JPS62101607A - Catalyst component and catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To prevent the polymerization activity from lowering with the lapse of time during polymerization and to dispense with a deashing step by decreasing the residual chlorine in the polymer, by polymerizing an olefin with the aid of a catalyst prepared by combining a specified titanium-containing catalyst component with a silicon compound and an organoaluminum compound. CONSTITUTION:This catalyst component for polymerizing an olefin is obtained by bringing calcium carbonate, a dialkoxymagnesium, an aromatic dicarboxylic acid diester, a halohydrocarbon and a titanium halide of the general formula: TiX4 (wherein X is a halogen) into contact with each other. A catalyst for polymerizing an olefin is formed by combining said catalyst component with a silicon compound of the general formula: SiRm(OR')4-m (wherein R is H, alkyl or aryl, R' is alkyl or aryl and m is in the range: 0<=m<=4) and an organoaluminum compound.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is directed to a highly active polymer that is highly active when subjected to the polymerization of olefins, and which can obtain a stereoregular polymer at an extremely high yield. Regarding performance catalyst components and catalysts, more specifically calcium carbonate, dialkoxymagnesium, diesters of aromatic dicarbonyl ν, halogenated hydrocarbons,
The present invention also relates to a catalyst component for polymerizing olefins obtained by contacting a titanium halide with a titanium halide, and a catalyst component for polymerizing olefins comprising the catalyst component, a silicon compound, and an aluminum compound.

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of solid titanium I/logonide as a catalyst component and an organoaluminum compound is well known and widely used. Since the sound absorption of the polymer per titanium in the catalyst component (hereinafter referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) is low, a so-called deashing step to remove the catalyst residue has been unavoidable. Since this deashing process uses a large amount of alcohol or chelating agent, it is essential to have a recovery device or a recycling device for the same, and there are many resource, energy, and other problems associated with it, and those skilled in the art will be able to quickly understand the problem. This was an important issue that needed to be resolved. In order to eliminate this complicated deashing step, many studies have been made and proposals have been made to increase the polymerization activity per titanium in the catalyst component, especially the catalytic component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used for polymerization of olefins, the polymerization activity of titanium in the catalyst component is dramatically increased. I've seen many proposals to raise the bar.

[Problem that the invention seeks to solve]

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage that it has a pervasive effect on the formed polymer, similar to the halogen element in titanium halides, and for this reason, the influence of chlorine is virtually eliminated. Some unresolved issues remained, such as negligible high activity being required or the need to keep the concentration of magnesium chloride itself low.

The present inventors aimed to reduce the residual chlorine in the produced polymer while maintaining a high degree of polymerization activity per catalyst component and the yield of the stereoregular polymer. f Kaisho 5
No. 9-91107, we proposed a method for producing a catalyst component for polymerizing olefins, and achieved our initial objective.

However, when using the catalyst component using magnesium chloride as a carrier, the catalyst component obtained in the above-mentioned Japanese Patent Application Laid-Open No. 59-91107, etc., the polymerization activity per unit time is high in the initial stage of polymerization, but as the polymerization time progresses. The resulting reduction is severe and causes problems in process operation, and it is almost impossible to use it practically in cases where longer polymerization times are required, such as in block copolymerization.

The present inventors have discovered a problem left behind in the prior art called ig7! )9
Let's solve it! 9-J ((product of polymer produced)
1] As a result of intensive research, we have arrived at the present invention and propose it to mosquitoes.

[Means to solve one problem in between]
a) calcium carbonate, (b) dialkoxymagnesium, (C) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (p) S'2 formula T1X4 (wherein X is a halogen element →; ) represented by the general formula SiRm(OR')a-m (in the formula, R
is hydrogen, an alkyl group is formed into an aryl group, R' is formed into an aryl group, and m is 0≦m≦4. ) (hereinafter referred to as silicon compound in n1) and (C) an organoaluminum compound, olefins ηf
Combined catalyst component and (A) (a) calcium carbonate, (b) dialkoxymagnesium, (C) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula T1
Catalyst component obtained by contacting a titanium halide (hereinafter sometimes simply referred to as titanium halide) represented by X4 (in the formula or a halogen element): (B) General formula siRm (oR'), -m (in the formula Rj
d is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. The present invention provides a catalyst for polymerizing olefins comprising a silicon compound represented by (C) (hereinafter sometimes simply referred to as a silicon compound); and (C) a specific aluminum compound.

There are no particular restrictions on the calcium carbonate used in the present invention, and ordinary commercially available products can be used.

Dialkoxymagnesium used in the present invention and I7teke, jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-butoxymagnesium, diter
Examples include t-butoxymagnesium and diisopropoxymagnesium, among which jetoxymagnesium and dipropoxymagnesium are preferred.

i: The diester of aromatic dicarbonyl hexaamine used in the invention is phthal he-! Diesters of t*n terephthalic acid are preferred, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl phthalate. , ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl butyl phthalate, and the like.

As the /-logenated hydrocarbon used in the present invention, chlorides of aromatic and aliphatic hydrocarbons that are liquid at room temperature are preferred, such as propyl chloride, butyl chloride,
Examples include butyl bromide, propyl iodide, 0-dichlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, cyclofluoron, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, etc. Chlorbenzene, propyl chloride, dichloroethane, chloroform, carbon tetrachloride, and methylene chloride are preferred.

In the general formula TiXa C used in the present invention, x is a halogen element. ) TiC44, TiBr4, Tj, I4
Among them, T i CI4 is preferable.

The silicon compound used in the present invention is:
Examples include phenylalkoxysilane and alkylalkoxysilane. Examples of phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriynepropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, and examples of alkylalkoxysilane. Examples include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane.

Specific aluminum compounds used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum cybarides, and mixtures thereof.

When obtaining the catalyst component in the present invention, the proportion of each raw material used and the number of contacts are arbitrary as long as they do not adversely affect the performance of the produced catalyst component, and are not particularly limited. Normally, the total of calcium and dialkoxymagnesium is 12, and the diester of aromatic dicarboxylic acid is preferably rL01 to 2y1.
19, and the titanium halide is [L12 or more, preferably 12 or more. Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably a bone capable of forming a suspension.

In addition, at this time, the contact 1σ of each original substance forming the catalyst component
Although the introduction and connection 6/k methods are not particularly limited,
The composition obtained after grinding calcium carbonate and dialkoxymagnesium in the first embodiment is contacted with a diester of an aromatic dicarboxylic acid and a titanium halide in the presence of a halogenated hydrocarbon;
Q 4p, preferably the composition obtained after grinding calcium carbonate, dialkoxymagnesium and diester of aromatic dicarboxylic acid is contacted with titanium halide in the presence of halogenated hydrocarbon.

The pulverization of calcium carbonate and dialkoxymagnesium in the first aspect is usually carried out for 5 minutes or more using a ball mill, vibration mill, etc., and the resulting composition is brought into contact with the diester of aromatic dicarboxylic acid and the titanium halide. is normally 0°C in the presence of halogenated hydrocarbons.
The process is carried out at a temperature ranging from 5 minutes to 100 hours up to the boiling point of the titanium halide used.

In the second embodiment, the charcoal 1'I calcium, dialkoxymagnesium, and diester of aromatic dicarboxylic acid are pulverized using a ball mill, vibration mill, etc.
Contact between the resulting composition and the titanium halide is carried out for at least 1 minute at 0° C. in the presence of a halogenated hydrocarbon.
to the boiling point of the titanium halide used for 5 minutes to 100 hours.

It is also possible to repeatedly contact the titanium halide with the composition obtained after contacting each component constituting the catalyst component, and it is also possible to wash it using a rich organic solvent such as n-hebutane. be.

These series of sweeps in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

As described above, the catalyst component produced by (-) has broad peaks around 2θ=32-1 and around 5a0 in its X-ray spectrum, and is used in combination with the silicon compound and organoaluminum compound for polymerization of olefins. The organoaluminum compound used has a molar ratio of 1 to 1000 per mole of titanium atoms in the catalyst component.
The silicon compound is used in a smol ratio of 1 or less, preferably 117 or 10, based on the mole of the organoaluminum compound.
It is used in the range of 05 to Q,5.

Polymerization can be carried out in the presence or absence of an organic solvent, and the olene 4-fluoride 31411 compound can be used in either a gas or liquid state. The degree of polymerization is below 200℃, preferably below 100℃, and the polymerization pressure is below 11,100kg/l-G, preferably @ 50
k7/cJ・G or less.

Olefins to be polymerized or copolymerized using the catalyst component of the present invention include ethylene, propylene, 1-butene, and the like.

〔Effect of the invention〕

Olefin 4 using 1 η (obtained by great invention)
When polymerization is carried out, the resulting polymer not only has extremely high stereoregularity, but also has extremely high activity, so it is necessary to keep the amount of catalyst residue in the resulting polymer extremely low. Since the amount of chlorine is almost negligible, no deashing step is required at all, and the shadow of chlorine on the produced polymer can be virtually eliminated.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration of the produced polymer itself and virtually eliminates f(R, etc.). The fact that it was possible to do so is extremely important for those skilled in the art.

Furthermore, the present invention is characterized by solving the essential drawback of so-called highly active supported catalysts, in which the activity per unit time υ of the catalyst decreases significantly as the polymerization progresses, and it The aim is to provide a catalyst that can be practically used for A, even in copolymerization.

In addition, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst component using magnesium chloride as a carrier has It had the disadvantage that activity and stereoregularity were significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained by the present invention, the activity and stereoregularity hardly decrease even when the MI of the resulting polymer is extremely high. Such effect 1 brings extremely great benefits to those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst components] Calcium carbonate 55 and jetoxymagnesium 45
2 was placed in a Wfil, OL vibrating mill box) K filled with 415 stainless steel poles of 25 wφ under a nitrogen gas atmosphere, and heated at a vibration frequency of 1430 v, p, m, and a scratching width of 55 mm. The grinding process was carried out at room temperature for an hour. Volume fl 50 fully purged with nitrogen gas and equipped with a stirrer
Composition 552 obtained by the pulverization process and O-dichlorobenzene 15- were placed in a 0 ml round bottom flask, and dibutyl phthalate 2.0- and Ti were added under stirring.
C42n O- was added, heated to 110° C. for 4 hours, and reacted with stirring for 2 hours. After the reaction was completed, it was washed 10 times with n-hebutane 200- at 40°C, and washed once at 40°C with TiCt4200-, and then further washed with TiCt, 2
00- was added, and the mixture was reacted at 110°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20°C of n-heptane was added.
Washing with 0- was repeatedly performed, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used. At this time, when the solid-liquid in the catalyst component was subjected to electrical distribution 1 and the titanium-containing chamber in the solid content was measured, it was found to be 561%.

[Overlapping]

Contents completely replaced with nitrogen gas g 2. 700 tons of n-heptane in an autoclave with a stirrer! 1
t, and while maintaining a nitrogen gas atmosphere, triethylaluminum 5a1vpy and phenyltriethoxysilane 6
411 Then, 13η of the catalyst component was charged as titanium atoms. Thereafter, 120° of hydrogen gas was charged, the temperature was raised to 70° C., and while propylene gas was introduced, a pressure of 6 to 9/−·G was maintained, and polymerization was carried out for 4 hours. After completion of polymerization, obtained f? : The solid polymer was separated from each other, heated to 80°C, and dried under reduced pressure. On the other hand, the weight of the polymer dissolved in the polymerization solvent obtained by condensing the P solution is defined as (A), and the weight of the solid polymer is defined as (B).

Further, the obtained solid polymer was extracted with S III n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this juice was designated as (C'').

The polymerization activity (D) per catalyst component was expressed by the formula, the yield (E) of the crystalline polymer was expressed by the formula, and the yield (F) of the total crystalline polymer was determined from the formula. Further, residual chlorine in the produced polymer is represented by (G), and MI of the produced polymer is represented by (H). The results obtained 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 6 hours. The results obtained are shown in Table 1.

Example 3 Example 1 except that 1.51 dipropyl phthalate was used.
An experiment was conducted in the same manner. Incidentally, the titanium content in the solid content at this time was 578% by weight. During the polymerization, an experiment was carried out in the same manner as in Example 1, except that 70 μm of phenyltriethoxysilane was used. The results obtained are shown in Table 1.

Example 4 A catalyst component was prepared in the same manner as in Example 1 except that the reaction temperature was 120°C. In addition, the titanium content in the solid content at this time! It was 7t103jusaki%. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 5 Calcium 52, jetoxymagnesium 45i with charcoal
i' and dipropylphthalate 15? was crushed in the same manner as in Example 1. The resulting composition 6i was thoroughly purged with nitrogen gas and stirred with a stirrer;
15 liters of 0-dichlorobenzene and TiC4200 were placed in a round bottom flask, heated to 110° C., and reacted with stirring for 2 hours. After the reaction was completed, the TiC4
200? / using 40℃te1r! After washing, 2200 m of TiO was further added and reacted at 110°C for 2 hours ('). After the reaction was completed, it was cooled to 40°C and further n-
Repeated cleaning with Hebutane 200mAK was completed when chlorine was no longer detected in the cleaning solution.
A catalyst component was obtained. Incidentally, the titanium content in the solid content at this time was 564% by weight.

For snowballs, an experiment was conducted in the same manner as in Example 1.

The results obtained are as shown in Table 1.

Claims (2)

[Claims] (1) (A) (a) calcium carbonate, (b) dialkoxymagnesium, (c) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula T
iX_4 (in the formula, X is a halogen element) obtained by contacting a titanium halide represented by
R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. ) A catalyst component for polymerizing olefins, which is used in combination with a silicon compound represented by (C) and an organoaluminum compound. (2) (A) (a) calcium carbonate, (b) dialkoxymagnesium, (c) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula T
A catalyst component obtained by contacting a titanium halide represented by iX_4 (in the formula, X is a halogen element); (B) General formula SiRm(OR')_4_-_m (in the formula, R
is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦m≦4. ); and (C) an organoaluminum compound.