JPH0339084B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a titanium trichloride solid catalyst component for olefin polymerization. For more details, α−
The present invention relates to a method for producing a titanium trichloride solid catalyst component for olefin polymerization that has high polymerization activity and stereoregularity and produces a small amount of cationic polymer by-products when applied to olefin polymerization.

Conventionally, in the industrial production of highly crystalline polymers of α-olefins such as propylene and butene-1, catalyst systems consisting of titanium trichloride and organoaluminum compounds have been used.

Since the polymerization proceeds in a manner that includes solid titanium trichloride, titanium trichloride remains in the obtained polymer, but this residue has a negative effect on the properties such as the hue and thermal stability of the polymer. Generally, a step of extraction and removal from the polymer was required. In addition, an amorphous polymer called an atactic polymer is produced as a by-product, but its contamination degrades the mechanical properties of polymer processed products and causes stickiness, so a cleaning and removal process is generally required. It was hot.

The existence of these additional steps causes economic disadvantages in terms of raw materials and energy, and simplification has been strongly desired. Up to now, various improvements have been made to the production method of titanium trichloride, and as a result, the polymerization activity and/or stereoregularity have been greatly improved, and it has become possible to industrialize the polymerization process by simplifying the above-mentioned additional steps. As one method for producing titanium trichloride, the present inventors previously reported
-33289, 53-51285, 53-111383, 53-
132081, 54-11985, 54-11986, 56-
proposed the method described in 116706.

However, when α-olefins are polymerized using a catalyst system consisting of titanium trichloride and an organoaluminium compound, an oily cationic polymer with a lower molecular weight is generally produced as a by-product in addition to the atactic polymer, which simplifies the cleaning process. In this case, the polymer powder tends to adhere to the molded product, and smoke is generated when the molded product is processed. In addition, when titanium trichloride is supplied to a polymerization tank using an α-olefin such as propylene as a carrier, it aggregates due to the viscous oily cationic polymer generated in the piping, resulting in the formation of bulk polymers in the polymerization tank. or the pipes may become clogged.

As a result of studies on the formation mechanism of cationic polymers, it was concluded that cationic polymers are formed from titanium trichloride solid catalysts. This is because when triethylaluminum or diethylaluminum chloride is brought into contact with propylene, almost no viscous oil is produced, whereas when titanium trichloride solid catalyst is brought into contact with propylene, it generally becomes viscous as shown in the example below. This is because it produces a viscous oily substance. The NMR spectrum shows that this oil is a cationic polymer.

As a result of extensive studies, the present inventors have discovered that when reacting a titanium trichloride composition with a halogen compound, an ether compound, and an electron donor, a specific electron donor is used and these compounds are reacted in a specific order. The inventors have discovered that by adding titanium trichloride, the by-product of cationic polymers can be suppressed without impairing the polymerization activity of the titanium trichloride solid catalyst, leading to the present invention.

That is, the present invention has the following formula: 1 General formula TiCl ₃ (R ¹ nAlX _3-o ) _p (E) _q (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and X is a halogen atom. E represents an ether compound. n, p, q are 0≦n≦2, 0≦p, respectively.
It is a number expressed by ≦1, 0≦q≦1. ) at least one halogen compound selected from the following (a), (b), and (c), (a) general formula X ₂ (where X is Cl , Br or I atom); (b) General formula XX'a (where X and X' are Cl, Br or
or an I atom, and a is a number of 1 or 3); (c) A halogen-containing hydrocarbon compound having 1 to 10 carbon atoms; 3 General formula R ² -O-R ³ (However, , R ² and R ³ represent an alkyl group having 1 to 10 carbon atoms, and R ² and R ³ may be the same group or different groups. Compound,
and 4 general formula R ⁴ R ⁵ R ⁶ N (however, R ⁴ , R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 30 carbon atoms, and each may be the same group or a different group) In a method for producing a titanium trichloride solid catalyst component for olefin polymerization by reacting with a tertiary amine represented by
Titanium trichloride for olefin polymerization, characterized in that the ether compound and the tertiary amine are added to a suspension of the titanium trichloride composition in an inert solvent, and after at least 3 minutes, the halogen compound is added. This is a method for producing a solid catalyst component.

General formula TiCl ₃ (R ¹ nAlX _3-o ) _p used in the present invention
(E) _q (However, R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, X is a halogen atom, and E is an ether compound. n, p, and q are each 0≦n≦
2, 0≦p≦1, 0≦q≦1) The titanium trichloride composition is preferably produced by the following method.

That is, the first method: (1) TiCl ₃ (AlCl ₃ ) _1/3 obtained by reducing titanium tetrachloride with metallic aluminum or activated by ball milling or the like. Titanium chloride composition; (2) Titanium tetrachloride has the general formula R ¹ _o ′AlX _3-o ′ (However, R ¹
represents a hydrocarbon group having 1 to 8 carbon atoms, and X represents a halogen atom. (3) A titanium trichloride composition obtained by the method (2) above; The reduced solids were dissolved at 100% in the presence or absence of an inert hydrocarbon solvent.
Titanium trichloride composition obtained by heat treatment at a temperature of ~200°C; (4) The reduced solid obtained by the method (2) above is expressed by the general formula
R ⁵ lAlX _3-l (However, R ⁵ is a hydrocarbon group having 1 to 8 carbon atoms, and X is a halogen atom. l is 1≦l
A titanium trichloride composition obtained by reacting with an aluminum compound represented by <1.5); Second method: The titanium trichloride composition obtained by the above first method is General formula R ⁶ -O-R ⁷ (However, R ⁶ and
R ⁷ represents an alkyl group having 1 to 10 carbon atoms, and R ₆ and
A titanium trichloride composition containing an ether compound obtained by reacting with an ether compound represented by R ⁷ may be the same group or a different group; Method of: General formula R ⁶ -O-R ⁷ (However, R ⁶ and R ⁷ represent an alkyl group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ may be the same group, or In the presence of an ether compound represented by (which may be a different group),
Titanium tetrachloride is represented by the general formula R ¹ _o ′AlX _3-o ′ (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and X is a halogen atom. n′ is expressed as 1≦n′≦3. )
A titanium trichloride composition containing an ether compound obtained by reduction with an organoaluminum compound represented by; Fourth method: Reacting the titanium trichloride composition obtained by the second method above with titanium tetrachloride. Titanium trichloride composition obtained by: General formula R ¹ _o ′AlX _3-o ′ (R ¹ has 1 to 8 carbon atoms) used in the production of the reduced solid in (2) of the first method above.
, X represents a halogen atom. n' is a number expressed as 1≦n'≦3. ) Specific examples of organoaluminum compounds represented by are methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, ethylaluminum sesquichloride, dimethylaluminum chloride, diethylaluminium chloride, di-n-propylaluminum chloride, and trimethylaluminum. , triethylaluminum, triisobutylaluminum, ethyldicyclohexylaluminum, triphenylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum bromide, diethylaluminum iodide, and the like.

Among these, diethylaluminum chloride and ethylaluminum sesquichloride give particularly preferable results.

The reduction reaction to obtain the reduced solid is carried out at a temperature between -60 and 60°C, preferably between -30 and 30°C.

There is no particular restriction on the reduction reaction time, but a time between 1 hour and 6 hours is usually suitably used.

After the reduction reaction is completed, a post-reaction is further carried out at a temperature of -30 to 100°C. The resulting reduced solid is separated into pentane, hexane, heptane, octane,
Washing is repeated several times with an inert hydrocarbon solvent such as decane, toluene, xylene, decalin, or tetralin.

The molar ratio of the organoaluminum compound and titanium tetrachloride can be freely changed depending on the purpose. Favorable results are obtained with 0.5 to 1.5 of diethylaluminum chloride per mole of titanium tetrachloride.
moles, in the case of ethylaluminum sesquichloride, from 1.5 to 2.5 moles.

Further, the reduction reaction is preferably carried out by diluting the titanium tetrachloride and the organoaluminum compound to a concentration of 10 to 70% by weight with an inert hydrocarbon solvent.

Next, in the method (3) above, the heat treatment of the reduced solid is carried out either in the presence or absence of an inert hydrocarbon solvent. The heat treatment temperature ranges from 100℃ to 200℃ depending on the purpose, but usually
A temperature range of 120-180°C gives more favorable results. There are no particular restrictions on processing time, but usually
Time periods between 30 minutes and 6 hours are preferably used.

In the method (4) above, the reduced solid is expressed by the general formula
R ⁵ lAlX _3-l (R ⁵ is a hydrocarbon group having 1 to 8 carbon atoms,
X represents a halogen atom. Alkylaluminum dihalogenide is preferable as the compound used when reacting with the aluminum compound represented by (l is a number expressed as 1≦l<1.5).

Alkylaluminum dichlorides give particularly favorable results.

Specific example compounds include methylaluminum dichloride, ethylaluminum dichloride,
n-propylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride, n-octylaluminum dichloride, phenylaluminum dichloride, cyclohexylaluminum dichloride, methylaluminum dibromide, methylaluminum diiodide, ethylaluminum diiodide, etc. can be given. Among these, ethylaluminum dichloride gives particularly favorable results.

In addition, the above aluminum compound may be used alone or in combination.
It may be a mixture of more than one type of aluminum compound. The above reaction is preferably carried out in the presence of an inert hydrocarbon solvent. Reaction temperature is 0~200
℃, preferably 30-150℃. There is no particular restriction on the reaction time, but a time between 30 minutes and 5 hours is usually suitably used. After the reaction, the titanium trichloride composition is separated and washed several times with an inert hydrocarbon solvent.

Next, in the second method, each of the titanium trichloride compositions obtained by the first method has the general formula R ⁶ -
The present invention relates to a titanium trichloride composition produced by reacting with an ether compound represented by O- ^R7 . As an ether compound, diethyl ether,
Di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, dineopentyl ether, di-n-hexyl ether, di-n
-octyl ether, methyl-n-butyl ether, methyl-isoamyl ether, ethyl-isobutyl ether and the like are preferred. Particularly preferred are di-n-butyl ether and diisoamyl ether.

The amount of ether compound to be used is between 0.0001 and 0.3 mol per gram of titanium trichloride composition, preferably
The amount is 0.001 to 0.002 mol, particularly preferably 0.002 to 0.01 mol. The reaction temperature is 0 to 150℃, preferably 10
~120℃. Further, the reaction time is preferably 5 minutes or more and 6 hours or less. The reaction is carried out diluted with an inert hydrocarbon solvent. After the reaction is completed, the solid is separated and washed several times with an inert hydrocarbon solvent to obtain a titanium trichloride composition containing an ether compound.

Next, a third method is carried out in exactly the same manner as in method (2) above, except that an ether compound represented by the general formula R ⁶ -O-R ⁷ is present in the process of producing the reduced solid. The amount of the ether compound used is preferably 0.5 to 5 mol, particularly 0.7 to 3 mol, per mol of titanium tetrachloride.

Next, the fourth method relates to a titanium trichloride composition produced by reacting each titanium trichloride composition obtained by the second method with titanium tetrachloride. The reaction is advantageously carried out in the presence of an inert hydrocarbon solvent. Inert hydrocarbons include pentane, hexane, heptane, octane,
Examples include compounds such as decane, toluene, xylene, decalin, and tetralin.

The concentration of titanium tetrachloride used is usually preferably in the range of 10% by volume to 70% by volume. The processing temperature is preferably from room temperature to 100°C, preferably from 30°C to 80°C. The processing time is preferably 30 minutes to 10 hours.

As a method for producing a titanium trichloride composition, the first and second methods are preferred, and the first method is particularly preferred. Among the first methods, methods (2), (3), and (4) are particularly preferred.

The titanium trichloride composition thus obtained is treated with 1) a halogen compound, 2) a general formula R ² -O-R ³ (however, R ²
and R ³ represents an alkyl group having 1 to 10 carbon atoms,
R ² and R ³ may be the same group or different groups) and 3) general formula R ⁴ R ⁵ R ⁶ N (however, R ⁴ , R ^Five
and R ⁶ represents a hydrocarbon group having 1 to 30 carbon atoms,
They may be the same group or different groups. ) is reacted with a tertiary amine represented by

The halogen compound is at least one compound selected from the following (a), (b), and (c).

( _a ) Halogen represented by the general formula , a is a number of 1 or 3); (c) A halogen-containing hydrocarbon compound having 1 to 10 carbon atoms; Iodine is preferred as the halogen. Examples of the interhalogen include bromine chloride, iodine chloride, iodine trichloride, and iodine bromide, with iodine trichloride being preferred. Examples of halogen-containing hydrocarbon compounds having 1 to 10 carbon atoms include chloromethane, dichloromethane, chloroform, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, chlorethylene, and dichloroethylene. ,
Trichlorethylene, tetrachlorethylene, chlorpropane, dichloropropane, trichlorpropane, tetrachlorpropane, hexachlorpropane, octachlorpropane, chlorbutane,
Dichlorobutane, trichlorobutane, tetrachlorobutane, chlorpentane, dichloropentane,
Trichloropentane, chlorhexane, dichlorohexane, dichlorooctane, dichlorocyclohexane chlorobenzene, dichlorobenzene, chloroethylbenzene, chlorotoluene, bromomethane, tribromomethane, bromoethane, dibromoethane, tetrabromoethane, bromopropane,
Bromobutane, bromopentane, bromohexane, bromotoluene, chlorobromoethane, ethylene chrome bromide, iodomethane, diiodomethane, iodoform, iodoethane, diiodoethane, iodopropane, diiodopropane, iodobutane, diiodobutane, iodopentane, iodohexane, iodobenzene, iodo Examples include toluene. As the halogen compound, iodine or an iodine-containing compound is preferred, and iodine is particularly preferred. The amount of halogen compound to be used is from 10 ^-5 to 5 x 10 ^-2 mol, preferably from 10 ^-4 to 10 ^-2 mol, per gram of titanium trichloride composition.

General formula R ² -O-R ³ (However, R ² and R ³ represent an alkyl group having 1 to 10 carbon atoms, and R ² and R ³ may be the same group or different groups. ) Examples of the ether compounds represented by diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, dineopentyl ether, di- Compounds such as n-hexyl ether, di-n-octyl ether, methyl-n-butyl ether, methyl-isoamyl ether, and ethyl-isobutyl ether are preferred. Particularly preferred are di-n-butyl ether and diisoamyl ether. The amount of ether compound used is 10 ^-4 per gram of titanium trichloride composition.
-0.03 mol, preferably 10 ^-3 -0.02 mol, particularly preferably 0.002-0.01 mol.

General formula R ⁴ R ⁵ R ⁶ N (However, R ⁴ , R ⁵ and R ⁶ represent hydrocarbon groups having 1 to 30 carbon atoms, and may be the same group or different groups. ) as the tertiary amine represented by triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, Tri-n-decylamine, trilaurylamine, tristearylamine, triphenylamine, tribenzylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylcoconutamine, dimethylmystylamine, dimethylpalmitylamine,
Dimethylstearylamine, dimethyloleylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, N,N-dimethyl-1-naphthylamine, N,N-dimethylcyclohexylamine, N,N-diethylaniline, N,N Compounds such as -diethyl-1-naphthylamine and N,N-diethylcyclohexylamine are preferred.

The amount of tertiary amine used is between 1 x 10 ^-4 and 1 x 10 ^-2 mol, especially 2 x
10 ⁻⁴ to 1×10 ⁻³ mol is preferred.

The reaction of the titanium trichloride composition, the halogen compound, the ether compound, and the tertiary amine is performed by adding the ether compound and the tertiary amine to a suspension of the titanium trichloride composition in an inert solvent, and after at least 3 minutes have elapsed. , by adding a halogen compound.

Inert solvents include aliphatic hydrocarbons such as hexane, heptane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene;
Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane can be used.

The amount of titanium trichloride composition in the inert solvent 1 is preferably between 50 and 600 g, particularly between 100 and 500 g.

The reaction temperature is 20-150°C, preferably 75-120°C. The reaction is preferably carried out while stirring the suspension of the titanium trichloride composition.

The ether compound and the tertiary amine may be added at the same time, or either may be added separately first, but it is preferable to add them at the same time.

Halogen compounds include ether compounds and tertiary compounds.
After at least 3 minutes have elapsed after adding the grade amine,
It is particularly preferable to add the mixture after 5 to 60 minutes have elapsed. Preferably, the solid halogen compound is added as a solution dissolved in an inert solvent.

The reaction time after adding the halogen compound is preferably 5 minutes or more and 6 hours or less, particularly 15 minutes or more and 2 hours or less.

After the reaction is completed, the solid is separated and washed several times with an inert hydrocarbon solvent to obtain the titanium trichloride solid catalyst component for olefin polymerization of the present invention.

If the halogen compound, ether compound, and tertiary amine are added in a different order than in the method of the invention described above, e.g., the three components are added simultaneously, or the halogen compound is added prior to the addition of the ether compound and the tertiary amine, the cation The suppressing effect of the present invention on polymer by-products is not exhibited.

In addition, when the reaction with a halogen compound and an ether compound is followed by washing or further drying, and then the reaction with a tertiary amine, the polymerization activity decreases, and moreover, the present invention has no effect on the by-product of cationic polymers. No suppressive effect occurs.

The titanium trichloride solid catalyst component for olefin polymerization of the present invention can polymerize α-olefin in high yield and with high stereoregularity by using an organoaluminum compound as an activator. On this occasion,
There is little by-product of cationic polymer. Examples of organoaluminum compounds include trialkylaluminum,
Dialkyl aluminum hydride, dialkyl aluminum halide, etc. are preferably used.

Particularly preferred are diethylaluminum chloride and a mixture thereof with triethylaluminum.

A known Lewis base may also be added to the above catalyst system. Typical examples of such Lewis bases include methyl methacrylate, ethyl benzoate, γ-butyrolactone, and ε-
These include ester compounds such as caprolactone, and phosphite ester compounds such as triphenyl phosphite and tri-n-butyl phosphite.

Polymerization is usually carried out at a temperature of 0 to 100°C and a pressure of about normal pressure to about 100 atm. Polymerization can be carried out either continuously or batchwise.

α-olefins having 2 to 10 carbon atoms are preferred, and propylene is particularly preferred. However, the solid catalyst of the present invention can also be suitably used for random copolymerization or heteroblock copolymerization of propylene with other olefins such as ethylene and/or butene-1.

Either slurry polymerization using an inert hydrocarbon or liquid monomer as a polymerization medium or gas phase polymerization in a gaseous monomer is possible.

The method of the present invention will be explained below using Examples, but the present invention is not limited thereto.

Example 1 A Production of titanium trichloride composition A 200 ml four-necked flask equipped with a stirrer and a dropping funnel was purged with argon, and 48 ml of n-heptane and 12 ml of titanium tetrachloride were put into the flask.
Keep this solution at -10°C. Next, 61ml of n-heptane
A solution consisting of 25 ml of ethylaluminum sesquichloride and ethylaluminum sesquichloride was added dropwise from the dropping funnel over 3 hours while maintaining the temperature inside the flask at -5 to -10°C.

After completion of the dropwise addition, the temperature was raised to 25°C in 30 minutes, stirring was continued for 30 minutes at 25°C, then the temperature was raised to 75°C in 30 minutes, and stirring was continued for an additional 2 hours. The mixture was then allowed to stand at room temperature for solid-liquid separation, washed four times with 100 ml of n-heptane, and then dried under reduced pressure to obtain a titanium trichloride composition.

B. Production of titanium trichloride solid catalyst component for olefin polymerization (hereinafter referred to as titanium trichloride solid catalyst) After purging a 200 ml flask equipped with a stirrer with argon, 20 g of the titanium trichloride composition and 54 ml of toluene were added. The temperature inside the flask was maintained at 95°C.

Add 21.9 ml of di-n-butyl ether and 3.4 ml of tri-n-octylamine into a flask and heat at 95°C.
Stirred for 30 minutes. Next, add 2.3g of iodine to toluene.
Add the solution dissolved in 46.1 ml and further incubate at 95℃ for 1 hour.
A time reaction was performed. After the reaction was completed, the mixture was allowed to stand at room temperature for solid-liquid separation, and then treated with 40 ml of n-heptane twice at room temperature.
After repeating washing twice with 40 ml of toluene and twice with 40 ml of n-heptane, it was dried under reduced pressure to obtain a titanium trichloride solid catalyst.

C Cationic polymerization test An autoclave with an internal volume of 130 ml was replaced with argon, and 1.055 g of the titanium trichloride solid catalyst obtained in B above was used.
was charged, and then 40 g of liquefied propylene was charged.

The autoclave was kept at 60°C for 4 hours while stirring with a magnetic stirrer.

After releasing the excess propylene, 100 ml of n-heptane was added to the autoclave and stirred at 60°C for 15 minutes.

After pouring the n-heptane solution into 30 ml of dilute hydrochloric acid aqueous solution and decomposing the titanium trichloride solid catalyst,
- The heptane layer was separated and evaporated to dryness at 80°C to obtain 142 mg of viscous extract.

Therefore, the amount of cationic polymer produced is 135 mg/g.
It was a solid catalyst.

D. Polymerization of propylene An electromagnetic induction stirring autoclave with an internal volume of 1 was purged with argon, 15 mg of triethylaluminum and 300 g of liquefied propylene were charged, and after stirring at 65° C. for 30 minutes, propylene was released. Then, after drying in an autoclave at 65℃ under reduced pressure, 0.66Kg/cm ²
Hydrogen equivalent to a partial pressure of was charged.

Next, 0.75 g of diethylaluminium chloride and 29.3 mg of the titanium trichloride solid catalyst obtained in B above were charged with 40 ml of n-heptane, and then 300 ml of liquefied propylene was added.
g was press-fitted into the autoclave.

The autoclave was kept at 65°C for 1 hour with stirring. After releasing the excess propylene, the obtained polymer was dried under reduced pressure at 60° C. for 6 hours to obtain 86.7 g of polymer. When the titanium content in the polymer was analyzed by fluorescent X-ray, it was found to be 74.2 ppm.

Therefore, the polymerization activity is 13480 gpp/g. It was Ti.

Comparative Example 1 In the production of the titanium trichloride solid catalyst B of Example 1, a toluene solution of iodine, di-n-
A titanium trichloride solid catalyst was obtained in the same manner as in Example 1, except that butyl ether and tri-n-octylamine were added instantaneously in this order and the reaction was carried out at 95°C for 1 hour.

Using the above titanium trichloride solid catalyst, the amount of cationic polymer produced was determined according to method C in Example 1, and the amount of cationic polymer produced was 198 mg/g.
It was a solid catalyst.

Further, when propylene was polymerized using the titanium trichloride solid catalyst according to method D of Example 1, the polymerization activity was 11,350 gpp/g. It was Ti.

Comparative Example 2 After purging a 500 ml flask equipped with a stirrer with argon, 59.3 g of a titanium trichloride composition obtained in the same manner as A of Example 1 and 141 ml of toluene were added, and then 7.3 g of iodine was added to the flask with toluene. 146 ml of the solution and 65 ml of di-n-butyl ether were added. After reacting at 95° C. for 1 hour, the mixture was allowed to stand at room temperature for solid-liquid separation, washed five times with 100 ml of n-heptane at room temperature, and dried under reduced pressure to obtain a titanium trichloride solid catalyst (2).

Next, a 100 ml flask equipped with a stirrer was purged with argon, 10 g of the solid catalyst () obtained above and 50 ml of toluene were added, the temperature was raised to 95°C, and 1.7 ml of tri-n-octylamine was added. and the reaction was carried out at 95°C for 1 hour. After the reaction, the solid-liquid was separated by standing at room temperature, washed twice with 20 ml of n-heptane, twice with 20 ml of toluene, and twice with 20 ml of n-heptane at room temperature, and dried under reduced pressure to obtain a titanium trichloride solid catalyst ( ) was obtained.

Using the above titanium trichloride solid catalyst (2), the amount of cationic polymer produced was determined according to method C of Example 1, and the amount of cationic polymer produced was 180
mg/g solid catalyst.

Further, when propylene was polymerized using a titanium trichloride solid catalyst () according to method D in Example 1, the polymerization activity was 10,980 gpp/g. It was Ti.

Example 2 In the production of the titanium trichloride solid catalyst in B of Example 1, di-n-butyl ether and tri-n-octylamine were added and stirred at 95°C for 5 minutes,
A titanium trichloride solid catalyst was obtained in the same manner as in Example 1, except that a toluene solution of iodine was added and the reaction was carried out at 95° C. for 1 hour.

Using the above titanium trichloride solid catalyst, the amount of cationic polymer produced was determined according to method C of Example 1, and it was found to be 116 mg/g solid catalyst.

Further, when propylene was polymerized according to method D of Example 1, the polymerization activity was 12420 gpp/
g. It was Ti.

Example 3 In the production of the titanium trichloride solid catalyst in B of Example 1, di-n-butyl ether and tri-n-octylamine were added, stirred at 95°C for 1 hour, and then a toluene solution of iodine was added, A titanium trichloride solid catalyst was obtained in the same manner as in Example 1, except that the reaction was further carried out at 95°C for 1 hour.

Using the above titanium trichloride solid catalyst, the amount of cationic polymer produced was determined according to method C of Example 1, and was found to be 119 mg/g solid catalyst.

Further, when propylene was polymerized according to method D of Example 1, the polymerization activity was 12,840 gpp/
g. It was Ti.

Comparative Example 3 In the production of the titanium trichloride solid catalyst in B of Example 1, n was used instead of tri-n-octylamine.
A titanium trichloride solid catalyst was obtained in the same manner as in Example 1 except that 2.1 ml of -butyl phosphate was used.

Using the above titanium trichloride solid catalyst, the amount of cationic polymer produced was determined according to method C in Example 1, and the amount of cationic polymer produced was 516 mg/g.
It was a solid catalyst.

Comparative Example 4 After purging a 200 ml flask equipped with a stirrer with argon, 14.6 g of the titanium trichloride composition synthesized under the same conditions as Example 1 A and 73 ml of toluene were added, and the temperature inside the flask was raised to 95°C. I kept it.

Next, 16.0 ml of di-n-butyl ether, 1.56 ml of n-butyl phosphate, and 2.4 g of iodine were added to the flask in this order, and a reaction was carried out at 95°C for 1 hour.
After the reaction is complete, leave it at room temperature for solid-liquid separation, and add 40 ml of n-heptane twice and 40 ml of toluene twice at room temperature.
After repeating washing twice with 40 ml of n-heptane, the mixture was dried under reduced pressure to obtain a titanium trichloride solid catalyst.

Using the above titanium trichloride solid catalyst, the amount of cationic polymer produced was determined according to method C in Example 1, and the amount of cationic polymer produced was 674 mg/g.
It was a solid catalyst.

[Brief explanation of drawings]

FIG. 1 is a flowchart of the catalyst preparation process to aid understanding of the present invention. This flowchart is a representative example of an embodiment of the present invention,
The present invention is not limited to this in any way.

Claims (1)

[Claims] 1 General formula TiCl ₃ (R ¹ _o AlX _3-o ) _p (E) _q (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and X is a halogen atom. Further, E represents an ether compound.n,
p and q are respectively 0≦n≦2, 0≦p≦1, 0≦
It is a number expressed by q≦1. ) at least one halogen compound selected from the following (a), (b), and (c), (a) general formula X ₂ (where X is Cl , Br or I atom); (b) General formula XX'a (wherein X and X' represent Cl, Br or I atoms, and a is a number of 1 or 3)
(c) A halogen-containing hydrocarbon compound having 1 to 10 carbon atoms; 3 General formula R ² -O-R ³ (wherein R ² and R ³ are alkyl groups having 1 to 10 carbon atoms) and R ² and R ³ may be the same group or different groups.), and ether compounds represented by the general formula R ⁴ R ⁵ R ⁶ N (however, R ⁴ , R ⁵ and R ⁶ each represent a hydrocarbon group having 1 to 30 carbon atoms, and may be the same group or different groups.) Tertiary amine represented by In a method for producing a titanium trichloride solid catalyst component for olefin polymerization by reacting with,
Titanium trichloride for olefin polymerization, characterized in that the ether compound and the tertiary amine are added to a suspension of the titanium trichloride composition in an inert solvent, and after at least 3 minutes, the halogen compound is added. Method for producing solid catalyst components.