JPS61103907A - Catalytic components and catalyst therefrom for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the titled catalytic components capable of giving stereo regular olefin polymer in high yield, in the combined form between a reaction product from fatty acid magnesium salt, aromatic dicarboxylic acid diester and titamium halide, a specific silicon compound and an organoaluminum compound. CONSTITUTION:The objective catalytic components in the combined form be tween (A) a reaction product from (i) fatty acid magnesium salt (pref. saturated fatty acid magnesium salt such as magnesium stearate), (ii) aromatic dicarboxylic acid diester [pref. dimethyl(tere)phthalate] and (iii) titanium halide of formula TiX4 (X is halogen) (pref. TiCl4), (B) a silicon compound of formula SiRm(OR')4-m (R is H, alkyl, or aryl; R' is alkyl or aryl; m is 0-4) (pref., phenyl or alkyl alkoxysilane) and (C) an organoaluminum compound (pref. triethylalu minum). Using this catalyst, an olefin such as ethylene, propylene or 1-butene will be polymerized.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a high-performance catalyst that exhibits high activity when used in the polymerization of olefins and is capable of obtaining stereoregular polymers in high yields. Regarding components and catalysts, more specifically, a catalyst component for olefin polymerization obtained by contacting fatty acid magnesium, a diester of an aromatic dicarboxylic acid, and a titanium halide, and olefins comprising the catalyst component, a silicon compound, and an organoaluminum compound. This invention relates to polymerization catalysts.

[Conventional technology]

Conventionally, as a 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 this polymer (hereinafter referred to as the polymerization activity of the catalyst component and the titanium in the catalyst component) is low, a so-called deashing step for removing catalyst residues was unavoidable. This deashing process uses a large amount of alcohol or chelating agent, so recovery or regeneration equipment is essential, and resources and
There are many energy and other related problems, and it is an important issue that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity of titanium in the catalyst component and the sieving catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium chlorides, which are active ingredients, on a carrier material such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of titanium in the catalyst component can be dramatically increased. There are many proposals for increasing the number of targets.

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 chlorine element in titanium/non-chloride compounds. There remained unresolved issues, such as the need for high activity so that the influence of superchlorine could be ignored, and the need to keep the concentration of magnesium chloride itself low.

In addition, when polymerizing olefins, especially stereoregular polymerization of propylene, 1-butene, etc., is carried out industrially, it is common to coexist an electron-donating compound such as an aromatic carboxylic acid ester in the polymerization system. It is essential for catalysts that use a catalyst component containing magnesium as a carrier in combination with an organoaluminum compound. However, this aromatic carboxylic acid ester imparts a characteristic ester odor to the produced polymer, and when used coexisting in the polymerization system, C
Partly because of their relatively large amounts, their removal has become a major problem in the industry.

In addition, in so-called highly active supported catalysts, such as catalysts using catalyst components using magnesium chloride as a carrier,
Although the activity is high at the initial stage of polymerization, the deactivation is large, which poses problems in process operation, and it is almost impossible to use it in practical situations such as block copolymerization, where a longer polymerization time is required. . In order to improve this point, for example, in JP-A No. 54-94590, a catalyst component was prepared using magnesium dihalide as a starting material, and organic aluminum compounds, organic carboxylic acid esters, M-
A method for polymerizing olefins in combination with a compound having an 0-R group has been shown, but since organic carbs/acid esters are used during polymerization, the problem of odor of the resulting polymer has not been solved. Furthermore, as can be seen from the examples, very complicated operations are required, and it cannot be said that practically sufficient results have been obtained in terms of performance and duration of activity.

In order to solve this problem, the present inventors have already filed a patent application in 1983-
No. 130873 (filed on July 20, 1982) proposes new catalyst components and catalysts.

#Japanese Patent Application No. 58-130873 states: ■ (a) fatty acid magnesium and (b) dialkoxymagnesium, (C) mono- or diester of aromatic dicarboxylic acid, (d) halogenated hydrocarbon, and (c)
)) General formula TiX4 (wherein X is) is a rogen 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.

) silicon compounds; and and C) organoaluminum compound A catalyst for polymerizing olefins is disclosed.

[Problem that the invention seeks to solve]

However, in addition to the above-mentioned problems with the prior art, in recent years there has been an increasing need in the technical field for catalysts that can yield polymers with narrow particle size distribution, high bulk density, and well-shaped shapes. Although the catalyst component and catalyst of the above-mentioned Japanese Patent Application No. 58-130873 have extremely excellent characteristics in terms of catalytic performance including durability of activity, they are not necessarily in a fully satisfactory state in this respect. The current situation is that this is not the case.

Adjusting the shape of the particles brings enormous benefits to painters, such as making it easier to handle the resulting polymer and making it possible to omit the granulation process, especially for use in gas-phase polymerization, which has recently been attracting attention. Considering this, it is of decisive importance.

One object of the present invention is to produce highly active olefins that can keep the amount of catalyst residue in the produced polymer extremely low and that do not require any deashing process because the amount of residual chlorine in the produced polymer is very small. An object of the present invention is to provide catalyst components and catalysts for polymerization.

Another object of the present invention is to provide a catalyst component and catalyst for polymerizing olefins that have high polymerization activity and exhibit little deterioration over time during polymerization.

Yet another object of the present invention is to provide a catalyst component and catalyst for polymerizing olefins that can yield a polymer with extremely high stereoregularity and no odor caused by aromatic carboxylic acid esters in high yield. It is to be.

Another object of the present invention is to provide a catalyst component and catalyst for polymerizing olefins in which the activity and stereoregularity hardly decrease even when olefins are polymerized in the coexistence of hydrogen and the resulting polymer has an extremely high Ml. The goal is to provide the following.

Another object of the present invention is that the particle size distribution is narrow.
Because the bulk density is high and the particle shape is extremely well-organized, it is possible to obtain a polymer that is easy to handle and can omit the granulation process, and it is also possible to increase the actual plant capacity. Another object of the present invention is to provide a catalyst component and a catalyst for polymerizing olefins, which can also be applied to gas phase polymerization.

[Means for solving problems]

That is, the present invention provides (A) (JL) fatty acid magnesium, (b) diester of aromatic dicarboxylic acid, and (C) general formula TiX4
(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, characterized in that it is used in combination with a silicon compound represented by C) and an organoaluminum compound; General formula TiX4 (
In the formula, X is a halogen element. ) Catalyst component obtained by contacting a tetanorogenide represented by is alkyl 1
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); and C) an organoaluminum compound.

As the fatty acid magnesium used in the present invention, saturated fatty acid magnesium is preferable, and magnesium stearate, magnesium octoate, magnesium decanoate, and magnesium laurate are particularly preferable.

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 7-talate, diethyl terephthalate, dipropyl 7-talate, dipropyl 7-talate, dibutyl phthalate, Examples include dibutyl terephthalate, diisobutyl phthalate, cyamyl phthalate, diisobutyl phthalate, ethyl butyl phthalate, ethyl isobutyl heptathalate, and ethylpropyl heptathalate.

The titanium halogenide represented by the general formula TiX4 (wherein X is a halogen element) used in the present invention includes TiC24, TiBr4, T, iI4, etc., and among them 'l'1C24 is preferable.

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 7, etc. Examples of alkylalkoxysilane Examples include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxine, ethyltriynepropoxysilane, and the like.

The organoaluminum compound used in the present invention includes trialkylaluminum, dialkylaluminum halide, alkylaluminum civalide, and mixtures thereof, with trialkylaluminum being preferred, and triethylaluminum and triisobutylaluminum being particularly preferred.

Although the order and method of contacting the raw materials forming the catalyst component are not particularly limited, preferred embodiments include: (1) pulverizing the components (a) and (b);
After pretreatment by suspension in a halogenated hydrocarbon or mixed contact in an organic solvent, the component (c) and the
A method of mixing and contacting at a temperature of ~130°C for 5 minutes to 100 hours; (2) After mixing and contacting the components (a) and (C), with the component (b) at a temperature of 0°C to 130°C (3) The components (a), (b) and (c) are mixed and contacted at a temperature of 0°C to 130°C, preferably 50°C to 130°C, for 5 minutes to 100 hours. , preferably for 10 minutes to 10 hours; and (4) after bringing any two of the components (a), (b) and (c) into contact with each other, the remaining two components are brought into contact. One example is a method of mixed contact.

It is also possible to coexist a surfactant at some point during the production process of the catalyst component. 〆.

The pulverization in the pretreatment is carried out at a temperature of 0° C. to 80° C. for 5 minutes to 100 hours using a ball mill, vibration mill, or the like.

Suitable examples of the halogenated hydrocarbon used in the pretreatment include chlorobenzene, orthodichlorobenzene,
Examples include one selected from benzyl chloride, propyl chloride, butyl chloride, dichloroethane, carbon tetrachloride, chloroform and methylene chloride, or a mixture thereof.

The organic solvent used in the pretreatment is preferably an aromatic hydrocarbon, such as toluene or xylene.

The mixing as the contacting means can be performed using a known mixing means such as a stirrer.

When obtaining the catalyst component of the present invention, the usage ratio of each raw material constituting the catalyst component is arbitrary, as long as it does not adversely affect the performance of the catalyst component to be produced, and is not particularly limited. , normal fatty acid magnesium 1? On the other hand, the diester of aromatic dicarboxylic acid has a molecular weight in the range of 0.01 to 21, and the titanium halide has a molecular weight in the range of 0.12 or more, preferably 12 or more.

It is also possible to contact the composition obtained after the above-mentioned contact with a titanium halide, and it is also possible to wash it using an organic solvent such as n-heptane.

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 organoaluminum compound used has a mole ratio of titanium atoms in the catalyst component in the range of 1 to 1000, and the silicon compound has a molar ratio of the organoaluminum compound of 1 or less, preferably 0.005. It is used in the range of ~0.5.

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
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
It is less than 00 #/I·G, preferably less than 504 #/G.

The olefins to be homopolymerized or copolymerized using the catalyst produced by the method of the present invention include ethylene, propylene,
1-butene, etc.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 Preparation of catalyst components
In a 01Rt round bottom flask was added 10 f of magnesium stearate, 0.6 f of dibutyl phthalate and TiC.
1425- was charged, and a stirring reaction was carried out at 110°C for 2 hours. After the reaction was completed, i was added with 100y of n-hebutane at 40℃
Washed o times, added TiC2425m and heated at 110°C.
The mixture was reacted with stirring for 2 hours. After completion of the reaction, washing with 100% of n-hebutane at 40° C. was carried out 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, when the solid and liquid in the catalyst component was separated and the titanium content in the solid was measured, it was found to be 2.3.
It was 9% by weight.

2. The internal volume is completely replaced with nitrogen gas. Into an O2 autoclave equipped with a stirrer, 700 mjt of n-heptane was charged, and while maintaining a nitrogen gas atmosphere, 301 v of triethylaluminum, 32 kg of phenyltriethoxysilane, and then 0.3 kg of the above catalyst components as titanium atoms were charged. After that, hydrogen gas 120- was charged, the temperature was raised to 70℃, and propylene gas was introduced while maintaining the pressure of 6φ pieces・G.
Time polymerization was performed. 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 the polymer dissolved in the polymerization solvent by concentrating the f solution is taken as a prisoner, and the amount of solid polymer is taken as ω). Further, the obtained solid polymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as C).

The polymerization activity per catalyst component (0) and the crystalline polymer yield (2) were expressed by the formula, and the total crystalline polymer yield ω was determined using the formula. Further, the residual chlorine in the produced polymer is represented by (6), the MI of the produced polymer is represented by (■), and the bulk density is represented by α). The results obtained are as shown in Table 1. The resulting polymer had a well-rounded shape, and when the particle size distribution was examined, it was found to be 10.
There were 95 inches of polymer between Oμ and 500μ.

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 A catalyst component was prepared in the same manner as in Example 1, except that magnesium octoate was used at lof in place of magnesium stearate, and dibutyl phthalate was used at 0.8 F. In addition, the titanium content of the solid agglomerate at this time was 2.6
It was 1% i-%. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are as shown in Table 1.

Example 4 Dipropyl phthalate was added to υ instead of dibutyl phthalate.
A catalyst component was prepared in the same manner as in Example 1 except that No. 51 was used. 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).

Table 1 [Effects of the Invention] When olefins are polymerized using the catalyst obtained by the present invention, not only the resulting polymer has extremely high stereoregularity, but also the catalyst has extremely high activity. Therefore, the amount of catalyst residue in the produced polymer can be kept extremely low, and the influence of chlorine on the produced polymer can be reduced to such an extent that a deashing process is not required at all. can.

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, and this has been reduced. This has extremely important meaning for those skilled in the art.

Furthermore, according to the present invention, the big problem of the odor of the polymerized product is solved by using the silicon compound instead of the aromatic carboxylic acid ester during polymerization. The essential drawback of so-called highly active supported catalysts, in which the activity per unit time decreases significantly over the course of polymerization, has been solved, and the catalyst can be practically applied not only to homopolymerization but also to copolymerization. is provided.

In addition, in the industrial production of olefin heptapolymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst using the catalyst component with magnesium chloride as a carrier In coexistence, the activity and stereoregularity were significantly reduced. However, when olefins are polymerized in the presence of hydrogen using the catalyst obtained according to the present invention, the M of the produced polymer is
There is little loss of activity and stereoregularity even when the molecular weight is extremely high, and such effects are of great benefit to those skilled in the art.

Furthermore, according to the present invention, it is possible to obtain a polymer product that has a narrow particle size distribution 6, a high bulk density, and an extremely well-organized particle shape, so that it is easy to handle and the granulation step can be omitted. In addition, catalyst components and catalysts for polymerizing olefins that can be applied to gas phase polymerization can be provided very easily.

Claims (21)

[Claims] (1) (A) (a) fatty acid magnesium, (b) diester of aromatic dicarboxylic acid and (c) general formula TiX_
(B) general formula SiR_m(OR')_4_-_m (In the formula, 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
It is. A catalyst component for polymerizing olefins, characterized in that it is used in combination with a silicon compound represented by (hereinafter sometimes simply referred to as a silicon compound) and (C) an organoaluminium compound. (2) Olefin polymerization according to claim (1), wherein the catalyst component is obtained by pre-treating the components (a) and (b) and then mixing and contacting the component (c). Catalyst component for use. (3) The catalyst component for polymerizing olefins according to claim (2), wherein the pretreatment is pulverization, suspension in a halogenated hydrocarbon, or mixed contact in an organic solvent. (4) The olefins according to claim (1), wherein the catalyst component is obtained by mixing and contacting the components (a) and (c) and then mixing and contacting the component (b). Catalyst component for polymerization. (5) The catalyst component comprises the components (a), (b) and (
The catalyst component for olefin polymerization according to claim (1), which is obtained by simultaneously mixing and contacting c). (6) The catalyst component comprises the components (a), (b) and (
The catalyst component for polymerizing olefins according to claim (1), which is obtained by contacting any two components among c) and then mixing and contacting the remaining two components. (7) Claims (1) to (6) in which a surfactant is allowed to coexist at some point during the manufacturing process of the catalyst component.
The catalyst component for polymerizing olefins according to any one of the above. (8) The catalyst component for polymerizing olefins according to any one of claims (1) to (7), wherein the fatty acid magnesium is saturated fatty acid magnesium. (9) The catalyst component for polymerizing olefins according to claim (8), wherein the saturated fatty acid magnesium is magnesium stearate, magnesium octoate, magnesium decanoate, or magnesium laurate. (10) The catalyst component for polymerizing olefins according to any one of claims (1) to (7), wherein the diester of aromatic dicarboxylic acid is a diester of phthalic acid or terephthalic acid. (11) The diester of phthalic acid or terephthalic acid is dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, dipropyl phthalate, dipropyl terephthalate, dibutyl phthalate, dibutyl terephthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate,
The catalyst component for polymerizing olefins according to claim 10, which is ethyl butyl phthalate, ethyl isobutyl phthalate, or ethyl propyl phthalate. (12) The catalyst component for polymerizing olefins according to any one of claims (1) to (7), wherein the titanium halide is TiCl_4. (13) The catalyst component for polymerizing olefins according to any one of claims (1) to (7), wherein the silicon compound is phenyl and alkylalkoxysilane. (14) The catalyst component for polymerizing olefins according to any one of claims (1) to (7), wherein the organoaluminum compound is triethylaluminum and triisobutylaluminum. (15) The catalyst component for polymerizing olefins according to claim (1), wherein the olefins are ethylene, propylene, and 1-butene, and the catalyst component is used for homopolymerization or copolymerization of these olefins. (16) (A) (a) magnesium fatty acid, (b) diester of aromatic dicarboxylic acid and (c) general formula TiX
A catalyst component obtained by contacting a titanium halide represented by _4 (in the formula, X is a halogen element); (B
) Represented by the 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). and (C) an organoaluminum compound. (17) The catalyst for polymerizing olefins according to claim (16), wherein component (A) is the catalyst component according to any one of claims (1) to (15). (18) The catalyst for polymerizing olefins according to claim (16), wherein the silicon compound is phenylalkoxysilane or alkylalkoxysilane. (19) The catalyst for polymerizing olefins according to claim (16), wherein the organoaluminum compound is trialkylaluminum. (20) The catalyst for polymerizing olefins according to claim (15), wherein the trialkylaluminum is triethylaluminum and triisobutylaluminum. (21) The catalyst for polymerizing olefins according to claim (16), wherein the olefins are ethylene, propylene and 1-butene, and the catalyst is used for homopolymerization or copolymerization of these olefins.