JPS6123604A - Olefin polymerization catalyst component and catalyst - Google Patents

Abstract

PURPOSE:A catalyst which has high activity and can give a steroregular polymer in high yields, comprising a specified catalyst component, an oxygen-containing organic compound and an organoaluminum compound. CONSTITUTION:A catalyst component is obtained by bringing 1g of a dialkoxymagnesium (e.g., diethoxymagnesium), 0.01-2g of a mono- or di-ester of an aromatic dicarboxylic acid (e.g., dimethyl phthalate) and 0.1g or above of a titanium halide compound of the formula: TiX4 (wherein X is a halogen) into contact with each other at -10 deg.C or higher for 10min-100hr in the absence of oxygen and water in a halohydrocarbon solvent (e.g., CCl4). This catalyst component is combined with an oxygen-containing organic compound of the formula (whrein R is an alkyl or an alkoxy) and an organoaluminum compound (e.g., triethylaluminum) to obtain an olefin polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a high-performance catalyst component and a method for producing the catalyst that act with high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. More specifically, a catalyst component for polymerizing olefins obtained by contacting dialkoxymagnesium, a mono- or diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon, and a titanium halide, and the catalyst component, an oxygen-containing organic compound, and an organic This invention relates to a catalyst for polymerizing olefins made of an aluminum compound.

Conventionally, as a catalyst for polymerizing olefins, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component is well known and widely used. The yield of this polymer (hereinafter referred to as titanium in the catalyst component and catalytic component)
This is called the polymerization activity. ) was so low that a so-called deashing step was necessary to remove catalyst residues. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment for these is indispensable, and there are many problems associated with resources, energy, etc., and those skilled in the art would like to solve them as soon as possible. This was an important issue.

In order to eliminate this complicated deashing step, many studies have been made and proposals have been made to increase the polymerization activity of the catalyst component, particularly titanium, in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of titanium in the catalyst component can be dramatically increased. There are many proposals to raise the standard.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the same disadvantage as the halogen element in titanium halides, which has a negative effect on the polymer produced, and for this reason, the effect of chlorine is virtually ignored. This left unresolved issues, such as the need to have as high an activity as possible, or the need to keep the concentration of magnesium chloride itself low.

The present inventors have developed a patent application filed in Japanese Patent Application No. 1983-1-1 with the aim of reducing the residual chlorine in the produced polymer while maintaining the polymerization activity of the catalyst component and the yield of the stereoregular polymer at a high level.
No. 200454, we proposed a method for producing a catalyst component for olefin polymerization, and achieved the intended purpose. Furthermore, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially, it is common to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential for catalysts that use a catalyst component having a carrier as a carrier in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the produced polymer, and its removal has become a major problem in the industry.

In addition, in so-called highly active supported catalysts, such as catalysts using catalyst components using magnesium chloride as a carrier,
Although the activity at the initial stage of polymerization is high, the deactivation is large, which causes problems in process operation, and it is not practical to use 11 in cases where it is necessary to lengthen the polymerization time, such as in block copolymerization.
It was almost impossible. In order to improve this point, for example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
Organoaluminum compound, organic carboxylic acid ester, M
A method for polymerizing olefins in combination with a compound having a -0-R group has been shown, but since an organic carboxylic acid ester is used during polymerization, the problem of odor of the resulting polymer has not been solved. In addition, as can be seen from the examples in the same publication, it requires very complicated operations and has poor performance.
However, it cannot be said that a sufficient level of activity has been obtained for practical purposes.

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 hereby propose the present invention.

That is, the features of the present invention are as follows: (1) ra) dialkoxymagnesium, (b) mono- or diester of aromatic dicarboxylic acid, (C) halogenated hydrocarbon, and (d) general formula TiX4 (wherein X is)・It is a rogen element. ) is obtained by contacting a titanium halide (hereinafter sometimes simply referred to as titanium halide), and is characterized in that it is used in combination with ω) an oxygen-containing organic compound and c>organoaluminium compound. and (A) (a) dialkoxymagnesium, (b) mono- or diester of aromatic dicarboxylic acid, (C) /S
An object of the present invention is to provide a catalyst for polymerizing olefins, which is obtained by contacting a logenated hydrocarbon and (d) a tethano-tetragenide, comprising: (a) an oxygen-containing organic compound and (c) an organoaluminum compound.

When olefins are polymerized using the catalyst obtained according to the present invention, not only the produced polymer has extremely high stereoregularity, but also the catalyst residue in the produced polymer is very high. Moreover, since the amount of residual chlorine is extremely small, the influence of chlorine on the produced polymer can be reduced to such an extent that a deashing step is not required at all.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself, and this has been reduced. has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized by not using an aromatic carboxylic acid ester during polymerization, which solves the major problem of the odor of the produced polymer, and by controlling the activity of the catalyst per unit time over the course of polymerization. The object of the present invention is to provide a catalyst that solves the essential drawbacks of so-called highly active co-supported catalysts, in which the activity of the catalyst decreases significantly with the increase in activity.

In addition, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but catalysts using the catalyst component having the magnesium chloride as a carrier coexist with hydrogen. However, it had the disadvantage that the activity and stereoregularity were significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the M of the produced polymer is
There is little loss of activity and stereoregularity even when the molecular weight is extremely high, and such effects are of great benefit to those skilled in the art.

To further comment on the effects of the present invention, in the industrial production of olefin polymers, the bulk specific gravity of the resulting polymer is a very big problem, but the catalyst obtained by the present invention has extremely excellent properties in this respect as well. It shows.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ee-butoxymagnesium, di-te
Examples include rt-butoxymagnesium, diimpropoxymagnesium, and the like, with jetoxymagnesium and dipropoxymagnesium being preferred.

The aromatic dicarboxylic acid mono- or diester used in the present invention is preferably a mono- or diester of 7-talic acid or terephthalic acid, such as dimethyl 7-talate, dimethyl terephthalate, diethyl phthalate,
Examples include diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diyne butyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl imbutyl phthalate, and ethyl propyl phthalate.

The halogenated hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature, such as propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane. Among them, propyl chloride, dichloroethane, chloroform, carbon tetrachloride, and methylene chloride are preferred.

The general formula 'l'1X4 used in the present invention (in the formula
is a halogen element. ) TiC44+ TjBrn + TiI4
Among them, TiC4n is preferable.

The oxygen-containing organic compound used in the present invention preferably has an alkyl group or an alkoxy group having 1 to 10 carbon atoms.

The organoaluminum compound used in the present invention includes trialkylaluminum, dialkylaluminum halide, alkylaluminum civalide, and mixtures thereof, with trialkylaluminum being preferred among these, triethylaluminum and triisof.

Chillaluminum is particularly preferred.

When obtaining the catalyst component of the present invention, the proportion of each raw material constituting the catalyst component is arbitrary and not particularly limited, as long as it does not adversely affect the performance of the catalyst component to be produced. However, the ratio of dialkoxymagnesium to 12 is usually 0.0 for mono- or diester of aromatic dicarboxylic acid.
In the range of 01 to 2, titanium halide is 0.1
The range is 9 or more, preferably 12 or more. Furthermore, the halogenated hydrocarbon can be used in any proportion, but is preferably an element capable of forming a suspension.

At this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but as a preferred embodiment, component (a) is suspended in component (c), and the resulting suspension is An example of a method is to add the suspension to component (d) and cause a contact reaction, and at some point during the reaction, component (b) is allowed to coexist.

In the present invention, the contact conditions for each raw material are as follows: When dialkoxymagnesium is suspended in a halogenated hydrocarbon, the halogenated hydrocarbon used in the presence or absence of a mono- or diester of an aromatic dicarboxylic acid is usually used from θ°C. for up to 100 hours, preferably at a temperature up to the boiling point of
It is preferable to maintain m drops within a range of 0 hours or less.

In the present invention, the suspension and the titanium halide are brought into contact in the presence or absence of a mono- or diester of an aromatic dicarboxylic acid, usually at a temperature ranging from -10°C to the boiling point of the titanium halide used, 10 minutes to 10
It is preferable to carry out the test for 0 hours.

It is also possible to contact the composition obtained after the above-mentioned contact with a titanium halide, and it is also possible to wash it using an organic solvent such as n-hebutane.

These series of operations in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

The catalyst component prepared as described above is combined with the oxygen-containing organic compound and the organoaluminum compound to form a catalyst for polymerizing oleynes. The organoaluminum compound used has a molar ratio of 1 to 1 ooo per mole of titanium atoms in the catalyst component, and the oxygen-containing organic compound has a simole ratio of 1 or less per mole of the organoaluminum compound, preferably o , o o s to 1.0.

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. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 H/cn・o or less, preferably 50 H/crl・
G or less.

The olefins to be homopolymerized or copolymerized using the catalyst produced by the method of the present invention include ethylene, propylene,
l-butene, etc.

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst components] A container Jft sufficiently purged with nitrogen gas and equipped with a stirrer
In a 200 mt Kunobo flask, 52 mg of jetoxymagnesium and 2. Of and 25-methylene chloride were charged to create a suspension and stirred under reflux for 1 hour. This suspension was then poured into a 50-volume container equipped with a stirrer.
0ff17! 'p1C1 at room temperature in a round bottom flask of
The mixture was pumped into a 4200°C, heated to 120°C, and reacted with stirring for 2 hours. n-Hebutane 2 at 40°C after the completion of the reaction
The mixture was washed 10 times with 100ml of TiC, and 200ml of TiC14 was newly added thereto, followed by reaction at 120°C for 2 hours with stirring.

After the reaction was completed, the temperature was cooled to 40C, and then 20% of n-hebutane was added.
Washing at 0 m/ was repeated, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used. At this time, when the solid and liquid in the catalyst component was separated and the titanium content of the solid was measured, it was found to be 2.21 wt.

[Overlapping]

700 m of n-hebutane was charged into an autoclave with a stirring device and an internal volume of 2.0 t that was completely purged with nitrogen gas.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
14, 82 cm of o-anisaldehyde, and then the above catalyst component was charged as titanium atoms in 02F'IF. Thereafter, 300 °C of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, a pressure of 61 cy/1yl-a was maintained, and polymerization was carried out for 4 hours. After the completion of polymerization, the obtained solid polymer was separated, heated to 80°C, and dried under reduced pressure.
32 solid polymers were obtained.

On the other hand, the P liquid was condensed to obtain a 6.9 F polymer. The solid polymer had an MI of 13 and a bulk specific gravity of 0.38.

Example 2 An experiment was carried out in the same manner as in Example 1 except that the polymerization time was 6 hours, and a solid polymer of 298f was obtained. The solid polymer had an MI of 11 and a bulk specific gravity of 0.40. Further, a 9.9P polymer was obtained by condensing the P liquid.

Example 3 Example 1 except that 0-anisaldehyde was used from 131
A similar experiment was conducted. As a result, a solid polymer of 1972 was obtained. The solid polymer has an MI of 13 and a bulk specific gravity of 0.
It was 38. Further, the P liquid was condensed to obtain a 6.22-weighted product.

Claims (2)

[Claims] (1) (A) (a) Dialkoxymagnesium, (b)
Obtained by contacting a mono- or diester of an aromatic dicarboxylic acid, (c) a halogenated hydrocarbon, and (d) a titanium halide represented by the general formula TiX_4 (wherein X is a halogen element), (B) An oxygen-containing organic compound (hereinafter sometimes simply referred to as an oxygen-containing organic compound) represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R is an alkyl group or an alkoxy group) and (C) A catalyst component for polymerizing olefins, characterized in that it is used in combination with an organoaluminum compound. (2) (A) (a) dialkoxymagnesium, (b)
A catalyst component obtained by contacting a mono- or diester of an aromatic dicarboxylic acid, (c) a halogenated hydrocarbon, and (d) a titanium halide represented by the general formula TiX_4 (wherein X is a halogen element): A catalyst for polymerizing olefins comprising (B) an oxygen-containing organic compound and (C) an organoaluminum compound.