JPS62177003A - Catalytic component for olefin polymerization and catalyst therefrom - Google Patents

Abstract

PURPOSE:To provide a catalyst acting in high activity when used in olefin polymerization, capable of obtaining stereoregular polymer in high yield, comprising a silicon compound, organoaluminum compound and a catalytic component prepared from dialkoxymagnesium, halogenated hydrocarbon, etc. CONSTITUTION:The objective catalyst comprising (A) a catalytic component prepared by contact between a dialkoxymagnesium, aromatic monocarboxylic ester (e.g. methyl benzoate), halogenated hydrocarbon and titanium halide, (B) a silicon compound of formula SiRm (OR')4-m (R is H, alkyl or aryl; R' is alkyl or aryl; 0<=m<=4) (e.g. phenyl alkoxysilane) and (c) an organo aluminum compound (e.g. trialkylaluminum).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a high-performance polymer that exhibits 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 dialkoxymagnesium, aromatic monocarboxylic acid esters, halogenated hydrocarbons, and titanium halides, and the catalyst components, silicon compounds, and organic This is a book about catalysts for polymerizing olefins made of aluminum compounds.

[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 is well known and widely used. Since the yield of polymer per titanium (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 catalyst residues 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 per titanium in the catalyst component, especially in the catalyst 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 in the polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. I've seen many suggestions for increasing it.

[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 an adverse effect on the formed polymer, similar to the halogen elements in titanium halides. However, there were still unresolved issues such as the requirement for high activity to the extent that the amount of magnesium chloride could be ignored, 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 a stereoregular polymer.
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. In addition to causing problems in process operation, 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 arrived at the present invention as a result of intensive research in order to solve the problems remaining in the prior art and further improve the quality of the produced polymer, and hereby propose the present invention.

[Failure to solve the problem]

That is, the features of the present invention are as follows: (A) (a) dialkoxymagnesium, (b) aromatic monocarboxylic acid ester, (C) halogenated hydrocarbon, and (d) titanium halide are brought into contact with each other; (9) General formula SiRm(OH2)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 It is.

) (hereinafter sometimes simply referred to as a silicon compound) and (C) a catalyst component for olefin polymerization, characterized in that it is used in combination with an organoaluminium compound, and (A) (a) dialkoxymagnesium , (b) aromatic monocarboxylic acid ester (C) /% halogenated hydrocarbon and (d) catalyst component obtained by contacting titanium halide; (B) general formula SiRm(OR')4-, (formula Medium R
is hydrogen, an alkyl group or an aryl group, R' is an alkyl group or an aryl group, and m is 0≦■≦4. ) (hereinafter sometimes simply referred to as a silicon compound); and (C) an organic albanium compound.

The dialkoxymagnesium used in the present invention includes jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-see-butoxymagnesium, di-tf・rt-butoxymagnesium, diisopropoxymagnesium, etc. Among them, jetoxymagnesium and dipropoxymagnesium are preferred.

Aromatic monocarboxylic acid esters used in the present invention include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopropyl benzoate, isobutyl benzoate, methyl p-toluate, p-ethyl toluate, Examples include propyl p-toluate, butyl p-toluate, methyl p-anisate, ethyl p-anisate, propyl p-anisate, and butyl p-anilate.

The halogenated hydrocarbon used in the present invention is preferably a chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature, such as propyl chloride, butyl chloride, butyl bromide, propyl iodide, 0-dichlorobenzene, Examples include benzyl chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, and methylene chloride A4, among which 0-dichlorobenzene, propyl chloride, dichloroethane, chloroform, and carbon tetrachloride. , and methylene chloride are preferred.

The titanium halides used in the present invention include TiC64, TiBr4. Examples include TiI4, among which Tit;t4 is preferred.

The silicon compound used in the present invention,
Examples include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of phenylalkoxysilane include toshite, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, etc. Examples of alkylalkoxysilane include , tetramethoxysilane, tetraethoxy7rane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane and the like.

The organic aluminium compounds used in the present invention include trialkylaluminiums, dialkylaluminum halides, alkylaluminum cybarides, and mixtures thereof.

When obtaining the catalyst component in the present invention, the proportions and contact conditions of each raw material are arbitrary as long as they do not adversely affect the performance of the catalyst component to be produced, and are not particularly limited. The total of alkoxymagnesium is 12, while the aromatic monocarboxylic acid ester is 00.
It ranges from 1 to 29, preferably from 0.1 to 12, and for titanium halides it ranges from 0.11 or more, preferably from 12 or more. Furthermore, although the no-logenated hydrocarbon can be used in any proportion, it is preferably in a form that can form a suspension.

At this time, the contact method and conditions for each raw material forming the catalyst component are not particularly limited, but the contact with dialkoxymagnesium, aromatic monocarboxylic acid ester, and titanium halide is usually carried out in a manner similar to that of halogenated hydrocarbons. The reaction is carried out for 5 minutes to 100 hours at a temperature ranging from 0° C. to the boiling point of the titanium halide used in the presence of the titanium halide.

It is also possible to repeatedly contact the composition obtained at this time with a titanium halide, and it is also possible to wash it using an organic solvent such as η-hebutane.

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 is combined with the silicon compound and organoaluminum compound to form a catalyst for polymerizing olefins. The organic albanium compound used has a molar ratio of 1 to 1 per mole of titanium atoms in the catalyst component.
The silicon compound is used in a molar ratio of 1 or less per mole of the organoaluminum compound.

Polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. The polymerization temperature is 20
(preferably below 0°C) is 1°. ℃ or less, and the polymerization pressure is 1°. kg/ewi'-G or less, preferably 50 kg
/ex”・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 component and catalyst obtained according to the present invention, the resulting polymer not only has high stereoregularity but also has very high activity. Moreover, since the amount of residual chlorine is extremely small, there is no need for a deashing step at all, and the influence of chlorine on the produced polymer can be reduced.

Chlorine that is frozen in the produced polymer causes corrosion of equipment used in processes such as granulation and molding, and also causes deterioration and yellowing of the produced polymer itself, but this has been reduced. This has extremely important meaning for those skilled in the art.

Furthermore, the present invention is characterized in that the activity per unit time of the catalyst component decreases significantly as the polymerization progresses.
The objective is to solve the essential drawbacks of so-called highly active supported catalysts and to provide a catalyst that can be practically applied not only to homopolymerization but also 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 MI control, but the catalyst component using magnesium chloride as a carrier does not become active in the coexistence of hydrogen. It also had the disadvantage that the stereoregularity was significantly reduced. but,
When olefins are polymerized in the coexistence of hydrogen using the catalyst components and catalysts obtained by the present invention, the activity and stereoregularity hardly decrease even when the M engineering of the resulting polymer is extremely high. , such an effect brings enormous benefits to those skilled in the art.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Preparation of catalyst components] A 50-volume tank sufficiently purged with nitrogen gas and equipped with a stirrer
Jetoxymagnesium 52 and O-dichlorobenzene 25- were placed in a round bottom flask, and while stirring, ethyl benzoate 1,5- and TiCl220- were added.
The temperature was raised to 90° C., and the reaction was carried out with stirring for 2 hours. After the reaction was completed, it was washed 10 times with 200% of n-hebutane at 40°C.
After washing once again at 40°C with TiCl4200-, TiC4200- was further added and reacted at 90°C for 2 hours with stirring.

After the reaction was completed, it was cooled to 40°C, and then 20% of n-hebutane 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, the solid and liquid in the catalyst component were separated and the titanium content in the solid was measured and was found to be 599% by weight.

[Overlapping]

η-hebutane 700- was charged into an autoclave with an internal volume of 2.0 t and equipped with a stirrer, which was completely purged with nitrogen gas.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
11n? , 130 m9 of phenyltriethoxysilane, and then 0.3 μm of the above catalyst component as titanium atoms were charged. Thereafter, 100 ml of hydrogen gas was charged, the temperature was raised to 70° C., and while propylene gas was introduced, a pressure of 6 kg/♂@G was maintained and polymerization was carried out for 4 hours. 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 solvent by condensing the P solution (8)
and the amount of solid polymer is 1B). Further, the obtained solid polymer was extracted with boiling η-hebutane for 6 hours to obtain a polymer insoluble in cohebutane, and this amount was designated as (C).

The polymerization activity (D) of the catalyst component Mli 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 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 changed to 6 hours. The results obtained are shown in Table 1.

Example 3 An experiment was conducted in the same manner as in Example 1 except that 2.02% of ethyl benzoate was used. Incidentally, the titanium content in the solid content at this time was 562% by weight. During the polymerization, an experiment was conducted in the same manner as in Example 1, except that 150 TWI of phenyltriethoxysilane was used. The results obtained are shown in Table 1.

Claims (2)

[Claims] (1) (A) (a) Dialkoxymagnesium, (b)
Obtained by contacting aromatic monocarboxylic acid ester, (c) halogenated hydrocarbon and (d) titanium halide, (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. ) 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) dialkoxymagnesium, (b)
Catalyst component obtained by contacting aromatic monocarboxylic acid ester, (c) halogenated hydrocarbon and (d) titanium halide; (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.