JPS6337802B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyalpha-olefins having a high degree of stereoregularity in the presence of a highly active catalyst consisting of a specific activated titanium compound, an organoaluminum compound, and an electron-donating compound. Since a method was proposed for polymerizing α-olefins in high yield per transition metal using a catalyst system consisting of a solid catalyst supporting a transition metal halide on a carrier such as magnesium halide, an organoaluminium compound, and an electron donor. (Japanese Patent Publication No. 39-12105), many improved methods have been developed, and methods are known that provide poly-α-olefins with high yield and stereoregularity per catalyst. The present inventors previously discovered that (A) an activated titanium compound obtained by contacting a product obtained by co-pulverizing a magnesium halide, an orthocarboxylic acid ester, and a halogenated hydrocarbon with a titanium halide; It was discovered that a catalyst system consisting of B) an organoaluminum compound and (C) an electron-donating compound gives a poly-α-olefin with extremely high yield per catalyst and highly stereoregularity. July
The application was filed on the 11th. However, even with the polymer obtained using this catalyst, it is difficult to use it in applications requiring high stereoregularity, such as in films, without completely removing the atactic polymer. The object of the present invention is to provide a method for producing poly-α-olefins with higher stereoregularity and higher yield per catalyst. The present invention provides a method for stereoregular polymerization of α-olefins using a catalyst system consisting of a supported titanium catalyst component, an organoaluminium compound, and a compound containing a C-N or C-O bond, as the supported titanium catalyst component, (a) Magnesium halide, (b) General formula X ¹ C (OR ¹ ) ₃ (wherein, R ¹ is a hydrocarbon residue having 1 to 12 carbon atoms ^,
indicates hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms)
Using an activated titanium compound obtained by co-pulverizing an orthocarboxylic acid ester represented by (c) a halogenated hydrocarbon and (d) an alcohol having 1 to 20 carbon atoms and then contacting it with a titanium halide. It is characterized by: Thus, the feature of the present invention is that, by coexisting an orthocarboxylic acid ester, a halogenated hydrocarbon, and an alcohol during co-pulverization for producing an activated titanium catalyst component, effects that cannot be obtained by each alone can be achieved. be. The orthocarboxylic acid ester used ^{as a} raw material for _producing the activated titanium catalyst component in the present invention has ^the general formula ^: Hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms), specifically HC
( _{OC2H5 ) 3} , _CH3C ( _{OC2H5 ) 3 , C2H5C} ( _{OC2H5 ) 3} ,
C ₃ H ₇ C (OC ₂ H ₅ ) ₃ , C ₆ H ₅ C (OCH ₃ ) ₃ , C ₆ H ₅ C
(OC ₂ H ₅ ) ₃ , p-CH ₃ C ₆ H ₅ C (OCH ₃ ) ₃ , C ₁₀ H ₇ C
(OCH ₃ ) ₃ etc. are exemplified. In addition, halogenated hydrocarbons include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons in which hydrogen is substituted with a halogen atom, and particularly hydrogen in hydrocarbons having 1 to 20 carbon atoms. 1 to 10
It is preferable that each of these atoms be substituted with a halogen atom.
Specifically, 1,1-dichloroethane, 1,2-
Dichloroethane, 1,4-dichlorobutane, carbon tetrachloride, carbon tetrabromide, tetrabromoethane, perchlorethylene, α,α-dichlorotoluene,
α, α, α-Trichlorotoluene, α, α, α,
4-tetrachlorotoluene, α, α, α, α′,
Examples include α', α'-hexachloroxylene. Furthermore, the magnesium halide used as a carrier is preferably substantially anhydrous magnesium halide, particularly magnesium chloride. In addition, the alcohol coexisting during co-grinding is a compound containing at least one OH group having 1 to 20 carbon atoms, and one of aliphatic, alicyclic, and aromatic groups.
or polyhydric alcohols are used. Specific examples include methanol, ethanol,
Propanol, butanol, hexanol, ethylene glycol, cyclohexyl alcohol, phenol, cresol, etc. are used. Active titanium component of the present invention (hereinafter referred to as component A)
The adjustment method will be explained below. First, a mixed product consisting of (a) magnesium halide, (b) orthocarboxylic acid ester, (c) halogenated hydrocarbon, and (d) alcohol is prepared. This adjustment method is a method of co-pulverizing the above four components. This pulverization is performed using a pulverizer such as a ball mill or a vibration mill. The grinding operation is carried out in a vacuum or in an inert gas atmosphere and must be carried out in the substantial absence of oxygen and moisture. There are no particular restrictions on the pulverization conditions, but the temperature is generally in the range of 0°C to 80°C, and the pulverization time varies depending on the type of pulverizer, but is usually about 2 to 100 hours. The usage ratio of (b) orthocarboxylic acid ester and (a) magnesium halide during pulverization is not particularly limited, but preferably per mole of (a) magnesium halide.
The amount ratio of (c) halogenated hydrocarbon to (a) magnesium halide is not particularly limited, but (a) magnesium halide 1
0.01 to 0.20 mole per mole. Furthermore, the quantitative ratio of (d) alcohol to (a) magnesium halide is not particularly limited, but is preferably 0.01 to 0.20 mol. Next, a mixed product prepared by co-pulverization from (a) magnesium halide, (b) orthocarboxylic acid ester, (c) halogenated hydrocarbon, and (d) alcohol is brought into contact with titanium halide. The titanium halides used in this treatment include titanium tetrachloride,
Examples include titanium tetrabromide, with titanium tetrachloride being particularly preferred. This treatment involves suspending the co-grinding composition in titanium halide at a temperature of 0°C to 200°C, preferably
After contacting at a temperature of 50 DEG to 135 DEG C., the activated titanium component of the present invention is obtained by separating the solid material and drying or washing with an inert solvent to remove free titanium halides. Of course, when treating with titanium halide, it is also possible to use a titanium halide diluted with an inert solvent. The inert solvent referred to herein is an aliphatic, alicyclic, aromatic hydrocarbon or a mixture thereof. The organoaluminum compound (hereinafter referred to as component (B)) used in the present invention has the general formula
AlR ² mX ² _3- m (in the formula: R ² is a hydrocarbon residue, X ² is an alkoxy group, hydrogen, or halogen atom, m is 1.5
≦m≦3), such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-
hexylaluminum, diethylaluminum monochloride, diethylaluminum halide,
Diethylaluminum ethoxide and the like can be used alone or in combination of two or more. Furthermore, compounds containing a C-O or C-N bond (hereinafter referred to as component (C)) include organic esters, aromatic orthocarboxylic acid esters, or silicon compounds in which at least one alkoxy group is directly bonded to silicon. etc. More specifically, methyl anisate, ethyl anisate, methyl toluate,
Examples include methyl benzoate, ethyl benzoate, methyl orthobenzoate, methyl orthotoluate, tetraethoxysilane, triethoxyphenylsilane, diethoxydimethylsilane, diethylaniline, hexamethylphosphoric acid amide, and the like. The above (A), (B), and (C) components may be combined in any order, but especially when some or all of the (C) components are brought into contact with the (A) component and (B) component, Preferably, it is present. The amount of component (C) used is preferably 0.1 to 4 mol per mol of magnesium halide.
Regarding component (B), the molar ratio of the organoaluminum compound to the titanium atoms in the active titanium component is arbitrary, but is generally about 1 to 500. The method of the present invention uses the general formula R-CH=CH ₂ (where R
represents an alkyl group having 1 to 10 carbon atoms), and α-olefin or ethylene homopolymerization;
-Used for copolymerization between olefins or copolymerization with ethylene. Examples of the α-olefin include propylene, 1-butene, 1-hexene, 1-4-methylpentene, and the like. For the polymerization reaction according to the method of the present invention, methods and conditions commonly used in the prior art can be employed. The polymerization temperature at that time is 0 to 100℃, preferably 20 to 90℃.
℃ range. In general, aliphatic, cycloaliphatic, aromatic hydrocarbons or mixtures thereof can be used as solvents in polymerization reactions, such as propane, hexane,
Heptane, cyclohexane, benzene, toluene, etc. and mixtures thereof are preferably used. Alternatively, bulk polymerization can be carried out using the liquid monomer itself as a solvent. Furthermore, it can also be carried out under conditions in which a solvent is substantially absent, that is, by a so-called gas phase polymerization method in which a gaseous monomer and a catalyst are brought into contact. The molecular weight of the polymer produced in the method of the present invention varies depending on the reaction mode, catalyst, and polymerization conditions, but can be controlled by adding hydrogen, alkyl halides, dialkylzinc, etc., if necessary. can. By using the method of the present invention, it is possible to obtain a highly crystalline poly-α-olefin in a high yield per catalyst without the need to substantially remove amorphous poly-α-olefin that adversely affects the physical properties of the polymer. It has very high practical value. The present invention will be explained in more detail below using Examples and Comparative Examples. Example 1 (A) A vibratory mill equipped with a grinding pot having an internal volume of 600 ml and containing 80 steel balls with a diameter of 12 mm is prepared.
Into this pot, 20 g of magnesium chloride, 2 ml of ethyl orthoacetate, 4 ml of 1,2-dichloroethane, and 0.1 ml of ethanol were added in a nitrogen atmosphere and pulverized for 40 hours. Add 10 g of the above pulverized product and 50 ml of titanium tetrachloride to a 200 ml round bottom flask and heat at 80℃ for 2 hours.
After stirring for an hour, remove the supernatant liquid by decantation, then add 100ml of n-heptane, stir at room temperature for 15 minutes, remove the supernatant liquid by decantation, repeat the washing operation 7 times, and then n
- 100 ml of heptane was added to obtain an active titanium component slurry. When a part of this active titanium component slurry was sampled and n-heptane was evaporated and analyzed, 1.56% Ti was found in the active titanium component.
It contained. (B) In a SUS-32 autoclave with an internal volume of 5, n-heptane 1 50 mg of the above active titanium component, 0.20 ml of triethylaluminum,
Diethylaluminium chloride 0.24ml, p-
0.14 ml of methyl toluate was charged. After exhausting the nitrogen in the autoclave with a vacuum pump, 1.5 kg of propylene was charged, and 2N of hydrogen was charged, and the contents of the autoclave were heated.After 5 minutes, the internal temperature was raised to 75℃, and then the temperature was increased to 75℃. Polymerization continued for 2 hours while maintaining internal temperature. After cooling the autoclave, unreacted propylene was purged and the contents were taken out and dried under reduced pressure at 60°C to obtain 620 g of white powder polypropylene. This polypropylene had a boiling n-heptane extraction residual polymer content (hereinafter abbreviated as Powder II) of 97.5%, a bulk specific gravity of 0.45 g/ml, and an intrinsic viscosity (measured at 135°C in tetralin, hereinafter the same) of 1.52. . In addition, the polymerization activity of the catalyst in the polymerization reaction is 6200g/g-
cat.h., and the yield per active titanium catalyst is
It was 12400g/g-cat (795Kg/g-Ti). Comparative Example 1 A titanium halide component was synthesized in the same manner as in Example 1 (A), except that ethanol was not added during co-pulverization, and polymerization was carried out in the same manner as in Example 1 (B). The results are shown in Table 1. Example 2 n-butanol instead of 0.1ml of ethanol
An active titanium component was synthesized in the same manner as in Example 1 (A) except that 0.15 ml was used, and polymerization was carried out in the same manner as in Example 1 (B). The results are shown in Table 1. Example 3 An active titanium component was synthesized in the same manner as in Example 1 (A) except that 0.3 ml of phenol was used instead of 0.1 ml of ethanol, and polymerization was carried out in the same manner as in Example 1 (B). The results are shown in Table 1. Example 4 An active titanium component was synthesized in the same manner as in Example 1 (A), except that 2 ml of methyl orthobenzoate was used instead of 2 ml of ethyl orthoacetate, and polymerization was carried out in the same manner as in Example 1 (B). The results are shown in Table 1. Comparative example 2 0.01ml of ethanol instead of 0.1ml of ethanol
An activated titanium component was synthesized in the same manner as in Example 1 (A), except that 1 was used, and the activated titanium component was polymerized in the same manner as in Example 1 (B).
The results are shown in Table 1. Comparative Example 1 shows almost no improvement in comparison.

【table】

[Table] Example 5 An activated titanium component was synthesized in the same manner as in Example 4, except that 0.2 ml of hexanol was used instead of 0.1 ml of ethanol, and polymerization was carried out in the same manner as in Example 1(B). Titanium content 1.92% by weight Activity 5100g/g. Ti cat.h Yield 531Kg/g, Ti intrinsic viscosity 1.62 Bulk specific gravity 0.44g/ml; total II 96.3% Example 6 Example 4 except that 0.1ml of ethylene glycol monoethyl ether was used instead of 0.1ml of ethanol
An activated titanium component was synthesized in the same manner as in Example 1.
Polymerization was carried out in the same manner as in (B). Titanium content 1.63% by weight Activity 5700g/g. Ti cat.h Yield 699Kg/g. Ti Intrinsic viscosity 1.80 Bulk specific gravity 0.45 g/ml; Total II 96.6% Example 7 An activated titanium component was synthesized in the same manner as in Example 1 (A), and trimethoxyl was used instead of 0.14 ml of methyl p-toluate. Polymerization was carried out in the same manner as in Example 1(B) except that 0.15 ml of phenylsilane was used. Activity 7800g/g-Ti cat.h Intrinsic viscosity 1.46 Bulk specific gravity 0.44g/ml; Total II 95.9%

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1 Supported titanium catalyst component, general formula AlR ² mX ² ₃ −
m (wherein R ² is a hydrocarbon residue, X ² is an alkoxy group, hydrogen, or halogen atom, m is 1.5≦m≦3
α using a catalyst system consisting of an organoaluminum compound represented by a positive number) and a compound selected from organic acid esters, aromatic orthocarboxylic acid esters, or silicon compounds in which at least one alkoxy group is directly bonded to silicon - In the stereoregular polymerization method of olefin, as the carrier-type titanium catalyst component, (a) magnesium chloride, (b) general formula X ¹ C
(OR ¹ ) ₃ (wherein R ¹ is a hydrocarbon residue having 1 to 12 carbon atoms, and X ¹ is hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms);
α- characterized in that it uses an activated titanium compound obtained by co-pulverizing (c) a halogenated hydrocarbon and (d) an alcohol having 1 to 20 carbon atoms, and then (e) contacting it with a titanium halide. Method for stereoregular polymerization of olefins. 2. The polymerization method according to item 1, wherein the alcohol (d) is an aliphatic, alicyclic, or aromatic monohydric or polyhydric alcohol.