JPH03265608A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a high-performance catalyst for the polymerization of an olefin which has high activity and can give a stereoregular polymer in high yields by mixing a specified solid catalyst component with an epoxy-p-menthane compound and an organoaluminum compound. CONSTITUTION:The title catalyst is obtained by mixing a solid catalyst component (A) obtained by washing a solid substance obtained by suspending diethoxymagnesium (a) in an alkylbenzene (c) in the presence of an alkoxytitanium compound (b) having at least one Ti-Cl bond, bringing the suspension into contact with TiCl4 (d) in an amount to give a volume ratio to the alkylbenzene (c) of 1 or below and adding phthaloyl chloride (e) to the product of contact at 40 deg.C or above, and reacting the mixture at 80-125 deg.C with alkylbenzene, reacting the product with compound (d) in an amount to give a volume ratio of compound (c) of 1 or below in the presence of compound (c) and repeating this operation at least three times with an epoxy-p-menthane compound (B) and an organoaluminum compound (C). This catalyst is highly active and can give a stereoregular polymer in high yields.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention exhibits an activity as high as previously expected when subjected to the polymerization of olefins, and is capable of producing stereoregular polymers. This invention relates to a high-performance catalyst for polymerizing olefins that can obtain polymers in high yield.

[Prior Art] Conventional Solid catalyst component for olefin polymerization consisting of dialkoxymagnesium, titanium tetrachloride, and an electron-donating compound, or olefin g [1] using the solid catalyst component
Various combination catalysts have already been developed and proposed.

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 disadvantage of reduced stereoregularity in the resulting polymer when hydrogen is used in hot air, dialkoxymagnesium obtained by a specific operation is combined with a halogenated hydrocarbon and the presence of an electron-donating compound. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide is disclosed below.

Analysis from Example 2, which specifically exemplifies this method, shows that 12! ! It is suspended in carbon chloride, dityl benzoate and titanium tetrachloride are added at 75°C, and the suspension is stirred for 12 to 2 hours while maintaining the temperature at 75°C. The generated solid was isolated and washed with iso-octane for 5 times, then suspended in 111 titanium oxide at 80°C, stirred for 2 hours, and then washed with iso-octane for 5 times 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 polymer yield when used for olefin polymerization. However, it cannot be said that it exhibits sufficient performance in terms of duration of activity.

Therefore, in order to solve this problem, the present invention No. 108611 discloses that a diester of dialkoxymagnesium and an aromatic dicarboxylic acid is added to a halogenated hydrocarbon and treated 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. However, in this industry, higher polymerization activity and stereoregularity yield of the produced polymer have been required, and therefore, the present inventors have succeeded in obtaining TIM characteristics remaining in the conventional technology.
As a result of intensive research to solve the problem, we have arrived at the present invention and hereby propose it.

[Means for Solving the Problems] That is, the present invention is characterized in that jetoxymagnesium (a) is dissolved in alkylbenzene (C) in the presence of alkoxytitanium (b) having at least one titanium-chlorine bond. After suspending, contact with titanium tetrachloride (d) in a volume ratio of 1 or less to the cough alkylbenzene (C), then add phthalic acid dichloride (e) at 40°C or higher, and further add phthalic acid dichloride (e) at 80°C to 125°C. The solid material obtained by reacting at a temperature range of Olefin polymerization characterized by comprising a solid catalyst component for olefin polymerization and a skeleton solid catalyst component, which are obtained by repeating the operation of reacting three or more times, and an epoxy paramenthane compound and an organoaluminum compound. It provides catalysts for use in

Examples of the alkoxytitanium compound (b) having at least one titanium-chlorine bond (hereinafter simply referred to as the substance (b)) used in the ays of the solid catalyst component of the present invention include tributoxytitanium chloride, dibutoxytitanium Dichloride, Butoxytitanium trichloride, Triethoxytitanium dichloride, Ethoxytitanium trichloride, Tripropoxytitanium chloride, Dipropoxytitanium dichloride, Propoxytitanium trichloride, Triisobutoxytitanium chloride, Diisobutoxytitanium chloride, Imbutoxytitanium trichloride, Trichloride isopropoxy titanium chloride,
Examples include diisobutoxytitanium chloride, impropoxytitanium trichloride, and the like.

In the production of the solid catalyst component of the present invention, jetoxymagnesium (&) (hereinafter simply referred to as (sometimes referred to as 0 product award))
Alkylbenzene (C) used to suspend
Examples of the substance (hereinafter sometimes simply referred to as substance (C)) include toluene, xylene, ethylbenzene, propylbenzene, and trimethylbenzene.

(b) used in the preparation of the solid catalyst component of the present invention
Substance and phthalic acid dichloride (e) (hereinafter simply referred to as (e)
) It is sometimes called a substance. ) usage ratio is (1) substance 1
．． 0g to 0. 01~0. It is in the range of 5sd. In addition, titanium tetrachloride (d) (hereinafter simply referred to as (d) substance) is 1.0 g per 1°0g of (a) substance.
g or more, and the volume ratio to the substance (C) is 1 or less. Note that it is necessary to use the substance (C) in an amount that can form a suspension with the substance (a).

The solid catalyst component of the present invention comprises: 0) the substance is suspended in the (c) substance in the presence of the (b) substance and then contacted with the (d) substance in a volume ratio of 1 or less to the (c) substance; Then 40℃
In the above, the solid material obtained by adding the substance (e) and further reacting at a temperature range of 80°C to 125°C is washed with alkylbenzene, and then in the presence of the substance (c), the solid substance is washed with the substance (c). It is obtained by repeating the operation of reacting the substance (d) with a volume ratio of 1 or less to 3 times or more, but at this time, the reaction at a temperature range of 80°C to 125°C is usually in the range of 10 minutes to 10 hours. It will be done. The alkylbenzene used in the above cleaning may be the same as or different from the substance (C) above. The temperature during cleaning is not particularly limited, but is 90°C or higher, up to the boiling point of the alkylbenzene used. is preferred. Examples of the alkylbenzene used for cleaning include those listed above in the example of substance (C).

Also, prior to washing with this alkylbenzene, it is also prohibited to perform washing with an organic solvent other than the alkylbenzene.

The solid material after this washing is then further processed (c)
In the presence of the substance, tX is reacted with the (d) substance in a volume ratio of 1 or less to the (c) 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. The preferred 12 temperature ranges for each of the above reactions are determined as appropriate depending on the type of (c) fl substance 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 (a) in the substance (c) 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 epoxy paramenthane compound (B) used in the catalyst of the present invention is 1.4- or 1.8-
-Epoxyparamenthane is preferred, but it is also possible to use these compounds with substituents such as alkyl groups and halogens.

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 to the titanium atoms in the solid catalyst component (A), and the epoxy paramenthane compound (B) has a molar ratio of 1 to 1000. 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 an organic solvent, and the olefin monomer can be used in either gas or liquid state.
℃ or less, preferably 100'C or less, and the polymerization pressure is 1
00kg/aI+”・G or less, preferably 50kg/■
2.G or less.

The olefins to be homopolymerized or copolymerized using the catalyst according to the present invention are ethylene and propylene.

These include 1-butene and 4-methyl-1-pentene.

[Functions 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 polyolefin 12, 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 as well. Has excellent properties.

Furthermore, the present invention is characterized in that the amount of titanium tetrachloride used in the preparation of the solid catalyst component is extremely small compared to the prior art. Titanium tetrachloride is a substance that is difficult to handle as it reacts with oxygen and moisture in the air to form hydrochloric acid gas, emitting white smoke and a strong pungent odor. Therefore, reducing the amount used will reduce costs. It offers great benefits in the production of solid catalyst components, such as ease of operation and prevention of pollution sources.

Zarawo 2 Since the catalyst according to the present invention exhibits a high activity that was completely unexpected in the past, it is possible to suppress the amount of catalyst residue present in the produced polymer to an extremely low level, and therefore the amount of residual chlorine in the produced polymer can also be reduced. This can be reduced to such an extent that a demineralization step is not required at all.

In addition, according to the catalyst according to the present invention, no organic carboxylic acid ester or nitrogen compound is added during the production of the solid catalyst component W8 and during polymerization using the solid catalyst component, resulting in the adhesion of odor to the produced polymer. It can also completely solve the problem.

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 fl olefin polymers, it is common practice to allow hydrogen to coexist during polymerization for MI sub-control. The catalyst used had the disadvantage that its activity and stereoregularity were significantly reduced in the coexistence of hydrogen. However, when the catalyst of the present invention was used to polymerize olefins in the coexistence of hydrogen, the resulting polymer Even when the MI of is very high, the activity and stereoregularity decrease. Such an effect was strongly desired by those skilled in the art.

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

Example 1 Preparation of solid catalyst component〉 Thoroughly purged with nitrogen gas. Capacity 50 equipped with a stirrer.
10 g of jetoxymagnesium in a 0- round bottom flask,
Dibutoxytitanium dichloride 3. O, N and 70111 g of toluene are charged to form a suspension, and then TiC1t 30 d is added to this suspension, the temperature is raised to 90° C., and 1.7-phthaloyl dichloride is added. Thereafter, the temperature was further raised to 115°C, and the mixture was stirred for 2 hours to react for 12 hours.
Washed twice with 0- toluene under reflux, added toluene 70- and TiC1,30-, and heated at 115°C.
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 0aQ. The titanium content in the solid catalyst component thus obtained was measured and found to be 2.91% by weight.

<Polymerization> Triethylaluminum 20011 was placed in an autoclave with a stirring device and an internal volume of 2.0Q that was sufficiently purged with nitrogen gas.
Ig, 70 mg of 1,8-divoxyparamenthane, and 3.0 mg of the solid catalyst component were charged.

Thereafter, 1.89% of hydrogen gas and 1.49% of liquefied propylene were 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 with boiling IN n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount was designated as (B).

The polymerization activity (C) per solid catalyst component used is expressed by the formula Expressed as

In addition, the yield (D) of the total crystalline polymer is expressed as: The titanium content in the obtained solid catalyst component is 3°20
An experiment was conducted in the same manner as in Example 1 for polymerization of 0% by weight. The results obtained are shown in Table 1.

(hereinafter referred to as blank space); furthermore, the MI of the produced polymer is (E), and the bulk specific gravity is (
The results obtained, denoted F), are shown in Table 1.

Example 2 Example 1 except that 1.5 d of phthalic acid dichloride was used.
An experiment was conducted in the same manner. Incidentally, the titanium content in the obtained solid catalyst component was 3.12% by weight.9 The polymerization was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 3 An experiment was carried out in the same manner as in Example 1 except that the same amount of triptoxytitanium chloride was used instead of dibutoxytitanium dichloride f, ft Table 4,

[Brief explanation of drawings]

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

Claims (1)

[Claims] (1) (A) The capacity for alkylbenzene (c) after suspending diethoxymagnesium (a) in the alkylbenzene (c) in the presence of an alkoxytitanium compound (b) having at least one titanium-chlorine bond. contact with titanium tetrachloride (d) at a ratio of 1 or less, and then at 40°C.
Add phthalic acid dichloride (e) to the above and further add 8
The solid material obtained by reacting in the temperature range of 0°C to 125°C is washed with alkylbenzene, and then in the presence of alkylbenzene (c), titanium tetrachloride ( d)
A solid catalyst component obtained by repeating the reaction three times or more; A catalyst for polymerizing olefins, characterized in that it consists of (B) an epoxy paramenthane compound and (C) an organoaluminum compound.