JPS6334169B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1 Technical Field The present invention relates to a method for producing titanium-containing compositions suitable for use as transition metal components of Ziegler-type catalysts. More specifically, the present invention provides a method for polymerizing α-olefins with remarkable stereoregularity and high polymerization activity by treating a solid component containing a magnesium compound, an alkoxytitanium compound, and an acid halogen compound in a specific manner. This invention relates to a method for producing a Ziegler type catalyst component.

2. Prior Art Ziegler type catalysts are well known as catalysts for stereoregular polymerization of α-olefins, and it is also well known that various methods have been proposed to further improve their activity and stereoregularity. Among these various improvement methods, a method that has a particularly remarkable improvement effect on activity is a method for producing a solid catalyst component in which a magnesium compound is incorporated into a Ziegler-type catalyst transition metal catalyst component (Japanese Patent Publication No. 39-1999). −
No. 12105, Special Publication No. 47-41676, Special Publication No. 47-46269
(Refer to each publication).

However, when α-olefins such as propylene are polymerized using catalysts produced by these methods, although the activity is extremely high, the stereoregularity of the resulting polymer is significantly reduced. It is also known that the practical value of α-olefin as a stereoregular polymerization catalyst has been largely lost.

Therefore, in α-olefin polymerization using a transition metal component of a Ziegler-type catalyst containing a magnesium compound, various methods have been proposed to improve the stereoregularity of the resulting polymer (Japanese Patent Application Laid-Open No. 1989-1999).
9342, 50-126590, etc.) These methods are commonly characterized in that an electron-donating compound such as an amine or an ester is further contained in a solid catalyst component containing a titanium compound and a magnesium halide compound. Similarly, for the purpose of improving the stereoregularity of the produced polymer, a method for producing the transition metal component of a Ziegler-type catalyst by producing a titanium compound, a magnesium compound, and an acid halide compound in a specific manner (Japanese Patent Application Laid-open No. 51-136625), and a method for producing a specific catalyst component that uses ether, a specific phosphorus compound, a silicon compound, and alcohol as essential components in addition to the above-mentioned components has also been proposed (Japanese Patent Application Laid-open No. 53-277). , No. 53-1276, No. 53-2583, No. 53-2583, No. 53-1276, No. 53-2583, No.
53-19395, etc.).

However, as far as the present inventors know, these Ziegler type catalyst transition metal catalyst components also have insufficient polymerization performance, and this may be due to the above-mentioned JP-A-53-
No. 277, No. 53-1276, No. 53-2583, No. 53-
In the methods described in Japanese Patent No. 19395 and the like, it is essential to further use an organic carboxylic acid ester when combining with an organoaluminum component to form an α-olefin polymerization catalyst. In addition, a method in which an electron-donating compound such as an organic carboxylic acid ester is contained in both the transition metal catalyst component and the trialkylaluminum component that forms the Ziegler type catalyst in combination with the transition metal catalyst component has also been disclosed
It is known from publications such as No. 16986, No. 16987, and No. 16988.

[] Summary of the Invention The purpose of the present invention is to provide a solution to the above-mentioned problems, and to produce a catalyst component for olefin polymerization by subjecting a solid composition consisting of specific components to a specific treatment. Therefore, it is an attempt to achieve this purpose.

Therefore, in the method for producing a catalyst component for olefin polymerization according to the present invention, a solid composition obtained by combining a), b), and c) below is mixed with a halogenated hydrocarbon solvent or an aromatic hydrocarbon solvent. A method for producing a catalyst component for olefin polymerization, characterized by using an inert solvent and treating under the following treatment conditions.

Solid composition a MgX ¹ ₂ (where X ¹ represents halogen), Mg
(OR ¹ ) ₂ (here, OR ¹ indicates an organic residue with 1 to 12 carbon atoms), Mg(OCOR ² ) ₂ (here, -OCOR ² indicates an organic residue with 1 to 12 carbon atoms)
~12 organic carboxylic acid residues) or mixtures thereof, b with general formula Ti(OR ³ ) _o X ² _4-o (where n is O<n≦
4, R ³ is an alkyl group having 1 to 12 carbon atoms, X ² is a halogen), c an alkoxytitanium compound represented by the general formula R ⁴ COX ³ (wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms),
aliphatic, cycloaliphatic or aromatic organic residues,
X ³ represents a halogen) Processing conditions When the inert solvent is a halogenated hydrocarbon solvent, the temperature is from room temperature to 100°C, and when the inert solvent is a halogenated hydrocarbon solvent, the temperature is from 50 to 140°C. Do it with

Effects Even when a solid composition obtained by combining a), b) and c) above is used as a transition metal component of a Ziegler type catalyst, it shows only a very low performance, and therefore this composition itself has no practical value. Although rare, treatment of this solid composition with an inert solvent significantly improves catalyst component performance.

As a result, if the catalyst component obtained according to the present invention is used in α-olefin polymerization, a polymer product having physical properties required by the market can be produced without removing catalyst residue from the produced polymer or removing attic polymer. The polymer can be produced in an economically advantageous manner with a very simplified polymer production process.

[] Detailed Description of the Invention 1 Solid Composition The solid catalyst component according to the present invention first consists of a solid composition consisting of a plurality of components a), b) and c).

1 Component (1) Magnesium compound (component a)) The magnesium compound has the general formula MgX ¹ ₂
(X is halogen such as chlorine, bromine, iodine), Mg
(OR ¹ ) ₂ (OR ¹ is an organic residue with 1 to 1.2 carbon atoms, such as an alkoxy group or a phenoxy group), Mg (OCOR ² ) ₂ (−
OCOR ² is an organic carboxylic acid residue with 1 to 12 carbon atoms)
and mixtures thereof are used.

Among these, magnesium chloride is preferably used as MgX ¹ ₂ , diethoxymagnesium is used as Mg(OR ¹ ) ₂ , and magnesium benzoate treated with PCl ₅ or SOCl ₂ is preferably used as Mg(OCOR ² ) ₂ . It will be done.

(2) Alkoxy titanium compound (component b)) The alkoxy titanium compound has the general formula Ti
A compound represented by (OR ³ ) _o X ² _4-o (O<n4, R ³ is an alkyl group having 1 to 12 carbon atoms, and X ² is a halogen) is used.

Specifically, there are the following.

1 Alkoxytitanium trihalides, such as methoxytitanium trichloride, ethoxytitanium trichloride, n-butoxytitanium trichloride, i-butoxytitanium tribromide.

2 Alkoxytitanium dihalides, such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diethoxytitanium dibromide.

3 Monohalogenated trialkoxytitanium, such as trimethoxytitanium chloride, triethoxytitanium chloride, tri-n-butoxytitanium chloride, triethoxytitanium bromide.

4 Tetraalkoxytitanium, such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium.

Among these, particularly preferred are ethoxytitanium trichloride, ethoxytitanium dichloride, and the like.

(3) Halogen compound (component c)) The acid halogen compound has the general formula R ⁴ COX ³
(R ⁴ is an aliphatic, alicyclic, or aromatic organic residue having 1 to 12 carbon atoms, and X ³ is a halogen).

Specifically, acetyl chloride, propionyl chloride, brityl chloride, stearoyl chloride, methacryloyl chloride, benzoyl chloride, toluoyl chloride,
Phthaloyl chloride, and iodine or bromide substituted products of these chlorines.

Among these acid halogen compounds, benzoyl chloride, toluoyl chloride, and the like are particularly preferred.

(4) Auxiliary component (component b)) The solid composition of the present invention has three components a) to c) as essential components, but may additionally contain an auxiliary component. Examples of auxiliary components include inorganic halides such as aluminum chloride, phosphorus trichloride, phosphorus pentachloride, silicon tetrachloride, electron-donating compounds such as alcohols, ethers, or PCl using magnesium benzoate as a magnesium compound. ₅ and reaction by-products when treated with SOCl ₂ .

2 Composition The component ratio of the three components a) to c) is arbitrary and not critical as long as the effects of the present invention are recognized. In general, the molar ratio of each component is as follows, given the order of a), b) and c) and the auxiliary component d).

(100-0.5) vs. 1 vs. (0.1-10) vs. (0-50)
Preferably the ratio is (50 to 1) to 1 to (0.5 to 5) (shown only for essential components).

3 Preparation of Solid Composition The solid composition of the present invention is obtained by combining the above constituent components a) to c). In this invention, "combining" these components means that these three essential components and optionally used auxiliary components as described above are brought into contact with each other all at once or in stages. means. Therefore, the solid composition of the present invention made by combining various components may be a mere mixture of these components, or some or all of the components may be interacting or reacting in some way. In some cases,
The present invention encompasses both cases.

Some specific preparation methods are as follows. Note that the present invention is not limited to these preparation methods.

a The three components of the magnesium compound, acid halide, and alkoxytitanium compound are simultaneously mixed and pulverized.

b A magnesium compound and an acid halide compound are mixed and ground in advance, and then an alkoxytitanium compound is added and mixed and ground.

c. In b) above, the order of addition of the acid halide and the alkoxytitanium compound is reversed.

d) A magnesium compound is alternately brought into contact with an acid halogen compound and an alkoxy titanium compound at least twice or more each to be pulverized.

e In methods b) to d) above, the acid halogen compound and the alkoxy titanium compound are mixed while being continuously added in a predetermined amount.

f. Reacting a magnesium compound and alcohol to synthesize an adduct of the magnesium compound and alcohol, reacting titanium halide in accordance with a conventional method to "in situ form" an alkoxytitanium compound on the magnesium compound, and then Contact with acid halide.

g After mixing and pulverizing a magnesium compound and an acid halide, they are brought into contact with a solution in which an alkoxytitanium compound is dissolved.

h After mixing and pulverizing a magnesium compound and an alkoxytitanium compound, they are brought into contact with a solution in which an acid halide is dissolved.

i The three components are brought into simultaneous contact with each other in a solvent, and then evaporated to dryness and further pulverized.

In the above method, the grinding is generally carried out for 5 hours or more. The duration is generally between 10 and 100 hours. Grinding is preferably carried out in an inert atmosphere. Further, when contact treatment is performed in a solvent, it is generally carried out at room temperature to 150°C for 30 minutes to 10 hours.

2. Treatment of Solid Composition Even if the solid composition obtained by the method described above is used as a Ziegler type catalyst component, it exhibits only low performance and cannot be of any practical value. Only by treating this composition with an inert organic solvent can the titanium composition targeted by the present invention, that is, the catalyst component for olefin polymerization, be obtained.

1 Inert organic solvent treatment Inert organic solvents used in the present invention include:
Aliphatic, alicyclic, aromatic hydrocarbon compounds or halogenated hydrocarbon compounds thereof are used. Among these, halogenated hydrocarbon solvents and aromatic hydrocarbon solvents are preferred. Specifically, hexane, hebutane, benzene, toluene,
Xylene, mesitylene, cyclohexane, methylcyclohexane, 1,2-dichloroethane, propyl chloride, butyl chloride, chlorobenzene, bromobenzene, etc. can be used. Alternatively, a mixed solvent of these can be used.

Treatment with an inert organic solvent is usually carried out by stirring at a temperature of about room temperature to 150°C for 30 minutes to 10 hours. Specifically, when the inert organic solvent is a halogenated hydrocarbon, the treatment may be carried out using 50 to 100 ml of the halogenated hydrocarbon per about 10 g of the pulverized solid at a temperature of room temperature to 100°C for 1 to 3 hours. In addition, when aromatic hydrocarbons are used as inert organic solvents,
It may be carried out under similar conditions at a temperature of 50 to 140°C. However, in any case, the change in catalyst performance due to treatment temperature is not critical. After treatment, it is preferable to wash thoroughly.

Since it is recognized that the titanium content of the solid composition to be treated is reduced by this inert organic solvent treatment, the end point of the inert organic solvent treatment can be said to be the point at which an appropriate reduction in the titanium content is achieved.
The optimum titanium content reduction amount depends on the preparation method of the solid composition, its composition, the type and amount of the inert organic solvent,
Although it varies depending on temperature, time, etc., it can be easily determined experimentally.

It is not necessarily clear why this solvent treatment is effective in the present invention. However, it is presumed that at least part of the reason for this is that some titanium compounds are extracted or eluted due to the reduction in the titanium content in the solid composition due to this treatment (however, this is not the case). The present invention is not limited by this).

2 Interhalogen or Halogen By allowing interhalogen or halogen to be present during the treatment of the solid composition with an inert organic solvent, the performance of the solid composition as an olefin polymerization catalyst component can be further improved.

Interhalogens and halogens used for such purposes are those defined by the general formula XYn. (When X=Y, n=1, X≠Y
(when n=1, 3, 5 or 7, X and Y are halogens). Specific examples include Cl ₂ , Br ₂ , I ₂ , ClF,
BrF, IF, BrCl, ICl, IBr, ClF ₃ , BrF ₃ , IF ₃ ,
Examples include ICl ₃ (or I ₂ Cl ₆ ), ClF ₅ , BrF ₅ , IF ₅ and IF ₇ . Among these halogen compounds, especially
ICl, _ICl3 , _Cl2 , _I2 are preferred.

The amounts used of these compounds are generally in molar ratio to the titanium compound in the solid composition ().
It may be about 0.001 to 20, preferably about 0.005 to 10.

The interhalogen or halogen does not necessarily need to be introduced during the process of producing the solid catalyst component during the treatment in an inert organic solvent, but may be introduced in advance during the catalytic combination stage of the magnesium compound, acid halide, and alkoxytitanium compound. You can also leave it there.

3 Polymerization of Olefin The titanium composition produced as described above contains, as the transition metal component of the Ziegler-type catalyst, a reducing compound of group ~~ of the periodic table, especially a compound with the general formula AlR ⁵ _n X ⁴ _3-n
(m = 1 to 3, X ⁴ = halogen, R ⁵ = H or a hydrocarbon residue having 1 to 10 carbon atoms). Form.

Examples of suitable organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium hydride, diethylaluminum chloride, and the like.

The organoaluminum compound to be used has a content of 1 to 300, preferably 1 per atom in the titanium composition.
~150 (weight ratio). Further, at this time, an electron-donating compound such as ether, amine, or ester may be additionally used for the purpose of improving the stereoregular polymerization ability of the catalyst.

Possible polymerization methods include a so-called slurry polymerization method using an inert hydrocarbon such as hexane or heptane as a solvent, a liquid phase polymerization method using a liquefied monomer as a solvent, or a gas phase polymerization method where the monomer exists as a gas phase. . As for the polymerization method, continuous method and batch method can be carried out. Polymerization temperature is 30-120
℃, preferably about 40 to 80 degrees Celsius, and the polymerization pressure is about atmospheric pressure to 100 atm, preferably about atmospheric pressure to 50 atm.

Olefins that can be monopolymerized or copolymerized with the catalyst from the titanium composition of the present invention include ethylene, propylene, 1-butene, 4-methylpentene-1, and the like. The titanium composition of the present invention is particularly suitable for polymerization of propylene and propylene and its 1 to 15
It is effective as a copolymerization catalyst component with weight% of ethylene. The molecular weight of the polymer can be adjusted by a known method using hydrogen or the like.

4 Experimental Examples Example 1 (1) Production of titanium composition 20 g of anhydrous MgCl ₂ in an argon atmosphere
and benzoyl chloride 7.3ml [benzoyl chloride/
MgCl ₂ = 0.3 (mole ratio)] was contact mixed in a vibrating mill with an internal volume of 1 liter (inside the pot,
Contains 800ml (apparent volume) of 12.7mm stainless steel ball (SUS-27). After 12 hours of contact grinding,
_TiCl3 (OEt) (ethoxytrichlortitanium), 12.6
g [Ti ₃ (OEt)/MgCl ₂ = 0.3 (molar ratio)] was added thereto and the contact pulverization treatment was performed again for 16 hours to obtain a pulverized solid composition.

Approximately 7 g of the obtained crushed solid was divided into 200 ml flasks, 100 ml of 1,2-dichloroethane was added thereto as an inert organic solvent, and the mixture was stirred at 80° C. for 2 hours. After this treatment, the solid was washed by decantation (100 ml of n-hexane
), target titanium composition (catalyst component of the present invention)
I got it. The titanium concentration in this titanium composition slurry was determined by colorimetric analysis using a hydrogen peroxide coloring method, and the slurry was subjected to the following polymerization test. When the titanium content in the solid titanium composition was analyzed, it was found that the solid contained 1.42% by weight of titanium.

(2) Polymerization of propylene (liquid phase polymerization) A solid composition containing 10 mg of triethylaluminum and 0.4 mg of titanium atoms from the titanium composition slurry (Al/Ti = 10.5 molar ratio ) were introduced in this order under a propylene gas atmosphere, and finally 750 ml of liquefied propylene was added and the temperature was raised to initiate polymerization. Polymerization was carried out at 70°C for 1 hour. After the polymerization was completed, residual monomers were purged to obtain 240.5 g of polymer (PP).

The atom yield to titanium (gPP/gTi) is 600,000, and the yield to titanium composition (gPP/g titanium composition) is 8,500. The stereoregularity (hereinafter referred to as total II) of this polymer was 87.7% as determined by a boiling n-heptane extraction test.

Comparative Example 1 Pulverized solid composition obtained in Example-1 (7.6% by weight
(containing titanium) was slurried in hexane without any treatment and subjected to a polymerization test. When polymerization was carried out under the same polymerization conditions as in Example-1, 44 g of propylene polymer was obtained. The atom yield to titanium was 110,000, and the yield to titanium composition was 8,400. Also, total II is 72.3%
It was hot.

Example 2 0.1 g of iodine trichloride was used during the treatment with an inert organic solvent using 1,2-dichloroethane solvent in Example 1 (all examples were the same except for the treatment using 9.0 g of pulverized solid). (same conditions as 1).
The titanium content in the catalyst solid composition after treatment is 1.56% by weight.

When a polymerization test was conducted using this solid composition catalyst slurry, the yield relative to titanium was 560,000, and the yield relative to titanium was 8,700. Also,
Total II was 93.5%.

Example 3 During treatment with an inert organic solvent using 1,2-dichloroethane solvent in Example-1, 0.1 g of iodine trichloride
and 0.5 g of phosphorus pentachloride (8.0 g of ground solid was used). The titanium content in the catalyst solid composition after treatment is 1.50% by weight. Using this catalyst solid composition slurry, a polymerization test similar to that in Example 1 was conducted [However, TEA8mg,
0.4 mg of titanium, 206 g of polymer with Al/Ti=8.4 (molar ratio) was obtained. The yield relative to titanium was 515,000, and the yield relative to titanium was 7,700. All II is 95.2
%.

Example 4 A pulverized solid was produced by reversing the contact order of benzoyl chloride and TiCl ₃ (OEt) with respect to MgCl ₂ in Example-1. That is, 12.6 g of TiCl ₃ (OEt) was added to 20 g of MgCl ₂ and pulverized for 12 hours, and then 7.3 ml of benzoyl chloride was added and pulverized again for 16 hours.
A time milling process was performed to produce a ground solid.

Using 7.0 g of this pulverized solid, an inert solvent treatment with 1,2-dichloroethane was performed under the same conditions as in Example 1 (the titanium content in the obtained solid catalyst composition was 1.41%).

A polymerization test similar to that in Example 1 was conducted using this solid catalyst composition [however, TEA12
mg, Ti=0.4 mg, Al/Ti=12.6 (molar ratio)], 92 g of polymer was obtained. The yield relative to titanium was 230,000, the yield relative to titanium was 3,200, and the total II was 93.1%.

Example 5 20 g of anhydrous MgCl ₂ , magnesium benzoate salt
9.9 g and 14 g of phosphorus pentachloride were charged into a vibrating mill pot and mixed in contact for 4 hours to obtain a solid containing a magnesium compound and benzoyl chloride. Further, 13.5 g of TiCl ₃ (OEt) was added thereto, and the mixture was mixed and pulverized for 16 hours to obtain a pulverized solid composition.

Using 7 g of this solid composition, an inert solvent treatment with 1,2-dichloroethane was performed in the same manner as in Example 1 (the titanium content in the obtained solid catalyst composition was 1.06% by weight). ).

A polymerization test similar to that in Example 1 was conducted using this solid catalyst composition.
0.4 mg of Ti, Al/Ti = 16.8 (molar ratio)], 128 g of polymer was obtained. The yield relative to titanium was 320,000, the yield relative to titanium was 3,400, and the total II was 92.0%.

[Brief explanation of drawings]

FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts.

Claims (1)

[Claims] 1. A solid composition obtained by combining a), b) and c) below is subjected to the following treatment using an inert solvent selected from a halogenated hydrocarbon solvent or an aromatic hydrocarbon solvent. 1. A method for producing a catalyst component for olefin polymerization, characterized by processing under certain conditions. Solid composition a MgX ¹ ₂ (where X ¹ represents halogen), Mg
(OR ¹ ) ₂ (here, OR ¹ indicates an organic residue having 1 to 12 carbon atoms), Mg(OCOR ² ) ₂ (here, -OCOR ² indicates an organic residue having 1 to 12 carbon atoms)
12 organic carboxylic acid residues) or a mixture thereof, b General formula Ti(OR ³ ) _o X ² _4-o (where n is 0<n≦
4, R ³ is an alkyl group having 1 to 12 carbon atoms, X ² is a halogen), c an alkoxytitanium compound represented by the general formula R ⁴ COX ³ (where R ⁴ is an alkyl group having 1 to 12 carbon atoms),
aliphatic, cycloaliphatic or aromatic organic residues,
X ³ represents a halogen) Processing conditions When the inert solvent is a halogenated hydrocarbon solvent, the temperature is from room temperature to 100°C, and when the inert solvent is a halogenated hydrocarbon solvent, the temperature is from 50 to 140°C. Do it with