JPS6334164B2 - - Google Patents

Description

[Detailed description of the invention]

[1] Background of the Invention The present invention relates to a transition metal component of a so-called Ziegler type catalyst. From another point of view, the present invention includes:
The present invention relates to a method for producing this transition metal component. According to the present invention, a highly active catalyst for olefin polymerization can be obtained. An olefin polymerization catalyst, generally known as a Ziegler type catalyst, is a combination of a transition metal component and a reducing organic component. However, for example, a combination of titanium trichloride and diethylaluminum chloride does not necessarily have a sufficiently high catalytic activity, resulting in a large amount of catalyst residue in the produced olefin polymer, and therefore the stability of the product polymer against heat and oxidation. In order to improve this, complicated purification processes such as catalytic decomposition with alcohol and neutralization with alkali are required. For this reason, highly active catalysts are desired, but improvement in catalytic activity seems to be primarily aimed at improving transition metal properties, and one such improvement is the use of magnesium compounds as a carrier. I have something to use. However, although catalysts containing titanium trichloride as a transition metal component and using a magnesium compound as a carrier are significant in terms of high activity per transition metal, many catalysts have insufficient activity per support. It is desirable that the catalytic activity not only be high per transition metal but also high per support. The present inventors have proposed a supported transition metal catalyst component prepared in a specific manner (Japanese Patent Application Laid-Open No. 54-4295
No. 54-40293 and No. 54-45696). [] Summary of the Invention The present invention aims to provide a solution to the above-mentioned problems and obtain a highly active catalyst, and attempts to achieve this purpose by means of a supported transition metal catalyst component prepared in a specific manner. It is something. Therefore, the olefin polymerization catalyst component according to the present invention is characterized in that it is a contact product of component A and component B described below, which is treated with a halogenated hydrocarbon. Component A Contains magnesium and titanium, and the following compounds
Contact products of (1) and (2). (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o (where R ¹ is alkyl, aryl, or cycloalkyl having 1 to 10 carbon atoms, is an integer of 0 < n < 2), (2) a titanium compound represented by the general formula Ti(OR ² ) ₄ (where R ² is an integer with a carbon number of 1 that is the same as or different from R ¹ );
~10 alkyl, aryl or cycloalkyl). Component B (3) Liquid titanium halogen compound. Effects When α-olefin is polymerized using the solid catalyst component according to the present invention as the transition metal component of a Ziegler catalyst, both the amount of polymer produced per transition metal and the amount of polymer produced per carrier are high. Even if any one of the compounds (1) to (3) and the treatment of the halogenated hydrocarbon is absent, a highly active catalyst cannot be obtained (see Comparative Examples below). For example, compound (1)
The catalyst system consisting only of (2) and (2) is
Although the catalytic activity per transition metal described in the above publication is at a fairly high level, the activity per carrier is still insufficient. In addition, compound (1) and
A catalyst system consisting only of (3) is described in Japanese Patent Publication No. 47-41676, but its per-body activity is still insufficient, like the system consisting only of the above-mentioned compounds (1) and (2). In addition, a catalyst system consisting only of the above compounds (1) to (3) is described in JP-A-54-45696 and has high activity per transition metal and high activity per support, but it is still sufficient. do not have. The reason why a Ziegler catalyst with such high activity per transition metal and per support can be obtained using the catalyst component of the present invention is not necessarily clear, but by treating with a halogenated hydrocarbon, compound (1) ~
It is presumed that part of the reason for this is that excess titanium compounds are extracted from the contact product in (3). [] Detailed Description of the Invention The catalyst component according to the present invention comprises compound A and compound B.
It consists of a product obtained by treating the contact product with a halogenated hydrocarbon. 1 Component A Component A is a composition obtained by contacting compounds (1) and (2). (1) Compound (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o . Here, R ¹ is an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms), a cycloalkyl group (preferably an alkyl group having 4 to 10 carbon atoms),
in particular 5-8 cycloalkyl), or aryl (preferably phenyl, tolyl or xylyl). X is halogen, preferably chlorine. n is a number (not necessarily an integer) that satisfies 0<n<2. Specific examples of such magnesium compounds include dihalogenated magnesium, e.g.
MgF ₂ , MgCl ₂ , MgPr ₂ , MgI ₂ , halohydrocarbyloxymagnesium e.g. Mg(OC ₂ H ₅ )
Cl, Mg( _{OC6H5 )} Cl, and others. Mixtures of these are also suitable. Such a magnesium compound may be any compound that can be represented by the above formula. Therefore, for example,
A mixture of MgCl ₂ and Mg(OC ₂ H ₅ ) ₂ is also included in the magnesium compound (compound (1)) in the present invention. A particularly preferred magnesium compound in the present invention is MgCl ₂ (the amount of compound (1) to be used will be described later). (2) Compound (2) A titanium compound represented by the general formula Ti(OF ₂ ) ₄ . Here, R ² is an alkyl, aryl, or cycloalkyl having 1 to 10 carbon atoms that is the same as or different from R ¹ (preferred among these are
(same as described above for R ¹ ). A specific example of such a compound is Ti(O
-iC ₃ H ₇ ) ₄ , Ti(O-nC ₃ H ₇ ) ₄ , Ti(O-nC ₄ H ₉ ) ₄ , Ti(O-iC ₄ H ₉ ) ₄ , Ti(OC ₆ H ₅ ), etc. be. A preferred titanium compound is Ti(O—nC ₄ H ₉ ) ₄ (the amount of compound (2) to be used will be described later). (3) Contact between compounds (1) and (2) Contact between the two can be carried out in any manner as long as the effect is observed. Upon contact between the two, compound (1) dissolves or swells with compound (2),
There may be some kind of reaction between the two. Specifically, both are heated as is or in the presence of a suitable diluent at -50 to 200°C, especially 0 to 100°C,
The contact may be made for about 0.5 to 5 hours at a moderate temperature.
Stirring is preferably performed. In addition, compound (1) is
Preferably, it is dissolved or dispersed in compound (2) to form a substantially liquid substance. Types of compounds (1) and (2), type of diluent used,
Depending on the contact conditions, the contact product or reaction product may be obtained in the form of a solid. In such a case, the produced solid can be recovered and washed as appropriate, or further subjected to pulverization, heat treatment, or other post-treatment before being brought into contact with component B. Even when the contact product of compounds (1) and (2) is obtained as a solution, the contact product can be recovered as a solid by cooling, adding a precipitant, or the like. 2. Component B Component B that is brought into contact with component A as described above is a liquid titanium halogen compound (compound (3)). (1) Compound (3) Here, "liquid" refers to not only those that are liquid themselves (including those that are complexed and become liquid), but also those that are liquid as a solution. shall be included. A typical compound has the general formula Ti(OR ³ ) _4-o
X ¹ _o (here, R ³ is the same or different from R ¹ and R ² ,
Preferred are titanium compounds represented by an alkyl group or an aryl group having 1 to 10 carbon atoms, X ¹ is the same or different halogen as X, and n is a number satisfying 0<n≦4. Specific examples include TiCl ₄ , TiBr ₄ , Ti(O-nC ₄ H ₉ )Cl ₃ , Ti(O
-nC ₄ H ₉ ) ₂ Cl ₂ , Ti(O-nC ₄ H ₉ ) ₃ Cl, Ti(O-
iC ₃ H ₇ ) ₃ Cl, Ti(O-iC ₃ H ₇ )Cl ₃ , Ti(O-
iC ₃ H ₇ ) ₂ Cl ₂ , Ti(O-iC ₃ H ₇ ), Ti(O-
Examples include C ₆ H ₅ ) ₃ Cl and Ti(OC ₆ H ₅ ) ₂ Cl ₂ . Another typical example of this titanium compound is a molecular compound obtained by reacting TiX ¹ ₄ (herein, X ¹ represents a halogen) with an electron-donating compound. Specific _examples include _TiCl4・_CH3COC2H5 , _{TiCl4 ・}
CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄・C ₆ H ₅ NO ₂ , TiCl ₄・
CH ₃ COCl, TiCl ₄・C ⁶ H ₅ COCl, TiCl ₄・
Examples include C ₆ H ₅ CO ₂ C ₂ H ₅ and TiCl ₄ ClCO ₂ C ₂ H ₅ . Among the above molecular compounds (and titanium compounds), those that are normally solid can be used by dissolving them in an appropriate solvent (the amount of compound (3) to be used will be described later). 3 Contact between component A and component B When component A and component B are brought into contact, even if component A is a solution, if they are brought into contact with liquid component B, a solid will precipitate. It is thought that some kind of reaction is occurring between the two. The contact between the two can be carried out by any method used to bring a magnesium-containing compound to be a carrier into contact with a liquid titanium compound. Generally, both components may be brought into contact at a temperature range of -50°C to 200°C. Contact time is 0.5~
It takes about 5 hours. The contact between the two components is preferably carried out under stirring, and further complete contact between the two components can be achieved by mechanically pulverizing them using a ball mill, vibration mill, or the like. Contact of both components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons and halogen hydrocarbons. Specific examples of hydrocarbons include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane. Specific examples of halogenated hydrocarbons include chloride n
-Butyl, n-butyl bromide, n-butyl iodide,
n-octyl chloride, n-decyl chloride, chlorobenzene, iodobenzene, O-chlorotoluene, m
-Chlorotoluene, p-chlorotoluene, benzyl chloride, benzylidene chloride 1,2-dichloroethane, methylene dichloride, chloroform, carbon tetrachloride, hexachlorobenzene, etc. These may be used in combination within each group or between each group. 4 Usage amount of compounds (1) to (3) The amount ratio of compounds (1) to (3) or the amount ratio of components A and B is arbitrary as long as the effect of the present invention is recognized, but generally is preferably in the following range. (a) The amount of Ti(OR ² ) ₄ (compound (2)) used is Mg
(OR ¹ ) 0.1 molar ratio to _2-o X _o (compound (1))
It may be in the range of ~100, more preferably 0.05~
Within the range of 20. (b) The amount of liquid titanium halogen compound (compound (3)) used is 0.01 molar ratio to Mg (OR ¹ ) _2-o X _o .
It may range from ~100, more preferably 0.05
~20. 5 Treatment with halogenated hydrocarbon The present catalyst component is obtained by treating the contact product of component A and component B with a halogenated hydrocarbon. Any halogenated hydrocarbon can be used, but generally it is a saturated aliphatic or aromatic hydrocarbon containing at least one halogen atom and having 1 to 12 carbon atoms, usually in liquid form alone. good. Specific examples of halogenated hydrocarbons include chloride n
-Butyl, n-butyl bromide, n-butyl iodide,
n-octyl chloride, n-decyl chloride, chlorobenzene, iodobenzene, O-chlorotoluene, m
- Chlorotoluene, p-chlorotoluene, benzyl chloride, benzylidene chloride, 1,2-dichloroethane, methylene dichloride, chloroform, carbon tetrachloride, hexachlorobenzene, etc. Among these halogenated hydrocarbons, n-butyl chloride and 1,2-dichloroethane are particularly preferred. Generally, the processing conditions include temperatures between -50℃ and 200℃.
℃ range, and the time range is about 0.1 to 5 hours. These treatments are preferably carried out under stirring. The amount of halogenated hydrocarbon used is Mg
((OR ¹ ) _2-o X _o (molar ratio of 0.1 to compound (1)
1000, preferably within the range of 1 to 100. Treatment of halogenated hydrocarbons may be carried out in an inert solvent. In this case, aliphatic, alicyclic, or aromatic hydrocarbons are used as the inert solvent. Specifically, there are hexane, heptane, decane, hexadecane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and the like. 6 Polymerization of α-Olefin (1) Formation of Catalyst The catalyst component of the present invention can be used in the polymerization of α-olefin in combination with an organometallic compound as the other catalyst component or cocatalyst. As the organometallic compound used as a cocatalyst, any of the organometallic compounds of groups 1 to 10 of the periodic table, which are known as cocatalysts for Ziegler type catalysts, can be used. Organoaluminum compounds are preferred, and specific examples include those with the general formula R ⁴ _3-o AlX ² _o or R ⁵ _3-n Al
(OR ⁶ ) _n (Here, R ⁴ , R ⁵ and R ⁵ are hydrocarbon residues having 1 to 20 carbon atoms, which may be the same or different, X ² is a halogen atom, and especially chlorine atoms n and m are each 0n<2, 0m1). As such organoaluminum compounds,
Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethyl Examples include alkyl aluminum halides such as aluminum dichloride, and (iii) alkyl aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, and diethylaluminium phenoxide. These organoaluminum compounds (a) to (c) can be used in combination within each group and between the groups, and these organoaluminum compounds may be combined with other organometallic compounds, such as R _3-n Al (OR ⁶ ) _n
An alkyl aluminum alkoxide represented by (1<m<3) can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum monochloride, a combination of diethylaluminum monochloride and diethylaluminium ethoxide, a combination of diethylaluminum monochloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminum monochloride, and diethylaluminum ethoxide. For example, it can be used in combination with The amount of these organometallic compounds to be used is not particularly limited, but it is preferably within the range of 0.5 to 1000 in weight ratio to the solid catalyst component of the present invention. As already proposed by the present inventors in JP-A-51-82385, etc., in addition to the solid component and organoaluminum compound component of the present invention, the general formula Ti(OR ³ ) _4-o X ¹ _o (X is halogen, n is 0
It is also possible to use a small amount of a titanium compound (number of 4 to 4) in combination. By using a titanium compound having the general formula Ti(OR ³ ) _4-o X ¹ _o , it is possible to increase the catalytic activity and control the bulk density of the produced polymer. (2) α-olefin The α-olefin polymerized using the catalyst system of the present invention is
It is represented by the general formula R--CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms and may have a substituent). Specifically, for example, ethylene, propylene, butene-
1, pentene-1, hexene-1,4-methyl-
There are olefins such as pentene-1. Particularly preferred are ethylene and propylene. Mixtures of these α-olefins can be used, for example in the case of the polymerization of ethylene, copolymerization with up to 20 weight percent, preferably 10 weight percent, of the α-olefins, based on ethylene, can be carried out. Furthermore, copolymerization with copolymerizable monomers other than the above α-olefin (eg, vinyl acetate, diolefin) can also be carried out. (3) Polymerization The catalyst system of the present invention is applicable not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization or gas-phase polymerization, which does not use a substantial solvent, and to continuous polymerization. It is applicable to both formal polymerization and prepolymerization. Polymerization solvents for slurry polymerization include heptane, hexane,
Saturated aliphatic or aromatic hydrocarbons such as pentane, cyclohexane, benzene and toluene may be used alone or in mixtures. The polymerization temperature is from room temperature to about 200℃, preferably
The temperature is 50 to 150°C, and hydrogen can be used as a molecular weight regulator. 7 Experimental Examples Example 1 Production of solid catalyst component 25 ml of thoroughly degassed and purified n-heptane was placed in a 1000 ml flask that had been replaced with N ₂ , and then MgCl ₂
(Compound (1)) 0.05 mol, Ti(O-nC ₄ H ₉ ) ₄ (Compound
(2)) 0.1 mol were each fed, the temperature was raised to 70°C, and the mixture was stirred for 2 hours. Next, 0.9 mol of TiCl ₄ (compound (3)) was added and reacted at 70°C for 2 hours with stirring. The obtained solid was added with chloride n
-2.9 mol of butyl and 300 ml of n-heptane were fed, and the mixture was stirred at 50°C for 0.5 hour. Next, it was thoroughly washed with n-heptane to obtain a solid catalyst component. Polymerization of ethylene Into a 1.5 liter stainless steel autoclave equipped with stirring and temperature control equipment, after repeating vacuum-ethylene displacement several times, 800 ml of thoroughly dehydrated and deoxygenated n-heptane was introduced.
Next, 100 mg of triethylaluminum and 2.0 mg of the aforementioned solid catalyst component were introduced. The temperature was raised to 85° C., and 4.5 Kg/cm ² G of hydrogen and 4.5 Kg/cm ² G of ethylene were introduced to make the total pressure 9 Kg/cm ² G. Polymerization was carried out for 1.5 hours. These conditions were kept the same during the polymerization. However, the pressure, which decreases as the polymerization progresses, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged and the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 150 g of white polymer (PE) was obtained. This means that 75,000 g of polymer was obtained per 1 g of solid catalyst component [yield relative to catalyst (g PE/g solid catalyst component) = 75,000]. For this polymer, ASTM
Melt index (MI ₂ ) was measured at 190℃ and a load of 2.16Kg using the method of ―D1238-65T. _MI2 =
It was 3.1. The bulk density of the polymer is 0.36 (g/
cc). Comparative Example 1 Production of solid catalyst component In production of solid catalyst component of Example-1
Only compound (2) was reacted with compound (1) without reacting TiCl ₄ (compound (3)), and the resulting solid was treated with n-butyl chloride and washed with n-heptane to obtain a solid component. . Polymerization of ethylene Ethylene polymerization was carried out in exactly the same manner as in Example 1, except that the amount of solid component introduced was 50 mg. Only traces of polymer were obtained. Comparative Example 2 Production of solid catalyst component In the production of the solid catalyst component of Example-1,
Compound (3) alone is reacted with compound (1) without reacting Ti(O-nC ₄ H ₉ ) ₄ (compound (2)), and the resulting solid is treated with n-butyl chloride and then with n-heptane. Wash and
It was used as a solid catalyst component. Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Comparative Example-1. Only 4 g of polymer was obtained. The yield based on catalyst was 80. Comparative Example 3 Production of solid catalyst component In the production of the solid catalyst component in Example-1, the reaction products with compounds (1) to (3) were washed with n-heptane without treatment with n-butyl chloride. This was used as a solid component. Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Example-1. 68g of white polymer was obtained. Catalyst yield =
34,000, and MI ₂ =2.0. The bulk density of the polymer was 0.35 (g/cc). Examples 2 and 3 In the production of the solid catalyst component of Example-1, instead of the halogenated hydrocarbon n-butyl chloride,
The polymerization of ethylene was carried out in exactly the same manner except that chlorobenzene and 1,2-dichloroethane were used respectively. Display the results.
Shown in 1. Examples 4 and 5 In the production of the solid catalyst component of Example-1, instead of 0.1 mol of Ti(O-nC ₄ H ₉ ) ₄ in compound (2), Ti
Polymerization of ethylene was carried out in exactly the same manner except that 0.04 and 0.025 moles of (O-nC ₄ H ₉ ) were used. The results are shown in Table-1. Examples 6 and 7 Using the solid catalyst component produced in Example-1, diethylaluminum ethoxide (DEAE) and diethylaluminum chloride (DEAC) were used instead of triethylaluminum (TEA) as the organoaluminum compound component of the cocatalyst. Polymerization of ethylene was carried out in exactly the same manner, except that a mixture of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride was used. Table 2 shows the results.
Shown below.

【table】

[Table] Example 8 Polymerization was carried out in exactly the same manner as in Example 1 except that an ethylene-propylene mixed gas containing 2% by weight of propylene was used instead of ethylene. 160 g of white polymer was obtained. The yield based on the catalyst was 80,000, and the MI ₂ was 4.2. The bulk density of the polymer was 0.35 (g/cc). Example 9 In the production of the solid catalyst component of Example-1
Ethylene polymerization was carried out in exactly the same manner except that Ti(O-nC ₄ H ₉ )Cl ₃ was used instead of TiCl ₄ .
126 g of white polymer was obtained. Catalyst yield =
63000, and MI ₂ =2.8. The bulk density of the polymer was 0.35 (g/cc). Example 10 Ethylene polymerization was carried out in exactly the same manner as in Example 3, except that triethylaluminum was changed to 50 mg, Ti(O-nC ₄ DH ₉ ) ₄ was added to 20 mg, and the polymerization temperature was changed to 70°C. Summer. 145 g of white polymer was obtained. The polymer bulk density of the obtained polymer was measured and found to be 0.919 (g/cc). Example 11 In the production of the solid catalyst component of Example-1,
The same procedure was carried out except that 0.4 mol of TiCl ₄ .C ₆ H ₅ CO ₂ .C ₂ H ₅ was used instead of TiCl ₄ . 100mg of solid components produced, triethylaluminum 1144
and 30 mg of benzoic acid ester were introduced in the order of triethylaluminum, ethyl benzoate and the solid component. Raise the temperature to 60℃ and add 7% of propylene.
Kg/cm ² G was enclosed, and propylene polymerization was carried out for 1 hour. 164 g of white polymer was obtained. In addition, total II and product II are 68% by weight and
It was 80% by weight.

[Brief explanation of the drawing]

FIG. 1 is intended to help understand the technical content of the present invention regarding Ziegler catalysts.

Claims (1)

[Scope of Claims] 1. A catalyst component for olefin polymerization, which is obtained by treating a contact product of component A and component B below with a halogenated hydrocarbon. Component A Contains magnesium and titanium, and the following compounds
Contact products of (1) and (2). (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o (where R ¹ is alkyl, aryl, or cycloalkyl having 1 to 10 carbon atoms, 0<n2), (2) a titanium compound represented by the general formula Ti(OR ² ) ₄ (where R ² is the same or different number of carbon atoms as R ¹⁾ ,
~10 alkyl, aryl or cycloalkyl. ) Component B (3) Liquid titanium halogen compound.