JP2657385B2 - Solid catalyst components and catalysts for olefins polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a high-performance solid which can act with high activity when used for the polymerization of olefins and can obtain a stereoregular polymer in a high yield. The present invention relates to a catalyst component and a catalyst for polymerization of olefins using the same.

[Conventional technology and its problems]

Conventionally, as a catalyst for olefins polymerization, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component is well known and widely used. Since the yield of the polymer (hereinafter, referred to as polymerization activity per catalyst component and titanium in the catalyst component) is low, a so-called deashing step for removing the catalyst residue was inevitable. This demineralization process requires a large amount of alcohol or chelating agent, and therefore requires a recovery device or a regenerating device. There are many resources, energy and other incidental problems, and those skilled in the art can solve the problem immediately. It was an important task to be desired. Numerous studies have been made and proposed to increase the polymerization activity of the catalyst component, particularly titanium in the catalyst component, in order to eliminate this complicated deashing step.

In particular, as a recent trend, when a transition metal compound such as titanium halide, which is an active ingredient, is supported on a carrier material such as magnesium chloride and used for the polymerization of olefins, the polymerization activity per titanium in the catalyst component is dramatically increased. There are many proposals for raising it.

However, chlorine contained in magnesium chloride, which is the mainstream as a carrier substance, has the disadvantage that it adversely affects the resulting polymer, as does the halogen element in titanium halide, and therefore, the effect of chlorine is virtually ignored. However, there remains an unsolved part such as the requirement for a high activity that can be achieved or the need to keep the concentration of magnesium chloride itself low.

In the case of industrially performing polymerization of olefins, particularly stereoregular polymerization of propylene, 1-butene, etc., it is usually necessary to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential for a catalyst using a catalyst component containing magnesium as a carrier in combination with an organic aluminum compound. However, the aromatic carboxylic acid ester imparts an ester odor peculiar to the produced polymer, and its removal has become a major problem in the art.

Further, in the case of a so-called highly active carrier type catalyst such as a catalyst using a catalyst component using magnesium chloride as a carrier, the activity is high at the initial stage of polymerization, but the deactivation is large, which causes a problem in the process operation. When it was necessary to extend the polymerization time, it was practically impossible to use it. 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, and an organic aluminum compound, an organic carboxylic acid ester, MO
Although the method of using for the polymerization of olefins in combination with a compound having an -R group is shown, since the organic carboxylic acid ester is used at the time of polymerization, the problem of the odor of the produced polymer has not been solved, and As can be seen from the examples in the publication, very complicated operations are required, and it cannot be said that practically sufficient ones have been obtained in terms of both performance and sustained activity.

On the other hand, various solid catalyst components for the polymerization of olefins comprising dialkoxymagnesium, titanium tetrachloride and an electron-donating compound or such solid catalyst components have already been developed and proposed.

For example, in Japanese Patent Application Laid-Open No. 55-152710, in order to obtain high activity of the catalyst, a large amount of an organoaluminum compound must be used during polymerization in order to control the molecular weight of the produced polymer. For the purpose of remedying the drawback that the stereoregularity of the produced polymer is reduced when hydrogen is added and used, dialkoxymagnesium obtained by a specific operation is treated with a halogenated hydrocarbon and an electron donating compound. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide in the presence of is disclosed.

Analyzing the method according to Example 2 which specifically illustrates this method, dialkoxymagnesium was suspended in carbon tetrachloride, ethyl benzoate and titanium tetrachloride were added at 75 ° C, and the suspension was heated to 75 ° C. Stir for 2 hours while maintaining. The resulting solid was isolated, washed 5 times with iso-octane, further suspended in titanium tetrachloride at 80 ° C., stirred for 2 hours, and then washed 5 times with iso-octane to remove the solid catalyst component. It has gained. Example 1 shows an example in which this solid catalyst component was used in combination with triethylaluminum as a catalyst for polymerization of olefins.

However, the solid catalyst component prepared by the method disclosed in JP-A-55-152710 is insufficient in polymerization activity, stereoregular polymer yield and activity persistence when used for olefin polymerization. It does not indicate performance.

In order to solve such a problem, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 61-108611 a diester of dialkoxymagnesium and an aromatic dicarboxylic acid added to a halogenated hydrocarbon and treated in a suspended state. Developed a catalyst for the polymerization of olefins comprising a solid catalyst component, a piperidine derivative and an organoaluminum compound obtained by reacting the suspension with a titanium halide, and was selected for its extremely high activity and its sustainability. Succeeded in obtaining the characteristics. However, the catalyst leaves room for further improvement in the stereoregularity and bulk specific gravity of the resulting polymer.

The present inventors have assiduously studied to solve the problems left in the prior art, and have reached the present invention and propose the present invention.

[Means for solving the problem]

That is, a feature of the present invention is that diethoxymagnesium (a) is suspended in alkylbenzene (b) and then contacted with titanium tetrachloride (c) having a volume ratio of 1 or less with respect to the alkylbenzene (b). Then, at 80 ° C. or lower, an alkoxytitanium chloride represented by the general formula Ti (OR) nX _4-n (wherein R is an alkyl group, X is chlorine, and n is an integer of 1 to 3) d) (hereinafter, sometimes simply referred to as "alkoxytitanium chloride (d)"), and further, phthalic acid dichloride (e) in a temperature range of 80C to 135C to obtain a reaction. The solid substance is separated and washed with alkylbenzene, and the solid substance is further treated with alkylbenzene (b).
A solid catalyst component for olefin polymerization, which is obtained by reacting the alkylbenzene (b) with titanium tetrachloride (c) having a volume ratio of 1 or less in the presence of Formula SiRm (OR ') _4-m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, and m Rs may be a combination of different groups;
R 'is an alkyl group. When R is an alkyl group, the alkyl group may be the same as or different from R '. m is 0 ≦ m ≦ 3. ) And an organoaluminum compound represented by the general formula RpAlX _3-p (where R is an alkyl group, X is a halogen element, and p is a real number satisfying 0 <p ≦ 3) (hereinafter simply referred to as “ The present invention provides an olefin-based polymerization catalyst characterized by comprising an “aluminum aluminum compound”.)

The alkoxytitanium chloride (d) used in the preparation of the solid catalyst component of the present invention includes triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride, tripropoxytitanium chloride, dipropoxytitanium dichloride, propoxytitanium trichloride,
Triisopropoxytitanium chloride, diisopropoxytitanium dichloride, isopropoxytitanium trichloride, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triisobutoxytitanium chloride, diisobutoxytitanium dichloride, isobutoxytitanium trichloride, etc. Is raised.

The alkylbenzene (b) used for suspending the diethoxymagnesium (a) in the preparation of the solid catalyst component of the present invention includes toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene and the like.

The ratio of the amounts of alkoxy titanium chloride (d) and phthalic dichloride (e) used in the preparation of the solid catalyst component of the present invention is in the range of 0.01 to 0.5 ml per 1.0 g of diethoxy magnesium (a). Also,
Titanium tetrachloride (c) is diethoxymagnesium (a) 1.
The amount is 1.0 g or more with respect to 0 g and 1 or less in terms of the volume ratio with respect to the alkylbenzene (b). It is necessary to use the alkylbenzene (b) in an amount capable of forming a suspension of diethoxymagnesium (a).

The solid catalyst component of the present invention is prepared by suspending diethoxymagnesium (a) in alkylbenzene (b) and then contacting the same with titanium tetrachloride (c) having a volume ratio of not more than 1 to the alkylbenzene (b). Add alkoxy titanium chloride (d) below, and add
The solid substance obtained by adding and reacting phthalic acid dichloride (e) at a temperature of 135 ° C. is washed with alkylbenzene, and the solid substance is further reacted with the alkylbenzene (b) in the presence of alkylbenzene (b). It is obtained by reacting titanium tetrachloride (c) having a volume ratio of 1 or less. At this time, the reaction in a temperature range of 80 to 135 ° C. is usually performed for 10 minutes to 10 hours. The alkylbenzene used for the above washing may be the same as or different from the alkylbenzene (b). The temperature at the time of washing is not particularly limited. Examples of the alkylbenzene used for washing include those listed in the above-mentioned examples of the alkylbenzene (b).

In addition, prior to the washing with the alkylbenzene, washing with an organic solvent other than the alkylbenzene is not prevented.

Next, the solid substance after the washing is reacted with titanium tetrachloride (c) having a volume ratio to the alkylbenzene (b) of 1 or less in the presence of the alkylbenzene (b).

The temperature at this time is not particularly limited, but is preferably in the range of 60 ° C. to 135 ° C., and this reaction is usually performed in the range of 10 minutes to 10 hours. A suitable temperature range in each of the above reactions is appropriately determined depending on the type of the alkylbenzene (b) used.

The above reaction is usually performed with stirring using a vessel equipped with a stirrer.

It is not particularly necessary to suspend the diethoxymagnesium (a) in the alkylbenzene (b) at around room temperature, but it is preferable because the operation can be performed easily and with a simple apparatus.

The solid catalyst component obtained in this way may be used if necessary.
-It is also possible to wash with an organic solvent such as heptane.
The solid catalyst component can be used as it is after washing, or after washing and dried, as a catalyst for polymerization of olefins.

Next, the olefin polymerization catalyst of the present invention using the solid catalyst component will be described.

The general formula (B) used in the catalyst of the present invention
SiRm (OR ′) _4-m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, m m may be a combination of different groups, and R ′ is an alkyl group When R is an alkyl group, the alkyl group may be the same as or different from R '.
Is 0 ≦ m ≦ 3. Examples of the silicon compound represented by) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane. Further examples of phenylalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. Examples of the alkylalkoxysilane include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane and the like.

Examples of the organoaluminum compound (C) used in the catalyst of the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, and mixtures thereof.

The organoaluminum compound (C) used in the catalyst of the present invention has a molar ratio of 1 to 1000 per mole of titanium atoms in the solid catalyst component (A), and the silicon compound (B) is the organoaluminum. It is used in a molar ratio of 0.01 to 0.5 per mole of the compound.

The polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either a gas or liquid state. Polymerization temperature is 20
0 ° C. or less, preferably 100 ° C. or less, the polymerization pressure is 100 kg /
cm ² · G or less, preferably 50 kg / cm ² · G or less.

Olefins homopolymerized or copolymerized using the catalyst according to the present invention are ethylene, propylene, 1-butene,
4-methyl-1-pentene and the like.

〔The invention's effect〕

When olefins are polymerized using the olefin polymerization catalyst according to the present invention, the resulting polymer has extremely high stereoregularity.

Further, in industrial production of polyolefin, the bulk specific gravity of the produced polymer becomes a very large problem from the viewpoint of the capacity of the polymerization apparatus, the capacity of the post-treatment step, and the like. Has excellent properties.

Further, the amount of titanium tetrachloride used in the preparation of the solid catalyst component of the present invention is particularly small as compared with the prior art. Titanium tetrachloride reacts with oxygen and moisture in the air to form hydrochloric acid gas, which is a difficult substance to handle, such as emitting white smoke or a strong pungent odor. It offers great benefits in the production of solid catalyst components, such as ease of operation and prevention of pollution sources.

Further, since the catalyst according to the present invention exhibits an unexpectedly high activity, the amount of the catalyst residue present in the produced polymer can be extremely reduced, and the amount of residual chlorine in the produced polymer can be reduced. The ash process can be reduced to the extent that it is not required at all.

Further, according to the catalyst of the present invention, there is also a large problem that odor adheres to the produced polymer by not adding an organic carboxylic acid ester or a nitrogen compound during the preparation of the solid catalyst component and the polymerization using the solid catalyst component. Can be completely solved.

Further, conventionally, there has been a common drawback in the so-called high activity supported catalyst, in which the activity per unit time of the catalyst is greatly reduced with the progress of polymerization, but in the catalyst according to the present invention, Since the decrease in activity with time is extremely small as compared with the conventionally known catalysts, it is extremely useful for prolonging the polymerization time such as copolymerization.

In addition, in industrial production of olefin polymers, it is generally considered that hydrogen coexists during polymerization in terms of MI control and the like, but conventional magnesium chloride is used as a carrier and organic monocarboxylic acid esters are used. The catalyst used had the disadvantage that the activity and tacticity were significantly reduced in the presence of hydrogen. However, when olefin is polymerized in the presence of hydrogen using the catalyst according to the present invention, the activity and stereoregularity do not decrease even when the MI of the produced polymer is extremely high. Such an effect has been strongly desired by those skilled in the art.

〔Example〕

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

Example 1 [Preparation of a solid catalyst component]
A 0 ml round-bottomed flask was charged with 10 g of diethoxymagnesium and 60 ml of toluene to form a suspension, then 40 ml of TiCl ₄ was added to the suspension, the temperature was raised to 70 ° C., and 1.5 ml of dibutoxytitanium chloride and 90 ml of Heat to ℃ and add 2.0 ml of phthalic dichloride. Then raise the temperature to 115 ° C and
The reaction was carried out with stirring for hours. After completion of the reaction, the mixture was washed twice with 200 ml of toluene at 90 ° C., and 60 ml of toluene and TiCl ₄ were newly added.
After adding 40 ml, the mixture was reacted at 115 ° C. with stirring for 2 hours.
After completion of the reaction, the reaction product was diluted with 200 ml of n-heptane at 40 ° C.
Washed twice. The titanium content in the solid catalyst component thus obtained was measured and found to be 2.87% by weight.

(Conjugation)

200 mg of triethylaluminum, 45 m of diphenyldimethoxysilane in an autoclave with a stirrer having an internal volume of 2.0
g, and 5.0 mg of the solid catalyst component. After that, hydrogen gas 1.8 and liquefied propylene 1.4 were charged,
Minutes of polymerization. After the polymerization is completed, the obtained polymer is
After drying under reduced pressure at ℃, the obtained amount is designated as (A). This was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is designated as (B).

The polymerization activity (C) per used solid catalyst component is calculated by the formula Expressed by

Further, the yield (D) of the all crystalline polymer is calculated by the formula Expressed by

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 specific gravity is represented by (G). The results obtained are as shown in Table 1.

Example 2 An experiment was performed in the same manner as in Example 1 except that the polymerization time was changed to 1 hour. The results obtained are shown in Table 1.

EXAMPLE 3 Toluene 100 ml, line experiment in the same manner except that the TiCl ₄ was used 40ml of Example 1 Natsuta. Incidentally, the titanium content in the obtained solid catalyst component was 2.80% by weight. An experiment was conducted in the same manner as in Example 1 for the polymerization. The results obtained are shown in Table 1.

Example 4 An experiment was conducted in the same manner as in Example 1 except that 2.0 ml of dibutoxytitanium chloride was used. Incidentally, the titanium content in the obtained solid catalyst component was 2.90% by weight. An experiment was conducted in the same manner as in Example 1 for the polymerization. The results obtained are shown in Table 1.

Example 5 An experiment was conducted in the same manner as in Example 1 except that the same amount of tributoxy titanium chloride was used instead of dibutoxy titanium dichloride. The titanium content in the obtained solid catalyst component was 3.03% by weight. An experiment was conducted in the same manner as in Example 1 for the polymerization. The results obtained are shown in Table 1.

[Brief description of the drawings]

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

Claims (2)

(57) [Claims] 1. A method for suspending diethoxymagnesium (a) in alkylbenzene (b) and contacting the same with titanium tetrachloride (c) having a volume ratio of not more than 1 to the alkylbenzene (b), An alkoxytitanium chloride (d) represented by the general formula Ti (OR) nX _4-n (R is an alkyl group, X is chlorine, and n is an integer of 1 to 3) is added, and the mixture is further heated to 80 ° C. A solid substance obtained by adding and reacting phthalic acid dichloride (e) in a temperature range of ~ 135 ° C is washed with alkylbenzene, and the solid substance is further subjected to a capacity for the alkylbenzene (b) in the presence of alkylbenzene (b). A solid catalyst component for olefin polymerization, which is obtained by reacting titanium tetrachloride (c) having a ratio of 1 or less. 2. (A) Diethoxymagnesium (a) is suspended in alkylbenzene (b) and then contacted with titanium tetrachloride (c) having a volume ratio of 1 or less to alkylbenzene (b), and then suspended. At lower than ℃, general formula Ti (OR) nX
_4-n (wherein R is an alkyl group, X is chlorine, and n is an integer of 1 to 3), and an alkoxytitanium chloride (d) is further added. The solid substance obtained by adding and reacting phthalic acid dichloride (e) is washed with alkylbenzene, and the solid substance is further added with alkylbenzene (b) in the presence of alkylbenzene (b) in a tetrachloride ratio of 1 or less by volume to the alkylbenzene (b). A solid catalyst component for the polymerization of olefins obtained by reacting titanium (c); (B) a general formula SiRm (OR ') _4-m (where R is an alkyl group,
It is a group selected from a cycloalkyl group, an aryl group or a vinyl group, m Rs may be a combination of different groups, and R 'is an alkyl group. When R is an alkyl group, the alkyl group may be the same as or different from R '. m is 0 ≦ m ≦ 3. And an organoaluminum compound represented by (C) a general formula RpAlX _3-p (where R is an alkyl group, X is a halogen element, and p is a real number satisfying 0 <p ≦ 3). An olefin polymerization catalyst, comprising: