JPS62169802A - Catalsyt for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a catalyst which is highly active, can decrease a residual chlorine content to such a low level that a deashing step can be eliminated and can give the titled highly stereoregular polymer, by using a specified solid catalyst component, a piperidine derivative and an organoaluminum compound. CONSTITUTION:The titled catalyst comprising a solid catalyst component obtained by contacting a product, obtained by copulverizing a substance obtained by reacting a metallic Mg powder with at least two mol, per mol or the metallic Mg powder, of an alkyl monohalide (e.g., n-butyl chloride) in the absence of any solvent in the presence of iodine with a phthalic diester (e.g., dibutyl phthalate) and TiCl4 with TiCl4 in the presence of a normally liquid aromatic (halo)hydrocarbon (e.g., toluene or chlorobenzene), a disubstituted or tetrasubstituted piperidine derivative (B) of formula I [wherein R<1>-R<4> are each H or a (substituted) alkyl and both of either R<1> or R<2> and either R<3> or R<4> are alkyls], e.g., a compound of formula II or III, and an organoaluminum compound (C) (e.g., triethylaluminum).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a high-density polymer that exhibits high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. This relates to performance catalysts. More specifically, the present invention combines metallic magnesium powder and alkyl monomer powder.
A substance obtained by reacting a halogenide in the absence of a solvent in the presence of iodine is co-pulverized with a diester of phthalic acid and titanium tetrachloride, and the resulting product is converted into an aromatic hydrocarbon that is liquid at room temperature. The present invention also relates to a catalyst for polymerizing olefins comprising a tetrasalt, a disubstituted or tetrasubstituted piperidine derivative, and an organoaluminum compound in the presence of an aromatic halogenated hydrocarbon.

[Prior art]

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

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

However, these cannot be said to have satisfactory properties for use on an industrial scale, and there are methods to improve various properties, such as those using jetoxymagnesium instead of magnesium chloride, and special ones as electron donors. Various methods have been proposed in which compounds are used, or methods of combining the substances, 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 has been disclosed in which an organoaluminum compound, an organic carboxylic acid ester, a compound having an M-0-R group, etc. are used in combination to polymerize olefins, and in JP-A-57-63310, an electron donor A method in which a catalyst component is prepared by combining various esters as esters, active magnesium chloride, and a titanium compound, and then propylene is polymerized using a compound having an Si-〇 bond or a 5i-N bond and an organoaluminum compound. is disclosed.

[Problem that the invention seeks to solve]

In the prior art, chlorine contained in magnesium chloride, which is the main carrier material, has a negative effect on the produced polymer, similar to the halogen element in titanium halides.
Since magnesium chloride has the disadvantage of having negative effects, countermeasures have been taken to counter this, such as requiring high activity to the extent that the effects of chlorine can be virtually ignored, or reducing the concentration of magnesium chloride itself. ing.

In addition, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially using the 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 catalysts using catalyst components having magnesium chloride as a carrier, the deactivation of so-called highly active supports over time is large and poses a problem in process operation, and when polymerization times such as block copolymerization are lengthened, 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, 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 liquid or gaseous monomers, almost all of it is produced. Currently, it is contained in the polymer, and therefore, it can be said that the problem of odor of the produced polymer occurs during polymerization. As can be seen from the examples, the method disclosed in the same publication requires very complicated operations, and the resulting catalyst is not sufficient for practical use in terms of performance and sustainability of activity. The reality is that this cannot be said.

In order to solve the various problems in the prior art, the present inventors conducted intensive research and succeeded in providing a novel catalyst for polymerizing olefins (Japanese Patent Application No. 1986-
263863).

The present invention is a further improvement of the above-mentioned catalyst, and provides a catalyst with which a polymer having higher activity and higher stereoregularity can be obtained.

[Disclosure of the invention]

The present invention is characterized in that (A+) a substance (a) obtained by reacting a metal magnesium powder and an alkyl monohalide of twice the mole or more in the absence of a solvent and in the presence of iodine is used as a diester of phthalic acid (b). A solid obtained by further contacting the product obtained by co-pulverizing with titanium tetrachloride (C) and titanium tetrachloride in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon that is liquid at room temperature. Catalyst component, (Bl
General formula (in the formula, R1, R2, R3, R' are hydrogen or an alkyl group which may have a substituent, and R1 and R
At least one of 2 is an alkyl group, and at least one of R3 and R' is an alkyl group. The present invention provides a catalyst for polymerizing olefins, which is characterized by comprising a di- or tetrasubstituted piperidine derivative represented by (C) and 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 and 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 as long as the above reaction proceeds sufficiently and are not particularly limited, but are usually heated at 10 minutes or more at 40°C or higher, preferably 1 minute at 40°C or higher. It goes up. This reaction is a Grignard type reaction, and when the R 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, inpro-el chloride, n-butyl chloride, etc. chloride, inbutyl chloride, pentyl chloride, hexyl chloride, octyl chloride, etc.
Hereinafter, the substances (simply referred to as (1)) include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate, ethyl butyl heptthalate, ethyl isobutyl phthalate, and ethylpropyl phthalate. For example,

In the present invention, (d) aromatic hydrocarbons or aromatic halogenated hydrocarbons that are liquid at room temperature (hereinafter simply referred to as (d) substance) include, for example, aromatic hydrocarbons such as toluene, xylene, and chlorobenzene. , O-dichlorobenzene, aromatic halogenated hydrocarbons such as fromobenzene, and the like.

Specific examples of the disubstituted or tetrasubstituted piperidine derivatives (B) in the present invention include 2.6-diitupropylpyridine, 2.6-:)butylgiberidine, 2.2.6.6- Chitramethylpi is lysine, 2,
Examples include 2,6,6-titraethylpiveridine, among which 2,2,6,6-titramethylpiveridine is preferred.

Examples of the organoaluminum compound (C) in the present invention include trialkylaluminum, dialkylaluminum halide P1 alkyl aluminum civalide, and mixtures thereof. Among them, trialkylaluminum is preferred, and triethyl aluminum and triisobutylaluminum are particularly preferred.

When obtaining the solid catalyst component (A) in the present invention, 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, the amount of the substance (1) is 0.01 for 1 gram of the substance (a), although it is not required to be
-1g, and for the titanium tetrachloride, when co-pulverizing with the substance (a) and substance (b), the titanium tetrachloride is in the range of 0.
When brought into contact with the product obtained by co-pulverization, it is in the range of 0.17 or more, preferably 17 or more. The amount of substance (d) coexisting during this contact is 0.01 to 10% per ml of titanium tetrachloride.
0+++l is preferably in the range of 0.1 to 10 ml.

The above (a) substance, (1)) substance and titanium tetrachloride (
The co-grinding in C) is usually carried out for 10 minutes or longer, preferably for 10 minutes or longer.

When the product obtained by said co-milling is contacted with titanium tetrachloride in the presence of substance (d), it is usually -10
It is preferable to carry out the treatment at a temperature ranging from °C to the boiling point of titanium tetrachloride for a period of about 10 minutes to 100 hours.

After this contact, the resulting product can be repeatedly contacted with further titanium tetrachloride. In the contact at that time, the substance (d) may or may not coexist. The product thus obtained may be washed with an organic solvent such as n-hebutane, if desired.

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 (A) in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

One component of the solid catalyst fA) prepared as described above is the (Bl) PIOIJ lysine conductor and the (C
) is combined with the organoaluminum compound to constitute the catalyst for polymerizing olefins according to the present invention.

The organoaluminum compound (C) used is titanium in the solid catalyst component. It is used in a molar ratio of 1 to 1,000 kills per atom to the aluminum compound, preferably in the range of 0.005 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
°C or less, preferably 100''C or less, and the polymerization pressure is 100 kg/crn2・G or less, preferably 50 kg/
cm”・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 the catalyst for polymerizing olefins according to the present invention is used to polymerize olefins, it exhibits a high activity that could not be expected in the past. The amount of residue can be kept extremely low, and since the amount of residual chlorine is extremely small, the influence of chlorine can be reduced to such an extent that a deashing step is not required at all on 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.

Further, according to the catalyst of the present invention, the major problem of ester odor adhesion to the produced polymer can be solved by not adding an organic carboxylic acid ester during polymerization.

Furthermore, conventionally, there has been a common drawback in so-called highly active supported catalysts 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 when polymerization times are longer, such as in copolymerization, and higher polymerization pressures are used. Since the increase in activity is large in this case, 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 high degree of stereoregularity can be obtained.

Furthermore, in the production of industrial olefin polymers, it is common to coexist hydrogen during polymerization from the viewpoint of controlling the M process, but using conventional magnesium chloride as a carrier and organic carboxylic acid ester. The catalyst used had the disadvantage that its 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 an effect was strongly desired by those skilled in the art. 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.

[Example, comparative example]

The present invention will be explained in more detail below using Examples and Comparative Examples.

Example I DJ (a) Preparation of materials Using a 2.0 t capacity round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, metal magnesium powder 307 and iodine 1.0? and 1.26 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 500 ml of n-butyl chloride, and then dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component Powdered substance 207 obtained in (1) above, 7.5 ml of dibutyl phthalate, and 4.0 ml of TiCz. In a dust atmosphere, a 1.0 t capacity vibrating mill pot filled with 415 stainless steel poles of 25 Hφ was charged, and the vibration frequency was 1430 V-p-m and the amplitude was 3.5 M.
Co-pulverization treatment was carried out for 17 hours.

Capacity 500+++A with a stirrer! Using a round-bottomed flask, the solid composition 51 obtained by the co-pulverization process was taken into the flask after the air was sufficiently purged with nitrogen gas, and 50 ml of TiC and 50 ml of toluene were added thereto, and the temperature was raised to 115°C. The mixture was allowed to react at a warm temperature for 2 hours. After the reaction, the supernatant was removed and the product was treated with fresh TlCt, 50 m
1 and 50 ml of toluene were added, and the mixture was reacted at 115°C for 2 hours. After the reaction was completed, it was cooled to 40'C and the product was washed once with 200 ml of n-heptane to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 2.17% by weight.

(3) Using an autoclave equipped with a stirring device and having an internal volume of propylene polymerization of 2.01 kg, after completely replacing the autoclave with nitrogen gas, 193 mg of triethylaluminum, 24 kg of 2,2.6.6-titramethylpiberidine and 3.0 m'i of the solid catalyst component was charged. After that, 1.8 tons of hydrogen gas, 1.8 tons of liquefied propylene.
4t was charged, and the 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). This product was still extracted with boiling n-hebutane 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.

Further, the total crystalline polymer yield (DJ) is expressed by the following formula.

Further, the amount of residual chlorine in the produced polymer is expressed as (E), the M strength and bulk density of the produced polymer are expressed as (G), and the obtained results are shown in Table 1.

Example 2 An experiment was carried out in the same manner as in Example 1, except that the polymerization time was changed to I 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 polymerization reaction was carried out in the following manner.

700 rnl of n-heptane was charged into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which had been completely purged with nitrogen gas, and triethylaluminum 301cm, 2,2,6.6-titramethyl was added while maintaining the nitrogen gas atmosphere. Biherizin 3
7 m9 and then 10.0 m of the solid catalyst component prepared by the method of Example 1 were charged.

After that, 150 mt of hydrogen gas was charged, the temperature was raised to 70°C, and while propylene gas was introduced, 6 kg/cry2.
The polymerization reaction was carried out for 1 hour while maintaining the pressure of G.

After the polymerization reaction is completed, the obtained solid polymer is distributed door to door and
It was heated to °C and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after condensing the p liquid is (H), and the amount of solid polymer is (1). 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 (J).

The polymerization activity (K) of the 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 (M) of the total crystalline polymer is determined by the following formula.

Furthermore, residual chlorine in the produced polymer is expressed as (N), M engineering of the produced polymer is expressed as (0), and bulk specific gravity is expressed as (P). The results obtained are shown in Table 2.

Example 4 An experiment was conducted in the same manner as in Example 3, 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 instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 2.
It was 13% 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 7.5 ml of dibutyl phthalate and 4.0 m of TiC
5.0 ml of dipropylphthalate and Ti instead of
A solid catalyst component was prepared in the same manner as in Example 1 except that 2.0 ml of Cum was used. Note that the titanium content in the solid catalyst component at this time was 1.86% by weight. 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 Powdered substance obtained in Example 1 (1) 20? <! : dibutyl phthalate) 5.0m/! and co-pulverized under the same conditions as in Example 1. Thereafter, the product 57 obtained by the co-pulverization was placed in a glass container with an internal volume of 500 ml under a nitrogen gas atmosphere, and 200 ml of TiC was added thereto.
The reaction was stirred at °C for 2 hours.

After the reaction, remove the supernatant and add 200ml of fresh mites T104.
was added and reacted at 120"C for 2 hours.

After the reaction is complete, cool at 40°C and add 200ml of n-hebutane.
1 for 10 times to obtain a solid catalyst component. At this time, the titanium content in the solid catalyst component was measured and found to be 1.
It was 61% by weight.

An experiment was carried out in the same manner as in Example 1, except that 6.0 μm of the above solid catalyst component was used during the polymerization. The results obtained are shown in Table 1.

Table 2 Comparative Example 2 and Comparative Example 3 according to the prior art are listed below.

Comparative Example 2 Commercially available MgCL220? , dibutyl phthalate 5.0
ml is ground under the same conditions as in Example 1. Thereafter, the pulverized composition 57 was heated under a nitrogen gas atmosphere with an internal volume of 500 mA!
The mixture was placed in a glass container, 200 ml of TiC was added thereto, and the reaction was stirred at 120''C for 2 hours.

After the reaction is complete, remove the supernatant and add a new T104200ml
was added and reacted at 120"C for 2 hours.

After the reaction is complete, cool to 40°C and add 200ml of n-heptane.
was washed 10 times to obtain a solid catalyst component. At this time, when the titanium content in the solid catalyst component was measured, it was 1.6.
It was 4 times t%.

During polymerization, add the above solid catalyst component to 6. The experiment was conducted in the same manner as in Example 1 except that Ogi was used. The results obtained are shown in Table 3.

Comparative Example 3 An experiment was conducted in the same manner as Comparative Example 2 except that the polymerization time was changed to the addition period. The results obtained are shown in Table 3.

Table 3

Claims (1)

[Claims] 1. Substance (a) obtained by reacting (A) metallic magnesium powder with at least twice the mole of alkyl monohalide in the absence of a solvent and in the presence of iodine, phthalic acid. The product obtained by co-pulverizing the diester (b) and titanium tetrachloride (c) is further brought into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon that is liquid at room temperature. Solid catalyst component obtained by: (B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2, R^3, R^4 are hydrogen or have a substituent. (at least one of R^1 and R^2 is an alkyl group, and at least one of R^3 and R^4 is an alkyl group). A catalyst for polymerizing olefins, comprising a substituted or tetrasubstituted piperidine derivative and (C) an organoaluminum compound.