JPH03212407A - Solid catalyst component and catalyst for polymerization of olefins - Google Patents

Abstract

PURPOSE:To provide the subject catalyst giving stereoregular polymers in high yields by compounding an organic Si compound and an organic Al compound with a solid substance prepared by treating a Mg compound with TiCl4, Al compound and phthalic dichloride in a solvent and subsequently reacting the product with TiCl4. CONSTITUTION:The objective polymerization catalyst comprises (A) a solid catalyst component, (B) a silicon compound of the formula (R is alkyl, aryl, etc.; R' is alkyl; 0<=m<=3) and (C) an organic aluminum compound, the solid catalyst component being prepared by reacting a solid substance with titanium tetrachloride in a volume ratio of <=1 based on the volume of an alkylbenzene and further repeating the process two times or more, the solid substance being prepared by suspending diethoxy magnesium in the alkylbenzene, bringing the suspension into contact with titanium tetrachloride in a volume ratio of <=1 based on the volume of the alkylbenzene, adding a trialkyl aluminum to the product at <=80 deg.C and further adding phthalic dichloride to the reaction product at 80-125 deg.C.

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 polymerizing olefins comprising dialkoxymagnesium, titanium tetrachloride, and electron-donating compounds or catalysts for polymerizing olefins using the solid catalyst components have already been developed and proposed. There is.

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, In order to improve the disadvantage of reduced stereoregularity in the resulting polymer when hydrogen is added, dialkoxymagnesium obtained by a specific operation is combined with a halokenated hydrocarbon and an electron-donating compound. 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 produced 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. I am getting . Example 1 shows an example in which this solid catalyst component was used in combination with triethylaluminum as a catalyst for polymerization of 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 stereoregular polymer yield when used for olefin polymerization. It cannot be said that it shows sufficient performance in terms of rate and duration of activity.

In order to solve this problem, the inventors of the present invention, in Japanese Patent Application Laid-Open No. 108611/1983, added a diester of dialkoxymagnesium and an aromatic dicarboxylic acid to a halogenated hydrocarbon and treated it 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. succeeded in obtaining. However, there has been a demand in the industry for higher catalytic activity and stereoregular yield of the resulting polymer.

Therefore, 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 propose the second invention.

[Means for Solving the Problems] That is, the feature of the present invention is that jetoxymagnesium (δ) 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), and then trialkoxyaluminum (d) was added at 80°C or lower, and the mixture was further suspended at 80°C. The solid material obtained by adding and reacting phthaloyl dichloride (e) in the temperature range of ~125°C is washed with alkylbenzene, and then the volume is reduced to the alkylbenzene (b) in the presence of alkylbenzene (b). Titanium tetrachloride (e) with a ratio of 1 or less
A solid catalyst component for olefin polymerization, which is obtained by repeating the operation of reacting three or more times, and a solid catalyst component having the general formula SiRm(OR')4-m (wherein R is an alkyl group, cyclo Alkyl group A group selected from an aryl group or a vinyl group, m R's may be in different combinations, and R' is an alkyl group.When R is a 7/l/ki/l/ group, the alkyl group The group may be the same as or different from R'. m is 0≦m≦3.

An object of the present invention is to provide a catalyst for polymerizing olefins, which is characterized by comprising a silicon compound and an organoaluminum compound represented by the following formulas.

The trialkylaluminium (d) (hereinafter sometimes simply referred to as (d) substance) used in the U8 solid catalyst component of the present invention includes triethoxyaluminum,
Examples include tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, triisobutoxyaluminum, and the like.

In the preparation of the solid catalyst component of the present invention, jetoxymagnesium (a) (hereinafter sometimes simply referred to as (a) substance) is used.

) used to suspend alkylbenzene (b
) (hereinafter referred to as (b) substance) 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 O,l+$1 with respect to Og.

In addition, titanium tetrachloride (C) (hereinafter sometimes simply referred to as (C) substance) is 1.0g per 1゜0g of (a) substance.
or more, and (b) the volume ratio to the substance is 1 or less. Note that it is necessary to use the substance (b) in an amount that can form a suspension with the substance (A).

The solid catalyst component of the present invention has a volume ratio of 1 or less to the (b) substance after suspending the (a) substance in the (b) substance.
alkylbenzene to a solid substance obtained by contacting with the substance c), then adding the substance (d) at a temperature below 80°C, and then adding the substance (e) at a temperature between 80°C and 125°C. 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 ~125°C is usually carried out for a period of 10 minutes to 10 hours. The alkylbenzene used for the above cleaning may be the same as or different from the substance (b) above.The temperature during cleaning is not particularly limited, but is at least 90°C and up to the boiling point of the alkylbenzene used. is preferred. 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 (b)
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
SiRm(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'. m is O≦m≦3.) As the silicon compound represented by phenylalkoxysilane, Alkylalkoxysilane, phenylalkylalkoxysilane,
Examples include cycloalkylalkoxysilane and cycloalkylalkylalkoxysilane.

Specifically, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethyl. Examples include silane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane, cyclohexyltriethoxysilane, 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 organic aluminum compound (C) used in the catalyst of the present invention has a molar ratio of 1 to 100o per mole of titanium atoms in the solid catalyst component (A), and the silicon compound (B) has a molar ratio of 1 to 100o per mole of titanium atoms in the solid catalyst component (A). The molar ratio per mole of the compound is 0.01 to 0. Used in the range of 5.

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℃ or less, and the polymerization pressure is 10
0kg/an'・G or less, preferably 50kg/cm"
・It is below C.

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

[Operations 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. It has convenient 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.

Further, according to the catalyst according to the present invention, the solid catalyst component U8v,
By not adding organic carboxylic acid esters or nitrogen compounds during polymerization using the solid catalyst component, it is possible to completely solve the major problem of odor adhesion to the resulting polymer.

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 even 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 for purposes such as MI control. The catalyst used had the disadvantage that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when olefins are 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 resulting polymer is extremely high. Such an effect was strongly desired by those skilled in the art.

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

Example 1 <Preparation of solid catalyst component> 50g amount fully purged with nitrogen gas and equipped with a stirrer
1 jetoxymagnesium in a 0+n11 round bottom flask
40 tons of TiCl was added to this suspension, the temperature was raised to 70°C, 1.5 g of tributoxyaluminum was added, and the temperature was further raised to 90°C. Warm and add phthalic acid dichloride2. OL1
! Add l. 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 d of toluene under reflux, and freshly added with toluene 6011IQ and T ICl a.
The operation of adding 40 ml of water and reacting at 115°C for 2 hours with stirring was repeated three times. Thereafter, the reaction product was washed 10 times with 200° C. of n-heptane at 40°C. The titanium content in the solid catalyst component thus obtained was measured and found to be 1.72% by weight.

<Polymerization> 200 μm of triethylaluminum was placed in an autoclave with a stirrer and an internal volume of 2.02 μm, which was sufficiently purged with nitrogen gas.
Cyclohexylmethyldimethoxysilane 45. And 3.0 mg of the solid catalyst component was charged. After that, 1.8L of hydrogen gas and 1.49L of liquefied propylene were charged, and 70"
Polymerization was carried out at C for 30 minutes. After completion of 0 polymerization, 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, and the yield (D) of the total crystalline polymer is expressed by the formula (), and the amount of residual chlorine in the produced polymer is expressed by (E). The obtained results are shown in Table 1, where MI is expressed as (F) and bulk specific gravity is expressed as (G).

Example 2 An experiment was conducted in the same manner as in Example 1 except that 2.0 g of tributoxyaluminum was used. Note that the titanium content in the obtained solid catalyst component was 1.89% 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 carried out in the same manner as in Example 1 except that the same amount of triisopropoxyaluminum was used instead of tributoxyaluminum. The titanium content in the obtained solid catalyst component was 2.36% by weight. An experiment was conducted in the same manner as in Example 1 for zero polymerization. The results obtained are shown in Table 1.

No. table 4,

[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)
of titanium tetrachloride (c) at a volume ratio of 1 or less, and then contact with trialkoxyaluminum (c) at 80°C or less.
d) and further reacted with phthalic acid dichloride in a temperature range of 80°C to 125°C, the solid material obtained by adding (e) is washed with alkylbenzene, and then in the presence of alkylbenzene (b). 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 with respect to the alkylbenzene (b) three or more times. (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 trialkoxyaluminum (d) and reacting with phthalic acid dichloride (e) in a temperature range of 80°C to 125°C is washed with alkylbenzene, and then alkylbenzene (b) is added. ) 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 SiRm(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, m R's 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.) (C) A catalyst for polymerizing olefins, comprising an organoaluminum compound.