JPS61141707A - Catalyst component and catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:The titled catalyst which can give a highly stereoregular polymer, retain a high activity and requires no step of deashing, comprising a catalyst component obtained by contacting a specified solid composition with an organoaluminum compound, a silicon compound and an organoaluminum compound. CONSTITUTION:A catalyst component (A) is obtained by contacting a solid composition (a) obtained by contacting 1g of a fatty acid magnesium salt (e.g., magnesium stearate) with 0.01-2g of a mono- or di-ester of an aromatic dicarboxylic acid (e.g., diphenyl phthalate), a halohydrocarbon (e.g., methylene chloride) and 0.1g or above of a titanium halide of formula I (wherein X is a halogen) with 0.01-100mol, per mol of Ti in component a, of an organoaluminum compound (b) at 100 deg.C or lower for 100hr. Component A is mixed with 1-1,000mol, per mol of Ti in component A, of an organoaluminum compound (B) and 1mol or below, per mol of component B, of a silicon compound (C) of formula II (wherein R' is alkyl or aryl, R is H or R' and <=m<=) to obtain the titled catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a high-performance polymer that exhibits high activity when subjected to the polymerization of ontwins, and can obtain stereoregular polymers in extremely high yields. Regarding catalyst components and catalysts, more specifically, a solid composition obtained by contacting fatty acid magnesium, an aromatic dicarboxylic acid monomer diester, a halogenated hydrocarbon, and a titanium halide is further added.
The present invention relates to a catalyst component for polymerizing olefins obtained by contacting with an organoaluminum compound, and a catalyst for polymerizing olefins comprising the catalyst component, a silicon compound, and an organoaluminum compound.

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of a solid titanium halide carbide and an organoaluminum compound as a catalyst component is well known and widely used. Since the yield of the polymer based on titanium in the component (hereinafter referred to as the catalyst component and the polymerization activity of the titanium in the catalyst component) is low, a so-called deashing step to remove the catalyst residue has been unavoidable. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment for these is indispensable, and there are many problems associated with resources, energy, etc., and those skilled in the art would like to solve them as soon as possible. This was an important issue. In order to eliminate this complicated deashing step, many studies have been made and proposals have been made to increase the polymerization activity of the catalyst component, particularly titanium, in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halide carbides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. There are many proposals to raise the standard.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the formed polymer, similar to the halogen element in titanium halides, and therefore, the effect of chlorine is virtually eliminated. This left unresolved issues, such as the need for negligible high activity and the need to keep the concentration of magnesium chloride itself low.

The present inventors have developed a patent application filed in Japanese Patent Application No. 1983-1-1 with the aim of reducing the residual chlorine in the produced polymer while maintaining the polymerization activity of the catalyst component and the yield of the stereoregular polymer at a high level.
No. 200454, we proposed a method for producing a catalyst component for olefin polymerization, and achieved the intended purpose. Furthermore, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially, it is common to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential for catalysts that use a catalyst component having a carrier as a carrier in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the produced polymer, and its removal has become a major problem in the industry.

In addition, in so-called highly active supported catalysts, such as catalysts using catalyst components using magnesium chloride as a carrier,
Although the activity at the initial stage of polymerization is high, the deactivation is large, which causes problems in process operation, and it is almost impossible to use it practically in cases such as block copolymerization where a longer polymerization time is required. In order to improve this point, for example, in Japanese Patent Publication No. 1983-94590, a catalyst component is prepared using magnesium dihalide as a starting material, and an organic aluminum compound, an organic carboxylic acid ester, an M-
A method for polymerizing olefins in combination with a compound having an 0-R group has been shown, but since an organic carboxylic acid ester is used during polymerization, the problem of odor of the resulting polymer has not been solved. Further, as can be seen from the examples, very complicated operations are required, and it cannot be said that practically sufficient results have been obtained in terms of performance and duration of activity.

Furthermore, the so-called highly active supported catalyst component using magnesium chloride as a carrier has the disadvantage that its performance deteriorates as the storage period becomes longer.

This is a very serious problem considering that industrial use of the catalyst components usually requires several months of storage, transportation, etc.

In addition, in industrial polymerization equipment, it is sometimes necessary to feed a catalyst into a high-temperature polymerization tank, and it is known that the performance of conventional supported catalysts is significantly reduced in such cases. There is. This is a big problem, especially in so-called continuous polymerization methods, and there has been a strong desire in this industry to improve it.

[Problem that the invention seeks to solve]

The inventors were left with such prior art! ! ! As a result of intensive research to solve this problem, we have arrived at the present invention and propose it to Tsuzumi.

[Means for solving problems]

That is, the features of the present invention are as follows: (A) (a) fatty acid magnesium, (b) mono- or diester of aromatic dicarboxylic acid, (C) non-logonated hydrocarbon, and (d) general formula TiX4 ( In the formula, X is /%
It is a Gl gene element. ) (hereinafter sometimes simply referred to as titanium halide).

) is further contacted with (e) an organoaluminum compound, and (B)
General formula S iRm (OR')4-m (wherein, R is hydrogen, an alkyl group or an aryl group, i, a/ is an alkyl group or an aryl group, and m is 0≦m≦4) A catalyst component for the polymerization of olefins, characterized in that it is used in combination with a silicon compound (hereinafter sometimes simply referred to as a silicon compound) represented by C) an organoaluminum compound, and K (A) (a) fatty acid. (b) a mono- or diester of an aromatic dicarboxylic acid, (C) a halogenated hydrocarbon, and (d) a general formula TiX4 (wherein X is) a rogon element. ) (hereinafter sometimes simply referred to as titanium halide carbide), a solid composition obtained by contacting the titanium chloride represented by K,
(e) Catalyst component obtained by contacting with an organoaluminum compound; 03) General formula SiRm(OR')4-m (in the formula, R
is hydrogen, an alkyl group or an aryl group, R/ is an alkyl group or an aryl group, and m is 0≦m≦4. An object of the present invention is to provide a catalyst for polymerizing olefins comprising a silicon compound represented by C) (hereinafter sometimes simply referred to as a silicon compound); and C) an organoaluminum compound.

As the fatty acid magnesium used in the present invention, saturated fatty acid magnesium is preferable, and magnesium stearate, magnesium octoate, magnesium decanoate and magnesium laurate are particularly preferable.

Note that it is preferable to use the fatty acid magnesium in a form with as much moisture removed as possible.

The mono- or diester of aromatic dicarboxylic acid used in the present invention is preferably a mono- or diester of phthalic acid or terephthalic acid, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate,
Examples include diethyl terephthalate, diethyl phthalate, diethyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl imbutyl 7-thaleate, and ethyl propyl phthalate.

The halogenated hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature, such as propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane. , trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, etc. Among them, propyl chloride, dichloroethane, chloroform, carbon tetrachloride, dichloride, and methylene chloride are preferred.

Examples of the titanium halide carbide represented by the general formula TiX4 (wherein X is a halogen element) used in the present invention include TiCl2, TiBr4. TiC4
Among them, TiC44 is preferable.

The silicon compound used in the present invention is c.
Examples include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of 7-ethyl alkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriynegloboxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, etc. Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriynepropoxysilane.

The organoaluminum compounds used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum cybarides, and mixtures thereof.

When obtaining the solid composition of the present invention, the proportions and contact conditions of each raw material are arbitrary as long as they do not adversely affect the performance of the catalyst component to be produced, and are not particularly limited. The mono- or diester of aromatic dicarboxylic acid is 0. O
1 to 22, preferably 0.01 to 0.52, and the titanium halide has a molecular weight of 0.1 r or more, preferably 1
The range is 2 or more.

Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably in an amount that can form a suspension.

Furthermore, the contact between each raw material is usually carried out at a temperature from 0°C to the boiling point of the titanium halide used for up to 100 hours.
It is preferably carried out for 10 hours or less.

At this time, the order and method of contacting each raw material are not particularly limited, and any suitable method can be selected.

It is also possible to contact the solid composition obtained after the above-mentioned contact with the titanium halide <9 times, and it is also possible to wash it using an organic solvent such as sb or n-hebutane.

The solid composition obtained as described above is brought into contact with the organoaluminum compound, preferably at 100° C. or lower, using 0.01 to 100 mol of the organoaluminum compound per 1 mol of titanium in the solid composition. is carried out at a temperature of 10° C. to 80° C. for up to 100 hours, preferably for 5 seconds to 10 hours.

These series of operations in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

The catalyst component produced as described above is combined with the silicon compound and organoaluminum compound to form a catalyst for polymerizing olefins. The organoaluminum compound used is in a molar ratio of 1 per mole of titanium atoms in the catalyst component.
-1000, and the silicon compound is used in a simole ratio of 1 or less, preferably 0.005 to 0.5, based on the mole of the organoaluminum 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. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
ooH, Otsu-・G or less, preferably Vi50 gauze/-・G or less.

The olefins to be homopolymerized or copolymerized using the catalyst produced by the method of the present invention include ethylene, propylene,
1-butene, etc.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 <Preparation of catalyst components> Volume J15 sufficiently purged with nitrogen gas and equipped with a stirrer
Magnesium stearate 20 in a round bottom flask
P1 dibutyl phthalate) 1. Of and 50-methylene chloride were charged to form a suspension, and the mixture was stirred under reflux for 1 hour. Next, this suspension K TSC14100- was added, the temperature was raised to 110°C, and the mixture was reacted for 2 hours with stirring. After the reaction was completed, the mixture was washed 10 times with 200 d of n-hebutane at 40°C, and TiCt4100- was added again, followed by reaction at 110°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20°C of n-heptane was added.
Washing with 0- was repeatedly performed, and when chlorine was no longer detected in the washing solution, the washing was completed, and a solid composition was obtained. Next, the solid composition 3f was placed in a round bottom flask with an internal volume of 500, and 100 of n-heptane and triethylaluminum in an amount equivalent to 2 mol per 1 mol of Ti atoms in the solid composition were added. In addition, the mixture was stirred at room temperature for 1 hour, and then washed five times with 200% n-hebutane at room temperature to obtain a catalyst component.

At this time, the titanium content in the catalyst component was measured and found to be 2.76% by weight.

Polymerization〉 Internal volume completely replaced with nitrogen gas 2. Charge n-hebutane 700 WLt into an OL autoclave with a stirring device, and while maintaining a nitrogen gas atmosphere, triethylaluminum 301"S' and phenyltriethoxysilane 32#v
Then, 0.3 kg of the catalyst component was charged as titanium atoms. Thereafter, 300 d of hydrogen gas was charged, the temperature was raised to 70° C., and while propylene gas was introduced, a pressure of 6 #/d·G was maintained, and polymerization was carried out for 4 hours. After the polymerization was completed, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after condensing the P solution is defined as ■, and the amount of solid polymer is defined as (B). Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as C).

The polymerization activity per catalyst component (0) is expressed by the formula, and the yield of crystalline polymer is expressed by the formula [) [F] = - ) I asked for it. Further, the residual chlorine in the produced polymer is expressed as G), and the MI of the produced polymer is expressed as 0. The results obtained are shown in Table 1).

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was changed to 6 hours. The results obtained are as shown in Table 1.

Example 3 A catalyst component was prepared in the same manner as in Example 1, except that the treatment with triethylaluminum was carried out at 0°C. In addition, the titanium content of the solid agglomerate at this time was 2.67% by weight.
Met. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are as shown in Table 1.

Example 4 An experiment was carried out in the same manner as in Example 1 except that triethylaluminum was used in an amount corresponding to 4 moles per mole of T1 atoms. Incidentally, the titanium content of the solid fraction at this time was 2.71% 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 5 A catalyst component was prepared in the same manner as in Example 1 except that diethylaluminum chloride was used instead of triethylaluminum. In addition, the titanium content of the solid condensate at this time was 2.93 weights! It was 1%. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Table 1 [[G[-1-C Effects of the Invention]] When olefins are polymerized using the catalyst component obtained by the present invention, compared to the case where a catalyst component that is not brought into contact with an organoaluminum compound is used. A polymer with higher stereoregularity can be obtained, and since the catalyst is extremely active, the amount of catalyst residue in the resulting polymer can be kept extremely low.Furthermore, since the amount of residual chlorine is very small, it is possible to obtain a polymer with higher stereoregularity. The effect of chlorine on the produced polymer can be reduced to such an extent that an ash step is not required at all.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself, and this has been reduced. This has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized by not using an aromatic carboxylic acid ester during polymerization, which solves the major problem of the odor of the produced polymer, and by controlling the activity of the catalyst per unit time over the course of polymerization. The purpose is to solve the essential drawbacks of so-called high-activity supported catalysts, which are significantly reduced with the increase in activity, and to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

Conventionally, in the industrial production of olefin polymers, it has been common to allow hydrogen to coexist during polymerization from the viewpoint of MI sub-control. However, it had the disadvantage that the activity and stereoregularity were significantly reduced.

However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the activity and stereoregularity hardly decrease even when the MI of the produced polymer is extremely high. Such an effect is of great benefit to those skilled in the art.

In addition, the catalyst components or catalysts produced according to the present invention do not show any deterioration in performance due to so-called aging periods such as storage and transportation, and there is almost no deterioration in performance even when supplied to a high-temperature polymerization tank. It also has extremely important properties.

Claims (2)

[Claims] (1) (A) (a) fatty acid magnesium, (b) mono- or diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) general formula TiX_4 (wherein X is a halogen element). A solid composition obtained by contacting a titanium halide represented by (e) with an organoaluminum compound, which is obtained by (B) general formula SiR_m(OR')_4_-_m (wherein R is hydrogen, an alkyl group, or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4.)
A catalyst component for polymerizing olefins, characterized in that it is used in combination with a silicon compound represented by: and (C) an organoaluminum compound. (2) (A) (a) fatty acid magnesium, (b) mono- or diester of aromatic dicarboxylic acid, (c) halogenated hydrocarbon, and (d) general formula TiX_4 (wherein X is a halogen element). A catalyst component obtained by further contacting a solid composition obtained by contacting a titanium halide represented by (e) with an organoaluminum compound; (B) General formula SiR_m(OR')_4_-_m (in the formula R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4); and (C) olefins consisting of an organoaluminum compound. Polymerization catalyst.