JPH03287611A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a stereoregular polymer in high yields in high catalytic activity by using a catalyst prepared by combining a titanium-containing solid catalyst component prepared by a specified process with an epoxy-p-menthane compound and an organoaluminum compound. CONSTITUTION:An olefin is polymerized by using a catalyst prepared by combining a solid catalyst component (A), prepared by suspending diethoxymagnesium in alkylbenzene, bringing the suspension into contact with titanium tetrachloride in an amount which corresponds to a volume ratio to the alkylbenzene of 1 or below, adding phthalic acid dichloride to the mixture at a temperature region of 80-125 deg.C, reacting the resulting mixture to obtain a solid substance, washing this substance with alkylbenzene, reacting this substance with titanium tetrachloride in an amount which corresponds to a volume ratio to the alkylbenzene of 1 or below in the presence of alkylbenzene and repeating this operation at least three times, with an epoxy-p-menthane compound (B) and an organoaluminum compound (C).

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention exhibits an unprecedentedly high activity when subjected to the polymerization of olefins, and also produces stereoregular polymers in high yields. This invention relates to a high-performance catalyst for polymerizing olefins that can be obtained in the following manner.

[Prior Art] Various solid catalyst components for polymerizing olefins comprising dialkoxymagnesium, titanium tetrachloride, and electron-donating compounds or catalysts for polymerizing olefins using the solid catalyst components have already been developed and proposed. There is.

For example, in JP-A-55-152710, it was discovered that in order to obtain high catalyst activity, a large amount of an organoaluminum compound must be used during polymerization, and that in order to control the molecular weight of the resulting polymer, In order to improve the drawback that the yield of stereoregularity of the resulting polymer decreases when hydrogen is added to the dialkoxymagnesium obtained by a specific operation, it is In the presence of sexual compounds,
A method for obtaining a catalyst component by contacting with a tetravalent titanium halide is disclosed.

Analysis from Example 2 specifically exemplifying this method reveals that dialkoxymagnesium is suspended in carbon tetrachloride,
Add ethyl benzoate and titanium tetrachloride at 5°C,
The suspension is stirred for 2 hours while maintaining the temperature at 75°C. The resulting solid valve was isolated and washed five times with iso-octane, then suspended in titanium tetrachloride at 80°C, stirred for 2 hours, and then washed five times with iso-octane to remove the solid catalyst component. I am getting . Example 1 shows an example in which this solid catalyst component was used in combination with triethylaluminum as a catalyst for polymerization of olefins.

[Problems to be Solved by the Invention] However, the solid catalyst component prepared by the method disclosed in JP-A-55-152710 has poor polymerization activity and stereoregular polymerization when used in the polymerization of olefins. It cannot be said that it shows sufficient performance in terms of yield and sustainability of activity.

Therefore, the present inventors solved the above problem in Japanese Patent Application Laid-open No. 108611/1983 by adding a diester of dialkoxymagnesium and an aromatic dicarboxylic acid to a halogenated hydrocarbon and treating it in a suspended state. Thereafter, they developed a catalyst for polymerizing olefins consisting of a solid catalyst component, a piperidine derivative, and an organoaluminum compound obtained by adding the suspension to a titanium halide and reacting the same, and developed a catalyst for polymerizing olefins that was excellent in terms of high activity and durability. succeeded in obtaining the characteristics. However, the industry has been demanding higher polymerization activity and stereoregular yield of the resulting polymer.

Therefore, the present inventors have arrived at the present invention as a result of intensive research in order to solve the problems remaining in the prior art, and propose it to the present invention.

[Means for Solving the Problems] That is, the present invention is characterized by replacing jetoxymagnesium (a) with alkylbenzene (b).
) and then brought into contact with titanium tetrachloride (C) in a volume ratio of 1 or less to the alkylbenzene (1)),
Next, phthalic acid dichloride (d) is added and reacted at a temperature range of 80"C to 125°C. The solid material obtained by this is washed with alkylbenzene, and then in the presence of alkylbenzene (b), the alkylbenzene 0
) with titanium tetrachloride (C) having a volume ratio of 1 or less, which is repeated three or more times, and an epoxy paramenthane compound and an organoaluminum compound. The purpose of the present invention is to provide catalysts for similar polymerizations.

In the preparation of the solid catalyst component of the present invention, jetoxymagnesium (a) (hereinafter simply referred to as (a) substance6)
) used to suspend alkylbenzene (
Examples of b) (hereinafter simply referred to as substance (b)) include toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, etc.

The usage ratio of phthalic acid dichloride (d) (hereinafter simply referred to as (d) substance) used in W8 production of the solid catalyst component of the present invention is 0 to 10 g of (a) substance.
．． It is in the range of 01 to 0.5-.

In addition, titanium tetrachloride (C) (hereinafter sometimes simply referred to as (C) substance) has a concentration of 1°08 per 1.0g of (a) substance.
or more, and (b) the volume ratio to the substance is 1 or less. It is necessary to use the substance (b) in such an amount that it can form a suspension with the substance (a).

The solid catalyst component of the present invention has a volume ratio of 1 or less to the (b) substance after suspending the (a) substance in the (b) substance.
c) The solid substance obtained by contacting with the substance and then adding and reacting the substance (d) at a temperature range of 80°C to 125°C is washed with alkylbenzene, and further (
It can be obtained by repeating the operation of reacting the (c) substance with a volume ratio of 1 or less to the (b) substance in the presence of the b) substance three or more times, at a temperature range of 80°C to 125°C. The reaction is usually carried out for a period of 10 minutes to 10 hours. The alkylbenzene used for the above cleaning is the above (b)
It can be the same as the substance or it can be different. The temperature during cleaning is not particularly limited, but 90℃ or higher,
Preferably it is up to the boiling point of the alkylbenzene used. Examples of alkylbenzenes used for cleaning include the above-mentioned (b).
Examples of substances include those listed as examples of substances.

Note that, prior to washing with this alkylbenzene, it is possible to perform washing with an organic solvent other than the alkylbenzene.

The solid material after this washing is then further processed (b)
React with the substance (c) in a volume ratio of 1 or less to the substance (b) in the presence of the substance.

The temperature at this time is not particularly limited, but is preferably in the range of 80°C to 125°C.
The duration ranges from 0 minutes to 10 hours. Suitable temperature ranges for each of the above reactions are determined as appropriate depending on the type of substance (b) used.

The above reaction is usually carried out under stirring using a container equipped with a stirrer.

Although it is not particularly necessary to suspend the substance 0) in the substance (b) at around room temperature, it is preferable because it is easy to operate and can be carried out using a simple device.

The solid catalyst component thus obtained can be used as n-
It is also possible to wash with an organic solvent such as hebutane. This solid catalyst component can be used as a catalyst for polymerization of olefins either as it is after washing or after being dried after washing.

Next, the catalyst for polymerizing olefins of the present invention using the above solid catalyst component will be explained.

The epoxyparamenthane compound (B) used in the catalyst of the present invention is preferably 1.4- or 1.8-epoxyparamenthane, but if these compounds have a substituent such as an alkyl group or halogen, It is also possible to use

Examples of the organoaluminum compound (C) used in the catalyst of the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum civalide, and mixtures thereof.

The organoaluminum compound (C) used in the catalyst of the present invention has a molar ratio of 1 to 1000 per mole of titanium atoms in the solid catalyst component (^), and the epoxy paramencun compound (B) has a It is used in a molar ratio of 0.01 to 0.5 per mole of the organoaluminum compound.

Polymerization can be carried out in the presence or absence of organic solvents, and the olefin monomer can be used in either gaseous or liquid form. Polymerization temperature is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0kg/am2・C or less, preferably 50kg/(to)
2.C or less.

Olefins to be homopolymerized or copolymerized using the catalyst according to the present invention include ethylene, propylene, 1-butene, 4
-methyl-1-pentene and the like.

[Operations and Effects of the Invention] When olefins are polymerized using the catalyst for olefin polymerization according to the present invention, the resulting polymer has extremely high stereoregularity.

In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem due to the capacity of the polymerization equipment, the capacity of the post-treatment process, etc., and the catalyst according to the present invention is extremely important in this respect. Has excellent properties.

Furthermore, the titanium tetrachloride used in the preparation of the solid catalyst component of the present invention is characterized in that it is used in an extremely small amount compared to conventional techniques. Titanium tetrachloride is a substance that is difficult to handle, as it reacts with oxygen and moisture in the air and turns into hydrochloric acid gas, emitting white smoke and a strong pungent odor. Reducing the amount of titanium used means lower costs, It offers significant benefits in the production of solid catalyst components, such as ease of operation and prevention of pollution sources.

Furthermore, since the catalyst according to the present invention exhibits a high activity that was completely unexpected in the past, the amount of catalyst residue present in the produced polymer can be kept extremely low, and therefore the amount of residual chlorine in the produced polymer can also be eliminated. The ash process can be reduced to such an extent that it is not required at all.

Moreover, according to the catalyst according to the present invention, the solid catalyst component i8I
! By not adding organic carboxylic acid esters or nitrogen compounds during polymerization using the solid catalyst component, it is possible to completely solve the major problem of odor adhesion to the resulting polymer.

Furthermore, the activity per unit time of conventional catalysts significantly decreases as the polymerization progresses, which is a common drawback of so-called high-activity supported catalysts, but the catalyst of the present invention has Since the decrease in activity over time is extremely small compared to conventionally known catalysts, it is extremely useful in cases where the polymerization time is longer, such as in copolymerization.

Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization for purposes such as MI control. The catalyst used had the disadvantage that the yield of active and stereoregular polymers decreased significantly in the presence of hydrogen. However, when olefin polymerization is carried out in the presence of hydrogen using the catalyst according to the present invention, the yield of active and stereoregular polymers does not decrease even when the MI of the produced polymer is extremely high. Such an effect has been strongly desired by those skilled in the art.

[Example code] The present invention will be specifically explained below using examples.

Example 1 Preparation of solid catalyst component
10g of dinitoxymacnesium and 60g of toluene were placed in a 0° round bottom flask to form a suspension, then 40g of T rCl a was added to this suspension, and the mixture was heated at 90°C.
2. Raise the temperature to phthalic acid dichloride. Add O and g.

Thereafter, the temperature was raised to 115'C, and the mixture was reacted with stirring for 2 hours. 200- for the solid material obtained after the completion of the reaction.
Washed twice under reflux with toluene of
The operation of reacting while stirring for 2 hours was repeated three times. The reaction product was then mixed with 20% n-hebutane at 40°C.
Washed 10 times with 01111. When the titanium content in the solid catalyst component thus obtained was measured, it was found to be 2.0.
It was 0 weight ■%.

Polymerization> 200 mg of triethylaluminum was placed in an autoclave with a stirrer and an internal volume of 2.02 that was sufficiently purged with nitrogen gas.
, 70 μm of 1.8-dipoxyparamenthane and 3.0 μm of the solid catalyst component. I loaded it.

After that, hydrogen gas 1.8G, liquefied propylene 1.42
was charged, and polymerization was carried out at 70°C for 30 minutes.

After the polymerization was completed, the obtained polymer was dried under reduced pressure at 80° C., and the obtained amount was designated as (A). Further, this was extracted for 6 hours with $200,000 n-hebutane to obtain a polymer insoluble in n-hebutane, and this amount was designated as (B).

The polymerization activity (C) per solid catalyst component used is expressed by the formula, and the yield (D) of the total crystalline polymer is expressed by the formula. Furthermore, the MI of the produced polymer is expressed by (E), and the bulk specific gravity is expressed by (E).
F). The results obtained are shown in Table 1.

Example 2 Example 1 except that 1.7-phthalic acid dichloride was used.
An experiment was conducted in the same manner. The titanium content in the obtained solid catalyst component was 2.161! :Amount%. !
In this case, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 3 An experiment was conducted in the same manner as in Example 1 except that the same amount of xylene was used instead of toluene. Note that the titanium content in the obtained solid catalyst component was 2.061% by weight. !
In this case, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

(A) No. 1 table 4,

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram illustrating the configuration of the present invention.

Claims (1)

[Claims] (1) (A) After suspending diethoxymagnesium (a) in alkylbenzene (b), it is brought into contact with titanium tetrachloride (c) at a volume ratio of 1 or less to the alkylbenzene (b), and then 80°C A solid substance obtained by adding and reacting phthalic acid dichloride (d) in a temperature range of ~125°C is washed with alkylbenzene, and further in the presence of alkylbenzene (b) at a volume ratio to the alkylbenzene (b). Titanium tetrachloride (c
A solid catalyst component obtained by repeating the reaction of (B) three or more times; A catalyst for polymerizing olefins, characterized by comprising (B) an epoxy paramenthane compound and (C) an organoaluminum compound.