JPS5841284B2 - Method for producing catalyst component for α-olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a catalyst component for stereoregular polymerization of α-olefins, and more specifically, a method for producing a catalyst component for stereoregular polymerization of α-olefins, and more specifically, a method for producing a catalyst component that has a high polymerization activity and a high proportion of stereoregular polymers, and which is uniform. The present invention relates to a method for producing a catalyst component for the polymerization of α-olefins that provides coalesced particles.

In general, catalysts used for the stereoregular polymerization of α-olefins include halogenides of low-valent transition metal elements, such as α-type titanium trichloride and titanium tetrachloride obtained by reducing titanium tetrachloride with hydrogen. A eutectic of α-type titanium trichloride and aluminum chloride obtained by reducing the eutectic with aluminum, and a δ-type titanium trichloride obtained by grinding this eutectic are known.

Other methods for modifying titanium trichloride include adding metal halides, alkylaluminum compounds, non-halogenated hydrocarbons, ethers, esters, ketones, etc. and pulverizing them, or simply crushing them. A method of adding a compound has been proposed.

For example, in JP-A-48-59185, α-type titanium trichloride is crushed into α-type titanium trichloride by adding a halogenated hydrocarbon such as carbon tetrachloride, chloroform, dichloromethane, hexachloroethane, etc. A method for modifying titanium trichloride is described.

However, this method is not effective for titanium trichloride other than α-type titanium trichloride, requires pulverization, and requires complicated preparation of the catalyst, and also has problems with polymerization activity and stereoregular polymers. It is still not satisfactory in terms of production rate, etc.

Furthermore, a method of extracting and removing aluminum compounds by treating a reduced solid containing titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound with a complexing agent, and then treating it with titanium tetrachloride (Unexamined Japanese Patent Publication No. Showa 47-3447
8), a method of treatment with carbon tetrachloride (Japanese Unexamined Patent Publication No. 1983-
112289), or a method in which a reduced solid containing titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound is treated with a mixture of a complexing agent and carbon tetrachloride (Japanese Unexamined Patent Publication No. 143790/1982). etc. are known.

However, the method of treatment with titanium tetrachloride is not economical because it requires a highly concentrated solution of expensive titanium tetrachloride.
Furthermore, the method using carbon tetrachloride has the advantage of using inexpensive carbon tetrachloride instead of expensive titanium tetrachloride;
Carbon tetrachloride tends to dissolve titanium trichloride, resulting in a low yield of titanium trichloride, and is not always satisfactory in terms of polymerization activity, stereoregular polymer formation rate, and polymer particle shape. do not have.

The present inventors have conducted intensive research to obtain a catalyst component for α-olefin polymerization that improves the drawbacks of titanium trichloride or titanium trichloride compositions that are known catalyst components for α-olefin polymerization. A solid component obtained by treating a reddish-purple reduced solid obtained by reducing titanium tetrachloride with a mixture of organoaluminum compounds with a complexing agent and a chlorinated hydrocarbon having 2 carbon atoms is used as a catalyst component for α-olefin polymerization. The present invention was completed by discovering that it has extremely excellent performance when used as a compound.

That is, the present invention reduces titanium tetrachloride with a mixture or complex compound of dialkyl aluminum monohalide and monoalkyl aluminum civalide, treats the resulting reddish-purple product with a complexing agent, and then separates the product. The present invention relates to a method for producing a catalyst component for α-olefin polymerization, which is characterized in that it is subsequently treated with a chlorinated hydrocarbon having 2 carbon atoms.

The reduced solid containing titanium trichloride (hereinafter simply referred to as reduced solid) used in the present invention is obtained by reducing titanium tetrachloride with a mixture or complex compound of dialkyl aluminum monohalide and monoalkylaluminum cybaride.

) is a reduced solid with a complex composition that contains aluminum compounds and exhibits a reddish-purple color.

Examples of dialkylaluminum monohalides include dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, diethylaluminium iodide, and the like, with diethylaluminum chloride being particularly preferred.

Examples of monoalkylaluminum cybarides include methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, and especially ethylaluminum dichloride. is desirable.

The present invention uses a mixture or a complex compound of a dialkyl aluminum monohalide and a monoalkyl aluminum civalide to reduce titanium tetrachloride. It is particularly desirable because it is easy to apply and shows excellent effects.

Reduction of titanium tetrachloride is usually performed by adding 150% titanium tetrachloride to a solution of titanium tetrachloride dissolved in an aliphatic hydrocarbon having 5 to 12 carbon atoms.
It is carried out by dropping a mixture or a complex compound of a dialkyl aluminum monohalide and a monoalkylaluminum civalide or a solution thereof over a period of 30 minutes to 3 hours at a temperature of .degree. C. to +30.degree. C., but the reverse method may also be adopted.

The amount of the mixture or complex compound of dialkyl aluminum monohalide and monoalkyl aluminum cybaride used is usually 1 gram atom of aluminum per gram atom of titanium.
to 5 gram atoms.

Titanium tetrachloride is converted into diethylaluminum chloride (DE
AC) and ethylaluminum dichloride (EADC)
When reducing with a mixture of TiCl4:D, the molar ratio is TiCl4:D
EAC: EADC=1:1:0.1~1:4:
It is appropriate to set it to 1.2.

Note that the mixture of titanium tetrachloride and organoaluminum compound may be further aged at a temperature of 20° C. to 100° C. for 1 to 3 hours, but this treatment is not necessarily required.

Next, the obtained reduced solid is separated by an appropriate method, washed with an inert solvent if necessary, and used as it is, or dried or heat-treated to obtain the reduced solid according to the present invention.

The reduced solid thus obtained contains in a homogeneous state at least 0.2 gram atoms of aluminum or a mixture or complex thereof as aluminum per gram of titanium.

Next, the thus obtained reduced solid is treated with a complexing agent, separated and further treated with a chlorinated hydrocarbon having 2 carbon atoms to obtain the catalyst component according to the present invention.

The complexing agent in the present invention means a compound containing one or more electron-donating atoms or groups.

That is, examples of the complexing agent used in the present invention include ethers, thioethers, thiols, organic phosphorus-containing compounds, organic nitrogen-containing compounds, ketones, and esters.

Specifically, the ethers include diethyl ether,
Diisopropyl ether, di-n-butyl ether,
Diyn butyl ether, diyn amyl ether, G2
- Ethylhexyl ether, di-2-ethylhbutyl ether, allyl ethyl ether, allyl butyl ether, diphenyl ether, anisole, phenetol, chloraninol, fromanisole, dimethoxybenzene, etc., and the thioethers include diethyl thioether, di-n-propyl thioether , dicyclohexylthioether, diphenylthioether, ditolylthioether, ethylphenylthioether, propylphenylthioether, diallylthioether, etc.; organic phosphorus-containing compounds include) IJ-n-butylphosphine, triphenylphosphine, triethylphosphite; , tributylphosphite, etc., and organic nitrogen-containing compounds such as diethylamine, trinylamine, n
-propylamine, di-n-propylamine, tri-n
-Propylamine, aniline, dimethylaniline, etc. are used.

Ethers are particularly preferred, and ethers having 4 to 16 carbon atoms are particularly preferred.

Inert solvents include hydrocarbons, for example aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, aromatic hydrocarbons such as benzene, toluene, etc., or mixtures thereof. Appropriate.

Examples of chlorinated hydrocarbons having 2 carbon atoms include hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane, dichloroethane, monochloroethane, tetrachlorethylene, trichlorethylene, dichloroethylene, and chloroethylene. The larger the number, the greater the effect, and hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane, and tetrachloroethylene are preferred, and hexachloroethane and pentachloroethane are particularly preferred.

Treatment of the reduced solid with a complexing agent is carried out by bringing the reduced solid into contact with the complexing agent, but in reality it is carried out by adding the complexing agent to the reduced solid or to an inert solvent containing the reduced solid. This is desirable because it is the simplest and most effective.

It is also possible to add a complexing agent and, if necessary, an inert solvent to the reduced solid for pulverization.

The reduced solid treated with the complexing agent is then separated, washed with an inert solvent if necessary, and then brought into contact with a chlorinated hydrocarbon having 2 carbon atoms.

The contact treatment is most preferably carried out by adding the chlorinated hydrocarbon or a mixture of the chlorinated hydrocarbon and an inert solvent to the complexing agent-treated reduced solid or to an inert solvent containing the reduced solid. It is desirable because it is simple and effective.

It is also possible to add the chlorinated hydrocarbon and, if necessary, an inert hydrocarbon to the reduced solid and perform the pulverization treatment.

When the reduced solid is first treated with a complexing agent and then treated with the chlorinated hydrocarbon, such as hexachloroethane, the conditions are as follows: contact with the complexing agent at a temperature of 0 to 120° C. for 5 minutes to 8 hours; It is preferably carried out at a temperature of 20 to 90°C for 30 minutes to 3 hours, and then contacted with hexachloroethane for 20 minutes to 3 hours.
30 minutes to 20 hours at a temperature of ~150°C, preferably 50
It is appropriate to carry out the reaction at a temperature of ~100°C for 1 to 10 hours.

In this case, the amounts of the complexing agent and hexachloroethane used are not particularly limited, but are usually 0.1 to 2.5 g mol of complexing agent, preferably 0.3 to 0.8 g mol, preferably 0.3 to 0.8 g mol of complexing agent per 1 gram atom of titanium.
The amount of hexachloroethane is suitably 0.2 to 3.0 gram mol, preferably 0.4 to 2.0 gram mol.

The catalyst component of the present invention obtained in this manner is separated from the chlorinated hydrocarbon and the inert solvent, washed with an inert solvent as necessary, and then treated as is or after further drying by a conventional method. It is used as a catalyst for α-olefin polymerization by contacting with an organoaluminum compound as a promoter.

The catalyst component of the present invention is 0.0 per gram atom of titanium.
an aluminum compound or mixture or complex compound corresponding to 0.001 to 0.2 gram atom of aluminum and 0.005 to 0.2 gram mol of chloroethane etc. and 0.005 to 0.2 gram mol of a complexing agent per gram atom of titanium. When it contains, the catalyst composition has the best performance.

The catalyst component of the present invention is made into a catalyst for α-olefin polymerization by contacting it with an organometallic compound normally used as a cocatalyst in a Ziegler type catalyst, such as monoalkylaluminum dichloride, dialkylaluminum monochloride, or trialkylaluminum, but additionally necessary Depending on the requirements, various compounds such as the complexing agent used in the present invention may be added as a third component.

The α-olefin polymerization catalyst comprising a catalyst component and an organoaluminum compound of the present invention is extremely excellent as a catalyst for the homopolymerization or copolymerization of α-olefins such as propylene and ptento-4-methylpentene-1. An industrially useful catalyst with extremely excellent performance such as extremely high polymerization activity and stereoregular polymer formation rate in inert solvents, liquid monomers, or gas phase polymerization of olefins, as well as uniform particles. It is.

The present invention will be explained in more detail below using examples.

For convenience, in the examples, titanium tetrachloride was used as DEAC and EADC.
Although the present invention is explained using a reduced solid obtained by reduction with a mixture of

Example 1 Twenty-one flasks equipped with a stirrer were placed in a thermostatic water bath kept at 0°C, and 700-liter purified hebutane and 25011 Ll of titanium tetrachloride were added and mixed.

Next, while maintaining the temperature of this hebutane solution of titanium tetrachloride at 0°C, 315 ml of DEAC (corresponding to 1.1 mol per 1 mol of titanium tetrachloride) and 117 rnl of EA were added.
A mixture of DC (corresponding to 0.5 mol per mol of titanium tetrachloride) and 400-purified hebutane was mixed dropwise over a period of 3 hours.

After dropping, heat the contents while stirring and heat for 1 hour.
The temperature was increased to 5° C., and the mixture was further stirred at this temperature for 1 hour to obtain a reduced solid.

The resulting reduced solid was separated, washed with purified hebutane, and then dried under reduced pressure at 65°C for 30 minutes.

The reduced solid obtained here has a reddish-purple color, and has a peak at 2θ-42.4° and a peak at 16.2° in the X-ray diffraction spectrum.
The peak at 2θ = 51.3° (δ type crystal) and the peak at 2θ = 15.00 (α type or γ type crystal) are considerably smaller than the peak at 2θ = 51.3° (both β type crystal) (see Figure 1). .

Next, a suspension is prepared by dispersing this reduced solid 251 in 100M purified hebutane, and then this suspension is mixed with 0.0.0% per gram atom of titanium in the reduced solid. After adding di-n-butyl ether in an amount corresponding to 10 gm mol and stirring for 1 hour at a temperature of 35°C, after separating the reduced solid,
Purification of rfLl was washed four times with butane and then an amount of hexachloroethane corresponding to 1 gram mole per gram atom of titanium in the reduced solid was added in the form of a heptane solution containing 251 hexachloroethane in 10011 Ll of hebutane. A catalyst component was obtained by heat treatment at 80° C. for 5 hours.

The obtained catalyst component was further washed five times with 100 TrLl of purified hebutane, and then dried at 65° C. for 30 minutes to obtain a powder of the catalyst component of the present invention.

The catalyst component of the present invention thus obtained is titanium 1
It contained an aluminum compound corresponding to 0.014 gram atom of aluminum per gram atom, 0.04 gram mole of di-normal butyl ether and 0.014 gram mole of hexachloroethane.

Next, a polymerization test was conducted on a polymerization catalyst using the catalyst component of the present invention.

After adding 100 μl of the catalyst component and an amount corresponding to 4 gmole of DEAC per gram atom of titanium to 11 autoclaves, 600 rILl (standard state) of hydrogen were added and then 800 TrLl of liquid propylene were introduced.

Subsequently, the contents of the autoclave were heated to 68°C and polymerized for 30 minutes, after which unreacted propylene was removed and decatalyzed by a conventional method to give a bulk density of 0.45ff/c.
150y of polypropylene powder of c was obtained.

Therefore, the polymerization activity (the number of polymers produced per 12 catalysts, that is, the catalyst efficiency, hereinafter expressed as E) is 150
It was 0.

The melt flow rate of this polypropylene (Melt
Flow Rate-ASTMD 1238 (hereinafter referred to as MFR) was 3.8.

In addition, this polypropylene was extracted with heptane using a Soxhlet extractor for 5 hours to extract the heptane-insoluble matter (
As a result of measuring the HI (hereinafter referred to as HI), the value was 97%.

These results are shown in Table-1.

Comparative Example 1 The results of a polymerization test conducted in exactly the same manner as in Example 1 except that a reduced solid that was not treated with di-n-butyl ether and hihexachloroethane was used instead of the catalyst component used in Example 1. It is shown in Table-1.

As is clear from these results, the performance of the catalyst components is significantly improved by the treatment with di-n-butyl ether and hexachloroethane of the present invention.

Comparative Example 2 The reduced solid was treated in exactly the same manner as in Example 1, except that the treatment temperature with the complexing agent was 80°C, the treatment time was 5 hours, and the treatment with hexachloroethane was not performed, followed by polymerization. The results of the test are shown in Table-1.

As is clear from this result, it is important to use hexachloroethane in the present invention.

In Example 1, the hexachloroethane treatment was performed at a treatment temperature of 35° C. and a treatment time of 16 hours without performing the complexing agent treatment to obtain a catalyst component.

Next, a polymerization test was conducted in the same manner as in Example 1 using this catalyst component, and the result was that E=400. A powdered polypropylene with HI-94% was obtained.

The above results show that it is important for the catalyst component of the present invention to treat the reduced solid with a complexing agent and hexachloroethane.

Example 2 Same as Example 1 except that the amount of di-n-butyl ether used when treating the reduced solid with di-n-butyl ether was 1.0 g mol per 1 gram atom of titanium in the reduced solid. A catalyst component was prepared and a propylene polymerization test was conducted.

The results are shown in Table-2. Example 3 A catalyst component was prepared in the same manner as in Example 1, except that the treatment temperature when treating the reduced solid with di-n-butyl ether was 65° C., and a propylene polymerization test was conducted.

The results are shown in Table-2.

Example 4.5 In Example 1, the reduced solid was treated with di-n-butyl-ether and then with hexachloroethane. The treatment temperature was 70°C (Example 4), 90°C
℃ (Example 5), a catalyst component was prepared in the same manner as in Example 1, and a propylene polymerization test was conducted.

The results are shown in Table 2. Comparative Example 4 A brown reduced solid was obtained in the same manner as in Example 1, except that titanium tetrachloride was reduced using DEAC alone at 1.1 mol per 1 mol of titanium tetrachloride.

20 = 42.4 of the X-ray diffraction spectrum of this solid 1
The peak at 6.2° (both β-type crystals) is much larger than that of the reduced solid in Example 1, and the peak at 2θ-51
, 3° (δ type crystal) and 2θ-15,00 (α type or γ type crystal)
The peak of the reduced solid in Example 1 is much smaller than that of the reduced solid in Example 1 (see Figures 1 and 2).

Next, this reduced solid was treated with di-n-butyl ether and then with hexachloroethane in the same manner as in Example 1 to obtain a catalyst component powder.

This catalyst component contains 0.015 per gram atom of titanium.
It contained an aluminum compound corresponding to gram atoms of aluminum, 0.050 gram moles of di-n-butyl ether.

Next, using this catalyst component, a polymerization test was conducted in exactly the same manner as in Example 1, and the results were as follows: E=1450, HI=94.0
%, bulk density=0.45P/cc.

Reference Example 1 Reduced solid obtained in Example 1 25? was suspended in butane to 100 rrLl of purified titanium, added with butyl ether equivalent to 1 gram mol and carbon tetrachloride equivalent to 4 gram mol per gram atom of titanium, and heated at 80° C. in the same manner as in Example 1.
When heated for 5 hours at a temperature of
Met.

Moreover, this catalyst component was brown in color.

Reference Example 2 The reduced solid 25P obtained in Example 1 was suspended in 100 TILl of purified hebutane, and butyl ether equivalent to 1 gram mol and carbon tetrachloride equivalent to 4 gram mol per 1 gram atom of titanium were added. 35℃ in the same way
The mixture was heated for 4 hours to obtain a catalyst component.

In this case as well, dissolution of titanium trichloride occurred, and the yield of the catalyst component was 40%.

Moreover, this catalyst component exhibited a blackish brown color.

Next, using this catalyst component, a polymerization test was conducted in the same manner as in Example 1, and the results showed that E=400, HI=85%, and bulk density 0.3? /CQ polypropylene powder was obtained.

Reference Example 3 25 kg of the reduced solid obtained in Example 1 was suspended in 1007711 purified hebutane, and di-n-butyl ether equivalent to 1 gram mole per 1 gram atom of titanium was added.
After treatment for 1 hour at 35°C, the reduced solid was separated and suspended in 100 TLl purified hebutane, followed by addition of carbon tetrachloride equivalent to 4 gmol per gram atom of titanium and kept at 35°C for 16 hours. A blackish brown catalyst component was obtained.

Moreover, the yield of this catalyst component was 40%.

Next, using this catalyst component, a polymerization test was conducted in the same manner as in Example 1, and as a result, E=670. A polypropylene powder with HI=84.5% and bulk density of 0.33 @/cc was obtained.

[Brief explanation of drawings]

FIG. 1 shows the X-ray diffraction spectrum of the reduced solid according to the present invention, and FIG. 2 shows the X-ray diffraction spectrum of the reduced solid in Comparative Example 4.

Claims (1)

[Claims] 1 Titanium tetrachloride is reduced with a mixture or complex compound of dialkylaluminum monohalide and monoalkylaluminum cybaride, the resulting reddish-purple product is treated with a complexing agent, and the product is then separated, after which the number of carbon atoms is reduced. 2
1. A method for producing a catalyst component for α-olefin polymerization, which comprises treating with a chlorinated hydrocarbon.