JPH0149292B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for polymerizing or copolymerizing α-olefins with high activity and good stereoregularity using a novel catalyst. Catalysts comprising titanium halides and organoaluminum compounds have been known as highly stereoregular polymerization catalysts for α-olefins. However, in polymerization using this catalyst system, although a highly stereoregular polymer is obtained, the catalyst activity is low, so it is necessary to remove catalyst residues from the produced polymer. In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals
It has been shown that a highly active catalyst can be obtained by using a catalyst component in which titanium tetrachloride is supported on an inorganic solid support such as MgCl ₂ . However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of atactic moieties formed in the polymer be as small as possible. As a result of intensive research on these points, the present inventors discovered a novel catalyst here. That is, the present invention relates to a method for producing polyolefins with extremely high activity and high stereoregularity using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and Due to the short polymerization time, the amount of catalyst residue in the produced polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of attic moieties produced in the produced polymer is also extremely small. Effects can be obtained. The present invention will be explained in detail below. The present invention provides [] (1) Magnesium dihalide (hereinafter abbreviated as magnesium halide) (2) General formula

[Formula] (where R ¹ , R ² and R ³ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁴ represents a hydrocarbon residue having 1 to 24 carbon atoms.
n is 1≦n≦30) and (3) general formula

[Formula] (where R represents hydrogen, a halogen atom, or a hydrocarbon residue having 1 to 24 carbon atoms, and R' represents a hydrocarbon residue having 1 to 24 carbon atoms. r, p, and q are integers. Yes, 1≦r≦
3,0≦p<6,0≦q<6,1≦r+p+q<
It is 6. ) with the solid substance obtained by contacting the compound represented by (4) general formula Ti(OR) _n × _4-n (where R is 1 carbon number
-20 alkyl, aryl or aralkyl groups, and X represents a halogen atom. m is 0≦m
≦4. ) A solid catalyst component supporting a titanium compound (hereinafter abbreviated as a titanium compound) represented by [] an organoaluminum compound (hereinafter abbreviated as an organometallic compound), and [](5) General formula

[Formula] (where R ¹ , R ² , R ³ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁴ represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1 ≦n≦30) using a catalyst consisting of a combination of compounds represented by
- Perform polymerization or copolymerization of olefin,
The present invention relates to a method for producing polyolefins with extremely high activity and high stereoregularity. In the present invention, (1) magnesium halide,
(2) General formula

Compounds represented by [Formula] call (3) General formula

There is no particular restriction on the method of contacting the compound represented by the formula to obtain the solid substance of the present invention, and the method is performed at a temperature of 20°C to 400°C, preferably 50°C, in the presence or absence of an inert solvent.
The reaction may be carried out by contacting under heating at -300°C for usually 5 minutes to 20 hours, by co-pulverization, or by an appropriate combination of these methods. Furthermore, there is no particular restriction on the reaction order of components (1) to (3). The inert solvent is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene,
Examples include various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, alcohols such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate, ethers, and esters. can. Co-pulverization is usually carried out using equipment such as ball mills, vibration mills, rod mills, and impact mills, and is usually carried out at temperatures between 0°C and
At a temperature of 200℃, preferably from 20℃ to 100℃, from 0.5 to
It is recommended to do this for 30 hours. In the present invention, a method of obtaining a solid material by co-pulverizing components (1) to (3) is particularly preferably employed. In the present invention, component (1) magnesium halide and component (2) general formula

The usage ratio of the compound represented by [Formula] is component (1):component (2) in molar ratio.
is 1:0.001-10, preferably 1:0.01-1. Component (3) general formula

The usage ratio of the compound represented by [Formula] is component (1):component (3) in molar ratio.
is 1:0.001-10, preferably 1:0.01-1. A solid catalyst component [] is obtained by supporting a titanium compound on the solid support thus obtained. A known method can be used to support the titanium compound on the carrier. For example, solid loading can be carried out by contacting an excess titanium compound under heating in the presence or absence of a solvent, preferably by bringing both together in the presence of a solvent such as 1,2-dichloroethane. 50℃~300℃,
It is convenient to carry out heating, preferably at 80°C to 150°C. Although the reaction time is not particularly limited, it is usually within 5 minutes, and although it is not necessary, there is no problem in making the contact for a long time. For example 5
Treatment times can range from minutes to 10 hours, preferably from 1 to 4 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. The means for removing unreacted titanium compounds after the completion of the reaction is not particularly limited, and it is possible to wash the Ziegler catalyst several times with an inert solvent and evaporate the washing liquid under reduced pressure to obtain a solid powder. Another method is to co-pulverize the solid support and the required amount of the titanium compound. Co-grinding is usually from 0°C to 200°C, preferably from 20°C to
The catalyst components of the present invention can be produced by co-milling at a temperature of 100° C. for 0.5 to 30 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred. General formula used in the invention

[Formula] (Here, R ¹ , R ² , R ³ represent a hydrocarbon residue or alkoxy group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, and R ⁴ represents a carbon number of 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. 18 hydrocarbon residues (n is 1≦n≦30). n-butoxysilane, monomethyltrisec-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonoethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyltrif Enoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoisopropyltrimethoxysilane, mono n-butyltrimethoxysilane, mono n
-butyltriethoxysilane, monosec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, tetraethoxysilane, tetraisopropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, Allyltriethoxysilane, vinyltriphenoxysilane, vinylethoxydiphenoxysilane, allyltriphenoxysilane, allylethoxydiphenoxysilane, and the repeating unit obtained by condensing the above compounds.

Examples include chain or cyclic polysiloxanes represented by the formula:
It is also possible to use a mixture of these. Among these compounds, component (2) is preferably one in which at least one substituent has an olefinic hydrocarbon group, such as vinyltrimethoxysilane,
Particularly preferred are vinyltriethoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and allyltriphenoxysilane. As component (5), at least one substituent preferably has an aromatic hydrocarbon group, and monophenyltrimethoxysilane and monophenyltriethoxysilane are particularly preferred. General formula used in the invention

[Formula] (where R is hydrogen, halogen atom, or carbon number 1
~24, preferably 1 to 18 hydrocarbon residues;
R' represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. r, p and q are integers, 1
≦r≦3, 0≦p≦6, 0≦q≦6, 1≦r+p
+q<6. ) as a compound represented by
Phenol, 1-naphthol, 2-naphthol,
2-Fuenance roll, 3-Fuenance roll,
Anthranol, methylphenol, ethylphenol, isopropylphenol, dimethylphenol, diethylphenol, dibutylphenol, trimethylphenol, triethylphenol, 2-chlorophenol, 3-bromophenol, 4-chlorophenol, 2,6-dichlorophenol, dichlorophenol, -t-butyl-p-cresol, 2
-Cyclohexylphenol, 2-allylphenol, 3-oxystyrene isopropenylphenol, catechol, hydroquinone, 2,6-dihydroxytoluene, vinylcatechol, pyrogallol, methoxyphenol, 2-isopropoxyphenol and the like. Among these compounds, phenol and 1-naphthol are particularly preferred. The titanium compound used in the present invention has the general formula _Ti (OR) _o n is 0≦n≦4), titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxy Titanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dichlorotitanium butoxydichlorotitanium,
Examples include monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. In the present invention, the amount of the titanium compound used is not particularly limited, but the amount of the titanium compound contained in the solid product is usually 0.5 to 20% by weight, preferably 1% by weight.
It is preferable to adjust the amount to 10% by weight. As the organometallic compound used in the present invention, an organoaluminum compound known as a component of Ziegler's catalyst is used. Specific examples include the general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
(OR) Organoaluminum compound _{of X and R 3 Al 2} are preferred, and triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-
butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride,
Examples include diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. In the present invention, the organometallic compound and component (5) general formula The proportion of the compound represented by the general formula of component (5) per mol of the organometallic compound is The compound represented by is usually used in an amount of 0.001 to 5 mol, preferably 0.01 to 2 mol. Component (5) general formula The usage amount of the compound represented by is such that the Si:Ti ratio is 0.1 to 100:1 to the titanium compound in the catalyst component [].
The range is preferably 0.3 to 20:1, and more preferably 0.3 to 20:1. In addition, in the present invention, organometallic compounds and components
(5) General formula A compound represented by can also be used as a reactant. In that case, the reaction ratio is the general formula of component (5) per mole of organometallic compound. The compound represented by is usually used in an amount of 0.001 to 5 mol, preferably 0.01 to 2 mol. Organometallic compounds and components (5) General formula The amount of the product obtained by reacting with the compound represented by is such that the Si:Ti ratio is 0.1 to 100:1, preferably 0.1 to 100:1 with respect to the titanium compound in the catalyst component [].
It ranges from 0.3 to 20:1. Organometallic compounds and components (5) General formula There are no particular limitations on the method for obtaining the reaction product with the compound represented by, and the method is not particularly limited.
There is also a method in which the reaction is carried out by contacting at a temperature of 5 minutes to 20 hours. In the present invention, the amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound. The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. In other words, all reactions take place in the gas phase, in a state where oxygen, water, etc. are essentially excluded.
Alternatively, it is carried out in the presence of an inert solvent or using the monomer itself as a solvent. The polymerization conditions for olefins include a temperature of 20°C to 300°C, preferably 40°C to 40°C.
The temperature is 180℃, the pressure is normal pressure to 70Kg/ ^cm2・G,
Preferably it is 2Kg/cm ² ·G to 60Kg/cm ² ·G. Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. The method of the present invention is applicable to the polymerization of all α-olefins that can be polymerized with Ziegler's catalyst, such as the homopolymerization of α-olefins such as propylene, butene-1, and 4-methylpentene-1, and the polymerization of ethylene, propylene, and α-olefins. It is suitably used for random and block copolymerization of α-olefins and other olefins. Copolymerization of α-olefin and diene is also preferably carried out for the purpose of modifying polyolefin. In the present invention, it can be particularly effectively used to polymerize or copolymerize α-olefins having 3 to 8 carbon atoms with good stereoregularity. Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto. Example 1 (a) Production of solid catalyst component [] 10 g (105 mmol) of anhydrous magnesium chloride and 1.52 g (8 mmol) of vinyltriethoxysilane,
1.51 g (16 mmol) of phenol was placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls, and ball milling was performed at room temperature under a nitrogen atmosphere for 24 hours. 6 g of the obtained solid powder, 30 ml of titanium tetrachloride and 30 ml of 1,2-dichloroethane were placed in a 200 ml round bottom flask and stirred at 80° C. for 2 hours under a nitrogen atmosphere. Then, after removing excess titanium tetrachloride, unreacted titanium tetrachloride washed with hexane was removed. Thereafter, it was dried under reduced pressure to obtain a solid catalyst component. Obtained solid catalyst component [] 1g
contained 25 mg of titanium. (b) Polymerization The stainless steel autoclave equipped with an induction stirrer in step 3 was purged with nitrogen, 1500 ml of hexane was added, 2.5 mmol of triethylaluminum, 1.4 mmol of phenyltriethoxysilane and 20 mg of the above solid catalyst component were added, and then hydrogen was added. was charged so that the gas phase partial pressure was 0.05 Kg/cm ² , and the temperature was raised to 50° C. while stirring. The vapor pressure of hexane brought the system to 0.5 kg/cm ² ·G, and then propylene was charged until the total pressure reached 7 kg/cm ² ·G to initiate polymerization. Propylene was continuously introduced so that the total pressure was 7 kg/cm ² ·G, and polymerization was carried out for 2 hours. After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried to obtain 220 g of white polypropylene. This is the total amount of the product, including the amorphous material. The catalyst activity was 850 g polypropylene/g solids.hr.C ₃ H ₆ pressure, and 34 kg polypropylene/g Ti.hr.C ₃ H ₆ pressure. The total extraction residue (total) with boiling n-heptane, including the solvent-soluble polymer, was 97.6 wt%, and the melt flow index (MFI) was 8.1. Catalytic activity compared to Comparative Example 1 and Comparative Example 2,
Everything was expensive. Comparative Example 1 In Example 1, a solid catalyst component was synthesized in the same manner as in Example 1, except that vinyltriethoxysilane was not used, and polymerization was carried out in the same manner as in Example 1, resulting in polypropylene. is 151
g was obtained. Catalytic activity is 580g polypropylene/
g solid/hr/C ₃ H ₆ pressure. Total is 80.4wt%
The MFI was 8.3. Comparative Example 2 In Example 1, a solid catalyst component was synthesized in the same manner as in Example 1, except that phenol was not used, and polymerization was carried out in the same manner as in Example 1. 16 g of polypropylene was obtained. It was done. Catalytic activity is 60g polypropylene/g solid・hr・C ₃ H ₆
It was hot under pressure. The total content was 87.0wt% and the MFI was 7.5. Examples 2 to 10 Solid catalyst components were synthesized in the same manner as in Example 1 using the various compounds shown in Table 1, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1. The stainless steel autoclave equipped with an induction stirrer from Example 11 3 was purged with nitrogen, 1500 ml of hexane was added, 2.5 mmol of triethylaluminum and 1.4 mmol of phenyltriethoxysilane were added, the temperature was raised to 80°C with stirring, and the reaction was carried out for 30 minutes. I let it happen.
After that, it was cooled to room temperature and 20 mg of the catalyst of Example 2 was added.
Furthermore, hydrogen was charged so that the gas phase partial pressure was 0.05 Kg/cm ² , and the temperature was raised to 50° C. with stirring. The vapor pressure of hexane was 0.5 kg/cm ² ·G in the system, but propylene was charged until the total pressure reached 7 kg/cm ² ·G to initiate polymerization. The following steps were carried out in the same manner as in Example 1. 228 g of polypropylene was obtained. Catalytic activity is
877g polypropylene/g solids・hr・C ₃ H ₆ pressure,
The pressure was 38.1Kg polypropylene/gTi・hr・C ₃ H ₆ pressure. The total content was 96.2wt%, and the MFI was 8.1.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1 [] (1) Magnesium dihalide, (2) General formula (Here, R ¹ , R ² , R ³ represent a hydrocarbon residue or an alkoxy group having 1 to 24 carbon atoms, and R ₄
represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦30), and (3) a compound represented by the general formula (Here, R represents hydrogen, a halogen atom, or a hydrocarbon residue having 1 to 24 carbon atoms, and R' represents a hydrocarbon residue having 1 to 24 carbon atoms. r, p, and q are integers, and 1 ≦r≦3, 0≦p<
6,0≦q<6,1≦r+p+q<6. ) with the solid substance obtained by contacting the compound represented by (4) general formula Ti(OR) _n X _4-n (where R is 1 carbon number
-20 alkyl, aryl or aralkyl groups, and X represents a halogen atom. m
is 0≦m≦4), [] an organoaluminum compound, and [] (5) General formula (Here, R ¹ , R ² , R ³ represent a hydrocarbon residue or an alkoxy group having 1 to 24 carbon atoms, and R ⁴
represents a hydrocarbon residue having 1 to 24 carbon atoms. 1. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an α-olefin using a catalyst system comprising a combination of compounds represented by n=1≦n≦30.