JPH03212406A - 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 catalyst component prepared by treating a Mg compound with a TiCl4, a Si compound and phthalic dichloride and subsequently reacting the reaction product with TiCl4. CONSTITUTION:The objective catalyst for polymerizing olefins comprises (A) a solid catalyst component, (B) a Si compound of the formula and (C) an organic Al compound, the solid catalyst component A being prepared by reacting a solid substance with TiCl4 in a volume ratio of 1: <=1 between an alkylbenzene and the TiCl4 and further repeating the process two times or more, the solid substance being prepared by suspending diethoxy Mg in the alkylbenzene, bringing the suspension into contact with TiCl4 in a volume ratio of <=1 based on the volume of the alkylbenzene, adding a Si compound of the formula (R is alkyl, aryl, etc.; R' is alkyl; 0<=m<=3) 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 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 is added to dialkoxymagnesium obtained by a specific operation with the aim of improving the drawback of reduced stereoregularity in the resulting polymer when hydrogen is used. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide is disclosed below.

Analysis from Example 2, which specifically exemplifies this method, shows that dialkoxymagnesium is suspended in carbon tetrachloride,
Ethyl benzoate and titanium tetrachloride were added at 75°C, and the suspension was stirred for 2 hours while maintaining the temperature at 75°C. do. The produced solid was isolated and washed 5 times with iso-octane, then suspended in titanium tetrachloride at 80°C and 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 Ming] However, when the solid catalyst component prepared by the method shown in JP-A-55-152710 is used for the polymerization of olefins, the polymerization activity and the yield of stereoregular polymers are low. And it cannot be said that it shows sufficient performance in terms of sustainability 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. succeeded in obtaining. However, there has been a demand in the industry for higher catalytic activity and stereoregularity yields of the resulting polymers.

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 hereby propose the present invention.

[Means for Solving the Problems] That is, the features of the present invention are (1) suspending diethoxymagnesium (a) in alkylbenzene (b) and then suspending the alkylbenzene (b).
and titanium tetrachloride (C) with a volume ratio of 1 or less, and then at 80°C or less General formula: SiRm(OR')
4-m (in the formula, R is an alkyl group cycloalkyl group
It is a group selected from an aryl group or a vinyl group, the m R's may be in different combinations, and R' is an alkyl group. When R is an alkyl group, the alkyl group is R'
may be the same or different. m is 0≦m≦
It is 3. ) by adding a silicon compound (d) represented by
Furthermore, the solid material obtained by adding and reacting phthalic acid dichloride (e) at a temperature range of 80°C to 125°C is washed with alkylbenzene, and then in the presence of alkylbenzene (b), the alkylbenzene (b) is
A solid catalyst component for polymerizing olefins, which is obtained by repeating the operation of reacting titanium tetrachloride (c) with a volume ratio of 1 or less three times or more, and a solid catalyst component having the 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, and m R's may be in different combinations (, R' is an alkyl group. When R is an alkyl group, The alkyl group may be the same as or different from R', and m is O≦m≦3.

) The present invention provides a catalyst for onfin neck polymerization characterized by comprising a silicon compound and an organoaluminum compound represented by the following.

The general formula used in the preparation of the solid catalyst component of the present invention is SiRm(OR')4-m (wherein R is a group selected from an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group, and m R's are different). (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.) Silicon compound (d) represented by (hereinafter sometimes simply referred to as (d) substance).

) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane. Specifically, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane. , trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, and the like.

Alkylbenzene (b) (hereinafter simply referred to as (a) substance) used to suspend (1) diethoxymagnesium (a) (hereinafter simply referred to as (a) substance) in U4'JA of the solid catalyst component of the present invention. b) Substances) 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 0.5-0g. In addition, titanium tetrachloride (C) (hereinafter sometimes simply referred to as (C) substance) is (a) 1.0 g or more per 1°0 g of the substance, and (b) a volume ratio of 1 or less to the substance. It is quantity. 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 (b) substance in the (b) substance.
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 it is preferably 90°C or higher, up to the boiling point of the alkylbenzene used. Examples of the alkylbenzene used for washing include those listed in the example of the substance (b) above. It will be done.

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.
It is carried out in the range of 0 minutes to 10 hours.

Suitable temperature ranges for each of the above reactions are used (b)
Windowing is done as appropriate depending on the type of substance.

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 iRm(OR' )4-m (wherein R is a group selected from alkyl groups, cycloalkyl groups, aryl groups, or vinyl groups, 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 the above (d ) The same or different substances can be selected and used from among the substances exemplified.

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 based on the mole of titanium atoms in the solid catalyst component (A), and the silicon compound (B) It is used in a molar ratio of 0.01 to 0.5 based on the mole of the aluminum 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 100kg/cI!12・C or less, preferably 50k
g/cm 2G or less.

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.

[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, it is possible to extremely reduce the amount of catalyst residue present in the produced polymer, and therefore, the amount of residual chlorine in the produced polymer can be suppressed to an extremely low level. This can be reduced to such an extent that a demineralization step 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 practice to coexist hydrogen during polymerization for MI sub-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] 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.
A 0aQ round bottom flask was charged with (1) 10 g of diethoxymagnesium and 1 g of toluene 60II to form a suspension, and then TiC1,40- was added to this suspension and 70
After raising the temperature to 0.degree. C. and adding ethyltriethoxysilane 1.7.9, the temperature was further raised to 90.degree. C. to obtain phthalic acid dichloride 2.2. 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 liters of toluene under reflux, and newly added with 60 liters of toluene and TiC1a40+.
The operation of adding ail and reacting at 115°C for 2 hours with stirring was repeated three times. Then the reaction product is 4
Washed 10 times with 200 ml of n-hebutane at 0°C. The titanium content in the solid catalyst component thus obtained was measured to be 1.82% by weight.

<Polymerization> 200 In of triethylaluminum was placed in an autoclave with an internal volume of 2.09 and a stirring device, which was sufficiently purged with nitrogen gas.
g, cyclohexylmethyldimethoxysilane 45. And 3.0 mg of the solid catalyst component was charged. After that, 1.8Q of hydrogen gas and 1.4Q of liquefied propylene were charged, and 70
Polymerization was carried out at ℃ 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, 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), 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 An experiment was conducted in the same manner as in Example 1, except that 100 mm of toluene and 40 mm of TiC1□ were used.

In addition, the titanium content in the obtained solid catalyst component was 1.8
It was 0% by weight. For IL combination, 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. The titanium content in the obtained solid catalyst component was 2. 00% by weight.

During polymerization, an experiment was conducted in the same manner as in Example 1. 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)
titanium tetrachloride (c) with a volume ratio of 1 or less to
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, and R' is an alkyl group. R is an alkyl group) , the alkyl group may be the same as or different from R', where m is 0≦m≦3. Phthalic acid dichloride (
The solid material obtained by adding e) and reacting is washed with alkylbenzene, and then reacted with titanium tetrachloride (c) in a volume ratio of 1 or less to the alkylbenzene (b) in the presence of alkylbenzene (b). A solid catalyst component for polymerizing olefins, characterized in that it is obtained by repeating the step 3 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 general formula 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. is an alkyl group, the alkyl group is R
′ may be the same or different. m is 0≦m≦
It is 3. ) and then reacted with phthalic acid dichloride (e) in a temperature range of 80°C to 125°C. The resulting hedral material is washed with alkylbenzene, and then washed with alkylbenzene. (b) in the presence of said alkylbenzene (b)
) A solid catalyst component for olefin polymerization characterized by being obtained by repeating the operation of reacting titanium tetrachloride (c) with a volume ratio of 1 or less to 1 or less three times or more; (B) General formula 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 it is an alkyl group, the alkyl group may be the same as or different from R'. m is 0≦m≦3.) and (C) an organoaluminum compound. A catalyst for polymerizing olefins characterized by: