JPS61291602A - Catalytic component for olefin polymerization and catalyst - Google Patents

Abstract

PURPOSE:To obtain a high-performance catalytic component acting with high activity when provided for olefin polymerization leading to the stereoregular polymer in high yield, by coming into contact between fatty acidaluminum salt, dialkoxy magnesium, aromatic dicarboxylic acid diester, etc. CONSTITUTION:The objective catalytic component can be obtained by contacting. (A) fatty acid aluminum salt, (B) dialkoxy magnesium (e.g., diethoxy magnesium), (C) aromatic dicarboxylic acid diester (e.g., dimethyl phthalate), (D) halogenated hydrocarbon, and (E) titanium halide of formula TiX4 (X is halogen). This component is combined with both Si-component of formula SiRm (OR')4-m (R is H, alkyl or aryl; R' is alkyl or aryl; 0<=m<=4) and organoaluminum compound (e.g., trialkylaluminum) to put into application as the objective olefin polymerization catalyst.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention has a high activity when subjected to the polymerization of olefins, and a stereoregular polymer that can be obtained with an extremely high degree of occlusion. Regarding performance catalyst components and catalysts, more details include fatty acid aluminum, dialkoxymagnesium,
The present invention relates to a catalyst component for polymerizing olefins obtained by contacting a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon, and a titanium halide, and a catalyst for polymerizing olefins comprising the catalyst component, a silicon compound, and an organoaluminum compound. .

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of a solid titanium halide and an organoaluminum compound as a catalyst component has been well known and widely used. Since the concentration of polymer per titanium in the catalyst (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. This deashing process uses a large amount of alcohol or chelating agent, so recovery equipment or regeneration equipment is essential, and there are many resource, energy, and other problems involved.
For those skilled in the art, this was an important issue that needed to be solved as soon as possible. In order to eliminate this complicated deashing step, many studies have been made and proposals have been made to increase the polymerization activity of the catalyst component, particularly titanium, in the catalyst component.

In particular, there is a recent trend in which transition metal compounds such as titanium halides, which are active ingredients, are supported on carrier materials such as magnesium chloride, and when used for polymerization of olefins, the polymerization activity per titanium in the catalyst component is There are many proposals to raise the standard.

[Problem that the invention seeks to solve]

However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having a negative effect on the produced polymer, similar to the norogen element in titanium halides, and for this reason, the effect of chlorine is virtually ignored. However, there remained unresolved issues such as the need to have as high an activity as possible, or the need to keep the concentration of magnesium chloride itself low.

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

However, when using a catalyst component having magnesium chloride as a carrier, or a catalyst component obtained in JP-A-59-91107, etc., the polymerization activity per unit time is high at the initial stage of polymerization, but decreases as the polymerization time progresses. This poses a problem in process operation, and it is almost impossible to use it practically in cases such as block copolymerization where a longer polymerization time is required.

The present inventors have arrived at the present invention as a result of intensive research and propose the present invention in order to solve the problems remaining in the prior art and further improve the quality of the produced polymer.

[Means for solving problems]

That is, the features of the present invention are as follows: (A) C&) fatty acid aluminum, (b) dialkoxymagnesium, (C) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula TiX, obtained by contacting a titanium halide (hereinafter sometimes referred to as titanium halide) represented by the formula (X is a halogen element), with the general formula SiRm (OR'), (In the formula, R is hydrogen, an alkyl group or an aryl group!', R' is an alkyl group or an aryl group and p), and m is 0≦m≦4. ) (hereinafter sometimes simply referred to as a silicon compound) and (C) a catalyst grade and catalyst for polymerizing olefins, characterized in that it is used in combination with an organoaluminum compound (a) fatty acid aluminum, ( b) dialkoxymagnesium, (c) diester of aromatic dicarboxylic acid,
(d) halogenated hydrocarbon, and (e) general formula TiX
4 (In the formula, X is a halogen element.) A catalyst component obtained by contacting a titanium halide (hereinafter sometimes simply referred to as a titanium halide); @)
General formula SiRm(OR'),! A silicon compound (hereinafter simply referred to as a silicon compound) represented by Il (wherein R is hydrogen, an alkyl group or an aryl group, R1 is an alkyl group or an aryl group, and m is 0≦m≦4) ); and (b) to provide a catalyst for polymerizing olefins comprising an organoaluminum compound.

・・・・・－・・・・・・・・・・・・・・・・・・・
...... φi6--・J The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-8
Examples include 6C-butoxymagnesium, di-tert-butoxymagnesium, and diisopropoxymagnesium, among which jetoxymagnesium and dipropoxymagnesium are preferred.

Note that it is preferable to use the fatty acid aluminum and dialkoxymagnesium in a form with as much moisture removed as possible.

The diester of aromatic dicarboxylic acid used in the present invention includes 7talr! 1 or diesters of terephthalic acid are preferred, such as dimethyl phthalate, dimethyl terephthalate, diethyl 7-thaleate, diethyl terephthalate, cyamyl 7-thaleate, sifurobir 7-thaleate, dibutyl 7-thaleate, dibutyl terephthalate, diisobutyl phthalate, cyamyl 7-thaleate, diisoamyl phthalate, Examples include ethyl butyl phthalate, ethyl isobutyl phthalate, and ethyl propyl phthalate.

The halogenated hydrocarbon used in the present invention is preferably an aromatic or aliphatic hydrocarbon chloride that is liquid at room temperature, such as propyl chloride, butyl chloride, butyl bromide, propyl iodide, 0-dichlorobenzene, benzyl Examples include chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, etc. Among them, %o-dichlorobenzene, furoyl chloride, dichloroethane, chloroform, Carbon chloride and methylene chloride are preferred.

Examples of titanium halides represented by the general formula TiX4 (wherein X is a halogen element) used in the present invention include TiC4, TiBr4. Among them, TiC4 is preferable.

The silicon compound used in the present invention is:
Examples include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of phenylalkoxysilane include 7enyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyljethoxy 7rane, etc. Examples of the silane include tetramethoxysilane, tetraethoxysilane, trimethoxyethyl silane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and edeltriisopropoxysilane.

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

When obtaining the catalyst component in the present invention, use of each raw material v
1 and contact conditions are optional as long as they do not adversely affect the performance of the catalyst component to be produced, and are not particularly limited, but usually for a total of 1f of fatty acid aluminum and dialkoxymagnesium, The diester of aromatic dicarboxylic acid is (LO1~2f, preferably (L1~
1y range, titanium halide is 111 or more,
Preferably, the range is 1 or more. Further, the halogenated hydrocarbon can be used in any proportion, but it is preferably one that can form a suspension.

Note that at this time, the order and method of contacting the raw materials forming the catalyst component are not particularly limited, but in the first embodiment, the composition obtained after pulverizing fatty acid aluminum and dialkoxymagnesium is The composition obtained after contacting diesters of aromatic dicarboxylic acids and titanium halides in the presence of hydrogenated hydrocarbons or, as embodiment g2, grinding fatty acid aluminum, dialkoxymagnesium and diesters of aromatic dicarboxylic acids. is preferably contacted with the titanium halide in the presence of a halogenated hydrocarbon.

The pulverization of fatty acid aluminum 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. This is usually carried out in the presence of a halogenated hydrocarbon at a temperature ranging from 0° C. to the boiling point of the titanium halide used for 5 minutes to 100 hours.

The fatty acid aluminum, dialkoxymagnesium, and diester of aromatic dicarboxylic acid in the second embodiment are usually pulverized using a ball mill, perturbation 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.
The process is carried out for 5 minutes to 100 hours at a temperature of 100°C to the boiling point of the titanium halide used.

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

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

The nine M-favorable ingredients produced as described above are:
, around 2θ=32° and 50° in the l spectrum
It has a broad peak in the vicinity, and forms a catalyst for polymerizing olefins in combination with the silicon compound and organoaluminum compound.

The organoaluminum compound used has a simole ratio of 1 to 1000 per mole of titanium atoms in the catalyst component, and the silicon compound has a simole ratio of 1 or less per mole of the organoaluminum compound, preferably rl, 0O5. ~0.5
Used within the range of

Polymerization can be carried out in the presence or absence of a solvent, and the olefin 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
00 kg/i-G or less, preferably 50 to 9/-.G or less.

Olefins that can be homopolymerized or copolymerized using the catalyst components of the present invention include ethylene, propylene, and 1-[tetene].

〔Effect of the invention〕

When olefins are polymerized using the catalyst components and catalysts obtained according to the present invention, the resulting polymer not only has extremely high stereoregularity but also has extremely high activity. In addition, since the amount of residual chlorine is so small that it can be almost overlooked, there is no need for a deashing process at all, and the effect of chlorine on the produced polymer can be substantially reduced. Can be made to disappear.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself. This has extremely important meaning 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 of the catalyst acid per unit time decreases significantly as the polymerization progresses.
The objective is to provide a catalyst that can be practically applied not only to homopolymerization but also to copolymerization.

In addition, in the industrial production of 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. but,
When olefins are polymerized in the presence of hydrogen using the catalyst component and catalyst obtained by the present invention, the activity and stereoregularity hardly decrease even when the MI of the produced polymer is extremely high. Such an effect is of great benefit to those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst components] Aluminum stearate 5f and jetoxymagnesium 451 were charged in a nitrogen gas atmosphere into a vibrating mill pot with a capacity of 102 filled with 475 stainless steel poles of 25 cod diameter, the total capacity, and subjected to vibration. @1430 v, p, m
, and a shaking width of 5 m +++ for 1 hour at room temperature. In a 500-capacity round-bottomed flask sufficiently purged with nitrogen gas and equipped with a stirrer, 55 t of the composition obtained by the above pulverization treatment and 15 t of 0-dichlorobenzene were placed.
Then, dibutyl phthalate 1.8- and TiC4200- were added under stirring, the temperature was raised to 110° C., and the mixture was allowed to react while stirring for 2 hours. After the reaction was completed, it was washed 10 times with n-hebutane 200-
After washing once at 40°C with 'I'iC4
200- was added thereto, 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 repeated (repeatedly), and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used. At this time, the solid and liquid in the catalyst component were separated and the titanium content in the solid was measured and found to be 2.55% by weight.

[Overlapping]

Contents completely replaced with nitrogen gas g 2. N-hebutane 700- was charged into an Ot autoclave equipped with a stirring device, and while maintaining a nitrogen gas atmosphere, triethylaluminum 3a1rrq, phenyltriethoxysilane 64-Misaki, and then the catalyst component was converted to titanium atoms. lL3■
I loaded it. After that, 120 tnl of hydrogen gas was charged and the temperature was raised to 70°C.
6 kg/e while increasing the temperature and introducing propylene gas.
Polymerization was carried out for 4 hours while maintaining the MP-G pressure. After the polymerization 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/combination solvent after condensing the filtrate is (A), and the type of solid polymer is (B).
shall be. Further, the obtained solid polymer was extracted with boiling N n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (C).

The polymerization activity (D) per catalyst component was expressed by the formula and the yield (E) of the crystalline polymer was expressed by the formula, and the yield (F) of the total crystalline polymer was determined by the formula. In addition, residual chlorine in the produced polymer (■, M of the produced polymer
I is represented by (H). 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 changed to 6 hours. The results obtained are as shown in Table 1.

Example 3 Example 1 except that 1.41 dipropyl phthalate was used.
An experiment was conducted in the same manner. Incidentally, the titanium content of the solid agglomerate at this time was 2.69% by weight. During the polymerization, an experiment was conducted in the same manner as in Example 1 except that phenyltriethoxysilane 7019 was used. The results obtained are as 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. Incidentally, the titanium content of the solid agglomerate at this time was 2.16%. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 5 Aluminum stearate 59. Example 1 Jetoxymagnesium 45f and dipropylphthalate 152
It was crushed in the same way. The obtained composition 61 was placed in a round bottom flask with a capacity of 500 inerts, which was sufficiently purged with nitrogen gas and equipped with a stirrer, and 0-dichlorobenzene 15r and TiC4200 were charged and the temperature was raised to 110°C. The mixture was reacted with stirring for 2 hours. After the reaction was completed, it was washed 10 times with 200°C of n-hebutane at 40°C, and freshly washed with TiC4200.
After washing once at 40°C with TiC
12200- was added, and the mixture was stirred and reacted at 90°C for 2 hours.

After the reaction was completed, it was cooled to 40°C, and further added with 200 ml of n-hebutane.
- The cleaning was repeated repeatedly, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed, and a catalyst component was obtained.

Incidentally, the titanium content of the solid fraction at this time was 2.41% by weight.

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

The results obtained are shown in Table 1.

Claims (5)

[Claims] (1) (A) (a) fatty acid aluminum, (b) dialkoxymagnesium, (c) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula TiX_4 (wherein X is halogen It is obtained by contacting titanium halide represented by (B)
Represented by the general formula SiRm(OR')_4_-_m (wherein, 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, characterized in that it is used in combination with a silicon compound and (C) an organoaluminum compound. (2) After grinding components (a) and (b), the resulting composition is mixed with components (c) and (e) in the presence of component (d).
) A catalyst component for polymerizing olefins according to claim (1), which is obtained by contacting with a catalyst component. (3) After crushing components (a), (b) and (c),
The catalyst component for polymerizing olefins according to claim (1), which is obtained by contacting the resulting composition with component (e) in the presence of component (d). (4) (A) (a) fatty acid aluminum, (b) dialkoxymagnesium, (c) diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (e) general formula TiX_4 (wherein X is halogen (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. (5) After the catalyst component mills components (a) and (b), the resulting composition is mixed with component (a) and (b) in the presence of component (d).
c) and (e) or component (a).
, (b) and (c) and then contacting the resulting composition with component (e) in the presence of component (d). Polymerization catalyst.