluminoxane and an organoaluminum compound. CONSTITUTION:An olefin is polymerized under conditions of a pressure of normal pressure -50kg/cm<2>G and a temperature of -50-200 deg.C in the presence of a catalyst comprising a transition metal compound of formula I (wherein Cp is cyclopentadienyl, M is Ti, Zr, or Hf, R<1> and R<2> are each H, a halogen, a 1-6C alkyl, or Cp), an aluminoxane obtained by reacting 1mol of a dialkylaluminum monochloride of formula II (wherein R<3> is methyl, or ethyl, and X<1> is a halogen) with 1-3mol of water, an organoaluminum compound of formula III (wherein R<4> is a 1-10C alkyl or cycloalkyl, X<2> is a halogen and m is 1-3) and, optionally, an electron-donating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins, and more particularly to a method for efficiently producing polyolefins such as polyethylene and polypropylene using a catalyst having a specific component composition.

Conventionally, a method using a so-called Ziegler catalyst has been widely known as a method for producing polyolefins, but a method using a polymerization catalyst consisting of a cyclopentagenyl compound of a transition metal such as titanium, zirconium, or hafnium and aluminoxane has also been proposed. (U.S. Patent No. 3)
, 242,099, JP-A-58-19309).

However, the aluminoxane used here has the drawbacks of poor production stability and insufficient performance stability. The present inventors further investigated this aluminoxane and found that halogen-containing aluminoxane, particularly aluminoxane obtained from dialkyl aluminum monohalides such as dimethylaluminum chloride, has excellent stability. The present inventors further discovered that polyolefins can be advantageously produced by using this aluminoxane and a specific organoaluminated compound17 in combination with a cyclopentadienyl compound of a transition metal7, leading to the completion of the present invention. .

That is, the present invention provides a method for producing a polyolefin by polymerizing an olefin in the presence of a catalyst, wherein (4) the general formula (Cp)2MR'R2...CD[
In the formula, Cp represents a cyclopentadienyl group, and M represents titanium, zirconium or hafnium. Also R'
, R2 each represent hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclopentagenyl group. ] A transition metal compound represented by

(B) General formula “AtR to Xl ... [■] [In the formula,
R3 represents a methyl group or an ethyl group, and Xl represents a halogen atom. ] Aluminum/xane obtained by reacting dialkylaluminum monohalide represented by water with water and (C) general formula AtR4mx23-m... [■] [wherein R4 is an alkyl group having 1 to 10 carbon atoms, cycloalkyl group, and X2 represents a halogen atom.

Moreover, m represents 1-3. The present invention provides a method for producing a polyolefin, which is characterized by using a catalyst containing an organoaluminum compound represented by the following as a main component.

The catalyst used in the method of the present invention is mainly the above-mentioned threat ①),
It consists of component (C). As mentioned above, component (4) of this catalyst is a transition metal compound represented by the general formula [1], that is, a transition metal compound having at least two cyclopentadienyl groups, and specifically, bis(
cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium methyl chloride, bis(cyclopentagenyl) zirconium chloride hydride.

Examples include bis(cyclopentagenyl titanium dichloride), bis(cyclopentagenyl) titanium methyl chloride, and Bia S(cyclopentagenyl) hafnium dichloride.

Next, component (B) is a dialkylaluminum monohalide represented by the general formula AtR'2X'C in which R5 and Aluminoxane produced by reacting dialkylaluminum monohalide with 1.0 to 3.0 moles of water using various methods has excellent production stability, and a catalyst containing this as component (B) has excellent production stability. It becomes highly active.

Next, component (C) is an organoaluminum compound represented by the general formula [m+], and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, triisobutylaluminum,
Trialkylaluminium compounds such as trioctylaluminum, diethylaluminum monochloride, diethylaluminum monochloride, diethylaluminium monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride.

Dialkylaluminum monohalides such as dioctylaluminum monochloride, or alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquipromide, )ethylaluminum sesquichloride, and further methylaluminum dichloride and ethylaluminum dichloride. Examples include monoalkylaluminum cibarides such as cyto, ethylaluminum dibromide, isoprobylaluminium dichloride, and isobutylaluminum dichloride.

In the method of the present invention, a premixed mixture of the above components (A), (B), and (C) may be supplied to the reaction system, or components (A), (B), and (C) may be supplied to the reaction system. They may be supplied separately.

In either case, the ratio of each component of the catalyst to be supplied to the reaction system is not particularly limited and may be determined appropriately depending on various conditions, but usually the total amount of aluminum in the components (B) and (C) is and (~ titanium, zirconium or
The ratio of hafnium is not particularly limited, but the former: the latter -1.
~10':l (atomic ratio), preferably 102-10':
1 (atomic ratio). Further, the ratio of the aluminoxane as the component (B) to the organoaluminum compound as the component (C) is Atr:latter = 0.3 to 3:1 (molar ratio), preferably 0.5 to 1.5: 1 (mole). It can be used within the range of

In the method of the present invention, olefin is used as a raw material, but
Examples of the olefin include ethylene, brohylene, butene-1, pentene-1, hexene-1, and styrene, but ethylene or propylene is mainly used. Further, ethylene and propylene may be copolymerized with other olefins.

In the method of the present invention, the above-mentioned (A), (B), (C
) components and, if necessary, components such as an electron-donating compound are added to the reaction system as a catalyst, and in the presence of these components, an olefin is introduced and polymerized to produce a polyolefin. The polymerization method and conditions at this time are not particularly limited, and include slurry polymerization and gas phase polymerization.

Both solution polymerization and continuous polymerization are possible.

Both discontinuous polymerizations are possible. The olefin pressure in the reaction system is from normal pressure to 50 to 4/ca G, and the reaction frequency is -50 to 4/ca G.
Molecular weight adjustment during polymerization to 200 DEG C., preferably 20 DEG to 150 DEG C. can be carried out by known means, such as temperature selection or hydrogen introduction. Further, the reaction time may be determined as appropriate, and for example, for ethylene, it may be from 1 minute to 1 hour, and for propylene, it may be from about 1 hour to 20 hours.

The method of the present invention as described above uses a specific aluminoxane as a component of the catalyst, so it is highly stable.
As a result, the reproducibility of catalyst preparation is good, and the polymerization reaction proceeds with good reproducibility, which is extremely advantageous in practice. Furthermore, since aluminoxane and organic aluminum are used together,
Only a small amount of aluminoxane is needed, and the catalyst has very high activity. In the case of polyethylene, the yield is 1000 Kf or more per hour of zirconium. In particular, as polypropylene, a high molecular weight atactic polymer can be obtained in high yield.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Production of aluminoxane Copper sulfate pentahydrate (CuSO4.5H20) pulverized in a ball mill for 2 hours in 100% toluene 9.38
A toluene solution containing 2 morphs of dimethylaluminum chloride at a concentration of 9.
7.5 tni (equivalent to 195 mmol) was gradually added dropwise, and the mixture was reacted at 20° C. for 24 hours. During this time, about 0
．． 1 mole of methane was evolved. Next, toluene is separated from this solution by F and removed, and chloroaluminoxane 5.
I got 82. This chloraluminoxane had a molecular weight of 580 as measured by the benzene freezing point depression method.

(2) For ethylene: 400 m/! of toluene in a stainless steel autoclave with an internal volume of 1 t! , 4.5 mmol of triethylaluminum, 4.5 mmol of the aluminoxane obtained in (1) above, and 0.003 mmol of bis(cyclopentadienyl)zirconium dichloride were added in this order, and the temperature was raised to 50°C. Next, ethylene was continuously introduced into this autoclave, and a polymerization reaction was carried out for 30 minutes while maintaining the total pressure at 8 Kf/cl G. After the reaction was completed, the catalyst component was decomposed with methanol and the produced polyethylene was dried.

The total weight of the obtained polyethylene was 148.22, and the catalyst activity was 1083 Kt/fZr11 hr.

Example 2 (1) Production of aluminoxane Copper sulfate, pentahydrate (CuSO4.5H20), which was ball milled in 100% toluene for 2 hours 14.1
? (56.2 mmol) was added to a toluene solution with a concentration of 2 mol/I of dimethylaluminum chloride.
Gradually drop 7.5mC (equivalent to 195 mm! J moles),
The reaction was carried out at 20°C for 24 hours. During this time, approximately 0.2
Moles of methane were generated. Next, by removing toluene from this solution separately from F, chloroaluminoxane 1
1. ．． I got 8 f. This aluminoxane had a molecular weight of 730 as measured by the benzene freezing point depression method.

(2) Polymerization of ethylene In Example 1 (2), the above (
4.5 ml of chloraluminoxane obtained in 1) was subjected to ethylene polymerization in the same manner as in Example 1 (2).

The yield of the obtained polyethylene was 30.5F,
The catalyst activity was 1337 Kg/t Zr-hr.

Example 3 400 g of toluene was placed in an autoclave with an internal volume of 1 t, and 400 g of toluene was added to the I:Iv3 aluminoxane obtained in Example 1 (1),
Add 5 mmol and 0.00 3 mmol of bis(cyclopentagenyl)zirconium dichloride to 3
After stirring for a minute, 4.5 mmol of triethylaluminum was added and the temperature was raised to 50C. Then, ethylene was continuously introduced into the autoclave, and the total pressure was increased to 8 Kp/cfI.
The polymerization reaction of ethylene was carried out for 10 minutes while maintaining the temperature at G. The yield of polyethylene obtained was 49.8? The catalyst activity was 1092 Kf/2.Zr-hr.

Example 4 4.5 mmol of toluene 40'0-trimethylaluminum in an autoclave with an internal volume of 1 t, Example 2 (1)
4.5 mmol of p-roalumutuxane obtained in 1 and 0.003 mmol of bis(cyclopentadienyl)luconium dichloride were added in this order, and the temperature was raised to 50°C. Then, ethylene was continuously introduced into the autoclave, the total pressure was maintained at 8V4/lr/IG, and the ethylene polymerization reaction was carried out for 10 minutes.

The yield of the obtained polyethylene was 5 5.3 9,
The catalyst activity was 1 2 1 2 Kg/fZrhr.

Example 5 Toluene 200m/! in an autoclave with an internal volume of lt! ,
Triethyl aluminum 1.8 mi! J mole, actual m example 2
1.8 mmol of chloroaluminoxane obtained in (1) and O. 006 mmol was added, and propylene was continuously introduced into the autoclave at room temperature to bring the total pressure to 8 Kq/
The polymerization reaction was carried out for 16 hours while maintaining cJc. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, molecular weight 3 1,0
00 7 tactical polypropylene 7.5f was obtained.

Comparative Example 1 (f'll 1) Polymerization was carried out in the same manner as in Example 1 (2) except that in (2), the amount of chloroaluminoxane used was 7.2 mmol and the polymerization reaction time was 1 hour. As a result, polyethylene was not obtained.

Comparative Example 2 Example 1 (2) except that 2 mmol of the chloroaluminoxane obtained in Example 2 (+), San 7, was used as the aluminoxane and the polymerization reaction time was 1 hour. Polymerization was carried out in the same manner as in 1(2). As a result, polyethylene was not obtained. □ Comparative Example 3 In Example 1 (2), no aluminoxane was used, the amount of triethylaluminum used was changed to 2 mmol, and bis(
Polymerization was carried out in the same manner as in Example 1 (2) except that the cyclopentadienyl) zirconium dihydride and the polymerization reaction time were changed to 1 hour. The yield of polyethylene obtained was 0.4f
The catalyst activity was 0.4 Kg/l·T1·hr.

Example 6 400-1 toluene and 3.25 mmol of toluethylaluminum were placed in an autoclave with an internal volume of 1 t, and Example 2 (
1) Add 3.25 mmol of fm or p-roalumituxane and 0.003 mmol of his(cyclopentagenyl)zirconium chloride hydride, and heat at 50°C.
The temperature rose to . Then, ethylene was continuously introduced into the autoclave, and the total pressure was maintained at 8 to 9/cdi G to conduct an ethylene polymerization reaction for 2 minutes.

The yield of the obtained polyethylene was 15. Of, and the catalyst activity was 1644'iy/y.Zr-hr.

Example 7 To an autoclave with an internal volume of 1 ton, 400 mmol of toluene, 10.0 mmol of triethylaluminum, and Example 2 (1
) and 0,001 mmol of bis(cyclopentadienyl)zirconium chloride hydride were added, and propylene was continuously introduced into the autoclave at 20° C. to bring the total pressure to 8 Kf/ad G. The polymerization reaction was carried out for 8 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 185v of atactic polypropylene was obtained.

Example 8 400 ml of toluene was added to an autoclave with an internal volume of 1 t. 4.5 mmol of triethylaluminum, Example 2 (l
4.5 mmol of chlorofluminoxane and 0 of bis(cyclopentagenyl)hafnium dichloride
009 mmol was added and the temperature was raised to 50°C. Then, ethylene was continuously introduced into the autoclave to bring the total pressure to 8Kq.
/ctdG, and the ethylene polymerization reaction was carried out for 1 hour. As a result, 135f polyethylene was obtained.

Example 9 Contents: 400 mmol of toluene, 9.0 mmol of triethylaluminum, Example 2 (1
) 9.0 mmol of chloroaluminoxane obtained in
and 0.018 mmol of bis(cyclopentagenyl)hafnium dichloride, and propylene was continuously introduced into the autoclave at 20 °C to bring the total pressure to 8 K.
The polymerization reaction was carried out for 8 hours while maintaining q/+JG. After the reaction, the catalyst component was decomposed with methanol and the resulting polypropylene was dried.

As a result, atactic polypropylene 1362 turned blue.

Patent applicant: Idemitsu Kosan Co., Ltd.

Claims (2)

[Claims] (1) In a method for producing polyolefin by polymerizing olefin in the presence of a catalyst, (N general formula (Cp)2M'R'R2C formula, Cp represents a cyclopentadienyl group, M is titanium , represents zirconium or hafnium. Also, R
1. R2 is hydrogen, halogen base seven carbons XB1 to 6, respectively
represents an alkyl group or a cyclopentagenyl group. ] A transition metal compound represented by (B) General formula AtR%X' [In the formula, R3 represents a methyl group or an ethyl group, and Xl represents a halogen atom. ] Aluminoxane obtained by reaction of dialkyl aluminum monohalide represented by and water and (C) general formula
AtR' 111X2S -m [wherein, R4 has 1 carbon number
~10 alkyl groups and cycloalkyl groups, and x2 represents a halogen atom. In addition, m represents 1 to 3. ] A method for producing a polyolefin, characterized by using a catalyst containing an organoaluminum compound represented by the following as a main component. (2) (A) The m-transfer metal compound is bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentagenyl)zirconium methyl chloride, etc. Bis(cyclopentagenyl) dilphenium chloride hydride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium methyl chloride or bis(cyclopentagenyl)
Claim 1 t which is hafnium dichloride
H method.