JPH03215505A - Solid catalyst component and catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To prepare a solid catalyst component which shows a high activity and enables a stereoregular polymer to be produced at a high yield in the polymn. of an olefin by treating diethoxymagnesium with titanium tetrachloride, trialkoxyboron, and phthalic dichloride in a specific manner. CONSTITUTION:Mg(OC2H5)2 suspended in an alkylbenzene (e.g. toluene) is brought into contact with TiCl4 in a vol. ratio to the alkylbenzene of 1 or lower; the treated product is mixed with B(OR)3 (wherein R is CH3, C2H5, C3H7, C4H9, etc.) at 80 deg.C or lower and then with phthalic dichloride at 80-120 deg.C; the resulting mixture is reacted to give a solid substance, which is washed with the alkylbenzene and reacted with TiCl4 in the presence of the alkylbenzene (in a vol. ratio of TiCl4 to the alkylbenzene of 1 or lower). These steps are repeated three times. The resulting product is used as a solid catalyst component for an olefin polymn. catalyst. and is combined with an organsilicon compd. shown by SiRn(OR')4-n and an organoaluminum compd. to give the 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. This article relates to a high-performance solid catalyst component that can be obtained from the above 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, With the aim of improving the disadvantage of a decrease in the yield of stereoregularity of the resulting polymer when hydrogen is used, dialkoxymagnesium obtained by a specific operation is combined with a halogenated hydrocarbon and electrons. In the presence of a donating compound,
A method for obtaining a catalyst component by contacting with a tetravalent titanium halide is disclosed. Analysis from Example 2 specifically exemplifying this method reveals that dialkoxymagnesium is suspended in carbon tetrachloride,
Ethyl acetinate 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, washed S times with iso-octane, further suspended in titanium tetrachloride at 80°C, stirred for 2 hours, and then washed five times with iso-octane to obtain a solid catalyst component. 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 polymerization when used in the polymerization of olefins. It cannot be said that it shows sufficient performance in terms of yield and 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, a catalyst for olefin polymerization consisting of a solid catalyst component obtained by adding the suspension to a titanium halide, a piverizine derivative, and an organoaluminum compound was developed, and the catalyst had excellent properties in terms of high activity and durability. I succeeded in obtaining . However, in the industry, higher polymerization activity and stereoregular yield of the resulting polymer have been required. Therefore, the present inventors have developed 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 feature of the present invention is that diethoxymagnesium (a) 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 added trialkoxyboron (d) 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) with a volume ratio of 1 or less to b) three or more times, and the solid catalyst component; Formula SiR+a(OR')4-+s (in the formula R
is a group selected from an alkyl group, a cycloalkyl group, 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 may be the same as or different from R'. m is O≦m≦3. ) The present invention provides a catalyst for polymerizing olefins characterized by comprising a silicon compound and an organoaluminum compound represented by Trialkoxyboron (d) (hereinafter sometimes simply referred to as (d) substance) used in the preparation of the solid catalyst component of the present invention includes trimethoxyboron, triethoxyboron, tribroboxyboron, and triisoproboxy Examples include boron, tributoxyboron, triisobutoxyboron, etc.

In the preparation of the solid catalyst component of the present invention, diethoxymagnesium (a) (hereinafter sometimes simply referred to as (a) substance) is used.
) used to suspend alkylbenzene (b
) (hereinafter simply referred to as (b) substance) include toluene, xylene, ethylbenzene, probylbenzene, trimethylbenzene, etc. (d) used in the preparation of the solid catalyst component of the present invention
substance and phthalic acid dichloride (C) (hereinafter simply referred to as (e)
) It is sometimes called a substance. ) usage ratio is (1) substance 1
．． It is in the range of 0.01 to 0.5 for 0g. In addition, titanium tetrachloride (C) (hereinafter sometimes simply referred to as (c) substance) is 1.0 g or more per 1.0 g of (insect) substance, and the volume ratio to (b) substance is 1 or less. 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 (a) 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. Reactions in the temperature range of °C are usually carried out for 10 minutes to 10 hours. The alkylbenzene used in 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 (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 is from 0 minutes to 10 hours. Suitable temperature ranges for each of the above reactions are determined as appropriate depending on the type of (b) substance used. The above reactions are usually carried out with stirring in 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 the 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-mentioned solid catalyst component will be explained. General formula of the above (B) used in the catalyst of the present invention
S iR+s(OR' )4-+* (wherein R is an alkyl group, a cycloalkyl group, an aryl group, or a vinyl group; When R is an alkyl group, the alkyl group may be the same as or different from R'. m is 0≦m≦3.) As a silicon compound represented by phenyl Examples include alkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane. Specifically, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriproxysilane,
Phenyltriisobroboxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisoproboxy Examples include silane, cyclohexyltriethoxysilane, and cyclohexylmethyldimethoxysilane.

The organoaluminum compound (C) used in the catalyst of the present invention includes 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 molar of titanium atoms in the solid catalyst component (A), and the silicon compound (B) 0.0 in molar ratio per mole of compound. It is used in the range of 01 to 0.5. 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. The temperature of 1 cup is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0kg/co+”・G or less, preferably 50kg/cm
2-G or less. Olefins that can be homopolymerized or copolymerized using the catalyst according to the present invention include ethylene, brobylene, 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, ! It itself 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 by an extremely small amount compared to conventional techniques.Titanium tetrachloride reacts with oxygen and moisture in the air, producing hydrochloric acid gas. This is a substance that is difficult to handle as it emits white smoke and a strong pungent odor, so the reduction in its usage was achieved through the use of solid catalyst components, such as lower costs, ease of operation, and prevention of pollution sources. It brings great benefits in manufacturing. 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 the extent that it is not necessary 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 has a common drawback in so-called highly active supported catalysts, that is, the activity per unit time decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, 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.

Additionally, in the industrial production of olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control. Conventional catalysts using magnesium chloride as a carrier and organic monocarboxylic acid esters have the disadvantage that the yield of activity and stereoregularity decreases significantly in the presence of hydrogen. However, when olefins are polymerized using the catalyst of the present invention in the coexistence of hydrogen, the yield of activity and stereoregularity does 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. [Examples] The present invention will be specifically explained below using examples. Example 1 <Preparation of solid catalyst component> After sufficient purging with nitrogen gas, t'L. 10 mg of jetoxymagnesium in a 500 d round bottom flask equipped with a stirrer.
g and 6 o's of toluene were charged to form a suspension, and then 7 o's of T r C 1 a 4 0 was added to this suspension.
After raising the temperature to 0°C and adding 1.5-triptoxyboron, the temperature was further raised to 90"C and phthaloyl dichloride 2.
Add 0-. 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 200.9 toluene under reflux, and freshly added toluene 60 and TiCI,40.12.
The operation of adding 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. It was 97% by weight. <Polymerization> 200% of triethylaluminum was placed in an autoclave with a stirrer and an internal volume of 2.0 g that was sufficiently purged with nitrogen gas. ,
Cyclohexylmethyldimethoxysilane 45. And 3.0 mg of the solid catalyst component was charged. After that, 1.89 g of hydrogen gas and 1.4 g of liquefied propylene were charged, and 70'
Polymerization was carried out at C for 30 minutes. After completion of the polymerization, the obtained polymer was dried under reduced pressure at 80"C, and the obtained amount was designated as (A). This was also extracted with boiling n-hebutane for 6 hours to remove the polymers that were insoluble in n-hebutane. 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 during coalescence is expressed as (E), the MI of the produced polymer is expressed as (F), and the bulk specific gravity is expressed as (G).The obtained results are shown in Table 1.Example 2 Toluene was added to 100% The experiment was carried out in the same manner as in Example 1, except that the titanium content in the obtained solid catalyst component was 1.93% by weight. An experiment was conducted. 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 solid catalyst component obtained was 2.04 M%. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1. 1 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)
Contact with titanium tetrachloride (c) at a volume ratio of 1 or less to The solid material obtained by the reaction is washed with an alkylbenzene, and then titanium tetrachloride (c) is added in a volume ratio of 1 or less to the alkylbenzene (b) in the presence of the alkylbenzene (b).
A solid catalyst component for polymerizing olefins, which is obtained by repeating the reaction three times or more. (2) (A) After suspending diethoxymagnesium (a) in alkylbenzene (b), it is brought into contact with titanium tetrachloride (c) at a volume ratio of 1 or less to the alkylbenzene (b), and then 80°C Below, trialkoxyboron (
d) and further reacted with phthalic acid dichloride (e) in a temperature range of 80°C to 125°C. The solid material obtained is washed with alkylbenzene, and then in the presence of 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 with respect to the alkylbenzene (b) three or more times; (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, 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 0≦m≦3.) and (C) organoaluminum. A catalyst for polymerizing olefins, characterized by comprising a compound.