JPH02166103A - Catalyst for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain an olefin polymer having a very high stereo-regularity in good yields in a very high catalytic activity by combining a specified titanium-containing solid catalyst component with an epoxy-p-menthane compound and an organo-aluminum compound. CONSTITUTION:This catalyst for olefin polymerization is formed from a solid catalyst component (I) obtained by bringing a product obtained by copulverizing a substance (a) obtained by reacting metallic magnesium powder with at least two mol, per mol of the metallic magnesium powder, of an alkyl monohalide in the presence of a dialkoxymagnesium with a phthalic diester (b) into contact with titanium chloride (c), an epoxy-p-menthane compound (II), and an organoaluminum compound (III). Component III is used in an amount of about 1-1000mol per g atom of the titanium of component (I), and component II is used in a molar ratio of component II to component III in a range of about 0.005-1.0.

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 provides a product obtained by co-pulverizing a material obtained by reacting a metallic magnesium powder and a fulkyl monohalide in the presence of dialkoxymagnesium and a diester of phthalic acid. The present invention relates to a catalyst for polymerizing olefins comprising a solid catalyst component obtained by contacting with titanium tetrachloride, an epoxy paramenthane compound, and an organoaluminum compound.

[Conventional technology]

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 one was a complex of an organic monocarboxylic acid ester and titanium tetrachloride as an electron donor, which was co-pulverized with magnesium chloride, or an organic monocarboxylic acid ester as an electron donor. There is a product obtained by co-milling carboxylic acid nysterte 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 there are methods that modify various properties, such as those that use jetoxymagnesium instead of magnesium chloride, and those that use jetoxymagnesium as an electron donor. Various methods have been proposed in which special compounds are used, or methods of combining the above-mentioned 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 is disclosed in which an organoaluminum compound, an organic acid ester, a compound having an M-0-R group, etc. are used in combination for the polymerization of olefins. A catalyst component is prepared by combining various esters as compounds and an active form of magnesila chloride and a titanium compound, and propylene is further polymerized using a compound having a 51-0 bond or an 81-11 bond and an organoaluminum compound. A method is disclosed.

[Challenges remaining in conventional technology]

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 such as high activity to the extent that the effects of chlorine can be virtually ignored are required, or measures such as keeping the concentration of magnesium chloride itself low are required. It is being

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 esthetic μ 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 compound or a boron acid ester during catalyst preparation and polymerization. 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 the organic acid ester contained in the catalyst is such that the problem of odor in 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 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 to solve the problem]

According to the present invention, (1) Substance (a) obtained by reacting metallic magnesium powder with twice or more moles of alkyl monohalide in the presence of dialkoxymagnesium, and phthalic acid diester A/6). The product obtained by co-pulverization is
A catalyst for polymerizing olefins is provided, which comprises a solid catalyst component obtained by contacting titanium tetrachloride (c); (Il) an epoxy buffmenthane compound; and (I) 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 presence of dialkoxymagnesium, but in this case, it is necessary to use 2 or more moles of alkyl monohalide per 1 mole of magnesium metal powder,
Dialkoxymagnesium is metal magnesium powder 1v
On the other hand, it is used in the range of L01 to 1t. Further, the reaction temperature and reaction time are arbitrary as long as the above reaction proceeds sufficiently, and are not particularly limited, but the reaction 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. . When the IR spectrum of the a3 substance obtained by this reaction is measured, absorption of the alkyl μ group is observed.

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

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

Examples of diesters of phthalic acid of the above-mentioned type in Zero School Mei include dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropylphthalate, dibutyl phthalate, diisobutyl phthalate, diethyl phthalate, diisoamyl Futaray F1 Ethyl Buti μ Futa V-)
, ethyl isobutyl phthalate (V-) and ethyl propyl phthalate.

The epoxy bafmenthane compound (II) in the present invention includes 1,4-epoxy bafmenthane, 1.8-
Epoxy paramenthane is preferred;
It is also possible to use those with substituents such as groups and halogens.

Examples of the organoaluminum compound of the above value in the present invention include trialkylaluminum, sialkylaluminum halide, alkyl aluminum dihalide, and mixtures thereof. Among these, triplekylaluminum is preferred, and , triethylaluminum and hydrisobutylaluminum are particularly preferred.

When obtaining the solid catalyst component (1) in the present invention, the proportion of each raw material constituting the solid catalyst component is arbitrary as long as it does not adversely affect the performance of the solid catalyst component to be produced. Typically, but not limited to ra
) For substance 1f, diester of phthalic acid (~) above (
Hereinafter, it may be simply referred to as (b) substance. ) is IILO1
~1t, and the titanium tetrachloride in (a) is α
The range is 1f or more, preferably 12 or more.

The co-milling of the substance (a) and the (1:+) substance is carried out using a ball mill/V or vibrating mill or similar mill 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 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 contacted with titanium tetrachloride one time and the resulting composition can be contacted with n-
Washing can also be carried out using an organic solvent such as 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 (1) above in the present invention is preferably carried out in the absence of oxygen, moisture, and the like.

The solid catalyst component (11) prepared as above is combined with the epoxy paramenthane compound (II) and the organoaluminum compound (Ill),
This constitutes a catalyst for polymerizing olefins according to the present invention.

The organoaluminum compound used is the titanium in the solid catalyst component? The epoxy paramenthane compound (In) is used in a molar ratio of 1 or less to the organoaluminum compound, preferably in the range of cL005 to 1.0.

The polymerization reaction using the polymerization catalyst according to the present invention can be carried out in the presence or absence of an organic solvent,
Further, the olefin monomer used can be used in either gas or liquid state. Polymerization temperature is 200
℃ or less, preferably 100℃ or less, and the polymerization pressure is 10
0 to 9/cm” - () or less preferably 50 kg7c
m”・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.

[Action and effect]

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 activity shows an unprecedentedly high value, the amount of catalyst residue present in the produced polymer can be kept extremely low, and since the residual chlorine is extremely small, the product can be desorbed. The influence of chlorine can be reduced to such an extent that no ash process is required.

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 was a common drawback in so-called high-activity supported catalysts in that the activity per unit time of the catalyst decreased significantly as the polymerization progressed, but the catalyst according to the present invention The decrease in activity over time is extremely small compared to conventionally known catalysts, making it useful for longer polymerization times such as copolymerization, and when using higher polymerization pressures. Since the increase in activity is large, it can be widely used in batch 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 M process control. Catalysts using esters have the disadvantage that their activity and stereoregularity are 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,
The activity and stereoregularity are not reduced even when the M engineering of the resulting polymer is extremely high. Such an effect was strong (desired) by those skilled in the art.In addition, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is extremely low due to the capacity of the polymerization equipment, the capacity of the post-treatment process, etc. However, the catalyst according to the present invention has extremely excellent characteristics in this respect as well.

〔Example〕

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

Example 1 (1) (a) Preparation of substances Using a 2.0 t capacity round bottom flask equipped with a stirrer,
After sufficiently replacing this with nitrogen gas, metal magnesium powder 30f1 dialkoxymagnesium 9. Of and 1.2 t 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 is complete,
The supernatant liquid was removed, and the product was washed three times with 500-g of n-butyl chloride, and then dried under reduced pressure to obtain a powdery substance.

(2) Preparation of solid catalyst component Substance 209 obtained in (1) above and dibutyl phthalate rho were placed in a 1.0 t capacity vibrating mill pot filled with a 25 φ stainless steel pole to the full volume. , frequency 1450 v, p, m, amplitude &
The grinding process was carried out at 5 m for 17 hours.

Using a 500-capacity round bottom flask equipped with a stirrer,
After sufficiently purging with nitrogen gas, 5 tons of the solid composition obtained by the pulverization process was poured into it, and TiO4 was added to it.
200- was added, the temperature was raised to 120°C, and the mixture was reacted for 2 hours. After the reaction is completed, the supernatant liquid is removed and the product is newly added with T i
Ot4200+d 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 d 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 1.69 weight.

(3) Polymerization internal volume2. Using an OT autoclave with a stirrer, after completely replacing the autoclave with nitrogen gas, triethylaluminum 19311I, 1.8-epoxy paramenthane 70
mg and the solid catalyst component &Oj9 were charged. After that, hydrogen gas 1.8/.

1.4 tons of liquefied propylene was charged, and a polymerization reaction was carried out at 70°C for 1 hour. After the polymerization reaction is completed, the produced polymer is
Dry under reduced pressure at 0°C, and the amount of the obtained product is referred to as (4).

In addition, this product was extracted with boiling n-hebutane for 6 hours and n-
A polymer insoluble in hebutane was obtained, and the amount of this was determined as l'B
).

The polymerization activity (c) of the solid catalyst component tooth 9 used is expressed by the following formula.

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

Φ) m) = x 1oo (A) Furthermore, the amount of residual chlorine in the produced polymer is expressed as (2)), the M concentration of the produced polymer is multiplied by fG), and the bulk specific gravity is expressed as fG), 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 same amount of dipropylphthalate was used instead of dibutyl phthalate. Note that the titanium content in the solid catalyst component at this time was 1.
It weighed 81 kg.

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

The results obtained are as shown in Table 1.

Example 4 Dibutyl phthalate 7 instead of dibutyl phthalate 5-
A solid catalyst component was prepared in the same manner as in Example 1, except for the durability. Incidentally, the titanium content in the solid catalyst component at this time was 2.16% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are the first
As shown in the table.

Example 5 An experiment was carried out in the same manner as in Example 1 except that diisobutyl phthalate v-) was used instead of dibutyl phthalate. In addition, the titanium content in the solid catalyst component at this time was 1.70
It was a heavy weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

No. table

[Brief explanation of the drawing]

No. The figures are schematic drawings to help understand the invention.

Claims (1)

[Claims] (1) (I) Co-pulverization of a substance (a) obtained by reacting metallic magnesium powder and at least twice the mole of alkyl monohalide in the presence of dialkoxymagnesium and a diester of phthalic acid (b). A solid catalyst component obtained by contacting the resulting product with titanium tetrachloride (c); (II) an epoxy paramenthane compound and (III) an organoaluminum compound. .