JPS62106905A - Catalyst component and catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To decrease the lowering in polymerization activity with the time during polymerization and to eliminate a deashing step by markedly decreasing the amount of catalyst residues in the formed polymer, by using a combination of a specified titanium-containing catalyst component with a silicon compound and an organoaluminum compound as a catalyst for the polymerization of an olefin. CONSTITUTION:A catalyst for the polymerization of an olefin is formed by combining the following three components A-C: (A) a catalyst component obtained by contacting calcium carbonate, fatty acid magnesium salt, an aromatic dicarboxylic acid diester and a titanium halide of the formula: TiX4 (wherein X is a halogen) with each other; (B) a silicon compound of the formula: SiRm(OR')4-m (wherein R is H, alkyl or aryl, R' is alkyl or aryl and m is in the range of 0<=m<=4); and (C) an organoaluminum compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a high-performance polymer that has high activity when subjected to the polymerization of olefins and can obtain stereoregular polymers in extremely high yields. Regarding catalyst components and catalysts, more specifically, catalyst components for polymerizing olefins obtained by contacting calcium carbonate, magnesium fatty acids, diesters of aromatic dicarboxylic acids, and titanium halides, and the catalyst components, silicon compounds, and organoaluminum compounds. [Regarding an olefin polymerization fluid consisting of]

[Conventional technology]

Conventionally, as a highly active catalyst for polymerizing olefins, a combination of a solid tetanorogenide as a melting medium component and an organoaluminum compound is well known and widely used. Since the yield of polymer per titanium in the catalyst component (hereinafter referred to as the catalyst component and polymerization activity per titanium in the catalyst component) is low, a ninth so-called deashing step to remove the remaining catalyst was unavoidable. Since this deashing process uses a large amount of alcohol or chelating agent, it is necessary to regenerate the recovery equipment or the chelating agent, and there are many resource, energy, and other problems involved, and those skilled in the art It was an expensive issue that they wanted to resolve as soon as possible. In order to eliminate this complicated deashing process, a number of proposals have been made to increase the polymerization activity per titanium in the catalyst component and the solvent component.

In particular, a recent trend has been to support active ingredients such as transition metal compounds such as titanium halides on carrier materials such as magnesium chloride, which dramatically increases the polymerization activity per titanium in the catalyst component when used in the polymerization of olefins. I see many proposals for a higher nine.

[Problem that the invention seeks to solve]

However, chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the polymer produced, similar to the halogen element in titanium halides.9 Therefore, the effect of chlorine is virtually ignored. However, there are still some unresolved issues, such as the need for 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 a high polymerization activity per catalyst component and a high yield of stereoregular monomers.
No. 91107, we proposed a method for producing a catalyst component for the polymerization of olefins, and achieved our initial objective.

However, when using the catalyst component using magnesium chloride as a carrier, or the 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 is a major problem and poses a problem in process operation, and is almost impossible to use in practical cases where longer polymerization times are necessary, such as in block copolymerization.

The present inventors, as a result of intensive research, have proposed 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) calcium carbonate, (b) fatty acid magnesium, (C) i'G group recarboxylic acid diester, and (d) general formula TiX, (wherein the Xe halogen element (B) is obtained by contacting a titanium halide (hereinafter simply referred to as titanium halide) coated with RU hydrogen, alkyl group or aryl group R/
n is an alkyl group or an aryl group, mba0≦m≦
It is 4. ) (hereinafter simply referred to as a silicon compound) and (C) a catalyst component for heavy olefins, characterized in that it is used in combination with an organoaluminium compound, and GA) (a) calcium carbonate, ( b) magnesium fatty acid, (C) diester of aromatic dicarboxylic acid, and (d) titanium halide (hereinafter sometimes simply referred to as titanium halide) represented by the general formula TiX, where Xμ is a halogen element. ): (B) General formula 5iR1n(OR'J4-m (in the formula, Ri is water system, alkyl group or fc is aryl group, R/
is an alkyl group and an aryl group, m i O≦m
≦4. ] (hereinafter sometimes simply referred to as a silicon compound) and (C) a catalyst for polymerizing olefins comprising an organoaluminum compound,
be.

The calcium carbonate used in the present invention is not particularly limited, and ordinary commercially available products can be used.

The fatty acid magnesium used in the present invention is preferably saturated fatty acid magnesium.

The diester of aromatic dicarboxylic acid used in the present invention is preferably a diester of phthalic acid or terephthalic acid, such as dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl tere7thalate, diethyl phthalate, dipropyl terephthalate,
Dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisoamyl 7-talate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethylpropyl 7-thalet, etc.

The titanium halide used in the present invention is represented by the general formula TIX, where x is a halogen element.Ti064. Although TiEr4°T1E4 and the like are available, TiCt is particularly preferred.

The silicon compound used in the present invention includes:
Examples include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriynepropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, etc. Examples of runes include tetramethoxysilane, tetraethoxysilane, tritoxyethersilane, trimethoxymethyl silane, trimethoxymethyl silane, ethyltriethoxysilane, ethyltriisopropoxysilane, and the like.

The organic aluminum compounds used in this publication include trialkylaluminiums, dialkylaluminum halides, alkylaluminum cybarides, and mixtures thereof.

When obtaining the catalyst component in the present invention, the usage ratio of each raw material, contact conditions, etc. are arbitrary and are not particularly limited as long as they do not adversely affect the performance of the catalyst component to be produced. However, usually α01 to 2F, preferably α1 to 1? titanium halide i[11r or more, preferably 1
It is in the range of 9 or more.

In this case, the order and method of contacting the raw materials forming the catalyst component are not particularly limited and may be selected arbitrarily.

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

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

The catalyst component produced as described above has broad peaks around 20=32° and around 50° in its X-ray spectrum, and when combined with the silicon compound and organoaluminum compound, it can be used as a catalyst for polymerizing olefins. Form.

The organoaluminum compound used is used in a molar ratio of 1 to 1000 per mole of titanium atoms in the rxw medium component, and the silicon compound is used in a molar ratio of 1 or less, preferably 1't( LOO5~0
．． Used in the range of 5.

Polymerization can be carried out in the presence or absence of organic solvents, and both gaseous and liquid forms of olefinic monomer can be used. Polymerization temperature ri2
oo°C or less, preferably 1000 or less, and the polymerization pressure is 100 Yu/c1nz-G or less, preferably 50 Yu/-.
G or less.

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

〔Effect of the invention〕

When olefins are polymerized using the catalyst obtained by the present invention, the resulting polymer not only has extremely high stereoregularity, but also has extremely high activity, so that catalyst residues in the resulting polymer are extremely reduced. can be kept low,
Moreover, since the amount of residual chlorine is so small as to be almost negligible, there is no need for a deashing step at all, and of course, the influence of chlorine on the produced polymer can be virtually eliminated.

The 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. The fact that this has been achieved 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 of the catalyst decreases significantly as the polymerization progresses, and by improving the degree of homopolymerization. Rather, the aim is to provide a catalyst that can be practically applied even to copolymerization.

In addition, in the production of industrial olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of M process control. It also had the disadvantage that the stereoregularity was significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the activity and stereoregularity hardly decrease even when the MI of the produced polymer is extremely high. This effect will greatly benefit those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst components] Calcium carbonate α51 and magnesium stearate 95? was placed in a round-bottomed flask with a capacity of 300 cm, which was sufficiently purged with nitrogen gas and equipped with a stirrer, and dibutyl phthalate 1.5- and TiO 4-100- were added under stirring,
The temperature was raised to 110° C., and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the mixture was washed 10 times with 100 d of n-hebutane at 40°C, and TiC4100ad was added to a new tank, 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 10% of n-hebutane was added.
Washing with 0 dK was repeated, and when no chlorine was detected in the washing solution, the washing was completed and used as a catalyst component. At this time, when the solid-liquid in the medium component was sampled nine times and the titanium ownership ratio of the solid content was measured, it was found to be 2.70 by weight.

[Overlapping]

N-hebutane 700- was charged into an autoclave with an internal volume of 201 and equipped with a stirrer, which was completely purged with nitrogen gas, and while maintaining the nitrogen gas atmosphere) IJ fluorium aluminum 301, phenyltriethoxy 7-ran 64q1 Next, the catalyst component α3q was charged as titanium atoms. After that, hydrogen gas was charged at 120°C, the temperature was raised to 70C, and propylene gas was introduced at a pressure of 6Y/-.G? 9. Continue polymerization for 4 hours. After completion of the I-combination, the obtained solid polymer was separated, heated to 80°C, and dried under reduced pressure. @
Got the heck out of it. On the other hand, the F solution was condensed to obtain a polymer of 5.22. Moreover, the MI of the solid polymer was 7.8.

Example 2 An experiment was carried out in the same manner as in Example 1 except that the polymerization time was changed to 6 hours, and a solid polymer of 3412 was obtained.

On the other hand, the liquid was condensed to obtain 7.2 t of polymer, ft7'
c. Further, the MI of the solid polymer was &1. Example 5 A catalyst component was prepared in the same manner as in Example 1 except that the reaction temperature was 100°C. Incidentally, the titanium content in the solid 9 at this time was 2.89% by weight. The polymerization was conducted in the same manner as in Example 1 to obtain a solid polymer of 2362.

- 4.8t of polymer was obtained by condensing the 10,000F liquid. Moreover, the M-factor of the solid polymer was 98.

Claims (2)

[Claims] (1) (A) (a) calcium carbonate, (b) fatty acid magnesium, (c) diester of aromatic dicarboxylic acid, and (d) titanium halogen represented by the general formula TiX_4 (wherein X is a halogen element) (B) general formula SiR_m(OR')_4_-_m (wherein R is hydrogen, an alkyl group or an aryl group, and 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 (C). (2) (A) (a) calcium carbonate, (b) fatty acid magnesium, (c) diester of aromatic dicarboxylic acid, and (d) titanium halogen represented by the general formula TiX_4 (wherein X is a halogen element) (B) General formula SiR_m(OR')_4_-_m (wherein R is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, m (0≦m≦4); and (C) an organoaluminum compound.