JPS5913630A - Manufacture of solid titanium trichloride for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To manufacture solid TiCl3 for the polymn. of alpha-olefin with superior transparency and impact strength when purple fine-grained solid TiCl3 is deposited from a liq. material contg. TiCl3, by adding TiCl4 in a specified ratio in the deposition stage. CONSTITUTION:TiCl4 is mixed with ether or further mixed with twice as much hydrocarbon or halogenated hydrocarbon solvent as the ether to prepare a uniform liq. material, and the TiCl4 is reduced to TiCl3 by adding an org. Al compound to the liq. material. The resulting liq. material contg. TiCl3 is treated at >=150 deg.C to deposit purple fine-grained solid TiCl3. Thus, solid TiCl3 for the polymn. of alpha-olefin is manufactured. In the deposition stage, after depositing TiCl3 by >=80% of the amount of all of TiCl3 to be deposited, TiCl4 is added in 0.2-10molar ratio of TiCl4 to all of TiCl3, and aging is continuously carried out at 60-120 deg.C. Purple fine-grained solid TiCl3 for the polymn. of alpha-olefin with superior transparency, impact strength and high commercial value can be manufactured in a high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing solid titanium trichloride useful as a catalyst component for alpha-olefin polymerization.

Specifically, it relates to three production methods in which solubilization was performed in the presence of ether.

Conventionally, α-olefins, especially propylene, butene-
(1) Titanium tetrachloride? Titanium trichloride obtained by reducing with hydrogen and then pulverizing in a ball mill to activate it (2) Titanium trichloride composition obtained by reducing with titanium tetrachloride gold metal aluminum and then pulverizing in a ball mill (3) Titanium tetrachloride After reducing with organic aluminum,
Examples include titanium trichloride compositions obtained by heat treatment.

However, these three-group monohititanium and titanium trichloride compositions have nine molecules+i in terms of catalytic activity and stereoregularity.
? Not only is it not possible to produce 4 pairs of polymers, it requires a process to remove the catalyst residue from the polymer and a process to remove the unswollen water agglomeration that is a by-product of Nagato, and the utilization rate of raw material monomers is low, etc. Its usefulness was low.

As an improvement of the method for producing these normal salt titanium compositions, titanium trichloride liquid fc liquefied in the presence of ether
A method is known in which purple fine-grained solid normal salt f titanium gold is obtained by precipitation treatment at a temperature below θ'0.

Also, for example, special public Sho SS-・fguj/issue, I-1
- Mado JJ-ZA No. 952 and JΔ°-♂0θ3 describe a method in which a liberating agent is completely added to liquefied titanium trichloride to precipitate purple fine-grained solid titanium trichloride.

Also, Tokko Akira! Coog/θg θ describes a method in which solid titanium trinomide is completely precipitated by adding a liberating agent and adding temperature control. Furthermore, hour lI? 3j,!
No.-♂937 describes a method in which solid titanium trichloride is precipitated by using a liberating agent or by controlling temperature.

Titanium trichloride obtained by these methods has high catalytic activity and stereoregularity, and it is possible to realize a simple process that completely omits the process of removing catalyst residual gold from the polymer and the process of removing by-product amorphous polymers. However, in a simple process in which no by-produced amorphous polymer is removed, the stereoregularity is still insufficient for some product applications, so it becomes necessary to further improve the stereoregularity. More than an example? There is a method in which a relatively large amount of a substance consisting of a child-injecting compound is added to the MB system as a third component. When implementing these methods, a prepolymerization tank and equipment for supplying the third component are required. Also, depending on the type of the third component, moss buildup within the system itself or its decomposition products may occur. This may adversely affect physical properties such as odor, transparency, and impact strength of the product, leading to a decrease in product value.

The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, they have arrived at the present invention. In other words, the gist of the present invention is to provide a liquid titanium trichloride liquefied in the presence of ether. l! In a method for producing purple fine particulate solid titanium trichloride by precipitation treatment at a temperature of θ゛0 or less, the amount of fine particulate solid titanium trichloride precipitated from a cough titanium trichloride liquid is at least ♂θchi. Then, the concentration of titanium tetrachloride in the system is θ with respect to the precipitated solid titanium trichloride. After the molar ratio is maintained at 0.5 molar ratio or less and the amount of precipitation reaches 1θ or more, titanium tetrachloride is added to reduce the amount of titanium tetrachloride in the system to 0.7 molar ratio relative to the precipitated solid titanium trichloride. A method for producing solid titanium trichloride for α-olefin polymerization, characterized in that the molar ratio is 10 to 10.

To explain in more detail, the ether used to prepare the titanium trichloride liquid is an ether soluble in a hydrocarbon solvent, and usually has the general formula:
Examples include ethers represented by R5 (wherein R? and RI' all represent the same or different hydrocarbon residues). In the formula, R4 and Hl are ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl,
Alkyl groups such as dodecyl, preferably linear alkyl groups; alkenyl groups such as butenyl, octenyl, decynyl, preferably linear alkenyl groups; aryl groups such as tolyl, xylyl, ethylphenyl, alkyl groups such as benzyl, etc. Can be mentioned. Preferred are dialkyl ether, dithyl, di-n-propyl ether, di-n-butyl ether, di-n-amyl ether, di-n-hexyl ether, di-n-hebutyl ether, di-n-octyl ether, di -n-acyl ether, sean-)”y
'sil, :r--te/l/, n-amyl-n-butyl ether, n-butyl-n-octyl ether, n-propyl-n-hexyl ether, bis(/-futhynyl)
Examples thereof include x-fl, bis(/-octenyl) ether, propyl-7-butenyl ether, and the like.

As a method for producing a liquid titanium trichloride in the presence of ether as described above, there are usually the following methods.

(A) A method in which titanium tetrachloride is used as a starting material and reduced with an organoaluminum compound in the presence of ether and an appropriate solvent as necessary. (B) A method in which titanium tetrachloride is used as a starting material and reduced with an organoaluminum compound in the presence of an appropriate solvent as necessary. First, method (A) will be explained. The organoaluminum compound used for reduction has the general formula AtflλX,
-n (in the formula, R6 is a hydrocarbon residue having a carbon atom number of / to -0, n represents a number of / to 3, or a halogen atom), preferably a compound represented by the formula Compounds in which R6 is an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl are exemplified. Specifically, tri'alkylaluminiumuno-nidimethylaluminum monochloride such as triethylaluminum, tripropylaluminum, and tributylaluminium, dialkylaluminum such as diethylaluminium monochloride, cyclobylaluminium monochloride, and diethylaluminium monobromide. Monohalides; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride; alkyl aluminum cybarides such as methyl aluminum dichloride and ethyl aluminum dichloride.

Specifically, the method for preparing a liquid in method (A) is as follows: (a) A method in which an organoaluminum compound is added to a homogeneous liquid consisting of titanium tetrachloride and ether, or the order of addition is reversed.

(b) A method in which a homogeneous liquid substance consisting of an organoaluminum compound and ether is added to titanium tetrachloride, or the order of addition is reversed.

(C) A solution consisting of titanium tetrachloride and ether, or a method in which the order of addition is reversed.

(b) Above (a) to (C) with addition of -Jθ°C or less
A method in which the temperature is raised at a specified temperature change.

etc. will be kicked off by =1.

The processing temperature is '>tli usually -3θ°0~3! °C suitable bite is selected from the range of o'o to 3j゛0. The number of each component used and the organoaluminum compound are expressed by the molar ratio of titanium in titanium tetrachloride to the hydrocarbon group (R6 in the general formula) in the organoaluminum compound, /:θ, /~/!
IO preferably /: from the range of 0.3 to /x/θ,
The ether is a molar ratio of ether: titanium tetrachloride, l:
θ, O! ~/:! Preferably /:θ, 2! ~t:ko,
Each is selected from the range of j.

Further, when preparing the liquid material or after preparing the liquid material fc, it is preferable that a suitable solvent, such as a hydrocarbon solvent or a halogenated hydrocarbon solvent, be present in an amount equal to or larger than the amount of ether. As a hydrocarbon solvent, n-
Saturated aliphatic hydrocarbons such as pentane, n-hexane, n-hebutane, n-octane, n-dodecane, liquid paraffin, etc. 3Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane; Aromatics such as benzene, toluene, xylene, etc. Group hydrocarbons: chlorobenzene, bromobenzene, ortho-,
Examples include halogenated hydrocarbons such as meta- and para-dichlorobenzene. Specifically, it is selected as appropriate depending on the type of ether mainly used. For example, when diethyl ether is used, a halogenated hydrocarbon solvent or a compound of a halogenated hydrocarbon solvent and a hydrocarbon solvent is selected. When using an ether in which at least one of R' and R'' in the above general formula is an alkyl group or alkenyl group having 3 or more carbon atoms, an aromatic hydrocarbon solvent is preferably used, followed by an alicyclic carbonization A hydrogen solvent is chosen and R4.
When using an ether in which Rm is an alkyl group or alkenyl group having a carbon number of g or more, a saturated aliphatic hydrocarbon aqueous bed solvent is preferably used.

Furthermore, a small amount of iodine, titanium tetrabromide, or titanium tetraiodide may be present when titanium tetrachloride is ring-formed with an organoaluminum compound in the presence of ether.

Next, to explain method (B), solid titanium trichloride may be, for example, solid titanium trichloride obtained by cyclizing titanium tetrachloride with hydrogen gas, aluminum or an organoaluminum compound, or solid titanium trichloride obtained in this way. Titanium chloride? Further examples include those that are ground in a ball mill.

Treatment of solid titanium trichloride with ether is carried out by mixing in a conventional manner. It is usually preferable to carry out such a treatment in the presence of a suitable solvent, such as a hydrocarbon solvent or a halogenated hydrocarbon solvent, in an amount of at least one time the amount of ether, as in the method (A). The hydrocarbon solvent and halogenated hydrocarbon solvent include those listed above, and are appropriately selected depending on the type of ether. (B) The amount of ether used in the method is such that the molar ratio of ether:titanium trichloride is preferably 1 or more.
-J' range.

The liquid thus obtained is a homogeneous solution or mixture of titanium trichloride ether in a hydrocarbon solvent, in which titanium trichloride produced from the ring element of titanium tetrachloride is complexed with ether, and the brown i yt is Yoshi green? It is a dark brown liquid, but in some cases there may be a small amount of solid component.
It may be f.

Titanium trichloride liquid prepared by the above method/! The precipitation treatment is performed at a temperature of 1W below 0°C.

There is no limit to the method of obtaining fine particulate solid titanium trichloride by precipitation from a liquid at a temperature of Δ0゛0 or less. After adding the halogenated hydrocarbon solvent, /Jθ
Temperature of 0° or less, usually 0°C~/20°C, preferably 0°0~20°C, particularly preferably ≦θ'O-
/θo'o to precipitate. In addition, the number of moles of titanium and aluminum in the titanium trichloride liquid is smaller than the number of moles of ether.
[Complete precipitation may be promoted by adding a chemical. As a liberating agent, the above-mentioned liquid 'f' has the function of reacting with the constituent complex of titanium trichloride and needle to precipitate titanium trichloride, which has stronger machinability than titanium trichloride. Examples of Lewis acids include boron trifluoride, boron trifluoride, sodium tetrachloride, ternary aluminum, alkyl aluminum dichloride, alkyl aluminum sesquichloride, dialkyl aluminum chloride, etc. , aluminum chloride, such as aluminum mitaka, alkylaluminium dichloride, etc. are preferred.The amount of Jt, p; It is preferably less than the culture mole.

In the above manner, three purple fine granular solids 1 are extracted from the liquid material.
Titanium precipitates.

The amount of precipitation! The concentration of titanium tetrachloride in the system is kept below 0.01 molar ratio to titanium trichloride until the concentration of titanium tetrachloride precipitates, and the concentration of titanium tetrachloride is maintained at a molar ratio of 0.01 or less to titanium trichloride until the concentration of titanium tetrachloride is precipitated. It is something that is added to the ♀.

If titanium tetrachloride is added at a stage when the amount of fine-grained solid titanium trichloride precipitated is too small, the final product will be fine-grained solid titanium trichloride. Polymerization kl? If the result is 'Y', fine powder may be formed in the produced propylene polymer powder, so it is preferable!
t L, <no. 9 powder in the polymer is, for example, −H<
6) It adheres to integral slurry piping and flux system piping, etc., causing blockages in these pipes, and impairing safety during handling of polymer powder. It is.

When adding titanium tetrachloride, the entire titanium tetrachloride may be added as it is, and in the present invention,
The precipitated amount of fine-grained solid titanium trichloride means -t i % of the titanium trichloride precipitated up to that point, based on the total titanium trichloride produced.

Here, "total produced titanium trichloride" refers to the theoretical production of solid titanium trichloride, and the number of moles thereof is the number of moles of titanium tetrachloride charged and the number of moles of R in the reducing agent Aj2Rnx, 7-n. Equal to the lesser of:

For example, as a reducing agent, 0 for 141 mol of TiC charged.
．． When 7 mol of diethylaluminium chloride is charged, the entire amount of titanium trichloride produced (in the present invention, it is initially liquefied, and substantially the entire amount is precipitated in the subsequent precipitation treatment) (
l'i, equal to one time diethylaluminum chloride.

There are no particular restrictions on the treatment time or temperature after cooling titanium tetrachloride, but in order to complete the precipitation of solid titanium trichloride, it is usually θ~〆λθ℃, preferably! o at θ~ioo°C,
"Age" for i~/θ hours.

The solid titanium trichloride thus obtained together with the cocatalyst has α
- When used in the polymerization of olefins, if unreacted titanium tetrachloride remains in the catalyst, the polymerization activity per solid catalyst will decrease, and if slurry polymerization is carried out carefully, the slurry properties of the resulting polymer will deteriorate. becomes worse. Therefore, it is preferable to wash the obtained solid titanium trichloride with a hydrocarbon solvent. The hydrocarbon solvent used for washing is not particularly limited as long as it is inert to the catalyst. It is convenient if the solvent is the same as that used during polymerization. Although the purple fine-grained solid titanium trichloride obtained by the method of the present invention contains a small amount of complexed ether, almost no aluminum compound component is detected, and even if there is a large amount, the amount of aluminum relative to titanium is The ratio will not exceed 1%.

The fine duck-like solid titanium trichloride obtained as above is
It is particularly useful as a catalyst component for α-olefin polymerization. That is, α-
When used in the polymerization of olefins, it has particularly high polymerization activity and exhibits very good stereoregularity.

To explain the case where it is used in the polymerization of α-olefin, the organoaluminum compound used as a cocatalyst has the general formula A4HoriY, -m (wherein R7 is an alkyl group with 1 carbon atoms, m is 1 an organoaluminum compound represented by the number ~3, Y represents a halogen atom),
Examples include dialkyl aluminum monohalides such as diethylaluminum monochloride, dimethylaluminum monochloride, di-n-propylaluminum monochloride, monochloride, di-n-butylaluminum monochloride, and di-n-hexylaluminum monochloride. . Among these, R7 is normal propyl or normal hexyl, Y is salt water, and m is /, 9! Compounds having the following formulas are particularly preferred in that they have high polymerization activity and provide α-olefin polymers with extremely good stereoregularity. In addition to the solid titanium trichloride and cocatalyst, an electron-donating compound can be used as a third catalyst component in the polymerization of α-olefins. Examples of such electron-donating compounds include trialkyl phosphites, triarylphosphites, carboxylic acid esters, and the like.

The ratio of each component of the catalyst to be used is usually selected from the range of /:/-/θ0, preferably from /:2 to 0, based on the molar ratio of titanium monoride to organoaluminum compound. When using the third catalyst component, the molar ratio of titanium trichloride to the third catalyst component is l:θ, 0/~/θ - fL< is l:θ, ρ
It is colored so that it becomes j~-. Examples of α-olefins that undergo polymerization include propylene, butene-/, goo-methylpentene-/, etc., and homopolymerization of these α-olefins, copolymerization of these with ethylene, and mutual polymerization of these α-olefins are possible. Copolymerization takes place. Immediately, a propylene homopolymer, a random copolymer containing propyfluoride to the 90th power R% or more, or propylene? It is suitable for stereoregular polymerization to produce all block copolymers containing θ or more. The polymerization reaction may be carried out by gas phase polymerization, or may be carried out by slurry polymerization in the presence of a diluent such as monopentane, hexane, hegetane, or liquid propylene. In addition, there are no particular requirements regarding the polymerization temperature and pressure, but they are usually 30 to 100%.
'O1 preferably Jθ~? θ゛C1 pressure is atmospheric pressure ~ l
It is about θθ atmospheric pressure. Note that during polymerization, known molecular weight control agents such as hydrogen and halogenated hydrocarbons can also be used.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, in Examples and Comparative Examples, catalyst efficiency (C”
The polypropylene production t (J) per titanium atom/y in the purple solid trivalent titanium. Also, the catalytic activity (K
) is per 777 titanium atoms per hour, propylene pressure tKg/cm per F) nopolyglopylene raw i nil (
, r). CE and K were calculated by preparing a press piece entirely from the produced polymer powder and quantifying the T1 content by fluorescent X-ray analysis (hereinafter referred to as FX analysis). Isotactic index (AE) represents the residual R (% by weight) when the produced polymer is extracted with boiling normal heptane in a modified Soxhlet extractor for a period of time.

Melt flow index (MF engineering) is A day TM-D
-/Measured by Ko3♂.

Example 1 (A) Production of purple solid titanium trichloride Purified benzene/
&j me and titanium tetrachloride/nij m moz
f preparation and further di-n-butyl ether/! Inm0
7- was added. Titanium tetrachloride and di-
It reacted with n-butyl ether and was uniformly dissolved in benzene to obtain an orange-yellow homogeneous solution. The solution was stirred at 3θ°0.
Add diethylaluminum monochloride ♂2. j mmol1f was gradually added to obtain a blackish brown homogeneous solution of titanium trichloride. The homogeneous solution of titanium trichloride was kept at 30°C for 30 minutes, then heated to 0°C by 4Jg, and continued stirring for 1 hour, whereupon the formation of a reddish-purple titanium trichloride precipitate was observed. At this time ↓ with purple solid at t11,
More titanium tetrachloride! 2. ! mmol (produced Ti0t.

molar ratio θ to Add all the ingredients, 9! After raising the temperature to 'Q' and continuing stirring for 1 hour, separate the precipitate and add toluene 3θOm
2-t of fine-grained purple titanium trichloride catalyst,
9g was obtained.

(J3) Cocatalyst di-ethylaluminum monochloride was introduced into a 21-liter stirred autoclave purged with polymerized nitrogen of propylene.
Complete preparation of mot, then hydrogen scum f / , 2 kg
/at, 20θg of liquefied propylene was charged. The temperature of the autoclave was raised, and when the internal temperature reached 2 g ° C, the fine particulate solid titanium trichloride fT1ct obtained in the above (A),
As 2! After 0.3 hours from the start of the polymerization reaction, the unreacted propylene was immediately allowed to cool in a barge L%, and 3♂2 g of white powdery polypropylene was obtained. The r1 content in the polymer according to fluorescent X-ray analysis is 20 p.
pm, 1jE=,j□θθθ K=,,t J
It was 'ri. In addition, engineering 1 was 91', 9%. Furthermore, the average particle size of the polymer powder is 3j′θμ, and 10
No fine powder of 0μ or less was observed.

Comparative Example 1 Example 1 ((
A brown solid titanium trinomide was obtained in exactly the same manner as in A).

Using this solid titanium trichloride, propylene was polymerized in the same manner as in Example (B).

The obtained polymer was subjected to the same measurements as in Example.

The results are shown in Table 1.

Example--! Example/f! in exactly the same manner as in Example 1 except that benzene substituted with sinitoluene was used. : Repeatedly. However, T1
014 added Jtt-each added Tic4/total produced TiC4
,=0. /10.0, /,0, was changed to 0 molar ratio. The obtained polymer was measured in the same manner as in Example 1.

The results are shown in Table VC.

Comparative Example J Example f'f: was repeated in exactly the same manner as in Example 1 except that toluene was used instead of benzene. However, Ti
Immediately after heating up when adding Cl2 ('r1cz
3. The amount of precipitation was changed to φ). The obtained polymer was subjected to 6111 tests of Tsubaki Example 1 and 1 Tsukasa. The results are shown in Table 1.

Example (A) A purple solid 1 bottle of titanium trichloride, which had been converted to #forming element by 14, was placed in a /θl autoclave with n-hexane! ,
0t1 and 3.0 moles of titanium tetrachloride were added, and 2 samples of G-n-octyledelco was added. Stir this 2! While holding at 0 °0, diethylaluminum monochloride 8 O mol f,
A solution of titanium trichloride was gradually added to obtain a blackish brown homogeneous solution of titanium trichloride.

When this titanium trichloride solution was heated to 1° C. over about 2 hours, a purple titanium trichloride precipitate was observed to form during the temperature rise.

When the temperature reaches t 'O, new titanium tetrachloride θ, t
mol was added and stirring was continued for 7 hours at 1°C. From another experiment, Ri! The amount of titanium trichloride precipitated when the temperature was raised to 0°C was 25% by weight based on the reduction equivalent of diethylaluminium monochloride.

Next, the precipitate tF was separated and washed repeatedly with n-hexane to obtain a finely granular purple solid titanium trichloride catalyst.

(B) Polymerization of propylene Propylene was polymerized in the same manner as in Example/(B) using the purple solid titanium trichloride obtained in (A) above.

The obtained polymer was subjected to the same measurements as in Example. The results are shown in Table 1.

Comparative Example 3 Example g (5) except that titanium tetrachloride was not additionally added.
)) Purple solid titanium trichloride was obtained in exactly the same manner as in )).

Using this solid titanium gold trichloride, propylene was polymerized in the same manner as in Example 1 (B).

The same measurements as in Example 1 were performed on the obtained polymer.

The results are shown in Table 1.

/ / Procedural amendment (voluntary) 1975/θ/2 Kazuo Wakasugi, Commissioner of the Patent Office 2 Name of the invention Process for producing solid titanium trichloride for α-olefin polymerization 3 Relationship with the case of the person making the amendment Application Person (Δ9≦) Mitsubishi Chemical Industries, Ltd. 4 Agents 2-5-2 Marunouchi, T-Daita-ku, Tokyo 100 (and 1 other person) 6 Contents of Sode Masaru (1) Specification 1 (Claims of 1) amend the attached circular.

(2) On the third page of the same page, from the third line to the last line, it says, “Usually, R1, R in the general formula R4-〇-R5, , , , , 8
'J' refers to ethers usually represented by the general 2R'-0-R2 (in the formula, R1 and R2 represent the same or different hydrocarbon residues).
Corrected to "R2".

(3) On the bottom line of page 7, r AtI(';,
,, -n (in the formula, R6 has 7 to 20 carbon atoms) is replaced with "AtR;
Corrected to "-θ's".

(4) On page 7, line 3 from the bottom, the phrase "preferably R6 in the formula is methyl" was replaced with "preferably R6 in the formula
3 is methyl,” corrected.

(5) From page F on the same page, in the line “(R6 in the general formula)
)” should be changed to “(R3 in the general formula)”.

(6) In the 3rd line from the bottom and the last line of page 1O, “R1,
"R'J" should be corrected to "R1, R2J.

(7) In the same No. 1/Sadagu line, line 70 and page 7.2, line j, “
Correct "ring element" to "reduction".

(8) In the first line of the same paragraph, the phrase ``... and the seven main points'' is corrected to ``... and the seventh main point.''

(9) In the same No. 77 line 2-70, “General formula MR-Y3-r
nC formula, R7 is "7" [general formula AIR disorder Y3-
m (where R4 is corrected).

(+[]) On page dθ′, line 6, “(Generated TiC/!
3J is corrected to ``(All generation Ti0t3J.

(Il+ Correct "toluene" to "benzene" on page 20', line 1).

Claims (1) of the appended claims (1) Condensation of liquid in the presence of ether +:! : A method for producing a purple fine granular solid titanium pentachloride by precipitating a liquid titanium trichloride at a temperature below θ°C.
The titanium tetrachloride concentration in the system should be kept at 0.0% relative to the precipitated solid titanium trichloride until the titanium trichloride liquid substance and the finely divided solid titanium trichloride concentration become at least 0%.
After the molar ratio is maintained at 0.01 molar ratio or less, and after the decoction reaches 0% or more, 4'' degenerated titanium is added to reduce the degree of titanium tetrachloride in the system to 0.01 molar ratio. 0 carved into titanium
．． Production and removal of solid titanium trichloride for combination of α-olefin 14 characterized by a molar ratio of 7 to 70.

Procedural amendment (spontaneous) July 26, 1983 Kazuo Wakasugi, Commissioner of the Patent Office 1 Indication of the case 1987 Patent Application No. 1.2 /
7 lI & No. 2 Name of the invention Process for producing solid titanium trichloride for α-olefin polymerization 3 Relationship to the case of the person making the amendment Applicant (!; 91.) Mitsubishi Chemical Industries, Ltd. 4 Agents 〒1
00; (1 other person) 6 Contents of the amendment (1) The scope of claims in the specification is corrected as shown in the attached sheet C. (2) The specification is correct! ;ii, 2~/4=in the line [i.e. in the manufacturing method. "Titanium trichloride liquid liquefied in the presence of ether - 41 days after precipitating purple fine granular solid titanium trichloride at a temperature below 0°C to prepare a trichloride for α-olefin polymerization. In a method of manufacturing 33-piece titanium.

After the amount of precipitated purple fine granular solid titanium trichloride reached 0% or more based on the total amount of titanium trichloride produced, titanium tetrachloride was added at a molar ratio of O9,2~/θ to the total amount of titanium trichloride produced. Add in an amount within the range of 60~
The present invention relates to a method for producing solid titanium trichloride for α-olefin polymerization, which is characterized by aging at 0°C. ” is corrected.

(3) Lines 11/R-7K [precipitation amount,...
・・・・・・・・・It is something. "After the amount of precipitation reaches at least go% of the total amount of titanium trichloride produced [(Of course, it is also possible to do this after the precipitation has substantially finished) [Up to this point, the concentration of titanium tetrachloride in the system ( The concentration of free titanium tetrachloride that is not complexed with ether is usually less than about O,OS molar ratio with respect to the total raw acid titanium trichloride.In the method (A) above, after the completion of the ring element, The ratio of each raw material component is adjusted so that the titanium tetrachloride concentration falls within this range. [In this case, the titanium tetrachloride concentration in the system is equal to or less than the total titanium trichloride produced. 0.2 to 10, preferably 0.
3 to 6] The main point is to subsequently ripen at Aθ°C to /2θ°C. ” is corrected.

(4) From page 1S, line 1g to page 1A, Hiroyuki, the text ``After the addition of titanium tetrachloride... ``ripens'''' has been changed to ``After the addition of titanium tetrachloride, Te10~/2
It is aged at θ°C, preferably at 0 to 100°C. In addition, there is no particular restriction on the aging time, but it is usually o,
Aging for i~/θ hours. ” is corrected.

(5) Insert the following sentence after line 7, page 20 of the same page.

``Surface area measurement was carried out using a Kinoshita surface area measuring device (BET method) using a constant volume multi-point BET low temperature gas adsorption method (based on N2J).

X-ray diffraction was measured using Rigaku Rotorflex 2ooPL (trade name) under the following conditions.

Ou K tube voltage gu OKV // turtle flow / g OmA full scale / X / 03C! 01]NT
P chu S Jiang.

Time constant U, O Scanning speed, z”/min
J(6) Insert the following sentence after line 3 on page 27.

"Reference Example/Example/In (A), the purple solid titanium trichloride precipitated at the time of the lIo°C-a time treatment was taken out and washed in the same manner as in Example/(A).This solid titanium trichloride B of
The surface area determined by the ET method is 3 rrVjJ, and the X-ray diffraction spectrum (OuKi) shows no peaks between -02/S and /7°, and it has a remarkable halo peak. How was it judged?

In addition, propylene was polymerized in the same manner as in Example/(B) to obtain 30 g of white powdered polypropylene. In this case Q g=4'/, 200- K='l
g 5, Eni = g 9%.

Reference example: Volume replaced with dry nitrogen! ;001 nl fourth flask, normal hexane 7! ;ml and titanium tetrachloride 0
．． /7 mol was charged. This 'I' 1014 in hexane 'g! Normal hexane//3rn1. A solution consisting of diethylaluminium monochloride (7.35 mol) was added over a period of 30 minutes.Then, the temperature was raised to 25° C., and the treatment was continued for 720 minutes, followed by repeated washing 5 times with 1.00 ml of n-hexane. The surface area of the obtained brown solid titanium trichloride according to the BFiT method is 2 o 7r + 7y, and the X-ray diffraction spectrum shows a sharp peak at θ=/A, 2°, which is characteristic of β-'I"i 013. Admitted.

In addition, when propylene was combined in the same manner as in Example/(B), a sticky polymer A-g was obtained,
cw=q, qqo.

K=9. ．． 7. j, any' 1.2.3% feather) Tsuda.

Reference Example 3 Volume A replaced with dry nitrogen; Normal hexane/soml and titanium tetrachloride 0 in a 001 rLl fourth flask.
．． 3°C mol was charged. The solution was cooled to 7°C, normal hexane//, 3rnl, diethylaluminum monochloride 0.3! A solution consisting of 290 mol
was added gradually over a period of minutes. Then, the temperature was raised to 43-℃ within 7 hours and stirred for 1 hour. U1: Key.

Thereafter, the same washing with S was repeated with 300 ml of normal hexane. The solid titanium trichloride obtained is brown in color and BJ
According to the UT method, the surface area was g.

In addition, when polymerization of 1[cobylene was carried out in the same manner as in Example/(B), a polymer of s7g was obtained, Qg = 7,
330, K-gA.

It was l1=3.

From Reference Examples/~3 and Examples//, the method for producing titanium trichloride of the present invention involves direct precipitation of purple (β-)TiO13'4j, and crystal dislocation of brown (β-)Ti, OIs Y by some treatment. It is clear that it does not cause δ to change.

Reference Example - The reduced solid obtained in Reference Example 3 was suspended in 72 ml of rg n-hexane, 25.4 ml of di-in amyl ether was added thereto, and stirring was continued at 33°C for 7 hours. Ta. Then, it was washed 5 times with 'fJOOml normal hexane.

This treated solid was suspended in 'I' 1014 gsml of normal hexane solution and stirred at BS℃ for 1 hour. Hexane 50θrne at ℃
was washed seven times to obtain solid catalyst complex 2AQ.

Using this catalyst complex 7, propylene polymerization was carried out in the same manner as in Example/(B) to obtain white powdery polypropylene, l#;t)9'fi.

This occasion, (:!E=JOtsu, 0QO11(=:Guyu01
■Work=9/,! %Met. ” (7) “Example U~S” in the 9th line from the bottom of page 2 of the same issue
It says "Example--Da" Vc cutting 1-.

(8) In the same No. - Kosada/ line, “Generation Ti013=0./
,0.3,/,0. The statement "A, 0 molar ratio" is corrected to "Produced Tie-, L3 = (1), J, /, 0.6.0 molar ratio."

(9) On page 2, line 13, "Example 6" is corrected to "Example S."

α1 In the same No. 2 page 2, lines 2-3, "(A) of Example B" should be replaced with "(AJJ of Implementation Ill 3) [Correction.

aυ　Table 1 on the left page of 2 of the same No. 2 is revised as follows.

Attachment 2, Claims (1) Solid titanium trichloride for α-olefin polymerization is prepared by precipitating purple fine particulate solid titanium trichloride from a liquid titanium trichloride liquefied in the presence of ether at a temperature of 130°C or less. In the method of crushing titanium, titanium tetrachloride is added with a mallet in a molar ratio of 01.2 to IO to the total titanium trichloride produced, and the tensile strength is 60 to 10%.
A method for producing solid titanium trichloride for α-olefin polymerization, which is characterized by aging at 20°C.

and if necessary, the scope of the patent claims should be
L method.

Claims (1)

[Claims] (1) A method for producing a purple fine granular solid titanium trichloride by liquefying it in the presence of ether and precipitating a titanium trichloride solid at a temperature of /O θ゛C or less, wherein the titanium trichloride liquid At least the amount of fine-grained solid titanium trichloride precipitated from objects! Until the titanium tetrachloride concentration in the system reaches θ%, the titanium tetrachloride concentration in the system is θ relative to the precipitated solid titanium trichloride. After the precipitated amount reaches fO% or more, titanium tetrachloride is added to maintain the titanium tetrachloride concentration in the system from 0.7 to 0.7 to 0.01 molar ratio relative to the precipitated solid titanium trichloride. A method for producing solid titanium trichloride for α-olefin polymerization, which is characterized by having a molar ratio of 70.