JPH03207702A - Solid catalytic component for olefin polymerization and catalyst therefrom - Google Patents

Abstract

PURPOSE:To provide the title catalyst capable of giving stereoregular polymers in high yield, made up of an organoaluminum compound, silicon compound and a component prepared by adding to a diethoxymagnesium-suspended solvent TiCl4, a tetraalkoxytitanium, phthaloyl dichloride and TiCl4 successively in this order. CONSTITUTION:(A) Diethoxymagnesium is suspended in an alkylbenzene, and the suspension is brought into contact with TiCl4<=1 in its volume ratio to the alkylbenzene, and the resultant suspension is incorporated with a tetraalkoxytitanuim at <=80 deg.C followed by phthaloyl dichloride at 80-125 deg.C to make a reaction into a solid material. This material is washed with the alkylbenzene followed by reaction with TiCl4<=1 in its volume ratio to the solid material in the presence of the alkylbenzene. This operation is repeated at least three times, thus obtaining a solid component. This component is then incorporated with (B) a Si compound of the formula (R is alkyl, aryl, etc., R' is alkyl; 0<=m<=3) and an organoaluminum compound, thus obtaining the objective polymerization catalyst.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention exhibits an unprecedentedly high activity when subjected to the polymerization of olefins, and also produces stereoregular polymers in high yields. The present invention relates to a high-performance solid catalyst component that can be obtained in the following manner and a catalyst for polymerizing olefins using the same.

[Prior Art] Various solid catalyst components for olefin polymerization consisting of dialkoxymagnesium, titanium tetrachloride, and electron-donating compounds or catalysts for olefin polymerization using the solid catalyst components have already been developed and proposed. ing.

For example, in JP-A-55-152710, it was discovered that in order to obtain high catalyst activity, a large amount of an organoaluminum compound must be used during polymerization, and that in order to control the molecular weight of the resulting polymer, The presence of halogenated hydrocarbons and electron-donating compounds in dialkoxymagnesium obtained by a specific operation is aimed at improving the disadvantage of reduced stereoregularity in the resulting polymer when hydrogen is added and used. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide is disclosed below.

Analysis from Example 2 specifically exemplifying this method reveals that dialkoxymagnesium is suspended in carbon tetrachloride,
Ethyl benzoate and titanium tetrachloride are added at 5°C, and the suspension is stirred for 2 hours while maintaining the temperature at 75°C. The generated solid was isolated and washed 5 times with iso-octane, then 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 polymerization catalyst for olefins.

[Problems to be Solved by the Invention] However, the solid catalyst component prepared by the method disclosed in JP-A-55-152710 has poor polymerization activity and yield of stereoregular polymers when used for olefin polymerization. It cannot be said that it shows sufficient performance in terms of rate and duration of activity.

Therefore, in order to solve this problem, the present inventors disclosed in JP-A-61-108611 that a diester of dialkoxymagnesium and an aromatic dicarboxylic acid was added to a halogenated hydrocarbon and treated in a suspended state. Later, he developed a catalyst for polymerizing olefins consisting of a solid catalyst component obtained by adding the suspension to titanium halide and reacting it, a piperidine derivative, and an organoaluminum compound, and achieved excellent properties in terms of high activity and durability. However, the industry has been demanding higher catalytic activity and stereoregular yield of the resulting polymer.

Therefore, 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 Su.

Means for Solving Problem C] That is, the feature of the present invention is that jetoxymagnesium (8) is replaced with alkylbenzene (b
), and then brought into contact with titanium tetrachloride (C) in a volume ratio of 1 or less to the alkylbenzene (b). Then, tetraalkoxytitanium (d) was added at 80°C or lower, and further at 80°C. The solid material obtained by adding and reacting phthalic acid dichloride (e) in the temperature range of ~125°C is washed with alkylbenzene, and then the alkylbenzene (
A solid catalyst component for polymerizing olefins, which is obtained by repeating the operation of reacting titanium tetrachloride (C) at a volume ratio of 1 or less with b) three times or more, and the solid catalyst component; Formula: SiR+a(OR')4-m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, m R's may be in different combinations, 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 O≦m≦3. An object of the present invention is to provide a catalyst for polymerizing olefins, which is characterized by the following.

Tetraalkoxytitanium (d) (hereinafter sometimes simply referred to as (d) substance) used in the preparation of the solid catalyst component of the present invention includes tetrabutoxytitanium, tetraisobutoxytitanium, tetrapropoxytitanium, and tetraisopropoxytitanium. etc. can be mentioned.

The alkylbenzene (
Examples of b) (hereinafter simply referred to as substance (b)) include toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, etc.

(d) used in the preparation of the solid catalyst component of the present invention
Substance and phthalic acid dichloride (e) (hereinafter simply referred to as (e)
) It is sometimes called a substance. ) usage ratio is (a) substance 1
．． It is in the range of 0.01 to 0.5 d with respect to 0 g. In addition, titanium tetrachloride (C) (hereinafter sometimes simply referred to as (c) substance) is 1.0 g or more per 1.0 g of (c) substance, and the volume ratio to (b) substance is 1 or less. It's the amount. Note that it is necessary to use the substance (b) in an amount that can form a suspension with the substance (a).

After suspending the solid catalyst component of the present invention in the substance (b), the solid catalyst component of the present invention has a volume ratio of 1 or less to the substance (b).
c) Contact with the substance, then add the substance (d) at a temperature below 80°C, and further add and react the substance (e) at a temperature range of 80°C to 125°C. It is obtained by repeating the operation of washing, and then reacting the substance (C) in the presence of the substance (b) with a volume ratio of 1 or less to the substance (b) three times or more. The reaction in the temperature range of °C is usually carried out for 10 minutes to 10 hours. The alkylbenzene used for the above cleaning may be the same as or different from the substance (b). The temperature during washing is not particularly limited, but is preferably 90° C. or higher and up to the boiling point of the alkylbenzene used. Examples of alkylbenzenes used for cleaning include those listed above in the example of substance (b).

Note that, prior to washing with this alkylbenzene, it is possible to perform washing with an organic solvent other than the alkylbenzene.

The solid material after this washing is then further processed (h)
React with the substance (c) in a volume ratio of 1 or less to the substance (b) in the presence of the substance.

The temperature at this time is not particularly limited, but is preferably in the range of 80°C to 125°C.
The duration ranges from 0 minutes to 10 hours. Suitable temperature ranges for each of the above reactions are determined as appropriate depending on the type of substance (b) used.

The above reaction is usually carried out under stirring using a container equipped with a stirrer.

Although it is not particularly necessary to suspend the substance (a) in the substance (b) at around room temperature, it is preferable because it is easy to operate and can be carried out using a simple device.

The solid catalyst component thus obtained can be used as n-
It is also possible to wash with an organic solvent such as hebutane. This solid catalyst component can be used as a catalyst for polymerization of olefins either as it is after washing or after being dried after washing.

Next, the catalyst for polymerizing olefins of the present invention using the above solid catalyst component will be explained.

-General formula of the above (B) used in the catalyst of the present invention
S 1Rio(OR' )4-m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, m R's 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', and 0m is 0≦m≦3.) Examples of silicon compounds represented by the formula include phenylalkoxysilane, Alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes and cycloalkylalkylalkoxysilanes can be mentioned, specifically phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane,
Phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane, cyclohexyl Examples include triethoxysilane and cyclohexylmethyldimethoxysilane.

Examples of the organoaluminum compound (C) used in the catalyst of the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum cybaride, 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 (^), and the silicon compound (B) has a molar ratio of 1 to 1000 per mole of titanium atoms in the solid catalyst component (^). It is used in a molar ratio of 0.01 to 0.5 per mole of the metal compound.

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. Polymerization temperature is 200
℃ or less, preferably 100'C or less, and the polymerization pressure is 100 kg/cm'-G or less, preferably 50 kg/cm'-G or less.
an”・G or less.

The olefins to be homopolymerized or copolymerized using the catalyst according to the present invention are ethylene and propylene.

These include 1-butene and 4-methyl-1-pentene.

Functions and Effects of the Invention When olefins are polymerized using the catalyst for olefin polymerization according to the present invention, the resulting polymer has extremely high stereoregularity.

Furthermore, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem due to the capacity of the polymerization equipment, the capacity of the post-treatment process, etc., and the catalyst according to the present invention is extremely important in this respect as well. Has excellent properties.

Furthermore, the titanium tetrachloride used in the preparation of the solid catalyst component of the present invention is characterized in that it is used in an extremely small amount compared to conventional techniques. Titanium tetrachloride is a substance that is difficult to handle as it reacts with oxygen and moisture in the air to form hydrochloric acid gas, emitting white smoke and a strong pungent odor. Therefore, reducing the amount of titanium used has led to lower costs. It offers great benefits in the production of solid catalyst components, such as ease of operation and prevention of pollution sources.

Furthermore, since the catalyst according to the present invention exhibits a high activity that was completely unexpected in the past, the amount of catalyst residue present in the produced polymer can be kept extremely low, and therefore the amount of residual chlorine in the produced polymer can also be eliminated. The ash process can be reduced to such an extent that it is not required at all.

In addition, according to the catalyst of the present invention, since organic carboxylic acid esters and nitrogen compounds are not added during the preparation of the solid catalyst component and during polymerization using the solid catalyst component, the major problem of odor adhesion to the resulting polymer can be avoided. can be completely resolved.

Furthermore, the activity per unit time of conventional catalysts significantly decreases as the polymerization progresses, which is a common drawback of so-called high-activity supported catalysts, but the catalyst of the present invention has Since the decrease in activity over time is extremely small compared to conventionally known catalysts, it is extremely useful in cases where the polymerization time is longer, such as in copolymerization.

Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of Ml control. The catalyst used had the drawback that its activity and stereoregularity were significantly reduced in the coexistence of hydrogen. However, when olefin polymerization was carried out using the catalyst according to the present invention in the coexistence of hydrogen, even when the MI of is extremely high.

Activity and stereoregularity are not reduced. Such an effect was strongly desired by those skilled in the art.

[Example] The present invention will be specifically explained below using examples.

Example 1 <Preparation of solid catalyst component> Sufficiently purged with nitrogen gas. Capacity 50 equipped with a stirrer.
10 g of tetrabutoxytitanium and 60 g of toluene were placed in a round bottom flask containing 1.0 g of tetrabutoxy titanium to form a suspension, and then 40 g of T i C1a was added to this suspension and the temperature was raised to 70° C. to obtain 1.0 g of tetrabutoxytitanium. After adding 5w1il,
The temperature was further raised to 90°C and phthalic acid dichloride 2. Add 〇-. Thereafter, the temperature was raised to 115°C, and the mixture was reacted with stirring for 2 hours.

After the reaction was completed, the solid catalyst material obtained was washed twice with 200 ml of toluene under reflux, and then washed with 600 ml of toluene twice.
The operation of adding 0- and TiC1a40- and reacting at 115°C for 2 hours with stirring was repeated three times.

The reaction product was then dissolved in 200°C of n-hebutane at 40°C.
Washed 0 times.

The titanium content in the solid catalyst component thus obtained was measured and found to be 2.23% by weight.

<Polymerization> Internal volume sufficiently purged with nitrogen gas2. Triethylaluminum 200cm in an autoclave with an oil stirring device
, 45 inches of cyclohexylmethyldimethoxysilane, and 3.0 inches of the solid catalyst component were charged. After that, hydrogen gas 1.8Ω and liquefied propylene 1.4Q were charged and heated to 70℃.
Polymerization was carried out for 30 minutes. After the polymerization was completed, the obtained polymer was dried under reduced pressure at 80° C., and the obtained amount was designated as (A). Further, this was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (B).

The polymerization activity (C) per solid catalyst component used is expressed by the formula, the yield (D) of the total crystalline polymer is expressed by the formula, the amount of residual chlorine in the produced polymer is expressed by (E), and the MI of the produced polymer is expressed by the formula is represented by (F), and the bulk specific gravity is represented by (G). The results obtained are shown in Table 1.

Example 2 Example 1 except that 2.0-tetrabutoxytitanium was used.
An experiment was conducted in the same manner. The titanium content in the obtained solid catalyst component was 2.26% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 3 An experiment was conducted in the same manner as in Example 1 except that the same amount of xylene was used instead of toluene. Note that the titanium content in the obtained solid catalyst component was 2.18% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Table 1

[Brief explanation of drawings]

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

Claims (2)

[Claims] (1) After suspending diethoxymagnesium (a) in alkylbenzene (b), the alkylbenzene (b)
Contact with titanium tetrachloride (c) at a volume ratio of 1 or less to titanium tetrachloride (d) at 80°C or less.
and further react with phthalic acid dichloride in a temperature range of 80 ° C to 125 ° C. The solid material obtained by adding and reacting with (e) is washed with alkylbenzene,
Next, in the presence of alkylbenzene (b), titanium tetrachloride (
A solid catalyst component for polymerizing olefins, which is obtained by repeating the reaction step (c) three times or more. (2) (A) Diethoxymagnesium (a) is suspended in alkylbenzene (b) and then brought into contact with titanium tetrachloride (c) in a volume ratio of 1 or less to the alkylbenzene (b), and then 80°C or less The solid material obtained by adding tetraalkoxytitanium (d) and reacting it by adding phthalic acid dichloride (e) at a temperature range of 80°C to 125°C is washed with alkylbenzene, and then alkylbenzene (b) is added and reacted. ) A solid catalyst component for polymerizing olefins, characterized in that it is obtained by repeating the operation of reacting titanium tetrachloride (c) with a volume ratio of 1 or less to the alkylbenzene (b) three or more times in the presence of ( B) General formula SiR_m(OR')_4_-_m (in the formula, R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, and m R's may be a combination of different groups, R ' is an alkyl group, and when R is an alkyl group, the alkyl group may be the same as or different from R'. m is 0≦m≦3.) (C) A catalyst for polymerizing olefins, comprising an organoaluminum compound.