JPS6250309A - Catalyst component and catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a catalyst which can give a stereoregular polymer of a uniform particle size distribution in high activity and good yields, comprising a specified catalyst component, a Si compound and an organoaluminum compound. CONSTITUTION:A catalyst component (A) is obtained by contacting 1g of a solid composition obtained by contacting 1g of a dialkoxymagnesium (e.g., dithoxymagnesium) with 0.01-2g of an aromatic dicarboxylic acid diester (e.g., dimethyl phthalate) and 0.1g or above of a titanium halide of formula I (wherein X is a halogen) for 100hr or shorter at a temperature of 0 deg.C to the b.p. of the titanium halide with 1g or below of water for 100hr or shorter at 100 deg.C or below. A catalyst for polymerization of an olefin is obtained by combining component A with 1-1,000mol, per mol of Ti in component A, of organoaluminum compound (B) and 1mol or below, per mol of component B, of a Si component (C) of formula II (wherein R is H, alkyl or aryl, R' is alkyl or aryl and 0<=m<=4).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention produces stereoregular polymers that act with high activity and have a uniform particle size distribution in extremely high yields when subjected to the polymerization of olefins. Regarding the high performance catalyst components and catalysts that can be obtained, more specifically, dialkoxymagnesium,
A catalyst component for polymerizing olelains obtained by contacting a solid composition obtained by contacting a diester of an aromatic dicarboxylic acid, a hydrogenated hydrocarbon, and a titanium hydrogenated compound with water. The present invention also relates to a catalyst for polymerizing olefins comprising the catalyst component, a silicon compound, and an organoaluminum compound.

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of a solid titanium chloride and an organoaluminum compound as a catalyst component has been well known and widely used. Since the yield of the polymer based on titanium in the catalyst component (hereinafter referred to as the catalyst component and the polymerization activity of titanium in the catalyst component) is low, a so-called demineralization step to remove the catalyst residue was unavoidable. . 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 titanium in the catalyst component and the sieving 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. The chlorine contained in magnesium chloride has the disadvantage of having a negative effect on the polymer produced, similar to the halogen element in titanium halides, and therefore, the effect of chlorine is virtually eliminated. For which negligible high activity is required,
Alternatively, there remained unresolved issues such as 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 is high at the initial stage of polymerization, the deactivation is large, which poses problems in process operation, and it is almost impossible to use it in practical situations such as block copolymerization, where a longer polymerization time is required. . In order to improve this point, for example, in JP-A No. 54-94590, a catalyst component was prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, M-
A method for polymerizing olefins in combination with a compound having an 〇-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. Further, as can be seen from the examples, very complicated operations are required, and it cannot be said that practically sufficient results have been obtained in terms of performance and duration of activity.

Furthermore, the so-called highly active supported catalyst component using magnesium chloride as a carrier has a drawback in that its performance deteriorates as the storage period becomes longer. This is a very serious problem considering that industrial use of the catalyst components usually requires several months of storage, transportation, etc.

In addition, in industrial polymerization equipment, it is sometimes necessary to feed a catalyst to a high-temperature polymerization tank, and it is known that the performance of conventional supported catalysts deteriorates considerably in such cases. . This is a big problem especially in so-called continuous polymerization methods, and its improvement has been a strong demand in the roux world.

In addition, the particle size distribution of the produced polymer is an extremely important issue from an industrial perspective in terms of plant operation, but each process requires a different particle size distribution, and it is difficult to respond to this in detail with conventional supported catalysts. Ta.

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

[Means for solving problems]

That is, the features of the present invention are as follows: (A) (a) dialkoxymagnesium, (b) diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) general formula TiX4 (in the formula is a halogen element.) A solid composition obtained by contacting a titanium halide (hereinafter sometimes simply referred to as titanium halide) represented by (e) water; General formula SiRm(OR')4. , (wherein R is hydrogen, an alkyl group or an aryl group (1), R' is an alkyl group or an aryl group, and m satisfies 0≦m≦4.

) (hereinafter simply referred to as a silicon compound) and (C) a catalyst component for olefin polymerization, characterized in that it is used in combination with an organoaluminum compound, and (A) (5) dialkoxymagnesium. , (b) diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) titanium halide (hereinafter simply referred to as titanium halide) represented by the general formula TiX4 (wherein X is a halogen element). (e) A catalyst component obtained by contacting the solid composition obtained by contacting with (e) water: ■) General formula SiRm (OR'
)4-m (wherein R is hydrogen, an alkyl group or an aryl group, R1 is an alkyl group or an aryl group,
m is 0≦m≦4. ) is a silicon compound (
Hereinafter, it may be simply referred to as a silicon compound. ): and (C) An object of the present invention is to provide a catalyst for polymerizing olefins comprising an organoaluminum compound.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, jetoxymagnesium, diphenomagnesium, dipropoxymagnesium, di-butoxymagnesium, di-tert
-butoxymagnesium, diisopropoxymagnesium, etc., among which jetoxymagnesium and dipropoxymagnesium are preferred.

The diester of aromatic dicarboxylic acid used in the present invention is preferably a diester of phthalic acid or terephthalic acid, such as dimethyl 7-talate;
Examples include dibutyl phthalate, dibutyl terephthalate, diimbutyl phthalate, cyamyl 7-talate, diisoamyl 7-talate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl butyl 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. , trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, etc. Among them, propyl chloride, dichloroethane, chloroform, carbon tetrachloride, and methylene chloride are preferred.

Examples of titanium halides represented by the general formula TiX4 (wherein X is a halogen element) used in the present invention include TiC4, TiBr4. Examples include TiI4, among which TiC14 is preferred.

The silicon compound used in the present invention includes:
Examples include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, etc. Examples of alkylalkoxysilane Examples include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethyl silane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane.

When obtaining the solid composition of the present invention, the proportions and contact conditions of each raw material are arbitrary as long as they do not adversely affect the performance of the resulting catalyst component, and are not particularly limited. Normal dialkoxymagnecrum 12
On the other hand, the number of aromatic dicarboxylic acid diesters ranges from 101 to 22, preferably from 0.1 to 11,
The titanium halide is in the range of 0.11 or more, preferably 12 or more. Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably in an amount that can form a suspension.

Furthermore, the contact between each raw material is usually carried out at a temperature between 0°C and the boiling point of the titanium halide used for up to 100 hours.
It is preferably carried out for 10 hours or less.

In this case, the order and method of contacting each raw material are not particularly limited, and any appropriate method can be selected.

It is also possible to contact the solid composition written 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.

The solid composition obtained as described above is brought into contact with water, usually using 11 or less water per 1 ton of the solid composition.
C. or less, preferably 50.degree. C. or less, for 100 hours or less, preferably 10 hours or less.

Note that the water used here is preferably used in a form contained in an aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon.

The catalyst component produced as described above is combined with the silicon compound and organoaluminum compound to form a catalyst for polymerizing olefins.

The organoaluminum compound used has a molar ratio of 1 to 1000 per mole of titanium atoms in the catalyst component, and the silicon compound has a smol ratio of 1 or less, preferably [1005 to 1005]. Used in the range +15.

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
00kg70-・G or less, preferably 5okg/cw'
・It is below G.

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

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 Preparation of catalyst component
Jetoxymagnesium 5 in a 0t1tt round bottom flask
9. Dibutyl phthalate) 1.5 r and methylene chloride 25- charged! ll! The mixture became cloudy and stirred under reflux for 1 hour. This suspension was then placed in a container equipped with a stirrer.
TiC420Ov at room temperature in a round bottom flask of i500-
The mixture was pumped into a tl tank, heated to 110°C, and reacted with stirring for 2 hours.

After the reaction was completed, it was washed 10 times with 200 d of n-heptane at 40°C to obtain a solid composition. Next, the solid composition 32 has an internal volume of 5
Into a round bottom flask of 00, 100 ml of n-heptane containing 10 ppm of water was added, and the mixture was stirred at room temperature for 1 hour, and then washed 5 times with 200 ml of n-heptane at room temperature.
TiCt4200- was newly added and reacted at 120°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, 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 used as a catalyst component.

At this time, the titanium content in the catalyst component was measured and found to be 50,111% by weight.

Polymerization> 700 d of n-heptane 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
1 W, phenyltriethoxy 7 run 521+9, and then the catalyst component was charged as a titanium atom in cL5.

Thereafter, 500 ml of hydrogen gas was charged, the temperature was raised to 70°C, and propylene gas was introduced while maintaining a pressure of 6 kg/tx"-G for 4 hours of polymerization. After the polymerization was completed, the obtained solid The 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 ν liquid is defined as (4), and the amount of the solid polymer is defined as Φ). In addition, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours and n-
An indeterminate polymer was obtained in hebutane, and this amount was designated as (C).

The polymerization activity (D) of the catalyst components was expressed by the formula and the yield (8) of the crystalline polymer was expressed by the formula, and the total crystalline polymer yield CF) was determined from the formula. Further, the residual chlorine in the produced polymer is represented by (G), and the MI of the produced polymer is represented by (6). The results obtained are as shown in Table 1. In addition, as a result of particle size distribution measurement of the produced polymer,
The amount of 100μ or less was 5% by weight.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 6 hours. The results obtained are as shown in Table 1. In addition, as a result of particle size distribution measurement of the produced polymer, 100μ
The following was 2% by weight.

Example 3 A catalyst component was prepared in the same manner as in Example 1, except that 20 rows of n-heptane containing 10 ppm of water was used. Incidentally, the titanium content in the solid 9 at this time was 511% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1. In addition, as a result of particle size distribution measurement of the produced polymer, 100p or less is 2% by weight.
Met.

Example 4 An experiment was carried out in the same manner as in Example 1, except that the treatment with water-containing n-hebutane was carried out at 50°C. Note that the titanium content in the solid 9 at this time was 104% by weight.

During polymerization, an experiment was conducted in the same manner as in Example j.

The results obtained are shown in Table 1. In addition, as a result of particle size distribution measurement of the produced polymer, 100μ or less is 2% by weight.
It happened.

Table 1 [Effects of the Invention] When olefins are polymerized using the catalyst component obtained according to the present invention, it is possible to keep the amount of catalyst residue in the produced polymer to an extremely low level because the catalyst has extremely high activity. Moreover, since the amount of residual chlorine is very 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. This is an extremely important point 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 purpose is to solve the essential drawbacks of so-called highly active co-supported catalysts, which are significantly reduced due to the increase in activity, and to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

Conventionally, in the industrial production of olefin polymers, it has been common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst using the catalyst component with magnesium chloride as a carrier In coexistence, 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 activity and stereoregularity hardly decrease even when the MI of the produced polymer is extremely high. Such an effect is of great benefit to those skilled in the art.

Further, the catalyst component or catalyst produced according to the present invention has a well-ordered particle size distribution, and can also have the industrially extremely beneficial effect of being able to control fL.

Claims (2)

[Claims] (1) (A) (a) Dialkoxymagnesium, (b)
A solid composition obtained by contacting a 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), , (e) obtained by contacting with water, (B)
Represented by the general formula SiRm(OR')_4_-_m (wherein, R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4). A catalyst component for polymerizing olefins, characterized in that it is used in combination with a silicon compound and (C) an organoaluminum compound. (2) (A) (a) dialkoxymagnesium, (b)
A solid composition obtained by contacting a 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), , (e) Catalyst component obtained by contacting with water; (B) General formula SiRm(OR')_4_-_m (in the formula R
is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. ); and (C) an organoaluminum compound.