JPS63241005A - Solid catalyst ingredient for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the title catalyst ingredient which is highly active and provides stereoregular polymers in high yields, by contacting a reaction product of a metallic magnesium, as alkyl monohalide and a dialkoxymagnesium with a diester of phthalic acid, TiCl4, etc. CONSTITUTION:Metallic magnesium powder is reacted with at least twice the moles of an alkyl monohalide (e.g. n-butyl chloride) in the presence of a dialkoxymagnesium (e.g. diethoxymagnesium). The reaction product is crushed together with a diester of phthalic acid (e.g. dibutyl phthalate) and titanium tetrachloride. The product is further contacted with titanium tetrachloride in the presence of a liquid aromatic hydrocarbon or aromatic halogenated hydrocarbon (e.g. chlorobenzene) to give the object solid catalyst ingredient for the polymerization of olefins. This catalyst ingredient is combined with an organoaluminum compound for use as a catalyst for the polymerization of olefins.

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 high-performance solid catalyst components.

[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 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-57-65510 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. The catalyst component is FA'J5 by combining various esters of , activated magnesium chloride and titanium compound, and further 51
A method for polymerizing propylene using a compound having a -0 bond or an 81-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 the disadvantage of having an adverse effect on the produced polymer, similar to the halogen elements in titanium halides. Therefore, countermeasures are being taken, such as requiring high activity to the extent that the influence of chlorine can be virtually ignored, or alternatively, reducing the concentration of magnesium chloride itself.

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 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 It was practically impossible to use it when the polymerization time was made longer.

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 such that it can be treated with a titanium halide or washed with an organic solvent to such an extent that the odor of the produced polymer can be ignored.

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 present inventors conducted extensive research in order to solve the various problems in the prior art, and succeeded in providing a novel solid catalyst component for polymerizing olefins.

[Disclosure of the invention]

The present invention is produced by co-pulverizing a substance ta+ obtained by reacting metal magnesium powder with an alkyl monohalide tridialkoxymagnesium in an amount of 2 times the mole or more, together with a diester of phthalic acid fbl and titanium tetrachloride tc). A solid catalyst component for the polymerization of olefins, characterized in that the product is further brought into contact with titanium tetrachloride (c) in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon (hydrocarbon) that is liquid at room temperature. It provides:

In the present invention, in order to obtain the substance obtained by reacting the tal metal magnesium powder with the alkyl monohalide in the presence of dialkoxymagnesium (hereinafter simply referred to as tal substance), commercially available metal magnesium powder and alkyl monohalide are used. A halide is reacted with dialkoxymagnesium in the presence of dialkoxymagnesium. At this time, it is necessary to use 2 mol or more of the alkyl monohalide per 1 mol of metal magnesium powder, and dialkoxymagnesium is reacted with metal magnesium powder 1F. On the other hand, it is necessary to use it within the range of α1 to α22. Further, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited, but it is usually carried out at 20°C or higher for 10 minutes or more, preferably at 40°C or higher for 50 minutes or more. . 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 above (al) substances are preferably chlorides of aliphatic hydrocarbons that are liquid at room temperature, such as n-propyl chloride, isopropyl chloride, n-butyl chloride. , isobutyl chloride, pentyl chloride, hemozyl chloride and octyl chloride.

The dialkoxymagnesium used in the production of the substance (a) is preferably one having an alkyl group having 1 to 5 carbon atoms, such as jetoxymagnesium, jetoxymagnesium, dibutoxymagnesium, and the like.

The diester of phthalic acid (1) in the present invention (
Hereinafter, the substances (simply referred to as 11)) include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, diptyl 7-thalate, schizubdel phthalate, cyamyl phthalate, diisoamyl 7-thalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl Examples include propyl phthalate.

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

When obtaining the above-mentioned solid catalyst component in the present invention, the usage ratio of each raw material constituting the solid catalyst component is arbitrary and not particularly limited as long as it does not adversely affect the performance of the solid catalyst component to be produced. However, usually the above (a
) Substance 1f, the above medium) substance Q is in the range of 01 to 1f, and when titanium tetrachloride is co-pulverized with the (al substance and (t)l substance), α01 to 1f.
When brought into contact with the product obtained by co-pulverization, the range is [1,1f or more, preferably 1 or more]. The amount of the substance (d) coexisting during this contact is in the range of 1 to 100 - preferably 11 to 10 - of CLO per 1 dK of titanium tetrachloride.

The above (IL) substance, (b) substance and titanium tetrachloride (
The co-pulverization in c) is usually carried out for 10 minutes or more, preferably for 30 minutes.
It lasts for more than a minute.

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 range from ℃ to the boiling point of titanium tetrachloride for a period of about 10 minutes to 100 hours = After this contact, the obtained product is further repeatedly contacted with titanium tetrachloride. can be done. 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 in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component prepared as described above is combined with an organoaluminum compound to constitute the catalyst for polymerizing olefins according to the present invention. It is preferable to coexist with an electron donating compound other than the aromatic carboxylic acid ester.

As the organoaluminum compound used in the present invention, trialkylaluminum is preferred, and is used in an amount of 1 to 1000 mol per 2 titanium atoms in the solid catalyst component,
Further, the molar ratio of the electron donating compound to the organoaluminum compound is 1 or less, preferably Q, 005 to 1.
．． Used in the range 0.

The polymerization reaction using the solid catalyst component for olefin polymerization according to the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer used can be in either a gas or liquid state. It can also be used. The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100 kg7cw? -G or less, preferably 50 VCg/-.G or less.

The olefins to be homopolymerized or copolymerized using the solid catalyst component for olefin polymerization according to the present invention are ethylene,
These include propylene and 1-butene.

〔Effect of the invention〕

When the solid catalyst component for polymerizing olefins according to the present invention is used to polymerize olefins, the amount of catalyst residue present in the resulting polymer is reduced because it exhibits an unexpectedly high activity. Furthermore, 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.

Further, according to the solid catalyst component of the present invention, since no organic carboxylic acid ester is added during polymerization, it is possible to solve the major problem of ester odor adhering to the resulting polymer.

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

Moreover, according to the solid catalyst component 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 olefins are polymerized in the presence of hydrogen using the solid catalyst component according to the present invention, the activity and stereoregularity do not decrease even if the resulting polymer has extremely high M engineering. Such an effect is
This was highly desired by those skilled in the art. Also,
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 the polymerization equipment, the capacity of the post-treatment process, etc., but the solid catalyst component according to the present invention also has a problem in this respect. , has extremely excellent properties.

[Example, comparative example]

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

Example 1 (1) Preparation of fil material Capacity 2. equipped with a stirrer. Using an ot round bottom flask,
After sufficiently replacing this with nitrogen gas, 30 g of metal magnesium powder, jetoxymagnesium &02 and n-
1.21 liters of butyl chloride was charged and reacted under reflux for 5 hours.

After the reaction was completed, the supernatant was removed and the product was purified by 500-n-
After washing with butyl chloride three times, it was dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component 20t1 diptylphthalate zO- and TiC/, 4.0 rnt of the powdered material obtained in (1) above was placed in a nitrogen gas atmosphere, and a stainless steel pole of 25 dia. / charged into a vibrating mill pot with a filled volume of H1-0/,
Co-pulverization treatment was carried out with a rolling motion number of 1450 v, p, m and a root width of 55117 hours.

Using a 500 d round bottom flask equipped with a stirrer,
After sufficiently purging with nitrogen gas, the solid composition 52 obtained by the co-pulverization process is poured into it, and 'l' is added to it.
Add io/450- and toluene 50- and heat to 115°C.
The temperature was raised to 1, and the mixture was allowed to react for 2 hours. After the reaction was completed, the supernatant liquid was removed, and Tie/50- and toluene 50- were newly added to the product, followed by reaction at 115°C for 2 hours. After the reaction was completed, it was cooled to 40°C and the product was dissolved in n-hebutane 200°C.
d 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 2.22% by weight.

(3) Polymerization internal volume of propylene2. Using an autoclave equipped with a stirrer, the autoclave was completely replaced with nitrogen gas, and then 195 mg of triethylaluminum, 2 atng of 2.2.6.6-tetramethylpiperidine, and the solid catalyst component xom9 were charged. After that, hydrogen gas 1,81, liquefied propylene 1
．． 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 used as a mass. Boil this again KW
Extraction with n-hebutane for 6 hours yields a polymer insoluble in n-hebutane, the amount of which is defined as (Bl).

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

(4) (fl Further, the yield (total) of the total crystalline polymer is expressed by the following formula.

0) l = -X i 00 (capture) Furthermore, the amount of residual chlorine in the produced polymer is expressed as (6), the M concentration of the produced polymer is expressed as (g), the bulk specific gravity is expressed as (Gl), and the obtained results are expressed as It is 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 polymerization reaction was carried out in the following manner.

N-hebutane 700- was charged into an autoclave with an internal volume of 201 and equipped with a stirrer that had been completely purged with nitrogen gas, and triethylaluminum 501- was charged while maintaining the nitrogen gas atmosphere.
η, 2,2,6.6-tetramethylpiperidine 37■,
Next, 1 (L) of the solid catalyst component prepared by the method of Example 1 was added.
O ■ Charged. After that, 150ft1t of hydrogen gas was charged, the temperature was raised to 70℃, and propylene gas was introduced.
1M?・The polymerization reaction was carried out for 1 hour while maintaining the pressure of G. After the completion of the polymerization reaction, the obtained solid polymer was separated into 8
It was heated to 0°C and dried under reduced pressure.

On the other hand, the amount of polymer dissolved in the polymerization solvent after condensing the r liquid is defined as (6), and the amount of solid polymer is defined as (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 (, Tl.

The polymerization activity (3) of the solid catalyst component is expressed by the following formula.

In addition, the yield of the crystalline polymer is expressed by the following formula, IJ) (C-X 100 (pleasure) The yield (goods) of the total crystalline polymer is determined by the following formula.

Furthermore, residual chlorine in the produced polymer (Kawa, M of the produced polymer
The weight is expressed as (0), and the bulk density is expressed as ``suke''. The obtained results are the second
The rules are shown in the table.

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 dipropyl 7-talate was used instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 2.
There were 20 people in charge.

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

The results obtained are shown in Table 1.

Example 6 Dibutyl phthalate 7.0- and Ti(!/, 4.
Dibutyl phthalate in place of 0-5. Ornt and Tic! A solid catalyst component was prepared in the same manner as in Example 1 except that /, AO- was used. Incidentally, the titanium content in the solid catalyst component at this time was 1.98% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Table 1 Table 2 Comparative Examples 1 and 2 according to the prior art are listed below.

Comparative Example 1 Commercially available MgC1,20f, dibutyl phthalate 5.0
- is crushed under the same conditions as in Example 1. Thereafter, the pulverized composition 5f was charged into a glass container having an internal volume of 500 mm under a nitrogen gas atmosphere, and then ticked.

200- was added and the reaction was stirred at 120°C for 2 hours. After the reaction was completed, the supernatant was removed and fresh Ti (3/420
0- was added and the mixture was reacted at 120°C for 2 hours.

After the reaction was completed, it was cooled to 40°C and diluted with 200°C of n-hebutane.
It was washed 0 times to obtain a solid catalyst component.

At this time, the titanium content in the solid catalyst component was measured and found to be 1.64% by weight.

An experiment was carried out in the same manner as in Example 1, except that 40 μm of the above solid catalyst component was used during the polymerization. The results obtained are shown in Table 3.

Comparative Example 2 An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization time was 50 minutes. The results obtained are shown in Table 3.

Table 5

[Brief explanation of drawings]

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

Claims (1)

[Claims] (1) Substance (a) obtained by reacting metallic magnesium powder with at least twice the mole of alkyl monohalide in the presence of dialkoxymagnesium, diester of phthalic acid (b) and titanium tetrachloride (c). An olefin characterized in that the product obtained by co-pulverization is further brought into contact with titanium tetrachloride (c) in the presence of an aromatic hydrocarbon or an aromatic halogenated hydrocarbon (d) that is liquid at room temperature. solid catalyst component for polymerization.