JPS62124106A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To provide a catalyst composed of a piperidine derivative, an organic Al compound and a solid component derived from metallic Mg and an alkyl monohalide, etc., exhibiting high catalytic activity and capable of producing a stereoregular polymer in high yield. CONSTITUTION:The objective catalyst is derived from (A) a solid catalyst component obtained by (1) reacting 1mol of metallic Mg powder with >=2mol of an monohalide (e.g. n-propyl chloride) in the absence of solvent and in the presence of iodine usually at >=40 deg.C for >=30min, (2) contacting the reaction product with a phthalic acid diester preferably by crushing both components and (3) contacting the product with TiCl4, (B) a di- or tetra-substituted piperidine derivative of formula (R<1>-R<4> are H or alkyl) and (C) an organic Al compound (e.g. trialkyl aluminum).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a high-performance catalyst that acts with high activity and can yield stereoregular polymers in high yields when used in the polymerization of olefins. This is related to. More specifically, the present invention relates to a "product" obtained by contacting a substance obtained by reacting a metal magnesium powder and an alkyl monohalide in the presence of iodine in the absence of a solvent with a diester of phthalic acid. The present invention relates to a catalyst for polymerizing olefins, which comprises a solid catalyst component obtained by contacting a compound with TlC14, a di- or tetrasubstituted biR-lysine derivative, and an organoaluminum compound.

Prior Art Recently, instead of the conventionally well-known titanium trichloride catalyst component as a catalyst for the polymerization of olefins such as propylene, there are many new types of catalysts in which the active component titanium is supported on magnesium chloride together with an electron donor. developed and proposed.

Among these, the earliest developed ones were organic monocarboxylic acids as electron donors; There is a product obtained by co-pulverizing organic monocarboxylic acid nistert with magnesium chloride and treating it with titanium tetrachloride.

However, these cannot be said to have satisfactory properties for use on an industrial scale, and methods to improve various properties, such as those using jetoxymagnesium instead of magnesium chloride, Various methods have been proposed in which special compounds are used, or methods in which the above-mentioned substances are combined, contact means, etc. are modified.

For example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
A method is disclosed in which organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. are used in combination for the polymerization of olefins, and JP-A-57-63310 discloses that organic aluminum compounds, organic carboxylic acid esters, compounds having an M-0-R group, etc. are used in combination for the polymerization of olefins. There is a method in which a catalyst component is prepared by combining various esters of , active magnesium chloride, and a titanium compound, and then propylene is polymerized using a compound having an Sl-〇 bond or a 5i-N bond and an organoaluminum compound. Disclosed.

Problems to be Solved by the Invention In the prior art, the chlorine contained in the magnesium chloride that occupies Tsuchiura as a carrier material, like the halogen element in the titanium halide, has a negative effect on the produced polymer.
However, since magnesium chloride has the disadvantage of having negative effects, it is necessary to have high activity to the extent that the effect of chlorine can be virtually ignored, or measures must be taken to keep the concentration of magnesium chloride itself low. There is.

However, when carrying out the industrial polymerization of olefins, especially the stereoregular polymerization of propylene, 1-butene, etc., using a catalyst component having magnesium chloride as a carrier in combination with an organoaluminum compound, when carrying out the polymerization reaction. It is essential to use an organic monocarboxylic acid ester as an electron donor. 'However, in this case, it is necessary to use an extremely large amount of organic monocarboxylic acid ester, and as a result, there is a problem in that the resulting polymer has a characteristic ester odor.

Furthermore, in so-called highly active supported catalysts, such as catalysts using catalyst components with magnesium chloride as a carrier, although the activity is high at the initial stage of polymerization, deactivation over time causes problems in process operation, and block copolymerization For longer polymerization times, it was virtually impossible to use it.

To improve this point, the above-mentioned Japanese Patent Application Laid-Open No. 54-9459
No. 0 has been proposed, but as is clear from the description in the same publication, in this case it is necessary to use an organic carboxylic acid ester during catalyst preparation and during polymerization. Generally, treatment with the organic carboxylic acid Nistelha or titanium halide contained in the catalyst, or washing with an organic solvent causes the resulting polymer to have a negligible odor problem. 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 liquid or gaseous monomers, almost all of it is produced. At present, it is contained in the 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 catalyst obtained is not sufficient for practical use in terms of performance and sustainability of activity. The reality is that this cannot be said.

The inventors of the present invention conducted extensive research to solve the problems remaining in the prior art, and as a result of the present invention, they succeeded in providing a novel catalyst for polymerizing olefins.

Means for Solving the Problems According to the present invention, (4) (a) A substance obtained by reacting a metal magnesium powder and an alkyl monohalide in an amount of twice the mole or more in the absence of a solvent and in the presence of iodine. and (b) a diester of phthalic acid, the product obtained by contacting (c)
Solid catalyst component obtained by contacting with TiCA'4; (wherein R1, R2, R5, and R4 are hydrogen or an alkyl group that may have a substituent,
At least one of 2 is an alkyl group, and at least one of R5 and R4 is an alkyl group. There is provided a catalyst for polymerizing olefins, characterized by comprising a di- or tetra-substituted piperidine derivative represented by (C) an organoaluminum compound.

In order to obtain the substance (hereinafter simply referred to as (a) substance) obtained by the reaction of (a) metal magnesium powder with the alkyl monohalide in the present invention, a commercially available metal magnesium powder and an alkyl monohalide are combined. The reaction is carried out in the absence of an organic solvent and in the presence of iodine, and in this case, it is necessary to use 2 or more moles of the alkyl monohalide per 1 mole of the metal magnesium powder.

The reaction temperature and reaction time are arbitrary and not particularly limited as long as the above reaction proceeds sufficiently, but 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. It will be done. 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; examples thereof include n-propyl chloride, isopropyl chloride, n-butyl chloride. , inbutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

In the present invention, the diesters of phthalic acid (b) include dimethyl 7-talate, diethyl 7-talate, diisopropyl phthalate, dipropyl 7-talate, dibutyl phthalate, diisobutyl 7-talate, cyamyl phthalate, diynamyl phthalate, ethyl butyl phthalate, and ethyl isobutyl. Examples include phthalate and ethylpropyl heptalate.

The piperidine derivative (B) in the present invention is preferably a disubstituted or tetrasubstituted derivative, and specifically, the general formula (wherein R1, R2, R5, and R4 are hydrogen or have a substituent) is preferable. an optional alkyl group, in which R1 and R
At least one of 2 is the alkyl group! llAlso, R
At least one of 5 and R4 is the alkyl group. ). More specific examples include: 2,6-diimbropylpiveridine, 2,6-cyptylpi is lysine, 2.2.6.6-f) lysine, 2.2.6.6-citra Examples include ethylbiperidine, among which 2,2,6,6-titramethylpyRlysine is preferred.

Examples of the organoaluminum compound (C) in the present invention include trialkylaluminum, dialkylaluminiramnolide, alkylaluminum civalide, and mixtures thereof, among which,
Trialkylaluminum is preferred, and triethylaluminum and triimbutylaluminum are particularly preferred.

In the present invention, when obtaining 7 g of the solid catalyst component, the proportion of each raw material constituting the solid catalyst component is arbitrary and particularly limited as long as it does not adversely affect the performance of the solid catalyst component to be produced. Usually (a
) The diester of phthalic acid (b) (hereinafter simply referred to as (b) substance) is 0.01 per gram of the substance.
The amount of TiCA4 (C) (hereinafter simply referred to as (C) substance) is in the range of 0.1y or more, preferably 1y or more.

Note that at this time, the order and method of contacting the raw materials constituting the solid catalyst component are not particularly limited. A preferred embodiment includes grinding the (a) substance and the (b) substance in a ball mill or vibratory mill and similar grinders and contacting the resulting composition with the (C) substance.

The above-mentioned substances (a) and (b) are pulverized for usually 10 minutes or more, preferably 30 minutes or more.

It is preferable that the composition obtained by the above-mentioned pulverization be brought into contact with the substance (C) at a temperature ranging from -10°C to the boiling point of the substance (C) for 10 minutes to 100 hours.

The composition obtained after the above contact can be repeatedly contacted with the substance c), and the composition obtained can also be washed using an organic solvent such as n-hebutane. All of these are included in one embodiment of the implementation of the present invention.

The series of operations related to the preparation of the solid catalyst component (A) in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component (4) prepared as described above is combined with the bilysine rust conductor (B) and the organic aluminum compound (C), and is used as a catalyst for polymerizing olefins according to the present invention. Configure.

The organoaluminum compound (C) used is used in an amount of 1 to 1000 mol per titanium I atom in the solid catalyst component, and the piperidine derivative has a molar ratio of 1 or less, preferably 0.005 to the organoaluminum compound.
It is used in the range of ~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 100C or less, and the polymerization pressure is 10
0 Kq/L2L2・G or less preferably 50 Kq/ry
m2・G 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.

Effects of the Invention When olefins are polymerized using the catalyst for olefin polymerization according to the present invention, the resulting polymer has extremely high stereoregularity. Furthermore, since the catalyst exhibits a previously unimaginable high value, the amount of catalyst residue present in the produced polymer can be kept extremely low, and since the amount of residual chlorine is extremely small, the product can be deashed. The influence of chlorine can be reduced to the extent that no process is required at all.

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.

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

Furthermore, conventionally, there has been a common drawback in so-called high-activity short-term catalysts in that the activity per unit time of the catalyst decreases significantly as the polymerization progresses, but in the catalyst according to the present invention, The decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, so it is useful in cases where the polymerization time is much longer, such as in copolymerization, and it can also be used at higher polymerization pressures. Since the increase in activity is large when it is used, it can be widely used in Merck polymerization and gas phase polymerization, which have recently been attracting attention.

Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control. These catalysts had the disadvantage that their activity and stereoregularity were significantly reduced in the presence of hydrogen. 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 effects were strongly desired by self-employed people. In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem in terms of the capacity of polymerization equipment, the capacity of post-treatment processes, etc., but the catalyst according to the present invention also has this problem. , has extremely excellent properties.

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1゜(1) (a) Preparation of substances Capacity equipped with a stirrer2. Using a round bottom flask of OL,
After the gas was sufficiently replaced 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 liquid was removed, and the product was washed three times with 500a of n-butyl chloride, and then dried under reduced pressure to obtain powdery substance (a).

(2) Preparation of solid catalyst component.
Volume i filled with 5 dragon φ stainless steel poles to the full volume
1. Pour into OJ's vibrating mill pot and set the vibration frequency to 1430.
Grinding was carried out for 17 hours at V-pm and shaking @ 3.5 tm.

Using a round bottom flask with a capacity of 1-500M equipped with a stirrer, after sufficiently purging with nitrogen gas, take the solid composition 5y obtained by the above-mentioned pulverization treatment, and add Ti(
'J4200M was added, the temperature was raised to 120°C, and the mixture was reacted for 2 hours. After the reaction was completed, the supernatant was removed, and Ti('14200at) was added to the product and reacted at 1200°C for 2 hours. After the reaction was completed, the product was cooled to 40°C and the product was
It was washed 10 times with 200M hebutane to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 1.61% by weight.

(3) Using an autoclave with a stirring device and a polymerization internal volume of 201 I, after completely replacing the autoclave with nitrogen gas, add triethylaluminum 193IIg, 2.2.6.6-titramethylpiveridine 24R9 and the solid catalyst component 6 .0 my was charged. Thereafter, 1.8 M of hydrogen gas and 1.41 ml of liquefied propylene were 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). Further, this product was extracted with boiling n-heaton for 6 hours to obtain a polymer insoluble in n-hebutane, and the amount of this product was designated as (B).

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

In addition, the yield of the total crystalline polymer (D> is expressed by the following formula, and the amount of residual chlorine in the produced polymer is expressed as (E), and the MI of the produced polymer is expressed as
is represented by (F) and the bulk specific gravity is represented by (G), and the obtained results are shown in Table 1.

Example 26 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 60 minutes. The results obtained are shown in Table 1.

Example 6 An experiment was carried out in the same manner as in Example 1, except that the polymerization reaction was carried out in the following manner.

Internal volume completely replaced with nitrogen gas2. 700 ml of n-hebutane was charged into an autoclave equipped with a stirrer, and triethylaluminum 3 was added while maintaining a nitrogen gas atmosphere.
01 #Iti, 2.2,6.6-titramethelpiveridine 37 #Ig, and then 14.0 JIfil of the solid catalyst component prepared by the method of Example 1 were charged. After that, 150M of hydrogen gas was charged, the temperature was raised to 70℃, and propylene gas was introduced, while maintaining the pressure of 6 Kq/1m2・G.
The polymerization reaction was carried out for a period of time. After the polymerization reaction was completed, the obtained solid polymer was taken from house to house, 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 lachrymal fluid is expressed as (I), and the amount of solid polymer is expressed as (I).The obtained solid polymer is heated in boiling n-heptane for 6 hours extract, n
- A polymer insoluble in hebutane is obtained, and this amount is designated as (J).

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

Further, the yield (L) of the crystalline polymer is expressed by the following formula, The yield (b) of the total crystalline polymer is determined by the following formula.

Furthermore, the residual chlorine in the produced polymer is represented by (9), the MI of the produced polymer is represented by (0), and the bulk specific gravity is represented by (P). The results obtained are shown in Table 2.

Example 4 An experiment was conducted in the same manner as in Example 6 except that the polymerization time was 2 hours. The results obtained are shown in Table 2.

Example 5 An experiment was carried out in the same manner as in Example 1 except that the same amount of dipropylphthalate was used in place of dibutyl phthalate. In addition, the titanium content in the solid catalyst component at this time was 1,
It was 78% 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 6 A solid catalyst component was prepared in the same manner as in Example 1 except that 7M of dibutyl phthalate was used. Note that the titanium content in the solid catalyst component at this time was 2.08% 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 Z The diisobutylphthane content in place of dibutyl phthalate was 1.647%. During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

Comparative example 1゜Commercially available (7) MgCl220 & Jib fA'7 TaL
/ -t5. Grind Qgo under the same conditions as in Example 1.

Thereafter, 5 g of the pulverized composition was charged into a glass container with an internal volume of 500 ar (7) under a nitrogen gas atmosphere, and TiC1
! 420 Qm was added and the reaction was stirred at 120°C for 2 hours.

After the reaction was completed, the supernatant was removed and fresh TiC1!4200 was added.
a was added and reacted at 120°C for 2 hours.

After the reaction was completed, the mixture was cooled to 40° C. and washed 10 times with 20[deg.] n-hebutane to obtain a solid catalyst component. At this time, when the titanium content in the solid catalyst component was measured, it was 1.64.
% by weight.

During polymerization, add the above solid catalyst component to 6. The experiment was conducted in the same manner as in Example 1 except that Dxa was used. The results obtained are shown in Table 1.

Comparative Example 2 An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization time was 30 minutes. The results obtained are shown in Table 1.

Comparative Example 6 An experiment was carried out in the same manner as in Comparative Example 1, except that the polymerization reaction was carried out in the same manner as in Example 6.

The results obtained are shown in Table 2.

As is clear from a comparison between Example 1.2 and Comparative Example 1.2, the catalyst according to the present invention exhibits extremely small decrease in activity over time of polymerization.

As is clear from a comparison between Example 1.3 and Comparative Example 1.3, the activity of the catalyst according to the present invention increases significantly when a higher polymerization pressure is employed.

Table 2 Mao Zoku Supplementary Book January 31, 1985

Claims (2)

[Claims] (1) (A) (a) A substance obtained by reacting a metallic magnesium powder and an alkyl monohalide in an amount of twice the mole or more in the absence of a solvent and in the presence of iodine, and (b) a diester of phthalic acid. (c) Solid catalyst component obtained by contacting the product obtained by contacting with TiCl_4; (B) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula R^1, R^2 , R^3, R^4 are hydrogen or an alkyl group which may have a substituent,
At least one of R^1 and R^2 is an alkyl group,
Further, at least one of R^3 and R^4 is an alkyl group. 1. A catalyst for polymerizing olefins, comprising a di- or tetra-substituted piperidine derivative represented by (C) and an organoaluminum compound. (2) The above-mentioned (a) substance obtained by reacting the metal magnesium powder with at least twice the mole of alkyl monohalide in the absence of a solvent and in the presence of iodine, and (b) the diester of phthalic acid. The catalyst for polymerizing olefins according to claim 1, wherein the contact is carried out by pulverization.