JPS5928572B2 - Polymerization method of α-olefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stereoregular polymerization of α-olefins, and more particularly to a method for stereoregular polymerization of α-olefins using a highly active catalyst consisting of a special titanium trichloride composition, ethers, and organoaluminum compounds. Concerning polymerization methods.

Conventionally, many catalyst systems have been proposed for use in the polymerization of α-olefins such as propylene or in the production of copolymers of α-olefins and other olefins.

For example, a method of producing a highly active catalyst by further solvent treating a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound in the presence of a special complexing agent;
Alternatively, a method has been proposed in which the yield of poly-α-olefin per transition metal is greatly increased by supporting a transition metal on a carrier such as magnesium halide. However, all of these methods require special operations and use a large amount of complexing agent, making the catalyst extremely expensive. Furthermore, when α-olefins are industrially polymerized using these catalysts, the physical properties of the resulting polymers may deteriorate, or when the polymers are removed by extraction, almost worthless American by-products may be produced. There are problems such as the fact that many polyα-olefins remain. The present invention, as a result of various studies aimed at completing a method for stereoregular polymerization of α-olefins that solves the above-mentioned problems, has revealed that the above-mentioned problems can be solved by using the following catalyst. The heading was completed.

That is, the catalyst used in the process of the present invention is a special activated titanium trichloride composition having the general formula R10R2, where R1 and R2 are the same or different hydrocarbon residues having 2 to 10 carbon atoms. ethers represented by the general formula AlR3mXh-m (wherein, R3 has 1 to 1 carbon atoms)
The catalyst is composed of an organoaluminum compound represented by the following hydrocarbon residue (X1 represents an alkoxy group, hydrogen or halogen atom, and m is a number of 1.5≦m≦3).

When the above-mentioned catalyst is used for the polymerization of α-olefin, its activity is very high, and even if the yield per catalyst is significantly increased, the stereoregularity hardly decreases.

Furthermore, in this type of catalyst, when the amount of organoaluminum compound used relative to titanium trichloride is small, stereoregularity generally decreases, but this phenomenon is not observed in the above catalyst. The special activated titanium composition used in the present invention is a composition obtained by co-pulverizing a eutectic of titanium trichloride and aluminum trichloride, an ether, and titanium tetrachloride, and then washing with a solvent, or a composition obtained by co-pulverizing titanium trichloride and aluminum trichloride, and then washing with a solvent. This is a composition in which a eutectic of aluminum trichloride and a complex or reaction product of aluminum trichloride and ether are co-pulverized and then washed with a solvent.

The purpose of further washing the co-pulverized composition with a solvent is to simultaneously improve the activity of the resulting catalyst and the stereoregularity of the product. The ethers used in the present invention include compounds represented by the above-mentioned general formula R10R2, and specifically diethyl ether, di-n-propyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, di- Examples include n-hexyl ether, diphenyl ether, ditolyl ether, and methyl phenyl ether, among which di-n-butyl ether, diisoaluminum ether, di-n-propyl ether, and the like are particularly preferred.

The proportion of the above ethers used varies depending on the catalyst system, but
O. per titanium atom in the activated titanium compound. 01-1
A molar range is preferred.

If the amount is less than this range, there is almost no effect on activity or stereoregularity, if the amount is more than that, there is almost no difference in effect from the above range, and if it is used in too large a amount, it will have little effect on activity or stereoregularity.
A decrease in stereoregularity occurs. The organoaluminum compound used in the present invention has the general formula AlR3ml0-
．． Specific examples of the compounds represented by the above include diethylaluminum chloride, di-n-propylaluminum chloride, triethylaluminum, diisobutylaluminum chloride, diethylaluminum ethoxide, diethylaluminium hydride, and mixtures thereof.

The proportion of the organoaluminum compound used varies depending on the catalyst system, but generally titanium 1 in the activated titanium compound is
O for an atom. 01-30 mol, preferably O. 1-1
It is 0 mole.

There is no particular limitation on the method of mixing the above-described special activated titanium composition, ethers, and organoaluminum compound, and the activated titanium trichloride composition (5) and the organoaluminum compound (0 are mixed, There is a method of mixing the group (B), or a method of simultaneously mixing the activated titanium trichloride composition (A), the ether (B), and the organoaluminum compound (0).

However, it is preferable to contact the activated titanium trichloride composition (A) and the ether (B) before contacting the organoaluminum compound (0) because the bulk specific gravity of the obtained polymer increases.The method of the present invention Examples of monomers polymerized by the method of the present invention include α-olefins such as propylene, 1-butene, 1-pentene, and hexene, and mixtures thereof, or mixtures of α-olefins and ethylene.The polymerization temperature according to the method of the present invention may be the temperature used for the polymerization of α-olefins using typical Ziegler-Natsuta catalysts, and is generally in the temperature range of 20 to 130°C, preferably 30 to 90°C.

On the other hand, the polymerization pressure is normal pressure to 50 k9/cd-G, preferably normal pressure to 40 kg/cd-G. According to the method of the present invention in which α-olefin is polymerized in the presence of a catalyst as detailed above, a poly α-olefin with high stereoregularity can be easily obtained, and the yield per catalyst can be significantly improved. be able to.

Since the yield can be increased in this way, the amount of alcohol and the amount of complexing agent used to remove catalyst residues that adversely affect the physical properties of the polymer can be significantly reduced. That is, the present invention can provide a method for polymerizing stereoregular α-olefins that is highly industrially economical and of great practical value. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 (A) Internal volume 600 containing 80 steel balls with a diameter of 12 mm
Titanium tetrachloride was reduced and ground with aluminum in the presence of aluminum chloride in a vibrating mill with a composition of approximately T.
A eutectic of titanium trichloride and aluminum trichloride equivalent to iCl3.1/3A1C13 (hereinafter abbreviated as AA type titanium trichloride) 30y1 diphenyl ether 1.57 and titanium tetrachloride O. 67 was charged, and the mixture was ground for 14 hours at room temperature under a nitrogen atmosphere.

The contents were separated from the steel balls under a nitrogen atmosphere to obtain a titanium trichloride composition. 207n of this titanium trichloride composition
- After stirring at 80° C. for 30 minutes using 200 ml of heptane, n-heptane was removed by decantation.
Next, 100 ml of n-heptane was added to this to form an activated titanium composition slurry. (B) S with an internal volume of 3 liters
n in a US-32 autoclave under a nitrogen atmosphere.
-Heptane 11, Doki activated titanium composition 647.3~
, 1.2 ml of diethylaluminum chloride and 0.06 ml of di-n-butyl ether. After evacuating the nitrogen inside the autoclave using a vacuum pump, hydrogen was pumped to O. 2k9/cd-G was charged, and propylene was further charged to make the pressure in the gas phase 2kg/cd-G. Next, the contents of the autoclave were heated to bring the internal temperature to 70° C. after 5 minutes, and polymerization was carried out at this temperature while charging propylene while maintaining the pressure at 5 kg/cd-G. After 100 minutes, when the amount of propylene introduced reached 5,007, the introduction of propylene was stopped, unreacted gas was released, and then methanol 300a was added and stirring was continued for 30 minutes to decompose the catalyst.

After cooling the autoclave, the contents were taken out, 200 ml of water was added, the contents were washed three times at 60°C, filtered, and dried under reduced pressure at 60°C to obtain white polypropylene 501.57.

The resulting polypropylene had an intrinsic viscosity of 2.18, a bulk specific gravity of 0.38, and a n-heptane extraction residue of 98.1% (residual polymer percentage after extraction with boiling n-heptane for 10 hours.Hereinafter abbreviated as powder ■) ). On the other hand, 8.77 g of amorphous polypropylene was obtained by evaporation of the filtrate. The polymerization activity of the catalyst in this polymerization reaction is 4697/7-cat-
It was h. In addition, the ratio of the boiling n-heptane extraction residual polymer to the total polymer (hereinafter abbreviated as total ■) is 9
It was 6.4%. Comparative Example 1 Activated titanium composition 679 obtained in Example 1(A).
Polymerization was carried out in exactly the same manner as in Example 1(B) except that 57 was used and di-n-butyl ether was not used.

At this time as well, the amount of propylene introduced was approximately 5,007. The results obtained are shown in Table 2. Example 2 Activated titanium composition 604.2 obtained in Example 1 (A) was placed in a 100 ml flask under a nitrogen atmosphere and thoroughly purged with nitrogen, and 50 ml of n-heptane 1 di-n-butyl ether O ．．
After adding 6 ml of O2 and thoroughly stirring at room temperature, 1.2 ml of diethylaluminum chloride was further added.

Polymerization was carried out in exactly the same manner as in Example 1(B) except that this catalyst mixture was used. At this time as well, the amount of propylene introduced was approximately 5,007. The results obtained are shown in Table 1. Example 3 The activated titanium composition 653.2 obtained in Example 1(A) was immediately di-n-butyl ether O. O6ml1
Diethylaluminum chloride O. Using 6ml,
Polymerization was carried out in exactly the same manner as in Example 2, except that the amount of diethylaluminum chloride was significantly reduced.

The results obtained are shown in Table 1. Comparative Example 2 Polymerization was carried out in exactly the same manner as in Example 3, except that di-n-butyl ether was not used.

The results obtained are shown in Table 2. Compared to the case where di-n-butyl ether is used, the total value of ■ is about 1% lower. Example 4
Activated titanium composition 405 obtained in Example 1(A).
9 Immediately, diethylaluminum chloride 0.84ml1
Di-n-butyl ether O. Polymerization was carried out in exactly the same manner as in Example 2, except that 2 ml of O was used.

The results obtained are shown in Table 1. Comparative Example 3 Activated titanium composition 453 obtained in Example 1(A).
Polymerization was carried out in exactly the same manner as in Example 2, except that 0.84 ml of diethylaluminum chloride was used and di-n-butyl ether was not used.

The results obtained are shown in Table 2. The activity and total ■ are lower than when di-n-butyl ether is used. Example 5 (A) Using the same vibration mill as in Example 1 (A), AA type titanium trichloride 30V, aluminum trichloride, and diphenyl ether complex 4.6y were co-milled at room temperature for 40 hours.

The obtained titanium trichloride composition 207 was mixed with n-heptane 20
After stirring at the boiling point for 30 minutes, the operation of removing n-heptane by decantation was repeated 4 times, and then 100 ml of n-heptane was added to obtain an activated titanium composition slurry. Ta. (B) Doji activated titanium composition 461.9W, diethylaluminum chloride 1.0TrLl1 di-n-butyl ether O,O
Polymerization was carried out in exactly the same manner as in Example 2, except that 6 ml was used.

The results obtained are shown in Table 1. Comparative Example 4 Activated titanium composition 446 obtained in Example 5(A).
8η, diethyl aluminum chloride 1. Polymerization was carried out in the same manner as in Example 2 except that Oml was used.

The results obtained are shown in Table 2. Example 6 Di-n-butyl ether O. Diisoamyl ether O instead of 06ml
．． Polymerization was carried out in exactly the same manner as in Example 2, except that 08 ml was used.

The results obtained are shown in Table 1. Example 7 Di-n-butyl ether O. Diphenyl ether 0.06ml instead of 0.06ml Polymerization was carried out in exactly the same manner as in Example 2, except that 0.07 ml was used.

The results obtained are shown in Table 1. Example 8 Polymerization was carried out in exactly the same manner as in Example 2, except that 1.2 ml of di-n-propylaluminum chloride was used instead of 1.2 ml of diethylaluminum chloride.

The results obtained are shown in Table 1. Comparative Example 5 Polymerization was carried out in exactly the same manner as in Example 8, except that di-n-butyl ether was not used.

The results obtained are shown in Table 2. Comparative Example 6 Polymerization was carried out in exactly the same manner as in Example 1 and Comparative Example 1, except that the titanium trichloride component co-pulverized in Example 1(A) and not washed with a solvent was used.

The results obtained are shown in Table 3. Comparative Example 7 Polymerization was carried out in exactly the same manner as in Example 5 and Comparative Example 4, except that the titanium trichloride component that was co-pulverized in Example 5 (A) and not washed with a solvent was used. Ta.

Claims (1)

[Claims] 1 In the regular polymerization method of α-olefin, (A)
A composition obtained by co-pulverizing a eutectic of titanium trichloride and aluminum trichloride, an ether, and titanium tetrachloride, and then washing it with a solvent, or a composition of a eutectic of titanium trichloride and aluminum trichloride, aluminum trichloride, and ether. A composition obtained by co-pulverizing the complex or reaction product and then washing with a solvent, (B) having the general formula R^1-O-R^2 (where R^1 and R
^2 means the same or different hydrocarbon group having 2 to 10 carbon atoms), (C) general formula AlR
^3mX^1_3_-_m, (in the formula, R^3 is the number of carbon atoms 1
~6 hydrocarbon residues, X^1 means an alkoxy group, hydrogen or halogen atom, and m is a number of 1.5≦m≦3), obtained by contacting an organoaluminum compound represented by A method characterized in that α-olefins are polymerized in the presence of a catalyst.