JPH085935B2 - Solid catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a high activity when subjected to the polymerization of olephins, and is capable of obtaining a stereoregular polymer in a high yield. It relates to a performance solid catalyst component. More specifically, the present invention relates to a substance obtained by reacting metal magnesium powder with an alkyl monohalide in the presence of iodine in the absence of a solvent, along with a diester of phthalic acid, titanium tetrachloride and magnesium fatty acid. Solid catalyst component for polymerization of olefins obtained by contacting titanium tetrachloride with the product obtained by co-pulverizing at low temperature in the presence of aromatic hydrocarbon or aromatic halogenated hydrocarbon which is liquid at room temperature. It is about.

[Prior art]

Recently, as a catalyst for the polymerization of olefins such as propylene, in place of the conventionally known titanium trichloride catalyst component, many new types of catalysts in which titanium, which is an active component, is supported on magnesium chloride together with an electron donor have been developed. Proposed.

The earliest of these was developed by co-milling a complex of an organic monocarboxylic acid ester as an electron donor and titanium tetrachloride with magnesium chloride, or an organic monocarboxylic acid as an electron donor. There is a product obtained by treating a co-ground product of an acid ester and magnesium chloride with titanium tetrachloride.

However, they cannot be said to have satisfactory properties for use on an industrial scale, and those which improve various properties, for example, diethoxymagnesium instead of magnesium chloride, and special electron donors are used. Various proposals have been made for those using a compound, or those obtained by modifying the combination method of the above-mentioned substances, the contact means and the like.

For example, in JP-A-54-94590, a catalyst component is prepared by using magnesium dihalide as a starting material, and an organoaluminum compound, an organic carboxylic acid ester and M
A method of combining a compound having a —O—R group and the like for use in the polymerization of olefins is disclosed, and JP-A-57-
In 63310, various catalysts as electron donors, magnesium chloride in active form, and a titanium compound are combined to prepare a catalyst component, and further Si—O bond or Si—
A method for polymerizing propylene using a compound having an N bond and an organoaluminum compound is disclosed.

[Problems to be solved by the invention]

In the prior art, chlorine contained in magnesium chloride, which occupies the main stream as a carrier material, has a drawback that it adversely affects the produced polymer, like the halogen element in titanium halides. On the other hand, it is required that the activity of chlorine be substantially negligible, or that the concentration of magnesium chloride itself be kept low.

Further, when a catalyst component having the above magnesium chloride as a carrier is used in combination with an organoaluminum compound to polymerize olefins, particularly when stereoregular polymerization of propylene, 1-butene, etc. is carried out industrially, when carrying out the polymerization reaction. It is essential to use an organic monocarboxylic acid ester as an electron donor. However, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, and as a result, there has been a problem that a peculiar ester odor is imparted to the produced polymer.

Furthermore, in so-called highly active supported catalysts such as catalysts using a catalyst component having magnesium chloride as a carrier, the activity at the initial stage of polymerization is high, but deactivation with time is large and it becomes a problem in process operation, and block copolymerization It was virtually impossible to use it if the polymerization time was longer.

JP-A-54-94590 has been proposed to improve this point, but as is clear from the description of the publication, in this case, an organic carboxylic acid ester is used both during catalyst preparation and during polymerization. Is needed.
Generally, the organic carboxylic acid ester contained in the catalyst is
By treatment with titanium halide or washing with an organic solvent, the amount of odor of the produced polymer is negligible. However, the organic carboxylic acid ester used during the polymerization is extremely large amount as compared with the amount contained in the catalyst as described above, and when the polymerization is carried out in a liquid or gaseous monomer, almost all of it is At present, it is contained in the produced polymer, and accordingly,
It can be said that the problem of the odor of the produced polymer cannot be solved as long as the organic carboxylic acid ester is used during the polymerization. Further, as can be seen from the examples, the method disclosed in the above publication requires extremely complicated operations and the obtained catalyst is practically sufficient in terms of performance and sustainability of activity. That is not the case.

The present inventors have conducted extensive studies to solve various problems in the conventional art, and succeeded in providing a novel solid catalyst component for polymerization of olephins to Mushroom.

[Disclosure of Invention]

In the present invention, a substance (a) obtained by reacting a metal magnesium powder with an alkyl monohalide in an amount of at least 2 times the molar amount in the presence of iodine in the absence of a solvent is used as a diester of phthalic acid (b) or The product obtained by co-milling with titanium chloride (c) and magnesium fatty acid (d) at a low temperature is further subjected to four-fold reaction in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon (e) which is liquid at room temperature. It provides a solid catalyst component obtained by contacting with titanium chloride (c).

In order to obtain a substance obtained by the reaction of the above-mentioned (a) metallic magnesium powder with an alkyl monohalide in the present invention (hereinafter simply referred to as (a) substance), a commercially available metallic magnesium powder and an alkyl monohalide are used. And are reacted in the presence of iodine in the absence of an organic solvent,
At this time, it is necessary to use 2 moles or more of the alkyl monohalide with respect to one monometal magnesium powder. Further, the reaction temperature and the reaction time are arbitrary as long as the above reaction proceeds sufficiently and are not particularly limited, but are usually 20 ° C. or higher and 10 minutes or longer, preferably 40 ° C. or higher.
30 minutes or more. This reaction is a Grineer type reaction, and the absorption of an alkyl group is observed when the IR spectrum of the substance (a) obtained by the reaction is measured.

The alkyl monohalide used in the production of the substance (a) is preferably an aliphatic hydrocarbon chloride that is liquid at room temperature, and examples thereof include n-propyl chloride, isopropyl chloride, n-butyl chloride, and the like. Examples thereof include isobutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

Examples of the (b) phthalic acid diester (hereinafter simply referred to as (b) substance) in the present invention include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate. , Ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl phthalate and the like can be mentioned as examples.

Examples of the above-mentioned (d) fatty acid magnesium (hereinafter simply referred to as (d) substance) in the present invention include magnesium stearate, magnesium cabriolate, magnesium laurate and the like.

In the present invention, the aromatic hydrocarbon or aromatic halogenated hydrocarbon which is liquid at room temperature (e) (hereinafter simply referred to as (e)
Examples of the substance) include toluene, xylene,
And aromatic halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene and bromobenzene.

When obtaining the solid catalyst component in the present invention, the use ratio of each raw material constituting the solid catalyst component is arbitrary and is not particularly limited as long as it does not adversely affect the performance of the produced solid catalyst component. However, the amount of the (b) substance is usually 0.01 to 1 g, relative to 1 g of the (a) substance,
The substance (d) is in the range of 0.1 to 2 g. When the titanium tetrachloride is co-ground with the substance (a) and the substance (b) at a low temperature, the content of the titanium tetrachloride is 0.01 to 1
It is in the range of 1 g, and when brought into contact with the product obtained by the co-milling, it is in the range of 0.1 g or more, preferably 1 g or more. The amount of substance (e) to be coexisted during this contact is 0.01 to 100 ml, preferably 0.1 to 10 ml, per 1 ml of titanium tetrachloride.
Range.

Substance (a), substance (b), titanium tetrachloride (c)
The co-milling of substances (d) and (d) is below 10 ° C, preferably 0
It is carried out at a low temperature of 0 ° C. or lower for usually 10 minutes or longer, preferably 30 minutes or longer.

When the product obtained by the above co-milling is contacted with titanium tetrachloride in the presence of substance (e), it is usually -10
Temperature range from ℃ to the boiling point of titanium tetrachloride for 10 minutes ~
It is preferable to perform the treatment for about 100 hours. After this contact, titanium tetrachloride can be repeatedly contacted with the obtained product. In that contact, the substance (e) may or may not be allowed to coexist. The product thus obtained may optionally be washed with an organic solvent such as n-heptane.

All of these aspects are included in one aspect in the practice of the present invention.

The series of operations for preparing the solid catalyst component in the present invention is preferably carried out in the absence of oxygen and water.

The solid catalyst component prepared as described above is combined with the organoaluminum compound to form the catalyst for olefin polymerization according to the present invention. At this time, if necessary, a piperidine derivative or an oxygen-containing organosilicon compound is added. It is possible to coexist.

The polymerization reaction using the catalyst for polymerization according to the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer used can be used in either gas or liquid state. it can. Polymerization temperature is 20
0 ℃ or less, preferably 100 ℃ or less, the polymerization pressure is 100kg /
cm ² · G or less, preferably 50 kg / cm ² · G or less.

The olefins homopolymerized or copolymerized by using the olefin polymerization catalyst according to the present invention are ethylene, propylene, 1-butene and the like.

〔The invention's effect〕

The solid catalyst component for polymerization of olefins according to the present invention, when used for the polymerization of olefins, shows a high activity which is unpredictable in the past, and therefore the amount of catalyst residue present in the produced polymer. Can be controlled to an extremely low level, and since the residual chlorine is extremely small, the effect of chlorine on the product can be reduced to the extent that no deashing step is required.

Since chlorine remaining in the produced polymer causes corrosion of equipment used in steps such as granulation and molding, it also causes deterioration of the produced polymer itself, yellowing, etc. Obtaining is of great benefit to the art.

Further, according to the solid catalyst component of the present invention, by not adding the organic carboxylic acid ester at the time of polymerization, it is possible to solve a big problem that an ester odor adheres to the produced polymer.

Furthermore, conventionally, there was a common drawback in so-called highly active supported catalysts, in which the activity per unit time of the catalyst significantly decreased with the progress of polymerization, but in the catalyst according to the present invention, the polymerization time The decrease in activity with the passage of is extremely small as compared with conventionally known catalysts, so that it is useful even when the polymerization time such as copolymerization is made longer, and when a higher polymerization pressure is adopted. Due to the large increase in activity, it can be widely used in bulk polymerization and gas phase polymerization, which have recently received attention.

Moreover, according to the solid catalyst component of the present invention, a polymer having a high degree of stereoregularity can be obtained.

In addition, in the industrial production of olefin polymers, coexistence of hydrogen at the time of polymerization is generally considered from the viewpoint of MI control and the like, but conventional magnesium chloride is used as a carrier and organic carboxylic acid ester is used. The catalyst had a drawback that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when the polymerization of olefin is carried out in the presence of hydrogen using the solid catalyst component according to the present invention, even when the MI of the produced polymer is extremely high,
The activity and stereoregularity are not reduced. Such an effect has been strongly desired by those skilled in the art.

[Examples and Comparative Examples]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of substance (a) A round-bottomed flask having a capacity of 2.0 l equipped with a stirrer was used, which was sufficiently replaced with nitrogen gas, and then 30 g of metallic magnesium powder, 1.0 g of iodine and n-butyl chloride were used. 1.2 l was charged and reacted for 5 hours at the boiling point of n-butyl chloride. After completion of the reaction, the supernatant was removed, the product was washed with 500 ml of n-butyl chloride three times, and then dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component 20 g of the powdery substance obtained in (1) above, 7.5 ml of dibutyl phthalate, 4.0 ml of TiCl ₄ and 5.0 g of magnesium stearate under a nitrogen gas atmosphere, the total volume of 25 mmφ stainless steel balls It was charged into a vibrating mill pot with a capacity of 1.0 liter filled with 4/5, and was subjected to co-pulverization treatment at a frequency of 1430 v.pm and an amplitude of 3.5 mm for 17 hours in a temperature atmosphere of -15 ° C.

Using a round bottom flask with a capacity of 500 ml equipped with a stirrer,
After sufficiently replacing with nitrogen gas, 5 g of the solid composition obtained by the co-milling treatment was taken into it, and TiCl ₄ 50 m
1 and 50 ml of toluene were added, and the temperature was raised to 115 ° C. to react for 2 hours. After completion of the reaction, the supernatant was removed, and 50 ml of TiCl ₄ and 50 ml of toluene were newly added to the product, and the mixture was reacted at 115 ° C. for 2 hours. After the reaction is completed, the product is cooled to 40 ° C.
-Washing with 200 ml heptane 10 times gave a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 2.36% by weight.

(3) Polymerization of propylene Using an autoclave equipped with a stirrer and having an internal volume of 2.0 l, this was completely replaced with nitrogen gas, and then 190 mg of triethylaluminum, 23 mg of 2,2,6,6-tetramethylpiperidine and the above solid catalyst were used. The ingredients 3.0 mg were charged. Then hydrogen gas
1.8 l and 1.4 l of liquefied propylene were charged, and the polymerization reaction was carried out at 70 ° C for 1 hour. After the completion of the polymerization reaction,
It is dried under reduced pressure at 0 ° C., and the amount of the obtained product is designated as (A). Further, this product was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and the amount of this product is designated as (B).

The polymerization activity (C) per the solid catalyst component used is represented by the following formula.

The yield (D) of all crystalline polymer is represented by the following formula.

Further, the amount of residual chlorine in the produced polymer is represented by (E), the MI of the produced polymer is represented by (F), 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 30 minutes. The obtained results are as shown in Table 1.

Example 3 An experiment was carried out in the same manner as in Example 1 except that the polymerization reaction was carried out by the following method.

700 ml of n-heptane was charged into an autoclave with a stirrer having an internal volume of 2.0 l, which was completely replaced with nitrogen gas, and 301 mg of triethylaluminum was added while maintaining a nitrogen gas atmosphere.
37 mg of 2,2,6,6-tetramethylpiperidine and then 10.0 mg of the solid catalyst component prepared by the method of Example 1 were charged. Then, 150 ml of hydrogen gas was charged, the temperature was raised to 70 ° C., and while introducing propylene gas, the polymerization reaction was carried out for 1 hour while maintaining the pressure of 6 kg / cm ² · G. After the completion of the polymerization reaction, the obtained solid polymer was separated, heated to 80 ° C., and dried under reduced pressure. On the other hand, the amount of the polymer dissolved in the polymerization solvent by condensing the liquid is (G), and the amount of the solid polymer is (H). Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours,
A polymer insoluble in n-heptane is obtained, and this amount is designated as (I).

The polymerization activity (J) per solid catalyst component is represented by the following formula.

Further, the yield (K) of the crystalline polymer is represented by the following formula, The yield (L) of all crystalline polymer is calculated by the following formula.

Further, the residual base in the produced polymer is represented by (M) and the MI of the produced polymer is represented by (N). The results obtained are shown in Table 2.

Example 4 An experiment was performed in the same manner as in Example 3, except that the polymerization time was changed to 2 hours. The results obtained are shown in Table 2.

Example 5 An experiment was conducted in the same manner as in Example 1 except that the same amount of dipropyl phthalate was used instead of dibutyl phthalate. The titanium content in the solid catalyst component at this time is 2.
It was 39% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Line preparation of the solid catalyst component in the same manner except for the use dipropyl phthalate 5.0ml and TiCl ₄ 2.0 ml instead of Example 6 dibutyl phthalate 7.5ml and TiCl ₄ 4.0 ml Example 1 Natsuta. The titanium content in the solid catalyst component at this time is 2.
It was 16% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Comparative Example 1 20 g of commercially available MgCl ₂ and 5.0 ml of dibutyl phthalate were ground under the same conditions as in Example 1. Then, 5 g of the pulverized composition was charged into a glass container having an inner volume of 500 ml under a nitrogen gas atmosphere, 200 ml of TiCl ₄ was added, and a stirring reaction was carried out at 120 ° C. for 2 hours. After completion of the reaction, the supernatant was removed, 200 ml of TiCl ₄ was newly added, and the reaction was carried out at 120 ° C for 2 hours.

After completion of the reaction, it was cooled to 40 ° C. and washed 10 times with 200 ml of n-heptane to obtain a solid catalyst component. At this time, the titanium content in the solid catalyst component was measured and found to be 1.64% by weight.

An experiment was conducted in the same manner as in Example 1 except that 6.0 mg of the above solid catalyst component was used for the polymerization. The results obtained are as shown in Table 1.

Comparative Example 2 An experiment was conducted in the same manner as in Comparative Example 1 except that the polymerization time was 30 minutes. The results obtained are as shown in Table 1.

Comparative Example 3 An experiment was performed in the same manner as in Comparative Example 1 except that the polymerization reaction was performed in the same manner as in Example 3. The results obtained are shown in Table 2.

As is clear from comparison between Examples 1 and 2 and Comparative Examples 1 and 2, the catalyst according to the present invention has an extremely small decrease in activity with the passage of polymerization time.

As is clear from comparison between Examples 1 and 3 and Comparative Examples 1 and 3, the catalyst according to the present invention shows a large increase in activity when a higher polymerization pressure is adopted.

[Brief description of drawings]

FIG. 1 is a schematic drawing for helping understanding of the present invention.

Claims (1)

[Claims] 1. A substance (a), a diester of phthalic acid (b), and a compound obtained by reacting a magnesium metal powder with a 2-fold or more molar amount of an alkyl monohalide in the presence of iodine in the absence of a solvent. The product obtained by co-milling titanium chloride (c) and fatty acid magnesium (d) at low temperature
A solid catalyst component for olefin polymerization, which is obtained by contacting titanium tetrachloride (c) in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon (e) which is liquid at room temperature.