JPH02170804A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the title catalyst of high activity, thus giving stereoregular polymer in high yield by using a specific solid catalyst component, an epoxy-p- menthane and an organoaluminum compound. CONSTITUTION:The subject catalyst is composed of (A) a solid catalyst com-ponent which is prepared by crushing a reaction mixture of (i) a metallic magnesium powder with double or more molar amount of an alkyl monohalide such as n-propyl chloride in the absence of a solvent, together with (ii) a diester of phthalic acid such as dimethyl phthalate, then bringing the product into contact with (iii), (B) an epoxy-p-menthane compound, preferably 1,8-epoxy-p- menthane and (C) an organoaluminum compound, preferably triethylaluminum or tri-isobutylaluminum.

Description

[Detailed Description of the Invention] [Industrial Applicability] The present invention provides a method for obtaining stereoregular washing polymers with high activity and high yield when subjected to the polymerization of olefins. This relates to high-performance catalysts that can be used. Furthermore, in Western terms, Akira Kio has developed a product obtained by co-pulverizing a substance obtained by reacting metallic magnesium powder with an alkyl monohalide in the absence of a solvent and a diester of phthalic acid. This invention relates to an olefin #A polymerization catalyst comprising a solid catalyst component obtained by melting the above with titanium tetrachloride, an epoxy paramenthane compound, and an organoaluminum compound.

[Conventional technology]

Recently, tita/l! trichloride, which has been well known as a catalyst for the polymerization of olefins including propylene, has been recently developed. ! In place of the Il medium component, many new types of catalysts have been developed and proposed in which the active component titanium is supported on magnesium chloride together with an electron donor.

Among these, the one that was developed most recently was one in which a complex of organic monocarbon μ as an electron donor (Fit Esthe μ) and titanium tetrachloride was co-pulverized with magnesium chloride; There is a co-pulverized product of organic monocarboxylic acid ester and magnesium chloride treated with titanium tetrachloride.

However, these cannot be said to have satisfactory properties for use on an industrial scale, and there are methods to improve various properties, such as those using jetoxymagnesium instead of magnesium chloride, and special ones as electron donors. Various methods have been proposed in which compounds are used, or methods of combining the substances, contact means, etc. are modified.

For example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
A method is disclosed in which an organoaluminum compound, an organic carboxyl ester, a compound having an M-0-R group, etc. are used in combination for the polymerization of olefins. A catalyst component was prepared by combining each Hajiester Lv as a compound with active magnesium chloride and a titanium compound, and further 81
A method for polymerizing propylene using a compound having a -0 bond or an 81 to N bond and an organoaluminum compound is disclosed.

[Challenges remaining with conventional technology]

In the prior art, chlorine contained in magnesium chloride, which is the main carrier material, has a 1% effect on the produced polymer, similar to the halogen element in titanium halides.
．． Since it has the disadvantage of exerting a negative influence on the environment, it is required to have high activity to the extent that the influence of chlorine can be virtually ignored, or even of magnesium chloride itself!
Measures are being taken to keep agricultural production low.

In addition, when carrying out the industrial polymerization of olefins, especially the stereoregular polymerization of propylene, 1-butene, etc., using the catalyst component having magnesium chloride as a carrier in combination with an organoaluminum compound, when carrying out the combination reaction, It is essential to use an organic monocarboxylic acid ester as an electron donor. However, in this case, it is necessary to use the organic monocarboxylic acid ester in a very large amount of electricity, and as a result, there is a problem in that the resulting polymer has a characteristic ester odor.

Furthermore, in so-called highly active supported catalysts, such as catalysts using catalyst components with magnesium chloride as a carrier, although the activity is high at the initial stage of polymerization, deactivation over time causes problems in process operation, and block copolymerization For longer polymerization times, it was virtually impossible to use it.

To improve this point, the above-mentioned Japanese Patent Application Laid-Open No. 54-9459
No. 0 has been proposed, but as is clear from the description in the same publication, in this case, it is necessary to use an organic carboxylic acid ester both during the catalyst p3111 and during the polymerization. Generally, the organic ester contained in the catalyst is treated with a titanium halide or washed with an organic solvent, so that the amount of the organic ester contained in the catalyst is such that the problem of noise in the produced polymer can be ignored.

However, as mentioned above, the organic carboxylic acid ester used during polymerization has an extremely high electric charge compared to the amount contained in the catalyst, and when polymerization is carried out in liquid or gaseous monomers, almost all of it is At present, it is contained in the produced polymer, and therefore, it can be said that the problem of staleness in the produced polymer cannot be solved unless an organic carboxylic acid ester is used during polymerization. Furthermore, as can be seen from the examples, the method disclosed in the same publication requires very complicated operations, and the catalyst obtained is not sufficient for practical use in terms of performance and sustainability of activity. The reality is that this cannot be said.

The inventors of the present invention conducted extensive research to solve the problems remaining in the prior art, and as a result of the present invention, they succeeded in providing a novel olefin If4ffi combination medium.

[Means to solve the problem]

According to the present invention, (1) a substance obtained by reacting metallic magnesium powder with an alkyl monohalide of twice the amount or more in the absence of a solvent and a diester of phthalic acid/L'ω);
The product obtained by co-pulverizing titanium tetrachloride fc
) A solid catalyst component obtained by fusion with (n) an epoxy paramenthane compound and (g) an organoaluminum compound is provided.

In order to obtain the substance obtained by the reaction of the metal magnesium powder and the alkyl monohalide (hereinafter simply referred to as (a) substance) in the present invention, a commercially available metal magnesium powder and an alkyl monohalide are used. The alkyl monohalide is reacted with the halide in the absence of an organic solvent, and at this time, the alkyl monohalide is
It is necessary to use 2 moles or more per mole. In addition, the reaction temperature and reaction time are arbitrary (as long as the above reaction proceeds sufficiently) and are not particularly limited, but usually 2
(This reaction is carried out at 1°C or above for 10 minutes or more, preferably at 40°C or above for 30 minutes or more. This reaction is a Grignard type reaction) and measures the IR/IL/ of the substance obtained by the reaction. Then, the alkyl monohalides used in the production of the alkyl E (a) substance are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-propyl chloride, isopropyl chloride, n-propyl chloride, etc. Examples include butyl chloride, isobutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

Lid/I/acid diester v of the above (b) in the present invention
1, Tehashimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate,
Examples include dibutyl phthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethylpropyl phthalate.

In the present invention, the epoxyparamenthane compound of <...) is 1.4-epoxyparamenthane or 1.8
-Epoxyparamenthane is preferred, but it is also possible to use those with a substituent such as an alkyl group or halogen.

Examples of the organic aluminum compound (2) in the present invention include trialkylaluminum, dialkylaluminum halide minium cibaride, and mixtures thereof, and among these, trialkylaluminum is preferred, and triethyl heptaluminium and Particularly preferred is triisobutylaluminum.

When obtaining the solid catalyst component (1) in the present invention, the proportion of each raw material constituting the cough solid catalyst component is arbitrary and does not adversely affect the performance of the solid catalyst component to be produced. Usually, but not limited to (a
) For 1 ton of substance, it may be referred to as ('b) lid A/acid diester (hereinafter simply referred to as ``Chapter'') substance. ) is CLO
I to 12), the titanium tetrachloride of <c> is
The range is α1f or more, preferably 1f or more.

The co-milling of the substances (a) and (b) is usually carried out for at least 10 minutes, preferably for at least 30 minutes, using a ball mill/L/or vibratory mill and similar mills.

It is preferable that the composition obtained by the above-mentioned pulverization be brought into contact with titanium tetrachloride at a temperature ranging from -10°C to the boiling point of titanium tetrachloride for 10 minutes to 100 hours.

The composition obtained after the above contact can be repeatedly contacted with titanium tetrachloride, and the composition obtained can be
Washing can also be carried out using an organic solvent such as hebutane.

All of these are included in the practice of the present invention.

The series of operations for preparing the solid catalyst component in (1) above in the present invention is preferably carried out in the absence of filtrate, water, and the like.

The solid catalyst component prepared as described above is
The above (■) epoxy paramenthane compound and the above (■)
It is combined with the organoaluminum compound of 4) to constitute the olefin direct reaction catalyst according to the present invention.

The organic aluminum compound (m) used is:
The epoxy paramenthane compound of (11) is used in a molar ratio of 1 or less to the organoaluminum compound, preferably in the range of 0.005 to 1.0. used.

Polymerization using the polymerization catalyst of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin yflit body used can be used in either a gas or liquid state. can. The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100kg/lx”・G or less, preferably so
Chill below kg/J.G.

Olefins to be homopolymerized or copolymerized using the catalyst for direct olefin synthesis according to the present invention include ethylene, propylene, 1-butene, and the like.

〔Effect of the invention〕

When olefins are polymerized using the olefin catalyst according to the present invention, the resulting polymer has extremely high stereoregularity. Furthermore, the amount of catalyst residue present in the resulting polymer can be kept to an extremely low level, and the amount of catalyst residue present in the resulting polymer is extremely low, and the amount of residual chlorine present in the resulting polymer is extremely low, and the resulting product can be deashed. The influence of chlorine can be reduced to the extent that no process is required at all.

Chlorine that persists in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, and can also cause deterioration and yellowing of the produced polymer itself. The results obtained will be of great benefit to the field of technology.

Further, according to the present invention, an organic carboxylic acid ester μ is added during polymerization.
By not adding ester, it is possible to solve the big problem of ester odor adhesion to the produced polymer.

Furthermore, conventionally, there has been a common drawback in so-called highly active supported catalysts that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, The decrease in activity over time of polymerization is extremely small compared to conventionally known catalysts, making it useful for longer polymerization times such as copolymerization, and employing higher polymerization pressures. Since the increase in activity is large in this case, it can be widely used in vacuum polymerization and gas phase polymerization, which have recently been attracting attention.

Furthermore, in the production of industrial kaolefin polymers, it is common to coexist hydrogen during polymerization from the point of view of MI control. Catalysts using this catalyst had the disadvantage that their activity and stereoregularity were significantly reduced 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,
Even when the MI of the resulting polymer is very high, the activity and stereoregularity are not reduced. Such an effect was strongly desired by those skilled in the art. In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem in terms of the capacity of polymerization equipment, the capacity of post-treatment processes, etc., but the catalyst according to the present invention also has this problem. , has extremely excellent properties.

〔Example〕

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

Example 1 (1) (a) Preparation of the substances Capacity 2. equipped with a stirrer. Using an OL round bottom flask,
After sufficiently replacing this with nitrogen gas, metal magnesium powder 30? and 1.2 t of n-butyl chloride were charged and reacted for 8 hours at the boiling point of n-butyl chloride. After the reaction was completed, the supernatant liquid was removed, and the product was washed three times with 500 tJ of n-butylchloride, and then dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component Powdered material obtained in (1) above 20? and dibutyl phthalate & low under a nitrogen gas atmosphere, the total volume of 475 259 mφ stainless steel bow μ was filled to a capacity of 1.0
Place it in a vibrating mill pot with a vibration frequency of 1430 v, p.
The pulverization process was carried out for 17 hours using 55 wafers.

Using a 500-volume round bottom flask equipped with a stirrer,
After sufficiently purging with nitrogen gas, take the solid composition 5f obtained by the pulverization treatment, and add TiC4 to it.
200- was added, the temperature was raised to 120°C, and the mixture was reacted for 2 hours. After the reaction is completed, the supernatant liquid is removed and the product is newly added with Ti.
C1°200- was added and reacted at 120°C for 2 hours.

After the reaction was completed, it was cooled to 40°C, and the product was washed 10 times with 200°C of n-hebutane to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be t57%.

3) Using an autoclave equipped with a stirring device and having an internal polymerization volume of 2.0 t, the autoclave was completely replaced with nitrogen gas, and then 195 μl of triethylaluminum, 70 μl of 1.8-epoxy paramenthane, and 6.0 LlIP of the solid catalyst component were added. I loaded it. After that, 1.8 t of hydrogen gas.

1.4 t of liquefied propylene was charged, and a mixture reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer is
Dry under reduced pressure at 0°C, and let the amount of the product obtained be (g). This product was also extracted with boiling n-hebutane for 6 hours.
- Obtain a polymer insoluble in hebutane and determine the amount of this (B
).

The polymerization activity (c) of the solid catalyst component photoυ used is expressed by the following formula.

Further, the yield Q)) of the total crystalline polymer is expressed by the following formula.

Furthermore, the amount of residual chlorine in the produced polymer is expressed as (Yes), the MI of the produced melon as (F>), and the bulk ratio as (G), and the obtained results are shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 50 minutes. The results obtained are as 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 dipropylphthalate was used instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time is t
It was 7o tolerance%.

Polymerization was carried out in the same manner as in Example 1.

The results obtained are shown in Table 1.

Example 4 A solid catalyst component was prepared in the same manner as in Example 1 except that dibutyl phthalate 5- was replaced with dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 1.99% by weight. The polymerization was tested in the same manner as in Example 1. The results obtained are the first
The standard is shown in the table.

Example 5 An experiment was carried out in the same manner as in Example 1 except that diisobutyl phthalate (pV-) was used instead of dibutyl phthalate. In addition, the titanium content in the solid catalyst component at this time is i, 6
It was 0 i%. After the polymerization was carried out, the addition and fermentation were carried out in the same manner as in Example 1. The results obtained are shown in Table 1.

Claims (1)

[Claims] (1) (I) Co-pulverizing the substance (a) obtained by reacting metallic magnesium powder with at least twice the mole of alkyl monohalide in the absence of a solvent and the diester of phthalic acid (b). A solid catalyst component obtained by contacting the product obtained by contacting with titanium tetrachloride (c); (II) an epoxy paramenthane compound and (III) an organoaluminum compound.