JPH07113046B2 - Olefilles polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention has a high activity when it is subjected to the polymerization of olefins and has a high activity, and a stereoregular polymer can be obtained in an extremely high yield. The catalyst, more specifically, a catalyst component for polymerization of olefins obtained by contacting a solid composition obtained by contacting a fatty acid magnesium, a diester of an aromatic dicarboxylic acid and a titanium halide with an organoaluminum compound, and the catalyst. The present invention relates to a catalyst for olefin polymerization, which comprises a component, a silicon compound and an organoaluminum compound.

[Conventional technology]

Conventionally, as a catalyst for olefin polymerization having high activity, a combination of a solid titanium halide as a catalyst component and an organoaluminum compound is well known and widely used. The so-called deashing process for removing the catalyst residue was unavoidable because the polymer yield per titanium (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) was low. Since this deashing process uses a large amount of alcohol or a chelating agent, a recovering device or a regenerating device for them is indispensable, and there are many resources, energy, and other incidental problems, and those skilled in the art can quickly solve the problem. This is an important issue that is desired. In order to eliminate this complicated deashing step, many studies have been made and proposed to increase the polymerization activity per catalyst component, especially titanium per catalyst component.

In particular, as a recent trend, when a transition metal compound such as titanium halide which is an active ingredient is supported on a carrier substance such as magnesium chloride and subjected to the polymerization of olefins, the polymerization activity per titanium in the catalyst component is dramatically increased. There are many proposals to raise the price.

[Problems to be solved by the invention]

However, the chlorine contained in magnesium chloride, which forms the mainstream as a carrier substance, has the drawback that it adversely affects the polymer produced as well as the halogen element in titanium halides, and therefore the effect of chlorine is virtually ignored. There was an unsolved part such as a high activity required, or the need to keep the concentration of magnesium chloride itself low.

The inventors of the present invention have disclosed that, in order to reduce the residual chlorine in the produced polymer while maintaining the polymerization activity per catalyst component and the yield of the stereoregular polymer at a high level, Japanese Patent Application No. 57-200
In 454, a method for producing a catalyst component for polymerization of olefins was proposed, and the intended purpose was achieved. Further, when the polymerization of olefins, particularly the stereoregular polymerization of propylene, 1-butene and the like is industrially carried out, it is usually necessary to make an electron donating compound such as an aromatic carboxylic acid ester coexist in the polymerization system. It is indispensable in a catalyst that uses a catalyst component having a carrier of (1) as a carrier in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts an ester odor peculiar to the produced polymer, and its removal is a major problem in the art.

Further, in a so-called highly active supported catalyst, such as a catalyst using a catalyst component having magnesium chloride as a carrier,
Although the activity at the initial stage of the polymerization is high, the deactivation is large, which causes a problem in the process operation, and when it is necessary to prolong the polymerization time such as block copolymerization, it is practically impossible to use. In order to improve this point, for example, in JP-A-54-94590, a catalyst component is prepared by using magnesium dihalide as a starting material and combined with an organic aluminum compound, an organic carboxylic acid ester, a compound having a MOR group, and the like. A method used for the polymerization of olefins is also shown, but since the organic carboxylic acid ester is used during the polymerization, the problem of the odor of the produced polymer has not been solved, and as seen from the examples, it is very In addition to requiring complicated operations, it cannot be said that practically sufficient ones have been obtained in terms of performance and sustainability of activity.

Further, the so-called highly active supported catalyst component using magnesium chloride as a carrier has a drawback that its performance deteriorates as the storage period becomes longer. This can be said to be an extremely serious problem in consideration of the fact that it usually takes several months for storage, transportation, etc. when the catalyst component is industrially used.

Further, although it is necessary to supply the catalyst to a high temperature polymerization tank in an industrial polymerization apparatus, it is known that the performance of the conventional supported catalyst is considerably lowered in such a case. . This is a big problem particularly in the so-called continuous polymerization method, and improvement thereof has been a strong demand in the field.

The inventors of the present invention have reached the present invention as a result of earnest research in order to solve the problems remaining in such conventional techniques, and make a proactive proposal.

[Means for solving problems]

That is, the features of the present invention are represented by (A) (a) magnesium fatty acid, (b) diester of aromatic dicarboxylic acid, and (c) general formula TiX ₄ (where X is a halogen element). A solid composition obtained by contacting a titanium halide (hereinafter, may be simply referred to as titanium halide)
(D) A catalyst component obtained by contacting with 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 a silicon compound represented by an aryl group and m is 0 ≦ m ≦ 4 (hereinafter, may be simply referred to as a silicon compound); and (C) an olefin polymerization catalyst comprising an organoaluminum compound. It is in the place of providing.

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

The fatty acid magnesium is preferably used in a form in which water is removed as much as possible.

The diester of aromatic dicarboxylic acid used in the present invention is preferably a diester of phthalic acid or terephthalic acid, for example, dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl. Examples thereof include terephthalate, diisobutylphthalate, diamylphthalate, diisoamylphthalate, ethylbutylphthalate, ethylisobutylphthalate and ethylpropylphthalate.

Examples of the titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element) used in the present invention include TiCl ₄ , TiBr ₄ , TiI _{4 and the} like, among which TiCl ₄ is preferable.

As the silicon compound used in the present invention,
Examples thereof include phenylalkoxysilane and alkylalkoxysilane. Further examples of phenylalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. Examples of the alkylalkoxysilane include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane.

Examples of the organoaluminum compound used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum dihalides, and mixtures thereof.

When obtaining the solid composition of the present invention, the use ratio of each raw material and the contact conditions are optional, and are not particularly limited, as long as they do not adversely affect the performance of the produced catalyst component. 1 g of fatty acid magnesium,
The diester of aromatic dicarboxylic acid is in the range of 0.01 to 2 g, preferably 0.1 to 1 g, and the titanium halide is in the range of 0.1 g or more, preferably 1 g or more.

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

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

The solid composition obtained after the contact may be repeatedly contacted with a titanium halide, or may be washed with an organic solvent such as n-heptane.

The contact between the solid composition obtained as described above and the organoaluminum compound is usually performed by using 0.01 to 100 mol of the organoaluminum compound with respect to 1 mol of titanium in the solid composition at 100 ° C. or less, preferably 10 ° C. It is carried out at a temperature of ℃ to 80 ℃ for 100 hours or less, preferably 5 seconds to 10 hours.

It is preferable that these series of operations in the present invention are performed in the absence of oxygen and water.

The catalyst component produced as described above is combined with the silicon compound and the organoaluminum compound to form a catalyst for olefin polymerization. The organoaluminum compound used is 1 in mole ratio per mole of titanium atom in the catalyst component.
Used in the range of up to 1000, and the silicon compound has a molar ratio of 1 or less per mol of the organoaluminum compound, preferably 1 or less.
Used in the range of 0.005-0.5.

The 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, the polymerization pressure is 100kg / c
m ² · G or less, preferably 50 kg / cm ² · G or less.

Olefins homopolymerized or copolymerized using the catalyst produced by the method of the present invention are ethylene, propylene,
1-butene, etc.

〔Example〕

 The present invention will be specifically described below with reference to examples.

Example 1 <Preparation of catalyst component> 300m fully replaced with nitrogen gas and equipped with a stirrer
10 g of magnesium stearate, 0.5 g of dibutyl phthalate and 100 ml of TiCl ₄ were placed in a round-bottomed flask having a volume of 1 and heated to 110 ° C. and reacted for 2 hours while stirring. 40 after reaction
After washing 10 times with 100 ml of n-heptane at ℃, add 100 ml of new TiCl ₄
l was added and reacted at 110 ° C. for 2 hours with stirring.

After the reaction was completed, it was cooled to 40 ° C, and then 100 ml of n-heptane
The washing was repeated, and when chlorine was no longer detected in the washing liquid, the washing was terminated to obtain a solid composition.
Next, 3 g of the solid composition was placed in a round bottom flask having an inner volume of 500 ml, 100 ml of n-heptane and triethylaluminum in an amount corresponding to 2 mol per 1 mol of Ti atom in the solid composition were added, and the mixture was added at 0 ° C. After treating under stirring for 1 hour, 200 ml of room temperature n-heptane was washed 5 times to obtain a catalyst component. At this time, the titanium content in the catalyst component was measured and found to be 3.05% by weight.

<< Polymerization >> 700 ml of n-heptane was charged into an autoclave equipped with a stirrer and having an internal volume of 2.0 l, which was completely replaced with nitrogen gas, and 301 mg of triethylaluminum, 32 mg of phenyltriethoxysilane, and then the above while maintaining a nitrogen gas atmosphere. The catalyst component was charged with 0.3 mg of titanium atom. Then 300 ml of hydrogen gas
6k while charging propylene gas and raising the temperature to 70 ° C and introducing propylene gas
Polymerization was carried out for 4 hours while maintaining the pressure of g / cm ² · G.
After completion of the polymerization, the solid polymer obtained was separated, heated to 80 ° C. and dried under reduced pressure. On the other hand, the amount of the polymer dissolved in the polymerization solvent by condensing the liquid is (A), and the amount of the solid polymer is (B). Also, the obtained solid polymer was heated to 6 with boiling n-heptane.
It is extracted with time to obtain a polymer insoluble in n-heptane, and this amount is designated as (C).

The polymerization activity (D) per catalyst component is calculated by the formula Express with.

Further, the yield (E) of the crystalline polymer is calculated by the formula The yield (F) of all crystalline polymer is expressed by I asked more. Residual chlorine in the produced polymer is represented by (G) and MI of the produced polymer is represented by (H). 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 room temperature. The titanium content in the solid content at this time was 3.12% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Example 4 An experiment was performed in the same manner as in Example 1 except that the treatment with triethylaluminum was performed at 50 ° C. The titanium content in the solid content at this time was 2.99% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Example 5 An experiment was conducted in the same manner as in Example 1 except that triethylaluminum was used in an amount corresponding to 4 mol per 1 mol of Ti atom. The titanium content in the solid content at this time is
It was 2.91% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Example 6 A catalyst component was prepared in the same manner as in Example 1 except that diethylaluminum chloride was used instead of triethylaluminum. The titanium content in the solid content at this time was 3.12% by weight. Example 1 for polymerization
An experiment was conducted in the same manner as in. The results obtained are as shown in Table 1.

Comparative Example 1 <Adjustment of catalyst component> 100 g of magnesium chloride and 31.5 g of ethyl benzoate were placed in a nitrogen gas atmosphere and a stainless steel ball in 25 mm was used as 4/5 of the total volume.
It was loaded into a vibrating mill pot with a capacity of 1.01 and the vibration frequency was 14
A pulverized composition was obtained by pulverizing at 30 υ.pm and a swing of 3.5 mm for 18 hours.

Into a round bottom flask with a stirrer having a capacity of 2.01 sufficiently replaced with nitrogen gas, 100 g of the pulverized composition was dispensed and charged, and then 500 g of titanium tetrachloride was added and the stirring reaction was carried out at 65 ° C. for 2 hours. went. After completion of the reaction, the mixture was cooled to 40 ° C, left to stand and the supernatant was removed by decantation, and then 1000 ml of n-heptane
The washing was repeated, and when the chlorine was not detected in the washing liquid, the washing was completed and the catalyst component was obtained.

At this time, the titanium content in the catalyst component was measured and found to be 1.28% by weight.

<< Polymerization >> In the polymerization, 1.0 mg of the above catalyst component was used as a titanium atom.
The same procedure as in Example 1 was carried out except that it was used. The results obtained are as shown in Table 1.

[Effects of the Invention] When olefins are polymerized using the catalyst component obtained according to the present invention, it has higher stereoregularity as compared with the case of using a catalyst component which is not brought into contact with an organoaluminum compound. A polymer can be obtained, and the catalyst has a very high activity, so that the catalyst residue in the produced polymer can be suppressed to a very low level, and the amount of residual chlorine is so small that no deashing step is required. It is possible to reduce the effect of chlorine on the produced polymer.

Chlorine contained in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, and also causes deterioration of the produced polymer itself, yellowing, etc. Has a very important meaning to those skilled in the art.

Further, the feature of the present invention is that not only the big problem of the odor of the produced polymer is solved by not using the aromatic carboxylic acid ester during the polymerization, but the activity per unit time of the catalyst is It is an object of the present invention to solve the essential drawback of so-called highly active supported catalysts, which is significantly reduced with the increase of the above, 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 generally said that hydrogen is allowed to coexist at the time of polymerization from the viewpoint of MI control and the like, but a catalyst using the above-mentioned catalyst component having magnesium chloride as a carrier coexists with hydrogen. Below, it had the disadvantage that 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 MI of the produced polymer is
The activity and stereoregularity are hardly deteriorated even when the value is extremely high, and such an effect brings an extremely great benefit to those skilled in the art.

Further, the catalyst component or the catalyst produced according to the present invention does not show a decrease in performance due to so-called aging such as storage and transportation, but the performance is almost deteriorated even when supplied to a high temperature polymerization tank. It also possesses the extremely important property of not doing so.

[Brief description of drawings]

FIG. 1 is a schematic drawing for helping understanding of the present invention.

Claims (1)

[Claims] 1. A) (a) fatty acid magnesium, (b)
Diesters of aromatic dicarboxylic acids and (c) the general formula Ti
A solid composition obtained by contacting a titanium halide represented by X ₄ (wherein X is a halogen element),
(D) A catalyst component obtained by contacting with an organoaluminum compound; (B) General formula SiRm (OR ') 4-m (wherein R is hydrogen, an alkyl group or an aryl group, and R'is an alkyl group or an aryl group). Group, and m is 0 ≦ 4), and a (C) organoaluminum compound, and a catalyst for olefin polymerization.