JPH0830086B2 - Catalyst for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a high-performance catalyst which acts highly active when subjected to the polymerization of olefins, and which can obtain a stereoregular polymer in a high yield. More specifically, the titanium halide is contacted with a suspension formed by dialkoxy magnesium, a chloride of an aromatic or aliphatic hydrocarbon which is liquid at room temperature, and a nonionic surfactant having an HLB of 3 to 12. And a solid catalyst component obtained by contacting the obtained composition with a phthalic acid diester and the titanium halide, a 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, and m is 0≤m≤4) Silicon compound and organoaluminum compound The present invention relates to a catalyst for olefin polymerization.

[Conventional technology]

Conventionally, a combination of a solid titanium halide and an organoaluminum compound is well known and widely used as a catalyst for olefin polymerization, but the catalyst component and the polymer yield per titanium in the catalyst component (hereinafter referred to as the catalyst) The so-called deashing process for removing the catalyst residue was unavoidable because the polymerization activity per titanium in the catalyst component and the catalyst component was low). This demineralization process requires a large amount of alcohol or chelating agent, and therefore requires a recovery device or a regenerating device. There are many resources, energy and other incidental problems, and those skilled in the art can solve the problem immediately. It was an important task to be desired. Numerous studies have been made and proposed to increase the polymerization activity of the catalyst component, particularly titanium in the catalyst component, in order to eliminate this complicated deashing step.

In particular, as a recent tendency, a transition metal compound such as titanium halide, which is an active ingredient, is supported on a carrier substance such as magnesium chloride, and when subjected to the polymerization of olefins, the polymerization activity per titanium in the catalyst component is dramatically increased. There are many proposals to raise the price.

For example, in Japanese Unexamined Patent Publication (Kokai) No. 50-126590, a carrier substance, magnesium chloride, is contacted with an aromatic monocarboxylic acid ester by mechanical means, and titanium tetrahalide is added to the obtained solid composition in a liquid phase. Is disclosed to obtain the catalyst component.

[Problems to be solved by the invention]

However, the chlorine contained in magnesium chloride is
Similar to the halogen element in titanium halide, it not only causes deterioration and yellowing of the polymer formed, but also causes corrosion of the equipment used in the processes such as granulation and molding, which is the effect of chlorine. Is required to be so high as to be negligible, but the catalyst using the catalyst component using magnesium chloride as a carrier substance disclosed in the above publications, etc., shows sufficient performance to date. Has not been obtained.

Further, when using a catalyst having the above-mentioned magnesium chloride as a carrier, or a highly active supported catalyst which has been recently proposed variously, the polymerization activity per unit time is high at the initial stage of the polymerization, but the decrease with the passage of the polymerization time is large. However, in addition to the problems in the process operation, it was almost impossible to use it in practice when it is necessary to prolong the polymerization time such as block copolymerization.

Further, these catalysts are generally required to coexist with an aromatic monocarboxylic acid ester at the time of polymerization, but the amount of the aromatic monocarboxylic acid ester used at this time is larger than that of the ester in the catalyst. Therefore, there is a drawback in that a peculiar ester odor is imparted to the produced polymer.

Further, in the industrial production of polyolefin, the bulk specific gravity of the produced polymer is also an important problem, but the present situation is that it cannot be said to be a sufficient value in the above catalyst system.

The present inventors have achieved the present invention as a result of earnest research in order to solve the problems left over in the prior art and to further improve the quality of the polymer produced.

[Means for solving problems]

That is, the features of the present invention are (I) (a) dialkoxymagnesium, (b) chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature (hereinafter simply referred to as "halogenated hydrocarbon"). And (c) in a suspension formed of HLB with a nonionic surfactant of 3-12,
(D) A titanium halide represented by the general formula TiX ₄ (where X is a halogen element) (hereinafter simply referred to as “titanium halide”) is brought into contact with the resulting composition, and (e) phthalate A solid catalyst component obtained by contacting an acid diester and (d) the titanium halide; (II) 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) (hereinafter sometimes simply referred to as a silicon compound) and (III) the general formula RnAlX ₃ -n (wherein R is an alkyl group having 1 to 4 carbon atoms, X is any one of hydrogen, chlorine, bromine, and iodine, and n is 0 <n ≦ 3. (Hereinafter, simply referred to as “organic”). Aluminum compound "
Say. The present invention provides a catalyst for olefin polymerization, which comprises

Examples of dialkoxy magnesium used in the present invention include diethoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, dipropoxy magnesium, di-sec-butoxy magnesium, di-tert.
-Butoxy magnesium, diisopropoxy magnesium and the like.

Examples of the halogenated hydrocarbon used in the present invention include propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, and tetrachloride. Examples thereof include carbon, chloroform, methylene chloride and the like, and among them, propyl chloride, dichloroethane, chloroform, carbon tetrachloride and methylene chloride are preferable.

Examples of the phthalic acid diester used in the present invention include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl. Examples include phthalate.

As the nonionic surfactant having an HLB of 3 to 12 used in the present invention, an appropriate one can be selected from various commercially available products and used.

Specific examples of the nonionic surfactant include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan distearate. Among them, sorbitan monolaurate, sorbitan monooleate and sorbitan distearate are preferable.

Examples of the titanium halide used in the present invention include TiCl ₄ , TiBr ₄ , TiI _4, etc. Among them, TiCl ₄ is preferable.

Examples of the silicon compound used in the present invention include phenylalkoxysilane and alkylalkoxysilane. Furthermore, examples of phenylalkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. As an example of alkylalkoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane,
Triethoxymethylsilane, ethyltriethoxysilane, ethyltriisopropoxysilane and the like can be mentioned.

Examples of the organoaluminum compound used in the present invention include trialkylaluminums, dialkylaluminum halides, alkylaluminum dihalides, and mixtures thereof.

The proportion of each component used in the present invention is arbitrary as long as it does not adversely affect the performance of the resulting catalyst, and is not particularly limited, but usually dialkoxymagnesium 1 g
On the other hand, phthalic acid diesters are 0.01 to 2 g, preferably
The nonionic surfactant having an HLB of 3 to 12 is used in the range of 0.01 to 1 g, and the titanium halide is used in the range of 0.1 g or more, preferably 1 g or more. Further, the halogenated hydrocarbon that is liquid at room temperature is used in any ratio as long as it is an amount capable of forming a suspension.

Suspension of dialkoxymagnesium in a halogenated hydrocarbon in the present invention is carried out at a temperature usually from room temperature to a boiling point of the halogenated hydrocarbon used for 100 hours or less, preferably 10 hours or less. At this time, it is necessary that the suspension does not become a uniform solution. Further, the contact between the suspension and the titanium halide and the contact between the composition obtained by the contact and the titanium halide are usually -20 ° C to the boiling point of the titanium halide used, preferably 50 ° C to 125 ° C. It is carried out at a temperature of ° C for 10 minutes to 10 hours.

The means for contacting each component in the present invention is not particularly limited as long as each component can be sufficiently contacted, but it is usually carried out by stirring using a container equipped with a stirrer.

In the present invention, the titanium halide may be diluted with the above-mentioned halogenated hydrocarbon and brought into contact with it, and after the contacting, it may be washed with an organic solvent such as n-heptane.

The organoaluminum compound used in the present invention has a molar ratio of 1 to 10 per mol of titanium atom in the solid catalyst component.
00, the silicon compound is used in a molar ratio of 0.01 to 0.5 per mol of the organoaluminum compound.

The 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. Polymerization temperature is 20
0 ℃ or less, preferably 100 ℃ or less, the polymerization pressure is 100kg /
cm ² · G or less, preferably 50 kg / cm ² · G or less.

Olefins homopolymerized or copolymerized using the catalyst produced by the method of the present invention are ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like.

〔The invention's effect〕

When olefins are polymerized using the catalyst for olefin polymerization according to the present invention, the polymerization conditions for formation have extremely high stereoregularity. Furthermore, since the catalyst shows an unexpectedly high value, the amount of catalyst residue present in the produced polymer can be suppressed to a very low level, and since the residual chlorine is extremely small, the product is deashed. The effect of chlorine can be reduced to the extent that no steps are required.

Since chlorine remaining in the produced polymer causes corrosion of equipment used in steps such as granulation and molding, it also causes deterioration of the produced polymer itself, yellowing, etc. What has been obtained brings great benefits to the art.

Further, according to the present invention, by not adding the organic carboxylic acid ester at the time of the polymerization, it is possible to solve the big problem that the ester odor adheres to the produced polymer.

Furthermore, conventionally, there was a common drawback in so-called highly active supported catalysts, in which the activity per unit time of the catalyst significantly decreased with the progress of polymerization, but in the catalyst according to the present invention, the polymerization time The decrease in activity with the passage of is extremely smaller than that of conventionally known catalysts, and therefore it is extremely useful even when the polymerization time such as copolymerization is prolonged.

In addition, in industrial olefin polymer production, coexistence of hydrogen during polymerization is generally considered from the viewpoint of MI control and the like, but with conventional magnesium chloride as a carrier, organic monocarboxylic acid ester is used. The catalyst used had the drawback that its activity and stereoregularity were significantly reduced in the presence of hydrogen. However, when olefin is polymerized in the presence of hydrogen using the catalyst according to the present invention, the activity and stereoregularity do not decrease even when the MI of the produced polymer is extremely high. Such an effect has been strongly desired by those skilled in the art. Also, in the industrial production of polyolefin, the capacity of the polymerization equipment,
The bulk specific gravity of the produced polymer becomes a very serious problem in terms of the ability of the post-treatment process, but the catalyst according to the present invention also has extremely excellent properties in this respect.

〔Example〕

 Hereinafter, the present invention will be described specifically with reference to Examples.

Example 1 [Preparation of catalyst component] A capacity of 50% which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
In a 0 ml round bottom flask, 0.5 g of diethoxymagnesium, 0.5 g of sorbitan distearate (brand name Emazole S-20, manufactured by Kao Corporation) and 25 ml of o-dichlorobenzene.
To prepare a suspension, and then add TiCl ₄ 200 to this suspension.
ml was added and the temperature was raised to 90 ° C and di-n-butylphthalate 1.8m was added.
l was added, the temperature was further raised to 120 ° C., and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the supernatant was removed and fresh TiCl ₄ 200
ml was added, and the mixture was reacted at 120 ° C. for 2 hours with stirring. After completion of the reaction, it was washed 10 times with 200 ml of n-heptane at 40 ° C to obtain a catalyst component. At this time, the solid content of the catalyst component was separated, and the titanium content in the solid content was measured and found to be 3.22% by weight.

〔polymerization〕

700 ml of n-heptane was charged into an autoclave with a stirrer having an internal volume of 2.0 l, which was completely replaced with nitrogen gas, and 301 mg of triethylaluminum was added while maintaining a nitrogen gas atmosphere.
64 mg of phenyltriethoxysilane and then 0.2 mg of the above catalyst component as titanium atoms were charged. Then hydrogen gas 150
While charging ml and raising the temperature to 70 ° C and introducing propylene gas
Polymerization was carried out for 4 hours while maintaining a pressure of 6 kg / cm ² · G. After completion of the polymerization, the obtained solid polymer was separated, heated to 80 ° C., and dried under reduced pressure. On the other hand, the liquid is concentrated and the amount of the polymer dissolved in the polymerization solvent is (A), and the amount of the solid polymer is (B). Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is designated as (C).

The polymerization activity (D) per catalyst component is calculated by the formula Express with.

Further, the yield (E) of the crystalline polymer is expressed by the formula The yield (F) of all crystalline polymer is expressed by I asked more. The residual chlorine in the produced polymer is represented by (G), the MI of the produced polymer is represented by (H), and the bulk specific gravity is represented by (I). The obtained results 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 6 hours. The results obtained are as shown in Table 1.

Example 3 Sorbitan distearate (trade name Emazole S-
The experiment was performed in the same manner as in Example 1 except that sorbitan monolaurate (trade name: Rheodor SP-L10, manufactured by Kao Corporation) was used instead of 20, manufactured by Kao Corporation.
The titanium content in the solid content at this time was 3.12% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Example 4 Sorbitan distearate (trade name Emazole S-
An experiment was performed in the same manner as in Example 1 except that sorbitan monooleate (trade name: Rheodor SP-O10, manufactured by Kao Corporation) was used instead of 20, manufactured by Kao Corporation. The titanium content in the solid content at this time was 3.27% by weight. An experiment was conducted in the same manner as in Example 1 during the polymerization. The results obtained are as shown in Table 1.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that Emamazole S-20 (manufactured by Kao Corporation) was not used.

The titanium content in the solid content at this time was 2.67% by weight.
Met. The results obtained are as shown in Table 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic drawing for helping understanding of the present invention.

Claims (1)

[Claims] 1. (I) (a) dialkoxymagnesium,
In a suspension formed by (b) a chloride of an aromatic or aliphatic hydrocarbon that is liquid at room temperature and (c) a nonionic surfactant having an HLB of 3 to 12, (d) the general formula TiX ₄ ( In the formula, X is a halogen element.) A solid catalyst component obtained by contacting a titanium halide represented by the formula (e) phthalic acid diester and (d) the titanium halide. (II) 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). And (III) a general formula RnAlX ₃ -n (wherein R is an alkyl group having 1 to 4 carbon atoms, X is hydrogen, chlorine, bromine or iodine, and n is 0 <n <3.) It is characterized by comprising an organoaluminum compound represented by Olefins such polymerization catalyst for.