JPH02255707A - Catalyst for polymerizing olefins - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst, consisting of a specific solid catalyst component, epoxy-p-menthane compound and organoaluminum compound, having high activity and capable of providing a highly stereoregular polymer with hardly any residual chlorine without requiring a deashing step. CONSTITUTION:The objective catalyst consisting of (A) a solid catalyst component obtained by reacting metallic Mg power with an alkyl monohalide in a molar mount of >=2 times in the presence of iodine, pulverizing the resultant substance together with a tetraalkoxytitanium and phthalic acid diester, successively adding the tetraalkoxytitanium, an aliphatic alcohol and the phthalic acid diester to the obtained product in the presence of an aliphatic hydrocarbon at >=10 deg.C, carrying out respective treatments, adding titanium tetrachloride to the resultant product and further treating the obtained mixture, (B) an epoxy- menthane compound and (C) an organoaluminum compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is capable of obtaining highly stereoregular polymer pairs that act with high activity and have a uniform shape when subjected to the polymerization of olefins. This relates to high-performance catalysts. More specifically, the present invention provides a catalyst for polymerizing olefins comprising a special solid catalyst component [1), an epoxy paramenthane compound [0), and an organoaluminum compound (8), as detailed later. It is.

[Conventional technology]

Recently, instead of the conventionally well-known titanium trichloride catalyst component as a solid catalyst component in catalysts for polymerizing olefins such as propylene, a new type of catalyst component has been developed in which the active component titanium is supported on magnesium chloride together with an electron donor. Many things have been developed and provided.

Among these, the earliest developed one was a complex of an organic monocarboxylic acid engineered ester and titanium tetrachloride as an electron donor, which was co-pulverized with magnesium chloride; There is a co-pulverized product of carboxylic acid ester and magnesium chloride treated with titanium tetrachloride.

[Problem to be solved by the invention]

However, when these are used in combination with organoaluminum compounds for industrial polymerization of olefins, especially stereoregular polymerization of propylene, 1-butene, etc., organic monocarboxylic acids are used as electron donors during the polymerization reaction. Since it is essential to use an ester, and in this case it is necessary to use an extremely large amount of an organic monocarboxylic acid ester, there is a problem in that the produced polymer has a characteristic ester odor.

Furthermore, although these catalysts have high activity at the initial stage of polymerization, their deactivation over time poses a problem in process operation, and when the polymerization time is longer, such as in block copolymerization, it is virtually impossible to use them. It was impossible.

In order to improve this point, JP-A-54-94590 discloses that a catalyst component is prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. A method is disclosed in which the combination is used for the polymerization of olefins, but as is clear from the description in the same publication, in this case it is necessary to use an organic carboxylic acid ester both during catalyst preparation and during polymerization. Generally, the amount of organic carboxylic acid ester contained in the catalyst is reduced to such an extent that the odor problem of the produced polymer can be ignored by treatment with a titanium halide or washing with an organic solvent. However, as mentioned above, the amount of organic carboxylic acid ester used during polymerization is extremely large compared to the amount contained in the catalyst, and when polymerization is carried out in a liquid or gaseous atmosphere, almost all of it is At present, it is contained in the produced polymer, and therefore, it can be said that the problem of odor in the produced polymer cannot be solved as long as an organic carboxylic acid ester is used during polymerization. Furthermore, as can be seen from the examples, the method disclosed in the same publication requires very complicated operations, and the resulting catalyst is insufficient for practical use both in terms of performance and sustainability of activity. The reality is that it cannot be called a reality.

[Means to solve the problem]

The present inventors have conducted extensive research to solve the various problems in the prior art as described above, and have found that the present invention provides a high-performance catalyst that can produce polymers with a high degree of stereoregularity. Successful.

That is, the present invention comprises the following solid catalyst component (1), the epoxy bara mencun compound (Ul) below, and the following (8).
The present invention provides a catalyst for polymerizing olefins, characterized by comprising an organoaluminum compound of the following.

(1) After pulverizing the substance <a) obtained by reacting metallic magnesium powder and twice or more moles of alkyl monohalide in the presence of iodine, tetraalkoxytitanium (b) and phthalic acid diester (c), Tetraalkoxytitanium (b), aliphatic alcohol (e) and phthalic acid diester (c) are sequentially added to the obtained product in the presence of an aliphatic hydrocarbon (d) at 100°C or higher, and each treatment is carried out, Add titanium tetrachloride (f) to the obtained product,
A solid catalyst component obtained by further treatment; fII) A catalyst for polymerizing olefins comprising an epoxy paramenthane compound and (8) an organoaluminum compound.

The catalyst for polymerizing olefins of the present invention will be explained in more detail below.

First, the solid catalyst component in [1] will be explained.

In order to obtain the substance obtained by reacting the metal magnesium powder and the alkyl monohalide in the above (a) in the presence of iodine (hereinafter simply referred to as the substance (a)), commercially available metal magnesium powder and the alkyl monohalide are used. is reacted in the absence of an organic solvent and in the presence of iodine,
At this time, it is necessary to use 2 or more moles of the alkyl monohalide per 1 mole of the metal magnesium powder. In addition, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited.
It is usually carried out at 20°C or higher for 10 minutes or more, preferably at 40°C or higher for 30 minutes or more. This reaction is a Grignard type reaction, and when the IR spectrum of the substance (a) obtained by the reaction is measured, absorption of alkyl groups is observed.

The alkyl monohalides used in the production of the substance (a) above are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-propyl chloride, isopropyl chloride, n-butyl chloride, Examples include isobutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

Tetraalkoxytitanium of (b) above (hereinafter simply referred to as (b)
As the alkoxy group, those having 1 to 10 carbon atoms are used, and those having 3 or 4 carbon atoms are particularly preferably used.

One type or two or more types of tetraalkoxytitanium can be used. The amount of the (b) substance used is usually in the range of 0.1 to 10 g in total per 1 g of the (a) substance.

The phthalic diesters (c) (hereinafter simply referred to as substance (c)) include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, Examples include ethyl isobutyl phthalate and ethyl propyl phthalate.

The amount of the above substance (c) is 0.1 d or more, preferably 0.2 to 1 d per 1 g of the (a) substance. Orn! , is used at a rate of .

The aliphatic hydrocarbon of (d) (hereinafter simply referred to as (d) substance) and the aliphatic alcohol of (e) (hereinafter simply referred to as (d))
e) substances) are all liquid at -30°C to 50°C.

(d) Preferred examples of the substance include aliphatic hydrocarbons having 5 to 12 carbon atoms, such as pentane, hexane, heptane,
Examples include octane, nonane, decane, dodecane, and isomers thereof, and preferred examples of the substance (e) include aliphatic alcohols having 2 to 10 carbon atoms, such as ethanol, propatool, butanol, pentanol, hexanol, Examples include octatool and isomers thereof.

Titanium tetrachloride (f) used in the present invention is (a)
It is used in a proportion of 1 g or more, preferably 5 g or more per 1 g of the substance.

The contact temperature at this time is usually 0°C or higher and 130°C or lower. The contact time is at least 10 minutes, preferably at least 30 minutes.

The obtained solid catalyst component (I) may be washed with an organic solvent such as n-hebutane or toluene, if necessary, or may be repeatedly treated with titanium tetrachloride (f).

All of these aspects are included in one aspect of implementing the present invention.

The series of operations related to the preparation of the solid catalyst component f1) in the present invention is performed in the absence of oxygen, moisture, and the like.

The solid catalyst component (1) prepared as described above is combined with the epoxy paramencune compound (■) and the organoaluminum compound (8), and the solid catalyst component of (1) is combined with the olefin polymerization catalyst according to the present invention. , but the above (n
1,4-epoxyparamenthane or 1,8-epoxyparamenthane is preferred as the epoxyparamenthane compound, but it is also possible to use compounds with substituents such as alkyl groups and halogens.

Examples of the organoaluminum compound (III) include trialkylaluminum, dialkylaluminum halide, alkyl aluminum civalide, alkylaluminum sesquihalide, and mixtures thereof, and among these, trialkylaluminum is preferred, and further, Particularly preferred are triethylaluminum and triisobutylaluminum.

The organoaluminum compound (III) is used in an amount of 1 to 1000 mol per g atom of titanium in the solid catalyst component, and the epoxy paramenthane compound has a molar ratio of 1 or less, preferably 0.0 to the organoaluminum compound.
It is used in the range of 05 to 1.0.

The polymerization reaction using the polymerization catalyst according to the present invention can be carried out in the presence or absence of an organic solvent,
Further, the olefin monomer used can be used in either gas or liquid state. Polymerization temperature is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0 Kg/cm2・G or less, preferably 50 Kg/cm”
6G or less.

Olefins to be homopolymerized or copolymerized using the olefin polymerization catalyst according to the present invention include ethylene, propylene, 1-butene, and the like.

[Functions and effects of the invention]

When the osinofin polymerization catalyst of the present invention is used to polymerize olefins, it exhibits a previously unexpected high activity, thereby minimizing the amount of catalyst residue present in the resulting polymer. In addition, since the amount of residual chlorine is extremely small, the influence of chlorine can be reduced to such an extent that no deashing process is required for the product.

Chlorine remaining in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, as well as deterioration and yellowing of the produced polymer itself. The results obtained will be of great benefit to the field of technology.

In addition, according to the catalyst of the present invention, by not adding an organic carboxylic acid ester during polymerization, it is possible to solve the major problem of adhesion of ester odor to the produced polymer.

Furthermore, conventionally, there was a common drawback in so-called high-activity supported catalysts in that the activity per unit time of the catalyst decreased significantly as the polymerization progressed, but the catalyst according to the present invention The decrease in activity over time is extremely small compared to conventionally known catalysts, making it useful for longer polymerization times such as copolymerization, and when using higher polymerization pressures. Since the increase in activity is large, it can be widely used in bulk polymerization and gas phase polymerization, which have recently been attracting attention.

Moreover, according to the catalyst according to the present invention, a polymer having a well-shaped structure and a high degree of stereoregularity can be obtained.

Furthermore, in the production of industrial olefin polymers, it is important to allow hydrogen to coexist during polymerization! Although it is common from the viewpoint of control, etc., conventional catalysts using magnesium chloride as a carrier and organic carboxylic acid esters have the disadvantage that their activity and stereoregularity are significantly reduced in the coexistence of hydrogen. Ta. However, when olefin polymerization is carried out in the presence of hydrogen using the catalyst according to the present invention,
Even when the MI of the resulting polymer is very high, the activity and stereoregularity are not reduced. Such an effect was strongly desired by those skilled in the art.

In addition, it does not produce fine powder polymers that are undesirable in the polyolefin manufacturing process, and is suitable for gas phase polymerization, which has been attracting attention recently, and has excellent fluidity, so it is suitable for so-called post-polymerization treatment processes such as pumping and centrifugation. In addition to making it easier to process, it also has various effects such as the ability to omit the granulation process due to its excellent particle shape.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) (a) Preparation of substances Using a 2.01 volume round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, 30 g of metal magnesium powder, 1.0 g of iodine, and 1.21 g of n-butyl chloride were charged, and the mixture was reacted for 5 hours at the boiling point of n-butyl chloride. After the reaction was completed, the supernatant was removed, and the product was washed three times with 500 d of n-butyl chloride.
A powdery substance was obtained by drying under reduced pressure.

(III) Preparation of solid catalyst component 30 g of the powdery substance obtained in the above [1], 1.0 ml of tetrabutoxytitanium, and 1 ml of n-dibutyl phthalate
．． 5- in a nitrogen gas atmosphere, the total volume of 475 stainless steel poles of 25 mmφ was filled. The mixture was placed in a vibrating mill pot of Ol, and pulverized for 17 hours at a vibration frequency of 1430 V, p, m, and a shaking width of 3.5 mm.

In a 500rd capacity round bottom flask equipped with a stirrer, 10 g of the above pulverized product was placed in a nitrogen gas atmosphere, and 75 g of n-decane was added.
- and 10 ml of tetrabutoxy titanium, 12
The temperature was raised to 5° C. and treatment was carried out for 1 hour while stirring. Next, a solution of 25 rnl of n-hebutane and 6.8 mf of 2-ethylhexyl alcohol was added dropwise to the mixture over a period of 30 minutes, and the mixture was reacted for 1 hour while maintaining the temperature at 125°C. Thereafter, the mixture was cooled to 70° C., and a mixed solution of 25 rnl of n-hebutane and 1.5 ml of n-butyl phthalate was added dropwise over a period of 30 minutes, and the mixture was heated to 90° C. and treated for 1 hour. The obtained product was heated to 200rn1.
of heptane five times, then TlC1475mj!
was added and reacted at 115°C for 3 hours. 20 minutes after completion of reaction
A solid catalyst component was obtained by washing 10 times with 0 ml of hebutane.

At this time, the titanium content in the solid catalyst component was measured and found to be 4.76% by weight.

(3) Polymerization internal volume of propylene2. After completely replacing the autoclave with nitrogen gas using an OL autoclave equipped with a stirring device, add 200 mg of triethylaluminum; 1. 70 mg of 8-epoxy paramencune and 3.0 mg of the solid catalyst component were charged. After that, hydrogen gas 1.8β, liquefied propylene 1.4
1 was charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer is dried under reduced pressure at 80° C., and the amount of the obtained product is referred to as (A). Boil this again
-Extract with hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, the amount of which is designated as (B).

The polymerization activity (c) per solid catalyst component used is expressed by the following formula.

The MI of the produced polymer is represented by (F), and 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 30 minutes. The results obtained are shown in Table 1.

Example 3 An experiment was carried out in the same manner as in Example 1 except that the same amount of dipropylphthalate was used instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 4.
It was 87% by weight.

During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

In addition, the yield (D) of the total crystalline polymer can be calculated using the following formula, and the amount of residual chlorine in the produced polymer can be calculated using the following table (B).

[Brief explanation of drawings]

FIG. 1 is a schematic drawing to help understand the present invention.

Claims (1)

[Scope of Claims] 1) (I) Substance (a) obtained by reacting metallic magnesium powder and at least twice the mole of alkyl monohalide in the presence of iodine, tetraalkoxytitanium (b) and phthalic acid diester After pulverizing (c), the obtained product is treated with tetraalkoxytitanium (b), aliphatic alcohol (e) and phthalic acid diester (c) at 100°C or higher in the presence of aliphatic hydrocarbon (d). A solid catalyst component obtained by adding titanium tetrachloride (f) to the obtained product and further processing; from (II) an epoxy paramenthane compound and (III) an organoaluminum compound. A catalyst for polymerizing olefins, which is characterized by: