JPH01275606A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To improve the activity so as to produce a stereoregular olefin polymer in a high yield, by blending a specific solid catalyst component with an epoxy-p-methane compound and an organoaluminum compound. CONSTITUTION:Diethoxymagnesium (a) is suspended in an alkylbenzene (b), and the suspension is brought into contact with TiCl4 (c) with 1.0g or more of the component (c) for 1.0g of the component (a) and the volume ratio of (c)/(b) being 1 or below. The product is reacted with phthalic acid dichloride in an amount of 0.01-0.5ml for 1.0g of the component (a) at 80-135 deg.C for 10min-10hr to produce a solid material. The solid material is reacted with the component (c) in the presence of the component (b) with the volume ratio of (c)/(b) being 1 or below at 60-135 deg.C for 10min-10hr to produce a solid catalyst component (A). The component (A) is blended with an epoxy-p-menthane compound (B) (e.g., 1,8-epoxy-p-menthane) and an organoaluminum compound (C) (e.g., triethylaluminum) with the molar ratio of (C)/Ti in the component (A) being 1-1,000.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a high-performance olefin that exhibits high activity when subjected to the polymerization of olefins and is capable of obtaining stereoregular polymers in ten thousand yields. This is related to similar catalysts for joint use.

[Prior art and its problems] Conventionally, as a catalyst for polymerizing olefins, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component is well known and widely used. Since the yield of the catalyst component and the polymer based on the titanium in the catalyst component (hereinafter referred to as the polymerization activity of the catalyst component and the titanium in the catalyst component) is low, a so-called deashing step is unavoidable to remove the catalyst residue. Rarely. Since this deashing process uses a large amount of alcohol or chemical agents, recovery equipment or regeneration equipment for these is indispensable.
There are many energy and other related problems, and it is an important issue that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing step, many studies have been conducted and proposals have been made to increase the polymerization activity per titanium in the catalyst component and the sieving catalyst component.

In particular, a recent trend has been to support a transition metal compound such as titanium halide, which is an active ingredient, on an O carrier material such as magnesium chloride, and when it is used for the polymerization of olefins, the polymerization activity of titanium in the catalyst component is There are many proposals that have dramatically improved the

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage that it has an adverse effect on the halogen element in the titanium halide and on the polymer produced, and therefore, in fact, the chlorine has no effect on the polymer. However, there remained unresolved issues such as the requirement for high activity to the extent that the amount of magnesium chloride could be ignored, and the need to keep the concentration of magnesium chloride itself low.

In addition, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially, it is common to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential for catalysts that use a catalyst component containing magnesium as a carrier in combination with an organoaluminium compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the produced polymer, and its removal has become a major problem in the industry.

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, the deactivation is large, causing problems in process operation, and block copolymerization, etc. However, it has been almost impossible to use it practically when it is necessary to increase the polymerization time. In order to improve this point, for example, in JP-A-54-94590, a catalyst component is prepared using magnesium dihalide as a starting material,
Organoaluminum compound, organic carboxylic acid ester, M
A method for polymerizing olefins in combination with a compound having a -0-R group has been proposed, but since an organic carboxylic acid ester is used during polymerization, the problem of odor of the resulting polymer has not been solved. Moreover, as can be seen from the implementation sequence in the same publication, it requires very complicated operations, and it cannot be said that it has been obtained that is practically sufficient in terms of performance and duration of activity.

On the other hand, various solid catalyst components for polymerizing olefins or solid catalyst components comprising dialkoxymagnesium, titanium tetrachloride, and an electron-donating compound have already been developed and proposed.

For example, in JP-A-55-152710, it was discovered that in order to obtain high catalyst activity, a large amount of an organoaluminum compound must be used during polymerization, and that the molecular structure of the produced polymer must be controlled. For the purpose of improving the drawback that the stereoregularity of the resulting polymer is reduced when hydrogen is added and used for this purpose, dialkoxymagnesium obtained by a specific operation is combined with a halogenated hydrocarbon and an electron-donating compound. A method for obtaining a catalyst component by contacting with a tetravalent titanium halide in the presence of is disclosed.

Analysis from Example 2, which specifically shows this method, shows that dialkoxymagnesium is suspended in tetracyclic carbon, and 7
Benzoic acid ether and titanium tetrachloride are added at 5°C, and the suspension is stirred for 2 hours while maintaining the temperature at 75°C. The produced solid was isolated and washed five times with in-octane, then suspended in titanium tetrachloride at 80°C, stirred for 2 hours, and then washed five times with in-octane to remove the solid catalyst component. I am getting .

Example 1 shows an example in which this solid catalyst component was used in combination with triethylaluminum as a catalyst for polymerization of olefins.

However, the solid catalyst component prepared by the method disclosed in JP-A-55-152710 has sufficient polymerization activity, stereoregular polymer yield, and activity sustainability when used for olefin polymerization. This cannot be said to indicate performance.

The inventors of the present invention have conducted extensive research to solve the problems remaining in the prior art, and as a result, they have come up with the present invention and present it to the public.

[Means for solving the problems] That is, the feature of the present invention is that jetoxymagnesium (a) is replaced with alkylbenzene (
1) After being suspended in the alkylbenzene), contact with titanium tetrachloride (C) in a volume ratio of 1 or less to the alkylbenzene);
Next, the solid substance obtained by adding and reacting phthalic acid dichloride (d) in the temperature range of 80°C to 135°C is separated and washed with alkylbenzene, and the solid substance is further treated with phthalic acid dichloride (d) in the presence of alkylbenzene (b). Titanium tetrachloride (to alkylbenzene) has a volume ratio of 1 or less to titanium tetrachloride (to alkylbenzene).
An object of the present invention is to provide a catalyst for polymerizing olefins, which is characterized by comprising a solid catalyst component obtained by reacting 0) with an epoxy paramenthane compound and an organoaluminum compound.

The alkylbenzene (1) used to suspend jetoxymagnesium (a) in the preparation of the solid catalyst component of the present invention includes toluene, xynon, ethylbenzene, propylbenzene, trimethylbenzene and the like.

The usage ratio of phthaloyl dichloride (d) used in the preparation of the solid catalyst component of the present invention is in the range of α01 to α5− to jetoxymagnesium (a) to t. Also, titanium tetrachloride (0) is jetoxymagnesium (a) 1. The amount is 1.02 or more with respect to Of, and 1 or less in terms of capacity ratio with respect to alkylbenzene (1)). Incidentally, it is necessary to use the alkylbenzene (b) in an amount that can form a suspension of jetoxymagnesium (a).

The solid catalyst component of the present invention is jetoxymagnesium (a)
is suspended in alkylbenzene (b) and then contacted with titanium tetrachloride (Q) at a volume ratio of 1 or less to the alkylbenzene (1)), and then phthalic acid dichloride (Q) is suspended in a hot air range of 80°C to 135°C. The solid material obtained by adding and reacting d) is washed with alkylbenzene, and the solid material is further reacted with titanium tetrachloride (0) in a volume ratio of 1 or less to the alkylbenzene) in the presence of the alkylbenzene). However, in this case,
80 to 155C (reactions in the D temperature range usually take 10 minutes to 10
It takes place over a period of time. The alkylbenzene used for the above washing may be the same as or different from the alkylbenzene (b).

The temperature during washing is not particularly limited.

Examples of the alkylbenzenes used for cleaning include those listed above as examples of alkylbenzenes.

Note that, prior to washing with this alkylbenzene, it is possible to perform washing with an organic solvent other than the alkylbenzene.

Next, the solid material after this washing is further treated with the alkylbenzene (1) in the presence of the alkylbenzene (1).
) with a volume ratio of 1 or less of titanium tetrachloride (a).

The temperature at this time is not particularly limited, but is preferably in the range of Fi 60°C to 135°C, and this reaction is usually carried out for 10 minutes to 10 hours. Suitable temperature ranges for each of the above reactions are appropriately determined depending on the ai of the alkylbenzene (1) used.

The above reaction is usually carried out under stirring using a container equipped with a stirrer.

Jetoxymagnesium (a) alkylbenzene (1
Although it is not particularly necessary to carry out the suspension in )) at around room temperature, it is preferable because it is easy to operate and can be carried out using a simple device.

The solid catalyst component thus obtained can be used as n-
It is also possible to wash with an organic solvent such as hebutane. This solid catalyst component is removed after washing! It is also possible to wash and dry the raw material and use it as an on-line polymerization catalyst.

Next, the catalyst for polymerizing olefins of the present invention using the above solid catalyst component will be explained.

1,8-epoxyparamenthane is preferred as the epoxyparamenthane compound of 03) used in the catalyst of the present invention, but it is also possible to use a compound with a substituent such as an alkyl group or a halogen. be.

The organoaluminum compound (0) used in the catalyst of the present invention includes trialkylaluminum,
Mention may be made of dialkylaluminum norlides, alkylaluminum sinolides, and mixtures thereof.

The organoaluminum compound (0) used in the catalyst of the present invention has a molar ratio of 1 to 1,000 molar equivalent to the titanium atoms in the solid catalyst component (B), and the epoxy paramenthane compound (B) has a mole ratio of 1 to 1,000. The organoaluminum compound is used in a molar equivalent molar ratio of 101 to (L5).

Polymerization can be carried out in the presence or absence of an organic solvent, and the offfin monomer can be used in either gas or liquid state. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00klI/('III''・G or less, preferably 50 klI/('III''・G or less).

Offfins to be homopolymerized or copolymerized using the catalyst according to the present invention are ethylene, globin, 1-7'ten,
4-methyl-1-pentene and the like.

〔Effect of the invention〕

When offfins are polymerized using the catalyst for olefin polymerization according to the present invention, the resulting polymer has extremely high stereoregularity.

Furthermore, in the industrial production of polyolefins, the bulk specific gravity of the produced polymer is a very big problem due to the capacity of the polymerization equipment, the capacity of the post-treatment process, etc., and the catalyst according to the present invention is extremely important in this respect as well. Has excellent properties.

Furthermore, the titanium tetrachloride used in the preparation of the solid catalyst component of the present invention is characterized in that it is used in an extremely small amount compared to conventional techniques. Titanium tetrachloride is a substance that is difficult to handle as it reacts with oxygen and moisture in the air, producing hydrochloric acid gas and emitting white smoke and a strong pungent odor. Therefore, reducing the amount used is a cost-effective material. This provides significant benefits in the production of solid catalyst components, such as reduced yield, ease of operation, and prevention of pollution sources.

Furthermore, since the catalyst according to the present invention exhibits a high activity that could not previously be expected, the amount of catalyst residue present in the produced polymer can be kept extremely low, and therefore the amount of residual chlorine in the produced polymer can also be reduced by deashing. It can be reduced to the extent that no process is required at all.

Furthermore, according to the catalyst of the present invention, since organic carboxylic acid esters and nitrogen compounds are not added during the preparation of the solid catalyst component and during polymerization using the solid catalyst component, the major problem of odor adhesion to the resulting polymer can be avoided. can also be completely resolved.

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, Since the decrease in activity with the passage of polymerization time is extremely small compared to conventionally known catalysts, it is extremely useful in cases where the polymerization time is longer, such as in copolymerization.

Furthermore, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization for purposes such as MI control. 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 catalyst according to the present invention, the activity and stereoregularity do not decrease even when the M engineering of the resulting polymer is extremely high. Such an effect was strongly desired by those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example row 1 [Preparation of solid catalyst component] A 50-liter container sufficiently purged with nitrogen gas and equipped with a stirrer.
A 0 d round bottom flask was charged with 10 f of jetoxymagnesium and 60 g of toluene to form a suspension, and the suspension was then treated with T 10 t.

40- was added, the temperature was raised to 90°C, and 2.2 d of phthaloyl dichloride was added. Thereafter, the temperature was raised to 115°C, and the mixture was reacted with stirring for 2 hours. Toluene 2 at 90℃ after the reaction
Washed twice with 00- and added toluene 60- and Ti
O440d was added and reacted at 115°C for 2 hours with stirring.

After completion of the reaction, the reaction product was heated at 40℃ on-hegetane 200-
Washed 10 times with When the titanium content in the solid catalyst component thus obtained was measured, it was found to be 540 jijiL.
It was s.

[Overlapping]

Triethyl aluminum 200j9, 1.8-epoxy paramenthane 70a9. And the solid catalyst component was charged in SOq. Thereafter, hydrogen gas taX and liquefied propylene tAL were charged, and polymerization was carried out at 70° C. for 30 minutes. Polymer f obtained after completion of polymerization: Dry under reduced pressure at 80° C., and the obtained amount is referred to as (F). This material was extracted with boiling n-hegetane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was
).

The polymerization activity (C) of the solid catalyst component used is expressed by the formula, and the yield Φ) of the total crystalline polymer is expressed by the formula (B) φ) == -X 100 @).

Furthermore, the residual chlorine Ji in the produced polymer is represented by @), the Ml of the produced polymer is represented by K), and the bulk specific gravity is represented by (G). The results obtained are as shown in Table 1.

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

Example 3 An experiment was carried out in the same manner as in Example 1 except that 20 m of 8O-1Ti04 was used for toluene.

In addition, the titanium content in the obtained solid catalyst component was 559
The weight was 1%. 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 An experiment was conducted in the same manner as in Example 1 except that 17 m of phthaloyl dichloride was used. Incidentally, the titanium content in the obtained solid catalyst component was 558% by weight. During polymerization, the experiment was conducted in the same manner as in Example fPU1. The results obtained are shown in Table 1).

Table 1

[Brief explanation of the drawing]

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

Claims (1)

[Claims] (1) (A) Diethoxymagnesium (a) is suspended in alkylbenzene (b) and then brought into contact with titanium tetrachloride (c) at a volume ratio of 1 or less to the alkylbenzene (b), and then 80°C to A solid substance obtained by adding and reacting phthalic acid dichloride (d) in a temperature range of 135 ° C. is washed with an alkylbenzene, and the solid substance is further treated in the presence of an alkylbenzene (b) in a volume ratio to the alkylbenzene. A catalyst for polymerizing olefins, characterized in that it consists of a solid catalyst component obtained by reacting 1 or less titanium tetrachloride (c); (B) an epoxy paramenthane compound and (C) an organoaluminum compound.