JPS62164702A - Catalyst component and catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To make it possible to obtain a polymer more stereoregular than those obtained with conventional catalysts and to eliminate a deashing process, by polymerizing an olefin with the aid of a catalyst formed by combining a specified titanium-containing catalyst component with a silicon compound. CONSTITUTION:A catalyst for polymerization of an olefin is formed by combinin a catalyst component (A) with a silicon compound (B) and an organoaluminum compound, (A): a composition obtained by contacting a dialkoxymagnesium (a) with an aromatic dicarboxylic acid diester (b), an aromatic hydrocarbon (c) and a titanium halide (d) and contacting the obtained solid composition with an organic aluminum compound (e) and (B): a silicon compound of the general formula: SiRm(OR')4-m (wherein R is H, alkyl or aryl, R' is alkyl or aryl and m is in the range of 0<=m<=4).

Description

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

[Conventional technology]

Conventionally, nine combinations of solid titanium halides and organoaluminum compounds as catalyst components are well known and widely used as highly active catalysts for polymerizing olefins. Since the yield of the titanium-containing polymer (hereinafter referred to as the catalyst component and the polymerization activity of the titanium-containing catalyst component) is low, a so-called deashing step to remove the catalyst residue has been unavoidable. This deashing process uses a large amount of alcohol or chelating agent, so recovery equipment or regeneration equipment is essential, and there are many resource, energy, and other problems involved.
For those skilled in the art, this was an important issue that needed to be solved as soon as possible. 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 halides, 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. I've seen many suggestions for increasing it.

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the same disadvantage as the halogen element in titanium halides, which has a negative effect on the polymer produced, and for this reason, the effect of chlorine is virtually ignored. This left unresolved issues, such as the need to have as high an activity as possible, or 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 a high degree of polymerization activity per catalyst component and the yield of a stereoregular polymer.
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 is high in the initial stage of polymerization, the deactivation is large, which poses problems in process operation, and it is almost impossible to use it in practical situations when it is necessary to lengthen the polymerization time, such as in block copolymerization. . In order to improve this point, for example, in JP-A No. 54-94590, a catalyst component was prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, 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 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 problems]

That is, the features of the present invention are as follows: (A) A compound obtained by contacting (a) dialkoxymagnesium, cb) diester of aromatic dicarboxylic acid, (C) aromatic hydrocarbon, and (d) titanium halide. The solid composition obtained by further contacting Ic, (e) an organoaluminum compound, CB)
is hydrogen, an alkyl group or an aryl group, x' is an alkyl group or an aryl group, and m is 0≦m≦4. ) (hereinafter sometimes simply referred to as a silicon compound) and (c) a catalyst component for polymerizing olefins, characterized in that it is used in combination with an organoaluminum compound, and K (A) (a) dialkoxy A solid composition obtained by contacting magnesium, (b) a diester of an aromatic dicarboxylic acid, (c) an aromatic hydrocarbon, and (d) a titanium halide is further contacted with (e) an organoaluminum compound. Catalyst component: (B) General formula 81
Rm (OR') 4-m (wherein, R is hydrogen,
It is an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. ) (hereinafter sometimes simply referred to as a silicon compound): and (C) an organoaluminum compound.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ea-butoxymagnesium, di-te
Examples include rt-butoxymagnesium, diimpropoxymagnesium, and the like, with jetoxymagnesium and dipropoxymagnesium being preferred.

The diester of aromatic dicarboxylic acid used in the present invention is preferably a diester of heptalic acid, such as dimethyl heptalaate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, cyamyl phthalate,
Examples include diisoamyl phthalate, ethyl butyl phthalate, ethyl imbutyl phthalate, and ethyl propyl phthalate.

The aromatic hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature.
Examples include toluene, xylene, ethylbenzene, flobylbenzene, and butylbenzene.

Examples of the titanium halide used in the present invention include Ti, O14, TiEr4, and Ti-4, among which TiOLm is preferred.

The silicon compound used in the present invention is:
Examples include phenylalkoxysilane and alkylalkoxysilane. In addition, phenylalkoxysilanes such as 7-enyltrimethoxysilane, phenyltriethoxysilane, phenyltrigloboxysilane, 7-enyltriinopropoxysilane, diphenyldimethoxysilane, and diphenyljethoxysilane may be mentioned. Examples of alkylalkoxysilanes include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxine, ethyltriisopropoxysilane, and the like.

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 ratio of each raw material used, contact conditions, etc. are arbitrary as long as they do not adversely affect the performance of the catalyst component to be produced, and are not particularly limited. Normal dialkoxymagnesium 1f
On the other hand, diesters of aromatic dicarboxylic acids have CLO1~
2? , preferably in the range of 1 to 1t, and the titanium halide is in the range of 0.11 or more, preferably 11 or more. Further, the aromatic 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 between 0°C and the boiling point of the titanium halide used for up to 100 hours.
It is preferably carried out for 10 hours or less.

In this case, the order and method of contacting each raw material are not particularly limited, and any appropriate method can be selected.

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

The solid composition obtained as described above and the organoaluminum compound are usually brought into contact at 101 to 100 mol of the organoaluminum compound per 1 mol of titanium in the solid composition at 100°C or lower, preferably at 100°C. It is carried out at a temperature of ~80°C for up to 100 hours, preferably from 5 seconds to 10 hours.

After the contact, it is also possible to contact the obtained composition with a titanium halide, and it is also possible to wash it using an organic solvent such as n-heptane.

These series of operations in the present invention are preferably carried out in the absence of oxygen and moisture. Forms a catalyst.

The organoaluminum compound used has a molar ratio of 1 to 1000 per mole of titanium atoms in the catalyst component, and the silicon compound has a molar ratio of 1 or less, preferably n, oos, per mole of the organoaluminum compound. It is used in the range of ~α5.

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
0 to 9/2・O or less, preferably 50 klil/
m”・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.

〔Effect of the invention〕

When olefins are polymerized using the catalyst component obtained according to the present invention, a polymer with higher stereoregularity can be obtained compared to conventional catalysts. The amount of catalyst residue in the polymer can be kept extremely low, and since the amount of residual chlorine is so small, the effect of chlorine on the produced polymer can be reduced to the extent that no deashing step is 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. has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized by not only solving the major problem of odor of the produced polymer by not using an aromatic carboxylic acid ester during polymerization, but also improving the activity of the catalyst per unit time as the polymerization progresses. The objective is to solve the essential drawbacks of so-called high-activity supported catalysts, which result in a significant decrease 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 controlling the M process, but conventional catalysts using a catalyst component with magnesium chloride as a carrier In the coexistence of hydrogen, 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 M engineering of the resulting 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.

Furthermore, in the industrial production of olefin polymers, the bulk specific gravity of the produced polymer is a problem, and the catalyst of the present invention has extremely excellent properties in this respect as well.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 Preparation of catalyst components
10 F of jetoxymagnesium and 80 m of toluene were placed in a 0-round bottom flask to create a suspended state. Next, Ti04420 d was added to this suspension, the temperature was raised to 70°C, and diptylphthalate 2.7- was added. then 115
The temperature was raised to 0.degree. C., and the mixture was reacted with stirring for 2 hours. After the reaction was completed, the reaction mixture was washed three times with 100 ml of toluene at 40°C, 80 d of toluene and 420 ml of TIQt were newly added, and the mixture was reacted at 115° C. with stirring for 2 hours.

After the reaction was completed, it was cooled to 40°C, and then 20°C of n-heptane was added.
Washing with 0- was performed 10 times to obtain a solid composition. Next, 3 tons of the solid composition was put into a round bottom flask with an internal volume of 500 mm, and 100 tons of h, n-hebutane and T1 in the solid composition were added.
Triethylaluminum was added in an amount equivalent to 2 moles per 1 mole of atoms, and the mixture was stirred at room temperature for 1 hour, and then washed five times with 200% n-heptane at room temperature to obtain a catalyst component. At this time, when the titanium content in the catalyst component was measured, it was found to be 2.66% by weight.

Polymerization> Into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which was completely purged with nitrogen gas, 700 g of n-heptane was charged.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1 mg, phenyltriethoxysilane 6019. Next, cL2H1 was charged as the catalyst component as titanium atoms.

Thereafter, 150 d of hydrogen gas was charged, the temperature was raised to 70°C, and propylene gas was introduced while maintaining a pressure of 6 kg/cm"G and polymerization was carried out for 4 hours. After the completion of polymerization, the solid weight obtained The combined product 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 F solution is (
A) and the amount of solid polymer is ω). 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 Φ) of the catalyst component is expressed as: In addition, the yield of crystalline polymer @) is expressed by the formula The yield of total crystalline polymer (I) was determined from the formula.

In addition, residual chlorine in the produced polymer (G), M of the produced polymer
The bulk density is expressed by (1).

The results obtained are as shown in Table @1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 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 in the solid content at this time was 2.41% 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 conducted in the same manner as in Example 1 except that the treatment with triethylaluminum was carried out at 50°C. Incidentally, the titanium content in the solid content 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 as shown in Table 1.

Example 5 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 in the solid content at this time was 2.38% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are as shown in Table 1.

Table 1

Claims (2)

[Claims] (1) (A) (a) Dialkoxymagnesium, (b)
A solid composition obtained by contacting a diester of an aromatic dicarboxylic acid, (c) an aromatic hydrocarbon, and (d) a titanium halide is further contacted with (e) an organoaluminum compound, (B) General formula SiR_m(OR')_4_-_m (wherein R is hydrogen, an alkyl group or an aryl group, and R'
is an alkyl group or an aryl group, and m is 0≦m≦4
It is. ) A catalyst component for polymerizing olefins, characterized in that it is used in combination with a silicon compound represented by (c) and an organoaluminum compound. (2) (A) (a) dialkoxymagnesium, (b)
A catalyst component obtained by further contacting a solid composition obtained by contacting a diester of an aromatic dicarboxylic acid, (c) an aromatic hydrocarbon, and (d) a titanium halide with (e) an organoaluminum compound; ( B) with the 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 for polymerizing olefins comprising a silicon compound represented by the above formula; and (C) an organoaluminum compound.