JPS63251403A - Solid catalyst ingredient for polymerization of olefin - Google Patents

Abstract

PURPOSE:To form a solid catalyst ingredient which is highly active, with its activity retained for a long time, and can provide streoregular polymers in a high yield in the polymn. of olefins, by a specified method using metallic magnesium, dialkoxymagnesium, titanium tetrachloride and other ingredients. CONSTITUTION:This solid catalyst ingredient for the polymn. of olefins is formed by the following method: A substance (a) obtd. be reacting a metallic magnesium powder with at least twice the moles of an alkyl monohalide in the presence of dialkoxymagnesium, a diester of phthalic acid (b) and titanium tetrachloride (c) are crushed together, and the product is further contacted with titanium tetrachloride (c).

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 along with an electron donor. has been proposed.

The earliest of these was developed by co-pulverizing a complex of an organic monocarboxylic acid ester and titanium tetrachloride as an electron donor with magnesium chloride, or by co-pulverizing a complex of an organic monocarboxylic acid ester as an electron donor with titanium tetrachloride. There is a co-pulverized product of acid ester and 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 for the polymerization of olefins, and in JP-A-57-63310, an electron donor A method in which a catalyst component is prepared by combining various esters, active magnesium chloride, and a titanium compound, and propylene is further polymerized using a compound having an Sl-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, 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. There is.

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 a very large amount of organic monocarboxylic acid ENTEL, 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, organic power is used during catalyst preparation and polymerization. It is necessary to use a boronic acid ester. Generally, the organic acid ester contained in the catalyst is treated with a titanium halide or washed with an organic solvent, so that the amount of organic acid ester contained in the catalyst is such that the problem of 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 a liquid or gaseous mass, 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 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 comprises: (a) a substance obtained by reacting a metallic magnesium powder and an alkyl monohalide in an amount of twice or more moles in the presence of dialkoxymagnesium; (b) a diester of phthalic acid; and (c) titanium tetrachloride. The present invention provides a solid catalyst component for polymerizing olefins, which is characterized in that the product obtained by co-pulverizing is further brought into contact with (c) titanium tetrachloride.

In order to obtain the substance (hereinafter simply referred to as substance (a)) obtained by reacting the metal magnesium powder and the alkyl monohalide of (a) in the present invention in the presence of dialkoxymagnesium, commercially available metal magnesium powder and an alkyl monohalide are reacted in the presence of dialkoxymagnesium. At this time, it is necessary to use 2 mol or more of the apkyl monohalide per 17 parts of metal magnesium powder; Refkin magnesium is 0.1 to 2 per gram of metal magnesium powder.
It is necessary to use it within the range of g. In addition, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited.
The heating is carried out for 0 minutes or more, preferably at 40° C. or more 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 crophyte, isopropyl chlorophyte, n-butyl chloride, etc. Examples include chloride, isobutyl chloride, pentyl chloride, hexyl chloride and octyl chloride.

The jetoxymagnesium 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.

In the present invention, the diesters of phthalic acid (b) include dimethyl butanoate, 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.

When obtaining the above-mentioned solid catalyst component in the present invention, the proportion 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, for 1 g of substance (a), the diester A/ of phthalic acid (b) (hereinafter sometimes simply referred to as substance (b)) is [], 01~
1 g of titanium tetrachloride, and when co-pulverized with the (a) substance and (b) substance, the titanium tetrachloride is 0.0 g.
The amount is in the range of 1 to 1 g, and when it is brought into contact with the product obtained by co-pulverization, it is in the range of 0.1 g or more, preferably 1 g or more.

The above-mentioned co-pulverization of substance (a), substance (b) and titanium tetrachloride (c) is usually carried out for at least 10 minutes, preferably for at least 30 minutes.

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

The composition obtained after the above contact can be further contacted with titanium tetrachloride. Moreover, the obtained composition 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 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 a catalyst for polymerization of onfins.
It is preferable to coexist with an electron-donating compound other than the aromatic μ-bonic acid ester, such as a silicon compound having an i-0 bond.

The organoaluminum compound used in the present invention is preferably a trialkylaluminium, used in an amount of 1 to 1000 mol per titanium I atom 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 polymerizing olefins 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 either gaseous or liquid. It can also be used in any state.

The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100 kg/cm2·G or less, preferably 50 kg/cm2·G or less.

Olefin haethylene which is homopolymerized or copolymerized using the solid catalyst component for olefin polymerization according to the present invention,
Chill with propylene, 1-butene, etc.

〔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. Moreover, 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.

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 adhering to the resulting polymer.

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 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 in cases where the polymerization time is longer, such as in copolymerization, and it 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 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 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 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 solid catalyst component according to the present invention has this problem. It also 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) (a) Preparation of substances Using a 2-OL round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, 30g of metal magnesium powder, jetoxymagnesium&Og and n-
1.2 t 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 transferred to 500ml (
After washing three times with D n-butyl chloride, the mixture was dried under reduced pressure to obtain powdered substance (a).

(2) Preparation of solid catalyst component 20 g of the powdery substance obtained in (1) above, 70 g of dibutyl phthalate, and 44.0 fR1 of TiCt were filled in a nitrogen gas atmosphere with 25 WIφ stainless steel po μ to the full volume 1. The material was placed in a .0t vibrating mill pot, and co-pulverized for 17 hours at a vibration frequency of 1430 V, p, m, and an amplitude of X5m5+.

Using a 500 volume round bottom flask equipped with a stirrer,
After sufficiently purging with nitrogen gas, take 5 g of the solid composition obtained by the co-pulverization treatment, and add TIC to it.
L4200- 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 the product was newly added with T.
i C1420〇- was added and reacted at 120°C for 2 hours.

After the reaction was completed, the reaction mixture was cooled to 40° C., and the product was washed 10 times with 200° C. 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 2.76% by weight.

(3) Polymerization Using an autoclave equipped with a stirring device with an internal volume of 2.0 t, after completely replacing the autoclave with nitrogen gas, triethylaluminum 193■, 2,2,6.6-titramethylpiveridine 24■ and The solid catalyst component Igomisaki was charged. Thereafter, 1.8 t of hydrogen gas and 1.4 t 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 defined as (g). Further, this product was 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 CB).

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

Further, the yield υ of the total crystalline polymer is expressed by the following formula.

Further, the amount of residual chlorine in the produced polymer was expressed as (g)), the MI of the produced polymer was expressed as (g)), and the bulk specific gravity was expressed as (c)), and the obtained results 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 polymerization reaction was carried out in the following manner.

70 rows of n-heptane was charged into an autoclave with an internal volume of 2-OL and equipped with a stirrer, which was completely purged with nitrogen gas.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1myS2. '2,1,6-tetramethymupiperidine 5
7 mf, and then 10.0 mf of the solid catalyst component prepared by the method of Example 1 were charged. After that, 150tnt of hydrogen gas was charged, the temperature was raised to 70℃, and propylene gas was introduced.
The polymerization reaction was carried out for 1 hour while maintaining a pressure of 6 to 9/cm2·G. After the polymerization reaction was completed, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure.

On the other hand, the amount of polymer dissolved in the polymerization solvent after condensing liquid f is defined as (A), and the amount of solid polymer is defined as (I).

Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, which was designated as (J).

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

In addition, the yield of crystalline polymer 4) is expressed by the following formula, (J) (L) = -X 100 (a) The yield (b) of the total crystalline polymer is determined by the following formula.

Furthermore, the residual chlorine in the produced polymer is expressed as (c), the MI of the produced polymer as (0), and the bulk specific gravity 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 The same amount of Sifuropi instead of dibutyl phtasort! An experiment was conducted in the same manner as in Example 1 except that phthalate was used. Note that the titanium content in the solid catalyst component at this time was 2.
It was 71% 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 (2) except that the reaction (twice) after adding TiC4200td was carried out at 130°C. In addition,
The titanium content in the solid catalyst component at this time was 2.51% 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 For comparison, cases based on the prior art are listed below as Comparative Examples 1 and 2.

Comparative Example 1 Commercially available MgCt2209, Djibouti lV7taV-) 5.0
1Rt is ground under the same conditions as in Example 1. Thereafter, 5 g of the pulverized composition was placed in a glass container with an internal volume of 500 g under a nitrogen gas atmosphere, and TiC4200- was added thereto for 12 g.
The reaction was stirred at 0° C. for 2 hours. After the reaction was completed, the supernatant liquid was removed, and 2200 ml of TiC was newly added, and the reaction was carried out at 120° C. for 2 hours. 4 After the reaction is completed, cool to 40°C and dilute 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 60 μm of the above solid catalyst component was used during the polymerization. The results obtained are as 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 30 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) A substance obtained by reacting (a) metallic magnesium powder with at least twice the mole of alkyl monohalide in the presence of dialkoxymagnesium, (b) diester of phthalic acid, and (c) titanium tetrachloride. A solid catalyst component for polymerizing olefins, characterized in that a product obtained by co-pulverization is further brought into contact with (c) titanium tetrachloride.