JP3301819B2 - Solid catalyst component for polymerization of olefins and polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a solid catalyst component for the polymerization of olefins, wherein a polyolefin having a very small amount of fine powder having a particle size of 100 .mu.m or less and excellent in stereoregularity can be obtained in a high yield. And a method for polymerizing olefins in the presence of

[0002]

2. Description of the Related Art A solid catalyst component for the polymerization of olefins comprising a titanium halide, a magnesium compound and an electron donating compound as essential components, and the solid catalyst component and an electron as a third component such as an organoaluminum compound and a silicon compound. Many proposals have been made on olefin polymerization methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising a donor compound.

For example, Japanese Patent Application Laid-Open No.
No. 3010 discloses a solid catalyst component prepared by subjecting a product obtained by contacting a dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon and a titanium halide to a powdery state, and an organic catalyst. An olefin polymerization catalyst comprising an aluminum compound and an organosilicon compound has been proposed, and its examples illustrate an olefin polymerization method in the presence of the catalyst.

Similarly, Japanese Patent Application Laid-Open No. 63-154705 discloses a magnesium compound obtained by reacting a metal magnesium powder with an alkyl monohalide in the presence of iodine, a tetraalkoxytitanium, an aliphatic hydrocarbon and an aliphatic hydrocarbon. In a mixed solution with an aromatic alcohol, titanium tetrachloride is added to precipitate a solid substance, and a solid product obtained by adding a diester of phthalic acid is brought into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon. And a catalyst for olefin polymerization comprising an organoaluminum compound and a silicon compound prepared by the method described above, and a method for polymerizing olefins in the presence of the catalyst is exemplified.

In Japanese Patent Application Laid-Open No. Hei 1-2221405, titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then a silicon compound and phthalic acid dichloride are added and reacted. A solid catalyst component prepared by washing the obtained solid product with alkylbenzene and further contacting with titanium tetrachloride in the presence of alkylbenzene, and a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, Illustrated is a method for polymerizing olefins in the presence of the catalyst.

[0006] These prior arts are intended to develop a catalyst component having a high activity so as to omit a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in a produced polymer. In addition, the present inventors have focused on improving the yield of the stereoregular polymer and increasing the sustainability of the catalytic activity during the polymerization, and excellent results have been confirmed.

However, recently, olefins are polymerized in the presence of a catalyst comprising such a highly active catalyst component and a so-called electron donating compound as a third component typified by an organoaluminum compound and a silicon compound. And, a large amount of fine powder having a particle size of 100 μm or less is contained in the produced polymer,
The particle size distribution is also widened, causing various inconveniences. In other words, when the amount of the finely divided polymer is increased, the continuation of the uniform reaction is hindered, or the process is hindered, such as blockage of the piping during the transfer of the polymer. Undesirable effects on processing. For this reason, in the art, there is as little as possible a fine powder having a particle size of 100 μm or less, which has a particularly large influence, and it is a factor for seeking a polymer having a uniform particle size and a narrow particle size distribution.

Therefore, solutions by mechanical means such as installing a fine powder removing device such as a filter in the process, or sieving by a sieving machine or air flow classification have been tried, but the installation cost of the device is reduced. There were technical problems required for maintenance, and unsolved parts remained.

As means for solving the above problems, a catalyst comprising a catalyst component, the catalyst component, an organoaluminum compound, an electron donor as an optional third component, and polymerization in the presence of the catalyst Many attempts have been made to improve the method to reduce the finely divided polymer and narrow the particle size distribution. For example, Japanese Patent Application Laid-Open No. 58-8 / 1983
No. 3006 discloses that when magnesium chloride is dissolved in 2-ethylhexyl alcohol, a solid catalyst component is precipitated with titanium tetrachloride, and olefin polymerization is carried out in the presence of this catalyst component, organic aluminum and an electron donor. And a polymer having a narrow particle size distribution can be obtained.

[0010] Japanese Patent Application Laid-Open No. 3-72503 discloses that
A solid catalyst component obtained by heating and reacting dialkoxymagnesium, tetraalkoxytitanate and an organosilicon compound as starting materials, and treating the resulting reaction product with a titanium halide and a carboxylic acid derivative such as metal orthophthalate. And a method of polymerizing an olefin in the presence of a catalyst comprising an electron-donating compound such as an organometallic compound and a piperidine derivative.

[0011]

However, in the above-mentioned method, a post-process of waste liquid treatment and a corresponding apparatus are required because a large amount of a solubilizing agent or a precipitant is used at the time of preparing a catalyst component, which makes the process complicated. Not only do
There is a problem that the effect of controlling the particle size distribution, especially the problem of reducing the fine powder polymer, is not sufficiently achieved. On the other hand, in the method disclosed in JP-A-3-72503, as apparent from the description of the examples, two kinds of titanium compounds as active components and substantially three kinds of electron donors are used at the time of preparing the catalyst component. Preparation methods are complicated, such as using components that require extremely close processing operations for stable synthesis, such as carboxylic acid derivatives such as metal orthophthalate, and the production and production costs on an industrial scale are expensive. There are many issues that need to be improved.

The present inventors have conducted various studies in order to solve the problems left in the prior art, and as a result, have developed a solid catalyst component prepared by simpler means, and have developed the solid catalyst component (A). When olefin polymerization was attempted in the presence of a catalyst consisting of an organoaluminum compound (B) and an organosilicon compound (C), the olefin polymerization functioned effectively to suppress the formation of a finely divided polymer having a size of 100 μm or less. It was also confirmed that the polymer yield was maintained at a high level.

The present invention has been developed on the basis of the above-mentioned findings, and its object is to obtain a polyolefin excellent in stereoregularity, containing almost no fine powder having a particle diameter of 100 μm or less, in good yield. An object of the present invention is to provide a solid catalyst component for olefin polymerization and a method for polymerizing olefins using the solid catalyst component.

[0014]

In order to achieve the above-mentioned object, the solid catalyst component for olefin polymerization according to the present invention comprises:
A suspension formed of (a) a spherical dialkoxymagnesium, (b) a liquid aromatic hydrocarbon at room temperature and (c) a phthalic acid diester, and (b) a liquid aromatic hydrocarbon at room temperature and the fragrance 1/2 by volume ratio to the total amount of aromatic hydrocarbons
After adding to the following mixed solution with (d) titanium tetrachloride, the temperature is raised and reacted in a temperature range of 80 to 130 ° C. to obtain a reaction product, and the reaction product is washed with an aromatic hydrocarbon, Further, (b) in the presence of an aromatic hydrocarbon which is liquid at normal temperature, (d) titanium tetrachloride having a volume ratio to the aromatic hydrocarbon of 1/2 or less is added and reacted in a temperature range of 80 to 130 ° C, Then, the weight ratio to the alkoxy magnesium was 1/2.
It is obtained by adding the following (e) polystyrene in which (a) polystyrene is dissolved in advance and (b) adding a liquid aromatic hydrocarbon at room temperature, and then reacting in a temperature range of 0 to 8 ° C.

The method for polymerizing olefins according to the present invention is characterized in that the solid catalyst component for polymerization of olefins (A) obtained in the above step, the organoaluminum compound (B) and the general formula SiR _m (OR ') _An organosilicon compound (C) represented by _{4- m} (where R represents hydrogen, an alkyl group or an aryl group, R 'represents an alkyl group or an aryl group, and m satisfies 0 ≦ m ≦ 4). It is a constituent requirement to polymerize or copolymerize an olefin in the presence of a catalyst consisting of

The (a) spherical dialkoxymagnesium (hereinafter, sometimes simply referred to as "(a) substance") used in the present invention includes diethoxymagnesium,
Di-n-dibutoxy magnesium, diphenoxy magnesium, di-n-propoxy magnesium, diisopropoxy magnesium, di-sec-butoxy magnesium, di-tert-butoxy magnesium, etc. Diethoxymagnesium is preferably used.

(B) Aromatic hydrocarbons that are liquid at room temperature (hereinafter sometimes simply referred to as “(b) substance”) include:
Examples include toluene, xylene, ethylbenzene, propylbenzene, and trimethylbenzene.

Examples of (c) phthalic acid diester [hereinafter sometimes simply referred to as "(c) substance"] include, for example, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-
Butyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl propyl phthalate and the like.

(E) polystyrene [hereinafter simply referred to as “(e)
) May be appropriately selected from commercially available products, and its physical properties are not particularly limited. The substance (e) is used in a state of being dissolved in the substance (b), and the dissolution conditions at that time are generally 0 to 10 g to 1000 ml of the substance (b) per 1 g of the substance (e). It is performed in a temperature range of ８０80 ° C.

Examples of the organoaluminum compound (B) to be blended with the solid catalyst component (A) composed of the above substances include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide and a mixture thereof. Further, phenylalkoxysilane, alkylalkoxysilane and the like correspond to the organosilicon compound (C). Of these, specific examples of phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyl-n-
Propoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.Specific examples of the alkylalkoxysilane include tetramethoxysilane, tetraethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, methyl Examples thereof include triethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, and ethyltriisopropoxysilane.

Next, the method for preparing the solid catalyst component for olefin polymerization in the present invention will be specifically described. First, the use ratio of each component is such that the blend of the substance (a) and the substance (b) is an arbitrary ratio within a range in which a suspension can be formed;
Titanium tetrachloride (hereinafter sometimes simply referred to as "(d) substance") is reduced to 0.1 g or more with respect to 1.0 g of (a) substance and 1/2 or less in terms of volume ratio to the total amount of (b) substance. Set. The substance (c) is 0.1 g per 1.0 g of the substance (a).
It is used in the range of 1.0 g.

The formation of a suspension with substances (a), (b) and (c) is usually carried out at a temperature between room temperature and the boiling point of the substance (b), for a period of up to 100 hours, preferably up to 10 hours. It is performed while stirring inside. At this time, care must be taken so that the suspension is not uniform.

The contact between the above suspension and the mixed solution of the substance (b) and the substance (d) is usually carried out in the vicinity of room temperature, preferably in the temperature range of 5 to 20 ° C. In order to avoid a rapid reaction, it is preferable to gradually add the suspension to the mixed solution while continuing stirring. After the completion of the contact, the temperature is raised and the reaction is carried out with stirring for 10 minutes to 10 hours in a temperature range of 80 to 130 ° C. The obtained solid substance is washed with an aromatic hydrocarbon. The aromatic hydrocarbon used for washing may be the same as or different from the substance (b).

The washed solid substance is brought into contact with the substance (d) having a volume ratio to the substance (b) of 1/2 or less in the presence of the substance (b). The contact reaction is carried out in a temperature range of 80 to 130 ° C. while stirring for 10 minutes to 10 hours. Next, the substance (b) in which the substance (e) is dissolved in advance in a weight ratio of 1/2 or less to the substance (a) is added, and 0 to 8 substances are added.
The solid catalyst component (A) is prepared by reacting with stirring at a temperature of 0 ° C for 5 minutes to 10 hours.

The solid catalyst component (A) prepared by the above operation is washed with an inert organic solvent such as n-heptane, and then dried as it is or as it is with the organoaluminum compound (B) and the organosilicon compound. The catalyst for olefin polymerization of the present invention is formed in combination with (C).
When forming the polymerization catalyst, the amount ratio of each component used is such that the organoaluminum compound (B) is in the range of 5 to 1000 in terms of mole ratio per mole of Ti atom in the solid catalyst component (A), and the organosilicon compound ( C) is in the range of 0.002 to 0.5 in a molar ratio per mole of the organic aluminum compound.

The polymerization of olefins in the present invention is carried out in the presence of the above-mentioned polymerization catalyst. In this case, an organic solvent may or may not be present, and the olefin monomer may be a gas or a liquid. Either state can be used. The olefins to be homopolymerized or copolymerized include ethylene, propylene, 1-butene, 4-methyl-1-pentene, and the like.
00 ° C or lower, preferably 100 ° C or lower, polymerization pressure is 10
It is set to 0 kg / cm ² · G or less, preferably 50 kg / cm ² · G or less.

[0027]

The polyolefin produced by the polymerization method of the present invention has almost no fine powder having a particle size of 100 μm or less, and its particle shape is almost spherical. Further, the yield of the stereoregular polymer is high, the yield of the polymer per unit catalyst component, that is, the polymerization activity is excellent, and the durability is extremely good.

[0028]

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

Example 1 Preparation of a solid catalyst component: After thoroughly replacing the inside of a 500 ml round bottom flask equipped with a stirrer with nitrogen gas,
30 ml of toluene and 20 ml of titanium tetrachloride were charged, and then 10 g of spherical diethoxymagnesium, 50 ml of toluene and di-n which had been brought into contact with this mixed solution in advance.
A suspension of 3.6 ml of -butyl phthalate was charged over 4 hours, the temperature was raised to 90 ° C., and the mixture was reacted with stirring for 1 hour. After the completion of the reaction, the mixture was washed twice with 100 ml of toluene at the boiling point, and 20 ml of titanium tetrachloride and 80 ml of toluene were newly added thereto, followed by a contact reaction with stirring at 110 ° C. for 2 hours.
Then, it was washed 10 times with 200 ml of heptane at 40 ° C., and polystyrene [made by Dow Chemical Co., grade 666D]
40 ml of toluene in which 0.8 g was dissolved was added and reacted at 40 ° C. for 1 hour. After completion of the reaction, heptane 40 at 40 ° C.
After washing 5 times with ml, a solid catalyst component was obtained. The solid catalyst component was subjected to solid-liquid separation to measure the titanium content in the solid, which was 2.44% by weight.

Formation of polymerization catalyst and propylene polymerization: In a 2.0-liter autoclave equipped with a stirrer completely replaced with nitrogen gas, 0.0066 mmol equivalent of the above solid catalyst component as Ti atom and triethylaluminum 1 .32 mmol and 0.1 phenyltriethoxysilane
3 mmol was added and stirred to form a polymerization catalyst. Thereafter, 1.8 l of hydrogen gas and 1.4 l of liquefied propylene were charged and a polymerization reaction was carried out at 70 ° C. for 30 minutes.

Evaluation of properties; total amount of polymer obtained, amount of insoluble polymer extracted with boiling n-heptane for 6 hours, polymerization activity per solid catalyst component, total crystalline polymer , The MI of the produced polymer, the average particle size of the produced polymer, the amount of fine powder of the produced polymer (accumulation of -100 μm) and the like were measured and evaluated. The results are shown in Table 1. The average particle size and the amount of fine powder were measured by a dry sieving method, and the polymerization activity per solid catalyst component and the yield of the total crystalline polymer were as follows:
The values are shown by the following equations (1) and (2).

[0032]

[0033]

Example 2 A polymerization catalyst was formed under the same conditions as in Example 1 except that 100 ml of toluene for dissolving polystyrene, 0.6 g of polystyrene and 100 ml of heptane were used, and a polymerization test was conducted. At this time, the titanium content in the solid catalyst component was 2.35% by weight. The properties evaluation results of the obtained polymer are also shown in Table 1.

Example 3 A polymerization catalyst was formed under the same conditions as in Example 1 except that 0.2 g of polystyrene was used, and a polymerization test was conducted. At this time, the titanium content in the solid catalyst component was 2.2.
It was 3% by weight. The properties evaluation results of the obtained polymer are also shown in Table 1.

Comparative Example 1 A polymerization catalyst was formed under the same conditions as in Example 1 except that the reaction with toluene in which polystyrene was dissolved was not performed, and a polymerization test was performed. At this time, the titanium content in the solid catalyst component was 2.54% by weight. The properties evaluation results of the obtained polymer are also shown in Table 1.

[0037]

[Table 1]

From the results shown in Table 1, the polymer obtained by the polymerization method of the present invention using the polymerization catalyst containing the solid catalyst component for the polymerization of olefins of the present invention was 100 μm or less as compared with that of the comparative example. The amount of the finely divided polymer was clearly reduced to such an extent that almost no polymer was present. In addition, the particle shape of the produced polymer was almost spherical, and it was confirmed that the polymerization activity per solid catalyst component and the yield of stereoregular polymer were maintained at a high level.

[0039]

As described above, according to the present invention, the particle shape is obtained by a polymerization method using a solid catalyst component for olefins polymerization obtained through a simple contact reaction step and a treatment step and a polymerization catalyst containing the same. Can be obtained, which is almost spherical and has almost no finely divided polymer having a particle size of 100 μm or less. Therefore, it is excellent in fluidity, and troubles such as blockage of pipes which cause an operation stop during pipe transportation are eliminated. In addition, the presence of the finely divided polymer reduces the bulk specific gravity and reduces the polymerization reaction efficiency.However, such a problem is solved at the same time, and the post-treatment process of the produced polymer becomes easy, so that the operation efficiency is improved and energy is improved. Greatly contributes to cost reduction based on labor saving.

Further, in order to maintain excellent performance in terms of the yield of the stereoregular polymer, high polymerization activity and its sustainability, the catalyst residue remaining in the produced polymer is reduced to a negligible level, and The effect of sufficiently adapting to a long-term polymerization reaction such as a block copolymer is also exhibited. In addition, the method for preparing the solid catalyst component (A) for use in forming the olefin polymerization catalyst of the present invention is easier to obtain than the conventionally known methods,
Since the preparation means is also simple, it is very useful as a solid catalyst component for polymerization and a polymerization method for industrial production of polyolefin.

[Brief description of the drawings]

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

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 4/65-4/654 CA (STN)

Claims (2)

(57) [Claims] 1. A suspension formed from (a) a spherical dialkoxymagnesium, (b) an aromatic hydrocarbon liquid at room temperature and (c) a phthalic acid diester, and (b) an aromatic liquid at room temperature. A mixture is added to a mixed solution of (d) titanium tetrachloride having a volume ratio of not more than 1/2 with respect to the total amount of the hydrocarbon and the aromatic hydrocarbon, and then the temperature is raised, and the reaction is performed in a temperature range of 80 to 130 ° C to form a reaction. And the reaction product is washed with an aromatic hydrocarbon, and (b) in the presence of a liquid aromatic hydrocarbon at room temperature, a volume ratio to the aromatic hydrocarbon of 1/2 or less (d). Titanium tetrachloride was added and reacted in a temperature range of 80 to 130 ° C., and then (e) polystyrene having a weight ratio of 1/2 or less to the alkoxymagnesium was previously dissolved. (B) Aromatic hydrocarbon liquid at room temperature After adding
A solid catalyst component for olefins polymerization, which is obtained by reacting in a temperature range of 0 to 80 ° C. 2. The solid catalyst component (A) for olefin polymerization according to claim 1, an organoaluminum compound (B), and a general formula SiR _m (OR ′) _4-m (where R is hydrogen, An alkyl group or an aryl group, and R ′ represents an alkyl group or an aryl group, and m represents 0 ≦ m ≦ 4.) An olefin is polymerized or polymerized in the presence of a catalyst comprising an organosilicon compound (C) represented by the formula: A method for polymerizing olefins, comprising copolymerizing.