JPH0128048B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a method for producing highly stereoregular alpha-olefin polymers.

<Prior art> Generally, as a method for producing crystalline olefin polymers, a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound of group ~ of the periodic table and a metal of group ~ or an organometallic compound is used. It is well known to do so. When alpha-olefin polymers such as propylene and butene-1 are produced industrially, catalysts in which titanium tetrachloride or titanium trichloride is supported on a titanium trichloride composition or a magnesium-containing halide carrier are used. .
In the conventional production method, an amorphous polymer is produced as a by-product in addition to a highly stereoregular olefin polymer which has high industrial utility value. This amorphous polymer has little industrial utility value, and has a large adverse effect on mechanical properties when the olefin polymer is processed into films, fibers, and other processed products.

In addition, the production of the amorphous polymer causes loss of raw material monomers, and at the same time requires production equipment for removing the amorphous polymer, which is an extremely large disadvantage from an industrial perspective.

Therefore, it would be a great advantage if such amorphous polymers were not produced at all, or if they were produced at all, but only to a very small extent. On the other hand, if catalyst residue remains in the olefin polymer, this catalyst residue causes various problems in terms of stability, processability, etc. of the olefin polymer, and equipment for removing and stabilizing the catalyst residue is required.

This drawback becomes more pronounced as the catalyst activity, expressed as the weight of the olefin polymer produced per unit weight, increases.
Moreover, the equipment for removing the catalyst residue becomes unnecessary, and the production cost necessary for producing the olefin polymer can be reduced.

For these purposes, attempts have been made to improve various polymerization catalysts, one of which is a magnesium-containing supported catalyst.

Examples of supported magnesium-containing catalysts include catalysts in which titanium tetrachloride is supported after activating commercially available anhydrous magnesium chloride (Japanese Patent Publication No. 47-41676);
Alternatively, there is a catalyst in which titanium tetrachloride is supported on a carrier obtained by treating magnesium chloride with an electron-donating compound (Japanese Patent Application Laid-Open No. 72383/1983).
In addition, by reducing titanium tetrachloride with an organomagnesium compound, a catalyst in which titanium trichloride is supported on a magnesium chloride carrier (Japanese Unexamined Patent Publication No. 46-4393), or a Grignard compound can be converted into a catalyst with gaseous HCl.
Catalyst in which titanium tetrachloride is supported on a magnesium chloride carrier obtained by reaction with (Japanese Patent Publication No. 47-41676)
There are also such things.

However, although these supported catalysts are very useful for the polymerization of ethylene, they produce a large amount of amorphous polymer as a by-product in the polymerization of propylene, etc., and have very low utility value.

Examples of supported catalysts for polymerizing α-olefins such as propylene include a method of co-pulverizing magnesium chloride, an inert solid organic substance, and a titanium tetrachloride-ester complex (Japanese Unexamined Patent Publication No. 1986-86482), magnesium chloride, a silicon compound, A method of co-pulverizing ester and then reacting it with titanium tetrachloride (Special Publication No. 52-36786)
(Japanese Unexamined Patent Publication No. 1989-1997), a method of reacting a halogen-free magnesium compound containing an alkoxy group or an aryloxy group with an electron donor and a titanium compound
-2580), or a method in which titanium tetrachloride is supported after treating magnesium chloride with alcohol, ester, aluminum halide compound (silicon halide compound), etc.
-28189, Publication No. 51-92885). The polymerization activity and stereoregularity of the catalysts produced by these methods are low, and the catalysts are unsatisfactory for industrial use in the stereoregular polymerization of alpha olefins. Furthermore, a pulverization step is often essential for catalyst production.

<Problems to be Solved by the Invention> The present inventors have conducted extensive studies in order to produce a catalyst that can obtain an alpha-olefin polymer with higher catalytic activity and excellent stereoregularity than the above-mentioned method. As a result, by using a solid catalyst obtained by catalytically treating a magnesium halide compound with a specific titanium compound in the presence of an inert solvent, alpha olefins such as propylene can be produced with extremely high activity and stereoregularity. The present invention has been achieved by discovering that it can be polymerized into a polymer.

<Means for solving the problems> That is, the present invention provides (A)(a) magnesium dihalide, (b) general formula Ti(OAr)nX _4-o (Ar is a phenyl group,
Substituted phenyl group, X represents halogen, n
is a number expressed by 0<n<1. ) with a solid catalyst obtained by contact reaction with a titanium _compound represented by represents halogen, m is 2≦
m≦3. ) in the presence of a catalyst system consisting of an activator made of an organoaluminium compound represented by the formula (1), homopolymerization of alpha olefin having 3 to 8 carbon atoms, or alpha olefin having 3 to 8 carbon atoms and ethylene or ethylene or 3 carbon atoms. The present invention relates to a method for producing a highly stereoregular alpha-olefin polymer, which is characterized by copolymerizing with other alpha-olefins of ~8.

In the present invention, the magnesium halogen compound used in the contact reaction with the titanium compound is magnesium dihalide, and among them, magnesium chloride is preferably used.

The magnesium dihalide is preferably in an active form before or during the contact reaction with the titanium compound. Here, the active form of magnesium dihalide refers to ordinary inactive magnesium dihalide in which the most intense diffraction line in the X-ray powder spectrum is changed into a halo. It is desirable to use magnesium dihalide in its active form because it allows for a greater amount of the titanium compound to be chemically bonded thereto.

The active form of magnesium dihalide can be obtained in various ways.

One preferred method is to mechanically grind commercially available magnesium dihalide.

Grinding is carried out using a ball mill, vibration mill, impact mill, or the like. The grinding time varies depending on the equipment, but is generally from 1 hour to 1000 hours. The grinding temperature is selected from room temperature to 100°C. Silicone oil or the like may be present in order to facilitate pulverization. Other inert solid fillers may also be present during grinding.

Another preferred method is to dissolve magnesium dihalide in a polar solvent such as alcohol, ether, or amine, and then precipitate a solid. Precipitation can be performed by cooling the solution or evaporating the solvent. The obtained precipitated solid is treated with a halogenating agent such as a silicon halide compound or an aluminum halide compound,
It is desirable to wash with an inert hydrocarbon solvent or the like.

Preferred magnesium halogen compounds include those obtained by decomposing organomagnesium compounds such as alkylmagnesium halides and dialkylmagnesiums with known decomposers such as HCl.

The organomagnesium compound can be used as a solution or suspension in an ether solvent, a hydrocarbon solvent, or a mixed solvent of both.

The magnesium halide compound (a) is subjected to the next contact reaction step with the titanium compound (b), but before that, it can be contacted with an electron-donating compound.

Examples of electron-donating compounds include amines, amides,
Examples include ether, ester, ketone, nitrile, phosphine, phosphite, and sulfide compounds, but ester compounds are preferred.

As the ester compound, aliphatic carboxylic acid ester, alicyclic carboxylic acid ester, aromatic carboxylic acid ester, etc. are used, but olefin carboxylic acid ester or aromatic monocarboxylic acid ester is preferable. Especially preferred are esters of aromatic monocarboxylic acids.

Specific examples include methyl benzoate, ethyl benzoate, and ethyl p-anisate. The amount of the electron donating compound used is 10 ^-5 mol to 0.1 mol, preferably 5 x 10 ^-4 mol to 0.02 mol, per gram of the magnesium halide compound. If it is less than 10 ^-5 mol, there is no effect of improving stereoregularity, and if it is more than 0.1 mol, the polymerization activity is significantly reduced.

The magnesium halogen compound and the electron-donating compound can be brought into contact with each other by any known method capable of bringing the two into contact, such as a slurry method or mechanical pulverization using a ball mill. In particular, a slurry method in which the two are brought into contact in the presence of a diluent is advantageous in terms of particle shape and particle size distribution.

Diluents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, benzene,
Aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and cyclopentane can be used.

The amount of diluent used is from 0.1 ml per 1 g of solid product.
It is 1000ml. Preferably 1ml to 100ml per 1g
It is. The reaction temperature is -50°C to 150°C, preferably 0°C to 100°C. The reaction time is 10 minutes or more, preferably 30 minutes to 3 hours.

After the contact treatment with the electron donating compound, washing with an inert hydrocarbon solvent or the like may be performed, or the next step of contact reaction with a titanium compound may be carried out without washing.

Although the contact treatment with such an electron-donating compound improves the activity and stereospecificity of the resulting solid catalyst to some extent, it generally increases the amount of hydrogen used for controlling the molecular weight.

The catalyst of the present invention is characterized in that it exhibits sufficiently high activity and stereospecificity even without the step of contacting with an electron-donating compound as described above.

The titanium compound used in the present invention has the general formula Ti
(OAr) nX _4-o (Ar represents a phenyl group, substituted phenyl group, _OAr )
It is a mixture with _TiX4 .

As the halogen X, chlorine is preferred among chlorine, bromine, and iodine.

The aryloxy group OAr is preferably a phenoxy group represented by the formula -OC ₆ H ₅ or a substituted phenoxy group.

Substituents in the substituted phenoxy group include hydrocarbon groups such as alkyl groups and aryl groups, oxygen-containing organic groups such as alkoxy groups, aryloxy groups, acyl groups, and ester groups, and sulfur-containing organic groups such as alkylthio groups and arylthio groups. Examples include nitrogen-containing groups such as amino groups, alkylamino groups, arylamino groups, nitro groups, and cyano groups, and halogens.

It may have a plurality of substituents.

Among these substituents, hydrocarbon groups, halogens,
An alkoxy group and an aryloxy group are preferred. A specific example of the aryloxy group OAr is p-
Methylphenoxy group, p-ethylphenoxy group,
p-isopropylphenoxy group, p-t-butylphenoxy group, p-phenylphenoxy group, 2-
Naphthyloxy group, p-chlorophenoxy group, p
-bromophenoxy group, p-iodophenoxy group, p-methoxyphenoxy group, p-ethoxyphenoxy group, p-phenoxyphenoxy group, 4-
Methyl-2-t-butylphenoxy group, o-methylphenoxy group, o-t-butylphenoxy group,
o-phenylphenoxy group, α-naphthyl group, o
-chlorophenoxy group, o-methoxyphenoxy group, o-phenoxyphenoxy group, m-methylphenoxy group, m-chlorophenoxy group, etc.

The number n is particularly preferably 0.02≦n≦0.8.
That is, the mixing ratio of Ti(OAr)X ₃ and TiX ₄ is preferably 0.02:0.98 to 0.8:0.2 in molar ratio.

By using such a specific aryloxytitanium halide compound, the contact reaction is more rapid than in the case of contact reaction with the corresponding titanium halide or in the case of contacting the support treated with the corresponding phenolic compound with the titanium halide. Activity and stereospecificity are dramatically improved.

A titanium compound can be synthesized by a known method.

One method is to synthesize it by a substitution reaction between a halogen-containing titanium compound and a phenol compound. When the two are mixed, hydrogen halide is generally generated and the reaction proceeds. For use in the present invention, it is necessary that the substitution reaction be substantially complete. Completion of the reaction can be confirmed by the presence or absence of absorption of OH groups in the infrared absorption spectrum of the reactant. For example, when 0.1 mol of titanium tetrachloride and 0.05 mol of p-cresol are mixed at 120°C, HCl gas is violently generated for about 30 minutes, resulting in a titanium compound with an average composition of (4-CH ₃ -C ₆ H ₄ O) _0.5 TiCl _3.5. ,
That is, a mixture of (4-CH ₃ -C ₆ H ₄ O), TiCl ₃ and TiCl ₄ in a molar ratio of 1:1 is obtained.

Alternatively, a reaction product resulting from a disproportionation reaction between an orthotitanate ester of a phenol compound and a halogen-containing titanium compound can also be used. For example, when 0.39 mol of titanium tetrachloride and 0.01 mol of tetrap-methylphenoxy titanium are mixed, a titanium compound with an average composition of (4-CH ₃ -C ₆ H ₄ O) _0.1 TiCl _3.9 , i.e., (4-CH ₃ -C ₆ H ₄ O) A mixture of TiCl ₃ and TiCl ₄ in a molar ratio of 1:9 is obtained.

Examples of the halogen-containing titanium compound used in the above synthesis include titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide, and halogenated titanates such as phenoxytitanium trichloride and diphenoxytitanium dichloride. However, titanium tetrahalides, especially titanium tetrachloride, are preferred.

Inert solvents used for titanium compound solutions include hexane, heptane, octane, aliphatic hydrocarbons such as liquid paraffin, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, aliphatic halogen hydrocarbons such as methylene chloride, dichloroethane, trichloroethaneethane, trichloroethylene, chlorobenzene, dichlorobenzene, trichlorobenzene Examples include aromatic halogenated hydrocarbons such as. A mixture of these solvents can also be used.

Among these, aromatic hydrocarbons and/or halogenated hydrocarbons are preferred, and aromatic halogenated hydrocarbons are particularly preferred.

The concentration of the titanium compound is preferably 0.1 to 0.7 in volume fraction, preferably 0.05 to 0.9.

By using such a specific titanium compound as a solution in the presence of a solvent, especially in the above concentration range, and carrying out a contact reaction treatment with a magnesium halide compound, it is possible to treat a magnesium halide compound in the presence of a solvent as well as in the absence of a solvent. Compared to the case of contact reaction,
The activity and stereospecificity of the catalyst are further improved dramatically.

For the contact reaction between a titanium compound and a magnesium halide compound which has or has not been subjected to a contact treatment with an electron donating compound in advance, other known methods such as a pulverization method using a ball mill, a vibration mill, etc. can also be used. Alternatively, a slurry method in which a magnesium halogen compound is slurried in a titanium compound solution or an impregnation method in which a magnesium halogen compound is impregnated with a titanium compound solution can also be used.

The amount of the titanium compound solution to be used per 1 g of the magnesium halogen compound is 0.1 ml to 100 ml, preferably about 0.5 ml to 50 ml.

This catalytic reaction is preferably carried out at a temperature of 0 to 150°C.

The reaction time is several minutes or more, preferably 30 minutes to 3 hours.

After the contact reaction, it is desirable to wash thoroughly with an inert solvent.

In this way, the solid catalyst of the present invention (A) is obtained.

The activator (B) used in the present invention has the general formula
R _n AlY _3-n (R is an alkyl group having 1 to 8 carbon atoms,
Y represents halogen, and m is a number represented by 2≦m≦3. ) is an organoaluminum compound represented by

Specific examples of the organoaluminum compound include trialkylaluminum, a mixture of trialkylaluminium and dialkylaluminum halide, and dialkylaluminum halide, with triethylaluminum and a mixture of triethylaluminum and diethylaluminum chloride being particularly preferably used.

The molar ratio of titanium atoms to activator in the solid catalyst used for alpha-olefin polymerization can be selected over a wide range from 10:1 to 1:1000, but a range of 2:1 to 1:600 is particularly preferred. used for.

In the method of the present invention, alpha olefin is polymerized or copolymerized in the presence of the solid catalyst (A) and the activator (B), but a known electron-donating compound (C ) can be added.

Addition of an electron-donating compound generally improves stereospecificity but decreases activity.

Examples of electron-donating compounds (C) include amines, amides, ethers, ketones, nitriles, phosphine,
Examples include phosphite and sulfide compounds, but ester compounds are preferred. As the ester compound, olefin carboxylic acid esters or aromatic monocarboxylic acid esters are particularly preferred. Specific examples include methyl methacrylate, ethyl benzoate, p-ethyl anisate, p-
- Examples include methyl toluate.

The molar ratio of activator and electron donating compound is 1:
In the range of 0.01 to 1:10, preferably 1:
It ranges from 0.1 to 1:1.

The electron-donating compound may be used in advance by mixing it with an activator. As the combination of the activator and the electron-donating compound, a system of triethylaluminum and an ester compound, and a system of triethylaluminum, diethylaluminium chloride and an ester compound are preferred.

Polymerization can be carried out over a temperature range of -30 to 200°C, but temperatures below 0°C result in a decrease in the polymerization rate, and temperatures above 100°C make it impossible to obtain highly stereoregular polymers. For these reasons, it is usually preferable to carry out the reaction at a temperature in the range of 0 to 100°C. Although there are no particular limitations on the polymerization pressure, a pressure of about 3 to 100 atm is desirable from the viewpoint of industrial and economical considerations.

The polymerization method can be continuous or batchwise. Also, propane, butane, pentane,
Slurry polymerization using an inert hydrocarbon solvent such as hexane, heptane, or octane, liquid phase polymerization without a solvent, or gas phase polymerization is also possible.

Next, alpha olefins that can be applied to the present invention have 3 to 8 carbon atoms, and specific examples include propylene, 1 butene, 1 pentene, 1 hexene, 1 3-methylpentene, 4 -methyl-pentene-1, etc., but the present invention is not limited to the above compounds. The polymerization according to the present invention can be either homopolymerization or copolymerization (including copolymerization with ethylene). During copolymerization, a copolymer can be obtained by contacting two or more types of alpha olefin in a mixed state.

Heteroblock copolymerization in which polymerization is carried out in two or more stages can also be easily carried out.

The method of the present invention will be explained below using Examples, but the present invention is not limited to these Examples in any way.

<Example> Example 1 (A) Grinding treatment of anhydrous magnesium chloride After replacing the pot of a vibrating mill with argon, the pot was equipped with a grinding pot with an internal volume of 500 ml and containing 60 stainless steel (SUS32) balls with a diameter of 12 mm. Commercially available anhydrous magnesium chloride (6 at 400℃ under reduced pressure)
Time firing) 20g was charged and pulverized for 100 hours.

(B) Synthesis of titanium compound After a 200 ml flask equipped with a stirrer and a thermometer was purged with argon, 70 ml of monochlorobenzene as a solvent, 30 ml of titanium tetrachloride, and 14.76 g of p-cresol were charged, and the temperature was raised to 120°C.
The reaction proceeded with the generation of hydrogen chloride gas.

After maintaining this temperature for 1 hour, 1 ml of the reaction solution
When the infrared absorption spectrum was measured, no absorption based on the stretching vibration of the OH group of p-cresol was observed, and the average composition of Ti(OC ₆ H ₄ -4
A liquid titanium compound represented by -CH ₃ ) _0.5 Cl _3.5 was obtained.

(C) Synthesis of solid catalyst 5 g of anhydrous magnesium chloride obtained in (A) above was charged into the liquid containing the titanium compound obtained in (B) above, and a contact reaction was carried out at 120°C for 1 hour with stirring. .

After the reaction was completed, the mixture was allowed to stand still and the supernatant liquid was extracted at 120°C.

Next, 50 ml of n-heptane was added, stirred at 90°C for 5 minutes, left to stand, and the supernatant liquid was extracted.
This operation was repeated 5 times for washing. After drying under reduced pressure, 4.5 g of solid catalyst was obtained.

This solid catalyst contained 1.7% by weight of titanium atoms.

(D) Polymerization of propylene () A stirred stainless steel autoclave with an internal volume of 5 was replaced with argon and dried heptane 1.5
, 0.75 g of triethylaluminum, 0.217 g of methyl toluate, and 47 mg of the solid catalyst synthesized in (C) above were charged, and hydrogen corresponding to a partial pressure of 0.14 Kg/cm ² was added.

Next, the temperature of the autoclave was raised to 70°C, and then propylene was pressurized to 6 kg/cm ² G to start polymerization, and the polymerization was continued for 90 minutes while replenishing propylene to maintain this pressure.

After the polymerization was completed, the introduction of monomers was stopped, unreacted monomers were purged, and 100 ml of butanol was added to decompose the catalyst.

The produced polymer was filtered through a Buchner filter, washed three times with 500 ml of heptane, and dried at 60°C, yielding 156 g of polypropylene.

Heptane was removed from the liquid by steam distillation, yielding 11.9 g of an amorphous polymer.

The proportion of heptane-insoluble parts (hereinafter abbreviated as HIP) in the total polymer yield was 92.9% by weight.
Further, the yield (g) of polypropylene per 1 g of solid catalyst (hereinafter abbreviated as PP/Cat) was 3570.

(E) Polymerization of propylene () In the polymerization of propylene () in (D), 52 mg of the solid catalyst synthesized in (C) was used, and 0.375 g of triethyl aluminum was used instead of 0.75 g of triethyl aluminum as the organoaluminum compound.
Polymerization of propylene was carried out in the same manner except that 0.397 g of a mixed organoaluminium compound of diethylaluminium chloride was used and 0.3 g of ethyl p-anisate was used instead of methyl toluate.

147 g of polypropylene powder was obtained. Also,
10.7 g of amorphous polymer was obtained.

Therefore, PP/Cat=3030 and HIP=93.2
It was in weight%.

(F) Polymerization of propylene () After purging a stirring stainless steel autoclave with an internal volume of 5 with argon, 0.65 g of triethylaluminum, 0.257 g of methyl toluate
g and 31 mg of the solid catalyst synthesized in (C) above were charged, and hydrogen corresponding to a partial pressure of 0.40 Kg/cm ² was added.

Then, 1.3 kg of liquid propylene was pressurized into the autoclave, and the autoclave was kept at 65°C to continue polymerization for 2 hours.

After the polymerization was completed, unreacted monomers were purged, and 100 ml of methanol was added to decompose the catalyst.

The produced polypropylene was filtered using a Buchner filter and dried under reduced pressure at 60°C to obtain 206 g of polypropylene.

PP/Cat=6650. Further, when Soxhlet extraction with boiling heptane was performed for 6 hours, the proportion of insoluble portion was 92.2% by weight.

Example 2 In the synthesis of the titanium compound of Example 1 (B), p
- Average composition Ti (OC ₆ H ₄ -4-CH ₃ ) _0.1 using the same method except that the amount of cresol used was changed to 2.95 g.
A monochlorobenzene solution of a titanium compound with Cl _3.9 was synthesized.

Ti(OC ₆ H ₄ −4−CH ₃ ) _0.5 Cl _3.5 instead of the above
_A solid catalyst was synthesized in the same manner as in Example 1 except that Ti( _{OC6H4-4 - CH3} ) _0.1Cl3.9 was used.

Polymerization of propylene was carried out under the same conditions as in Example 1 (D) using 35 mg of the above solid catalyst.

PP/Cat=3420, HIP=93.0% by weight.

Example 3 In the synthesis of the titanium compound of Example 1 (B), p
- Average composition Ti(OC ₆ H ₄ -4-CH ₃ ) _0.7 using the same method except that the amount of cresol used was changed to 20.66 g.
A monochlorobenzene solution of a titanium compound represented by Cl _3.3 was synthesized.

Ti(OC ₆ H ₄ −4−CH ₃ ) _0.5 Cl _3.5 instead of the above
_A solid catalyst was synthesized in the same manner as in Example 1 except that Ti( _{OC6H4-4 - CH3} ) _0.7Cl3.3 was used.

Using 42 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=3110, HIP=92.4% by weight.

Comparative Example 1 In the synthesis of the titanium compound of Example 1 (B), p
- The average composition of Ti (OC ₆ H ₄ -4-CH ₃ ) was obtained using the same method except that the amount of cresol used was changed to 29.51 g.
A monochlorobenzene solution of a titanium compound represented by Cl ₃ was synthesized.

Ti(OC ₆ H ₄ −4−CH ₃ ) _0.5 Cl _3.5 instead of the above
_A solid catalyst was synthesized in the same manner as in Example 1 except that Ti( _OC6H4-4 - _CH3 ) _Cl3 was used.

Using 57 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=2080, HIP=90.9% by weight.

Comparative Example 2 In the synthesis of the titanium compound of Example 1 (B), p
- Average composition Ti(OC ₆ H ₄ -4-CH ₃ ) _1.5 using the same method except that the amount of cresol used was changed to 44.27 mg.
A monochlorobenzene solution of a titanium compound represented by Cl _2.5 was synthesized.

Ti(OC ₆ H ₄ −4−CH ₃ ) _0.5 Cl _3.5 instead of the above
_A solid catalyst was synthesized in the same _manner as in Example 1 except that Ti( _OC6H4-4 - _CH3 ) _1.5Cl2.5 was used.

Using 64 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=1570, HIP=90.5% by weight.

Comparative Example 3 In the synthesis of the titanium compound of Example 1 (B),
A solid catalyst was synthesized in the same manner as in Example 1 except that monochlorobenzene as a solvent was not used.

Using 71 mg of this solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=1900, HIP=92.0% by weight.

Example 4 (A) Synthesis of ethyl benzoate-treated solid A 100 ml flask equipped with a stirrer and a dropping funnel was purged with argon, and then 6.5 g of anhydrous magnesium chloride prepared in (A) of Example 1 was charged.
65 ml of n-heptane was added to form a slurry.

Subsequently, 1.95 ml of ethyl benzoate was charged with stirring, and the reaction was carried out at 30°C for 1 hour.

After the reaction, the mixture was allowed to stand, and the supernatant was separated, washed three times with 50 ml of n-heptane, and dried under reduced pressure to obtain 6.2 g of ethyl benzoate-treated solid.

(B) Synthesis of solid catalyst Ethyl benzoate treated solid 5 synthesized in (A) above
A solid catalyst was synthesized under the same conditions as in Example 1 (B) and (C) except that g was used.

(C) Polymerization of propylene Using 32 mg of the solid catalyst synthesized in (B) above, the amount of triethylaluminum used was 0.15 g in the propylene polymerization () in (D) of Example 1,
Polymerization of propylene was carried out in a similar manner except that methyl toluate was not used.

300 g of polypropylene powder was obtained. Also,
33 g of amorphous polymer was obtained.

Therefore, PP/Cat=10400, HIP=90.0
It was in weight%.

Example 5 (A) Synthesis of magnesium compound A 200 ml flask equipped with a stirrer, a dropping funnel, and a reflux condenser was purged with argon, and then 10 g of commercially available anhydrous magnesium chloride (calcined under reduced pressure at 400°C for 6 hours) was charged. is. While stirring, 36.4 ml of ethanol was added dropwise from the dropping funnel at 70°C.

After completely dissolving the magnesium chloride,
MgCl ₂ 6C ₂ H ₅ OH by cooling to 20℃
was prepared.

Next, after adding 300ml of silicon tetrachloride,
The reaction was carried out under reflux for 12 hours.

After the reaction, let it stand and remove the supernatant,
Washing 5 times with 50 ml of n-heptane and drying under reduced pressure gave a white solid product.

(B) Synthesis of titanium compound After purging a 200 ml flask equipped with a stirrer and a thermometer with argon, 70 ml of n-heptane as a solvent and 0.034 mol of Ti(OC ₆ H ₄ −4−CH ₃ ) ₄ were added.
0.239 mol of TiCl ₄ was charged and the temperature was raised to 95°C.
By reacting at this _temperature for 1 hour, a liquid titanium compound having _{an average composition of Ti(OC6H4-4-CH3)0.5Cl3.5 was synthesized .}

(C) Synthesis of solid catalyst 5 g of the solid product obtained in (A) above was charged into the liquid containing the titanium compound obtained in (B) above, and a contact reaction was carried out at 95°C for 1 hour with stirring. .

After the reaction was completed, the mixture was allowed to stand still and the supernatant liquid was extracted at 95°C.

Next, 50 ml of n-heptane was added, and after stirring for 5 minutes, the mixture was allowed to stand, and the supernatant liquid was extracted. This operation was repeated 5 times for washing.

A solid catalyst was obtained by drying under reduced pressure.

(D) Polymerization of propylene Example 1 Using 53 mg of the solid catalyst obtained in (C) above,
Polymerization of propylene was carried out under the same conditions as in (D).

PP/Cat=3100, HIP=92.6% by weight.

Example 6 In the synthesis of the titanium compound of Example 1 (B),
The average composition Ti (OC ₆ H ₄ -2-C ₆ H ₅ ) A liquid titanium compound with a concentration of _0.5 Cl _3.5 was synthesized.

In the synthesis of the solid catalyst in Example 1, the magnesium compound obtained in the same manner as in Example 5 (A) was used instead of anhydrous magnesium chloride, and the above Ti(OC ₆ H ₄ -2 −C ₆ H ₅ ) _0.5
A solid catalyst was synthesized in the same manner as in Example 1 except that Cl _3.5 was used.

Using 60 mg of this solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=3640, HIP=93.1% by weight.

Example 7 In the synthesis of the titanium compound of Example 1 (B),
70ml of dichlorobenzene was used as a solvent instead of monochlorobenzene, and α-cresol was used instead of p-cresol.
In the same way except using 19.68 g of naphthol,
A liquid titanium compound having an average composition of Ti(OC ₁₀ H ₇ ) _0.5 Cl _3.5 was synthesized.

In the synthesis of the solid catalyst of Example 1, the magnesium compound obtained by the same method as in Example 5 (A) was used instead of anhydrous magnesium chloride, and the above Ti(OC ₁₀ H ₇ ) _0.5 was used as the liquid titanium compound. A solid catalyst was synthesized in the same manner as in Example 1 except that Cl _3.5 was used.

Using 66 mg of this solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=3210, HIP=92.2% by weight.

Example 8 In the synthesis of the titanium compound of Example 1 (B),
The average composition was determined in the same manner except that 70 ml of 1,2-dichloroethane was used as the solvent instead of monochlorobenzene, 17.55 g of p-chlorophenol was used instead of p-cresol, and the reaction temperature was 80°C.
A liquid titanium compound represented _{by Ti(OC6H4-4-Cl)0.5Cl3.5 was synthesized .}

In the synthesis of the solid catalyst in Example 1, the magnesium compound obtained in the same manner as in Example 5 (A) was used instead of anhydrous magnesium chloride, and the above Ti(OC ₆ H ₄ -4 −Cl) _0.5 Cl _3.5
A solid catalyst was synthesized in the same manner as in Example 1 except that the contact reaction temperature was 80°C.

Using 75 mg of this solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=2960, HIP=92.3% by weight.

Comparative Example 4 In the synthesis of the solid catalyst of Example 1, Ti(OC ₆ H ₄ -4-CH ₃ ) _0.5 Cl _3.5 was used as a liquid titanium compound.
A solid catalyst was synthesized in the same manner as in Example 1 except that TiCl ₄ was used instead.

Using 140 mg of this solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=840, HIP=89.2% by weight.

Comparative Example 5 (A) Synthesis of p-cresol treated solid After purging a 200 ml flask equipped with a stirrer with argon, 10 g of anhydrous magnesium chloride prepared under the same conditions as in Example 1 (A) was charged.
100 ml of n-heptane was added to form a slurry.

Subsequently, 5.69 g of p-cresol was added while stirring, and the mixture was reacted at 50°C for 1 hour.

After the reaction, it was washed with n-heptane and dried under reduced pressure to obtain a p-cresol treated solid.

(B) Synthesis of solid catalyst A solid catalyst was synthesized in the same manner as in Example 1 except that the p-cresol treated solid synthesized in (A) above was used and titanium tetrachloride was used as the titanium compound.

(C) Polymerization of propylene Propylene was polymerized under the same conditions as in Example 1 (D) using 72 mg of the solid catalyst synthesized in (B) above.

PP/Cat=1150, HIP=88.4% by weight.

Example 9 In the synthesis of the titanium compound of Example 1 (B),
The average composition of Ti was determined using the same method except that the amount of monochlorobenzene added was changed to 90 ml, the amount of titanium tetrachloride added was changed to 10 ml, and the amount of p-cresol added was changed to 4.92 g.
A liquid titanium compound represented by _{( OC6H4-4 - CH3} ) _0.5Cl3.5 was synthesized.

A solid catalyst was synthesized in the same manner as in Example 1 except that this titanium compound was used.

Using 56 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=2570, HIP=92.1% by weight.

Example 10 In the synthesis of the titanium compound of Example 1 (B),
The average composition was prepared using the same method except that the amount of monochlorobenzene added was changed to 40 ml, the amount of titanium tetrachloride was changed to 60 ml, and the amount of p-cresol added was changed to 29.51 g.
A liquid titanium compound represented _by Ti( _{OC6H4-4 - CH3} ) _0.5Cl3.5 was synthesized.

A solid catalyst was synthesized in the same manner as in Example 1 except that this titanium compound was used.

Using 42 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=3060, HIP=92.5% by weight.

Example 11 After purging the pot of a vibrating mill equipped with a 500 ml grinding pot containing 60 stainless steel (SUS32) balls with a diameter of 12 mm with argon, the pot was replaced with commercially available anhydrous magnesium chloride (under reduced pressure, at 400°C). Time firing) 20g was charged and pulverized for 100 hours.

Next, a monochlorobenzene solution containing 2 g of a titanium compound synthesized under the same conditions as in Example 1 (B) and having an average composition of Ti(OC ₆ H ₄ -4-CH ₃ ) _0.5 Cl _3.5 was added. The grinding process was carried out for 24 hours.
After washing with n-heptane, the solid catalyst was dried under reduced pressure to prepare a solid catalyst.

Using 57 mg of the above solid catalyst, propylene polymerization was carried out under the same conditions as in Example 1 (D).

PP/Cat=2400, HIP=92.2% by weight.

<Effects of the invention> (1) Catalytic efficiency per solid catalyst and per titanium atom is extremely high. As a result, there are extremely few transition metal (titanium) residues or halogen residues that remain in the produced polymer and deteriorate the physical properties of the product polymer, such as hue, thermal stability, corrosion resistance, and foamability.
No catalyst residue removal step is required.

(2) In addition to being highly active as described above, sufficiently high stereoregularity can be obtained. In other words, since the amount of amorphous polymer produced is small and has low industrial value and remains in the produced polymer and deteriorates physical properties such as mechanical properties and blocking properties of the film, there is no need for a step to remove it. .

(3) The manufacturing process of the solid catalyst is extremely simple, and a solid catalyst with high activity and high stereospecificity can be obtained at low cost.

(4) The amount of hydrogen used for controlling the molecular weight during polymer production can be reduced, making it easy to control the molecular weight.

[Brief explanation of drawings]

FIG. 1 is a flowchart to aid in understanding the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited thereto.

Claims (1)

[Claims] 1 (A)(a) Magnesium dihalide, (b) General formula Ti(OAr)nX _4-o (Ar is a phenyl group,
Substituted phenyl group, X represents halogen, n
is a number expressed by 0<n<1. ) with a solid catalyst obtained by contact reaction in the presence of an inert solvent, and (B) general formula R _n AlY _3-n (R is an alkyl group having 1 to 8 carbon atoms). , Y represents halogen, m is 2≦
m≦3. ) in the presence of a catalyst system consisting of an activator made of an organoaluminium compound represented by the formula (1), homopolymerization of alpha olefin having 3 to 8 carbon atoms, or alpha olefin having 3 to 8 carbon atoms and ethylene or ethylene or 3 carbon atoms. A method for producing a highly stereoregular alpha-olefin polymer, comprising copolymerizing it with another alpha-olefin of ~8.