JPS6334165B2 - - Google Patents

Description

[Detailed description of the invention]

[] Background of the Invention The present invention relates to a transition metal component of a so-called Ziegler type catalyst. In another aspect, 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, resulting in poor 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 these reasons, highly active catalysts are desired, but improvement in catalytic activity seems to be primarily aimed at improving the transition metal components, and one such improvement is the use of magnesium compounds as carriers. There is something. However, although catalysts containing magnesium compounds as carriers and titanium trichloride, titanium tetrachloride, etc. as transition metal components have been significant in terms of high activity per transition metal, the activity per carrier is still insufficient. There are many things.
The catalyst activity is preferably high not only per transition metal but also per support. As one such supported catalyst, one has been proposed that consists of a component made by blending a transition metal compound with a halide of a Group 2 element of the periodic table containing water or alcohol, and an organometallic compound component ( (See Special Publication No. 34092). This known catalyst is useful in that it has increased activity per carrier. However, the activity per carrier is at a level that the present inventors believe is not sufficient. The present inventors have also proposed a supported transition metal catalyst component prepared in a specific manner (Japanese Patent Application Laid-open No.
No. 4295, No. 54-40293 and No. 54-45696). SUMMARY OF THE INVENTION The purpose of the present invention is to solve the above-mentioned problems and obtain a highly active catalyst, and to achieve this purpose by using a supported transition metal catalyst component prepared in a specific manner. . Therefore, the olefin polymerization catalyst component according to the present invention is characterized by being a contact product of component A and component B described below. Component A Contains magnesium and titanium, and the following compounds
A contact product of (1), (2) and (3), in which the contact produces a compound after contacting compound (1) with compound (2).
A solid composition obtained by contacting (3) with (2) and (3) without substantially dissolving compound (1) in (2) and (3) during this contact. (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,
(2) A titanium compound represented by the general formula Ti(OR ² ) ₄ (where R ₂ is a carbon 1-10 that is the same as or different from R ¹
alkyl, aryl or cycloalkyl). (3) Electron-donating compound component B (4) Effect of liquid titanium halogen compound When α-olefin is polymerized using the solid catalyst component according to the present invention as the transition metal component of a Ziegler catalyst, it is more effective than the above-mentioned known catalyst. Both the amount of polymer produced per transition metal and the amount of polymer produced per carrier are high. The reason why a Ziegler catalyst with such high activity per transition metal and per carrier can be obtained using the catalyst component of the present invention is not necessarily clear, but unlike the case of the above-mentioned known catalyst, compound (2) is more active than compound (1). It is presumed that part of the reason lies in the fact that it plays an important role in activation. In addition, although the above-mentioned catalysts already proposed by the present inventors have a considerably high level of activity, the basic units of each component during the production of the catalyst are not necessarily good, and the production cost tends to increase in industrial production. However, in the present invention, this manufacturing cost problem is also solved. [] Detailed description of the invention The catalyst component according to the invention consists of a contact product of component A and component B. 1 Component A (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 carbon number 1
~10 alkyl, preferably of 1 to 4 carbon atoms, or cycloalkyl, preferably of 4 to 10 carbon atoms, especially 5 to 8 carbon atoms, or aryl, preferably phenyl, tolyl or xylyl . X is halogen, preferably chlorine. n is a number (not necessarily an integer) that satisfies 0<n2. Specific examples of such magnesium compounds include magnesium dihalides, such as MgF ₂ , MgCl ₂ , MgBr ₂ , MgI ₂ , halohydrocarbyloxymagnesium, etc.
Mg(OC ₂ H ₅ )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 (component (1)) referred to in the present invention. Particularly preferred 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(OR ² ) ₄ . Here, R ₂ is an alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms, which is the same as or different from R ¹ (the preferred ones among these are the same as those described above for R ¹ ). Specific examples of such compounds include:
Ti(O-iC ₃ H ₄ ) ₄ , Ti(O-nC ₃ H ₄ ) ₄ , Ti(O
-nC ₄ H ₉ ) ₄ , Ti(O-iC ₄ H ₉ ) ₄ , Ti(OC ₆ H ₅ ) ₄
etc. (the amount of compound (2) used is described later). (3) Compound (3) is an electron-donating compound. Any compound known as an electron donating compound can be used in the present invention, but generally water, alcohols,
These include phenols, ethers, ketones, aldehydes, carboxylic acids, esters, nitriles, and silanols. Specifically, for example, there are the following. (a) Alcohols: approximately 1 to 20 carbon atoms, preferably 2 to 4 carbon atoms
Monohydric or polyhydric alcohols (up to about tetrahydric), especially monohydric alcohols, are suitable. Examples include methanol, ethanol, isopropanol, n-butanol, hexanol, octanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoacetate, and others. (b) Phenols: about 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms
phenols, especially dihydric phenols, are suitable. Specifically, examples include phenol, cresol, xylenol, naphthol, cumylphenol, butylphenols, and others (the amount used will be described later). (c) Ethers Mono- or tetraethers having a total carbon number of about 2 to 20, such as diethyl ether,
Dibutyether, dihexyl ether, dioctyl ether, didedyl ether, tetrahydrofuran, dioxane, trioxane, ethylene glycol monomethyl ether (mentioned above), and others. (iv) Chthones Ketones having a total carbon number of about 3 to 20, such as acetone, methyl ethyl ketone, and others. (e) Aldehydes Aldehydes having about 1 to 10 carbon atoms, such as acetaldehyde, propionaldehyde, benzaldehyde, and others. (F) Carboxylic acids Mono- or tetracarboxylic acids having about 1 to 20 carbon atoms, such as acetic acid, poropion, valeric acid, benzoic acid, phthalic acid, and others. (g) Esters Esters of the above alcohols and carboxylic acids, especially aromatic carboxylic acid esters,
For example, methyl acetate, methyl acrylate,
Methyl methacrylate, methyl benzoate, ethyl benzoate, mono- or dibutyl phthalate, and others. (H) Nitriles Mono- to dinitrile having about 1 to 20 carbon atoms, such as acetonitrile, acrylonitrile, benzonitrile, and others. (li) Silanols Silanols having about 1 to 20 carbon atoms in total, such as trimethylsilanol, dimethylsilanediol, phenylsilanetriol, and others. (iii) Water Among these electron-donating compounds, water, alcohols, phenols, or silanols are preferable (compound (3)
The amount used is described later). (4) Contacting Compounds (1) to (3) Contacting these compounds brings together Compound (1) and Compound (2) without substantially dissolving Compound (1) in (2) and (3). After the contact, the compound (3) is brought into contact. Compound (1) is formed by contacting these compounds.
is partially dissolved or swollen by compounds (2) and (3), and there is a possibility that some kind of reaction occurs between these compounds. Specific contact conditions include using these compounds as they are or in the presence of an appropriate diluent.
-50~200℃, especially 0~100℃,
The contact may be made for about 0.5 to 5 hours. Preferably, the contact is carried out by stirring or grinding. Compound (1) may be partially dissolved in compounds (2) and (3) by this contact, but should be present in a substantially solid state. Depending on the types and quantitative ratios of compounds (1), (2) and (3), the type of diluent used, and contact conditions,
The contact products or reactive components may be in complete solution. In the present invention, in order to avoid such a situation, the quantitative ratio is determined so that the contact product is obtained in the form of a solid. The resulting solid may be further subjected to grinding, heat treatment, or other post-treatment before being brought into contact with component B. 2. Component B Raw component B, which is brought into contact with component A as described above to produce the catalyst component of the present invention, is a liquid titanium halogen compound. Here, "liquid" means
In addition to those that are liquid themselves (including those that are complexed to become liquid), they include those that are liquid as a solution. A typical compound has the general formula Ti(OR ³ ) _4-
o ^_ _{_} ^{_ _ _} indicates the number of 0<n4). 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 ) ₂ Cl ₂ , Ti(O-iC ₃ H ₇ ) ₃ Cl, Ti(O-
C ₆ H ₅ ) Cl ₃ , Ti(O—CH ₆ H ₅ ) ₂ Cl ₂ and the like. Another representative example of this titanium compound is _TiX′4
(Here, X' represents halogen) is a molecular compound in which a so-called electron donor is reacted. 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・
C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・C ₆ H ₅ NH ₂ , TiCl ₄・
Examples include ClCO ₂ C ₂ H ₅ . Among the above-mentioned molecular compounds (and titanium compounds), those in a solid state can be used by dissolving them in an appropriate solvent. 3. Contact between Component A and Component B The catalyst component of the present invention is obtained by contacting Component A and Component B as described above. The contact between the two can be carried out by any method that can be used to bring the magnesium-containing solid carrier and the liquid titanium compound into contact. Generally, both components may be brought into contact at a temperature range of -50°C to 200°C. The contact time is
Usually it takes about 10 minutes to 5 hours. The contact between the two is
It is preferable to carry out the process with stirring, and further complete contact between the two components can be achieved by mechanically grinding with 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, halogenated hydrocarbons, dimethylpolysiloxane, and the like. Specific examples of hydrocarbons include hexane, heptane, benzene, toluene, and cyclohexane, and specific examples of halogenated hydrocarbons include n-butyl chloride, n-butyl bromide, n-butyl iodide, chlorobenzene, and chloride. Examples include n-octyl, n-butyl chloride, chloroform, carbon tetrachloride, O-chlorotoluene, m-chlorotoluene, p-chlorotoluene, benzyl chloride, benzylidene chloride, iodobenzene, and the like. These can be mixed and used within each group or between each group. 4. Quantization The amount of each compound or component to be used may be any amount as long as the effect of the present invention is observed, but it is generally preferred to be within the following range. (a) The amount of Ti (OR ² ) ₄ (compound (2)) used is Mg
The _molar ratio (compound ( ₂ )/compound ⁽ 1)) to (OR 1 ) 2 ^- o Within the range less than 1.0. (b) The amount of electron donating compound used is Mg (OR ¹ ) _2-o
X _o (1×10 ^-3 to 5 in molar ratio to compound (1)
may be within the range of , more preferably 0.1 to 1.5
is within the range of (c) The amount of the liquid titanium halogen compound (component B) to be used is preferably within the range of 0.1 to 100 in molar ratio to Mg(OR ¹ ) _2-o X _o (compound (1)), and more preferably is within the range of 0.5 to 20. 5. 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 that is the other catalyst component or cocatalyst of the Ziegler type catalyst. . 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. In particular, any organoaluminum compound can be used. Organoaluminum compounds are preferred, and specific examples thereof include the general formula R ⁴ _3-o AlX″ _o or
R ⁵ _33-n Al(OR ⁶ ) _n (where R ⁴ , R ⁵ and R ⁶ are hydrocarbon residues having 1 to 20 carbon atoms which may be the same or different, X″ is a halogen atom, n and m
are the numbers 0n2 and 0m1, respectively). Specifically, such organic aluminum compounds include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, and tridecylaluminum, and (b) diethylaluminum monochloride, diisobutylaluminum. Alkyl aluminum halides such as monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c)
Examples include alkyl aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, and diethylaluminium phenoxide. These (a)~
The organoaluminum compounds (c) can be used in combination within each group and between each group, and in addition to these organoaluminum compounds, other organometallic compounds, such as R ⁵ _3-n Al(OR ⁶ ) _n (1< m
An alkyl aluminum alkoxide represented by 3) can also be used in combination. For example, a combination of triethylaluminum and diethylaluminium monochloride, a combination of diethylaluminium monochloride and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and ethylaluminum diethoxide, a combination of triethylaluminum and diethylaluminum monochloride and diethylaluminium. Can be used in combination with ethoxide. 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. In addition, the present inventors have already published JP-A-51-82385
As proposed by et al _. , a tetravalent titanium compound represented by ^the general formula Ti(OR ⁷ ) _o is a halogen atom, and n is an integer of 0 to 4.As the hydrocarbon residue, alkyl groups and aryl groups having 1 to 8 carbon atoms can generally be used, but lower groups having 3 to 4 carbon atoms are preferably used. It is also possible to use them together (preferably those derived from alcohol). Specific examples of the tetravalent titanium compound include titanium tetrachloride, titanium tetrabromide, ethyl titanate, isopropyl titanate, butyl titanate, phenyl titanate, diethoxydichlorotitanium, and dibutoxydichlorotitanium. By using this tetravalent titanium compound, the catalyst activity can be increased and the density of the produced polymer can be controlled. (2) α-Olefin The α-olefin polymerized using the catalyst system of the present invention has the general formula R-CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, may have a substituent). Specifically, for example, ethylene, propylene, butene-1, pentene-
1, hexene-1,4-methyl-pentene-
There are olefins such as 1. Particularly preferred are ethylene and propylene. Mixtures of these α-olefins can also be used, for example in the case of ethylene polymerization, copolymerization with up to 20 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 can be applied not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization or gas-phase polymerization, which uses substantially no solvent, as well as continuous polymerization. It is applicable to both formal polymerization and prepolymerization. Polymerization solvents for slurry polymerization include hexane, pentane, cyclohexane,
Saturated aliphatic or aromatic hydrocarbons such as benzene and toluene may be used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 50°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time. 6 Experimental Examples Example 1 Manufacture of catalyst components Into a 500 ml flask that had been replaced with _N2 , put 100 ml of thoroughly degassed n-heptane, and then add MgCl ₂
(1) 0.05 mol, Ti(O-nC ₄ H ₉ ) ₄ (2) 0.014 mol, and further introduced 0.04 mol of n-C ₄ H ₉ OH(3), and raised the temperature to 70°C. , and stirred for 1 hour.
Although MgCl ₂ was slightly refined, it was not completely dissolved (manufacturing of component A). Next, 0.8 mol of TiCl ₄ (component B) was introduced,
Stirred for 1 hour. The obtained solid was thoroughly washed with n-heptane and used as a catalyst component. The Ti content in the catalyst component was measured by colorimetric method and was found to be 7.8% by weight. 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. 100 mg of triethylaluminum and 2.0 mg of the catalyst component synthesized above were introduced. The temperature was raised to 85℃, hydrogen was introduced at a partial pressure of 4.5Kg/ ^cm2 , and ethylene was introduced at a partial pressure of 4.5Kg/ ^cm2 , resulting in a total pressure of 9Kg/cm2.
cm ² G. Polymerization was carried out for 15 hours. These were kept under the same conditions 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, the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 158 g of white polymer was obtained. This means that 79,000 polymers (PE) were obtained per 1 g of catalyst component [yield to catalyst (g PE/g solid catalyst) =
79000〕. The melt index (MI ₂ ) of this polymer was measured at 190° C. under a load of 2.16 kg by the method of ASTM-D1238-65T. MI ₂ = 2.2.
The bulk specific gravity of the polymer was 0.32 (g/cc). Examples 2 to 8 Catalyst components were produced in exactly the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of n-C ₄ H ₉ OH. Ethylene polymerization was carried out under exactly the same conditions as in Example 1. The results are shown in Table-1.
The amounts of _MgCl2 and _TiCl4 used are 0.05 mol and 0.8 mol, respectively.

【table】

[Table] Example 9 In the production of the catalyst component of Example-2, Ti(O
- Using Ti(O-iC ₃ H ₇ ) ₄ instead of nC ₄ H ₉ ) ₄ ,
The polymerization of ethylene was carried out in exactly the same manner except that TiCl ₃ (O-nC ₄ H ₉ ) was used instead of TiCl ₄ . 136 g of polymer was obtained, with a catalyst yield of 68,000. MI ₂ =2.1 Polymer bulk specific gravity = 0.31 (g/cc). Examples 10 to 11 Ethylene was produced in exactly the same manner except that the catalyst component produced in Example 1 was used, and the organoaluminum compound components shown in Table 2 below were used in place of triethylaluminum under the ethylene polymerization conditions. Polymerization was carried out. The results are shown in Table-2.

[Table] Example 12 Polymerization was carried out in exactly the same manner except that the catalyst component prepared in Example 2 was used and an ethylene-propylene mixed gas containing 2% by weight of propylene was used instead of ethylene. 156 g of polymer was obtained. The yield based on the catalyst was 78,000, the MI ₂ was 3.6, and the bulk specific gravity of the polymer was 0.31 (g/cc). Example 13 The same procedure was used except that the catalyst component produced in Example 2 was used, an ethylene-butene mixed gas containing 10% by weight of butene was used instead of ethylene, and the polymerization temperature was lowered to 65°C. Polymerization was carried out. 112g
of polymer was obtained. Yield to catalyst = 56000, MI ₂ = 1.8, polymer bulk specific gravity = 0.33
(g/cc). Example 14 In the production of the catalyst component of Example-3, 100 ml of chlorobenzene was used instead of n-heptane,
The catalyst component was produced in exactly the same manner except that 0.4 mol of TiCl ₄ .C ₆ H ₅ CO ₂ C ₂ H ₅ was used instead of TiCl ₄ . 100 mg of this catalyst component, 114 mg of triethylaluminum, and 30 mg of ethyl benzoate were each introduced, and propylene polymerization was carried out at 60° C. and 7 kg/cm ² G for 1 hour. 163g of polymer was obtained. In addition, total II and product II are 69% by weight and 80% by weight. Comparative Examples 1 to 3 The catalyst components of Examples-1, -2, and -4 were produced in exactly the same manner except that Ti(O-nC ₄ H ₉ ) ₄ was not used, and the solid catalyst components were introduced. Ethylene polymerization was carried out in exactly the same manner except that the amounts were changed to 5 mg each. The results are shown in Table-3.

[Table] Example 15 In the polymerization of ethylene in Example-2, triethylaluminum was changed to 50 mg, and Ti(O-
Ethylene polymerization was carried out in exactly the same manner except that 20 mg of nC ₄ H ₉ ) ₄ was added and the polymerization temperature was changed to 70°C.
186 g of white polymer was obtained. The density of the obtained polymer was measured and found to be 0.918 (g/cc). Example 16 The catalyst component of Example _{1 was produced except that a mixture of MgCl 2 and} Mg(OC ₂ H ₅ ) ₂ (weight ratio 1:1, pulverized product for 24 hours in a ball mill) was used instead of MgCl 2. The polymerization of ethylene was carried out in the same manner. The Ti content in the catalyst component is 8.1
It was expressed as a weight percent. 146 g of white polymer was obtained, yield on catalyst = 73000, _MI2 = 2.1. The bulk specific gravity of the polymer was 0.31 (g/cc).

[Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] 1. A catalyst component for olefin polymerization, which is a contact product of component A and component B below. Component A Contains magnesium and titanium, and the following compounds
A contact product of (1), (2) and (3), which after this contact brings compound (1) and compound (2) into contact,
A solid composition obtained by contacting (3) with (2) and (3) without substantially dissolving compound (1) in (2) and (3) during this contact. (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,
(2) A titanium compound represented by the general formula Ti(OR ² ) ₄ (where R ² is the same as or different from R ¹ and has a carbon number of 1 to
10 alkyl, aryl, or cycloalkyl), (3) Electron-donating compound component B (4) Liquid titanium halogen compound