JPS6037805B2 - Method for producing carrier for olefin polymerization catalyst - Google Patents

Description

Detailed Description of the Invention The present invention relates to an olefin polymerization (in the present invention, the term includes copolymerization) catalyst carrier, which has a high density, a spherical shape, a narrow particle size distribution, and has good powder flowability. A carrier for an olefin polymerization catalyst that is particularly useful for producing a catalyst for producing an olefin polymer (in the present invention, the term includes copolymerization), which has excellent collapse resistance, is inexpensive, and is available. The present invention relates to a method for producing a carrier for an olefin polymerization catalyst, which can be manufactured from magnesium halide easily and industrially and advantageously by easy operations.

When polymerizing olefins or olefins and dienes and other comonomers using an olefin polymerization catalyst formed from a transition metal compound catalyst component and an organometallic compound catalyst component, the transition metal compound component is Many proposals have been made regarding the use of catalyst components supported on bodies.

It is known that the use of a spherical carrier as such a supported transition metal compound catalyst component has the advantage of imparting a preferable spherical shape to the resulting olefin polymer. Furthermore, if the yield of olefin polymer per supported transition metal compound catalyst component is sufficiently large, there is a great advantage in industrial operations that deashing of the obtained olefin polymer can be omitted; Furthermore, if it becomes possible to form an olefin polymer with high density and good particle size distribution by using such a transition metal compound catalyst component with rods, the molding operation will be easier, and in some cases, it may be possible to form an olefin polymer with a good particle size distribution. The effect of making it possible to omit the granulation process can be expected.

Several proposals are known for providing a spherical olefin polymerization catalyst carrier as described above.

For example, Tokukan Sho 49-6599y discloses that particles obtained by spray granulating a hydrated melt of magnesium halide or spray granulating an alcoholic solution of magnesium halide are used as an olefin polymerization catalyst. It has been proposed to use it as a carrier. However, the olefin polymer particles obtained using the olefin polymerization catalyst prepared using the particles obtained by this proposed method as a carrier,
For example, during post-polymerization operations and handling such as pumping and centrifugation, the polymer particles do not exhibit sufficient collapse resistance and tend to disintegrate to form powdery particles or irregularly shaped particles. It itself did not exhibit sufficient collapse resistance and had deficiencies that made it difficult to form polymer particles with a satisfactory spherical shape. In order to overcome these difficulties and deficiencies, Japanese Patent Application Laid-Open No. 52-3859 proposed using a magnesium halide hydrate produced by a complicated and difficult special manufacturing method as the raw material magnesium halide. Are known.

However, the proposed magnesium halide hydrate is difficult to obtain, and its production method requires a complicated and difficult special production method, which also has the disadvantage of poor reproducibility of carrier quality. The present inventors conducted research to provide a spherical carrier for an olefin polymerization catalyst that overcomes the above-mentioned difficulties, defects, and disadvantages.

As a result, we have developed a spherical olefin polymerization catalyst support that can utilize magnesium halide, which is easily available on the market, and has satisfactory collapse resistance, by an industrially easy and inexpensive means, and with reproducible support quality. I discovered that it can be easily manufactured. That is, according to the research of the present inventors, organic liquid medium A containing about 0.1 to about 40% by weight of siloxane
A suspension containing key particles of magnesium halide and an active hydrogen compound in a molten state is rapidly cooled to solidify the complex particles. It has been discovered that even when magnesium genide is used as a raw material, a carrier having an excellent spherical shape and satisfactory collapse resistance can be produced. Furthermore, when the transition metal compound catalyst component is supported on the obtained carrier, it is possible to obtain an olefin polymer that is highly active, has a high bulk density, has a narrow particle size distribution, is spherical, and does not easily disintegrate, and therefore has good fluidity. It has been discovered that an excellent carrier can be produced that allows for the production of coalescence. Therefore, an object of the present invention is to provide a method for producing a carrier for an olefin polymerization catalyst that can achieve the above-mentioned improvements.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The magnesium halide may be a complex compound containing other metals such as aluminum, tin, silicon, germanium, etc.

These may be synthesized by any method, and may be a mixture of two or more. For example, organomagnesium compounds or organomagnesium aluminum composite compounds and their reaction products with organosilicon compounds such as siloxane, silanol, alkoxysilane compounds, organic acid salts of magnesium, alkoxides,
Allyloxide, acetylacetonate, etc. with halogens such as chlorine, hydrogen halides such as hydrogen chloride, PC13, POC
13, BC13, SOC12, SIC14, MCI3,
Products halogenated with halogenating agents such as AI-alkyl monohalides, Yamaichi alkyl dihalides, alkoxy AI halides, and penzoyl chloride, liquids or powders of halogen-containing compounds such as the above halogenating agents. Examples include a mixed milling product of the above magnesium compound, a reaction product of magnesium metal with an alcohol and a halogenating agent such as a hydrogen halide or a halogen-containing silicon compound, and a decomposition product of a Grignard reagent. Among these, magnesium dihalides or complex compounds thereof are preferred, such as magnesium chloride, magnesium bromide, and magnesium iodide. Examples of the active hydrogen compound forming the chain include alcohols, phenols, carboxylic acids, and amines.

Particularly preferred active hydrogen compounds are alcohols.
Examples of alcohols include methanol, ethanol,
N-fu. ro/gnol, isopro/gnol, n-butanol, isobutanol, sec-phthanol, n-r
t-butanol, n-bentanol, n-hexanol, n-octanol, 2-ethynolehexa/nole, n
-Alcohols with 1 or 18 carbon atoms, such as alcohol, n-hexadecyl alcohol, stearyl alcohol, and oleyl alcohol;
Phenol, cresol, xylenol, ethylphenol, isof. Phenols with 6 or 15 carbon atoms such as propylene phenol, p-buty/lephenol, n-octylphenol, n-nonylphenol, cumylphenol, naphthol; formic acid, acetic acid, propionic acid, butyric acid, caproic acid , caprylic acid, lauric acid,
1 to 18 carbon atoms, such as stearic acid and oleic acid
Carboxylic acids; methylamine, ethylamine, diethylamine, n-propylamine, n-hexylamine,
Examples include amines having 1 to 16 carbon atoms such as laurylamine, cyclohexaneamine, aniline, benzylamine, and ethanolamine. Two or more of these active hydrogen compounds may be used in combination.
When the magnesium halide is represented by MgX2 and the active hydrogen compound is represented by Y, the complex can be represented by the formula MgX2.Yn.

Here, n represents a number from 1 to 10. Among such complexes, the melting point is low, and therefore it is easy to suspend in the molten state in the organic liquid medium A, and moreover, it is easy to obtain a high-performance catalyst when a transition metal compound component is supported. Therefore, it is particularly preferable to use an alcohol rust body. The complex is suspended in the organic liquid medium A in the molten state.

Therefore, the organic liquid medium A must not exhibit such high affinity that a suspension of rust particles and rust particles cannot be formed in a molten state. Examples of such an organic liquid medium A include hydrocarbons such as hexane, heptane, octane, decane, kerosene, cyclohexane, benzene, toluene, xylene, cumene, cymene, diisopropylbenzene, tetralin, decalin, and dimethylnaphthalene. Although particularly preferred, other solvents such as halogenated hydrocarbons, ethers, etc. can also be used. A plurality of these organic liquid media A can also be used in combination. The amount of siloxane coexisting in the organic liquid medium A is preferably from about 0.1% to about 40% by weight, and more preferably from about 0.2% to about 10% by weight.

Examples of suitable siloxane compounds include the following. {i' General formula Q(Q2Si○)nS
A linear polysiloxane represented by iQ3 (where Q is hydrogen, a hydroxyl group, an alkyl group containing, for example, 1 to 4 carbon atoms, a cycloalkyl group containing, for example, 3 to 8 carbon atoms, a carbon atom such as 6 An aryl group containing none or 8 carbon atoms, an alkoxy group or phenoxy group containing, for example, 1 to 12 carbon atoms, and a plurality of Qs may be the same or different.

However, this excludes the case where all Qs are hydrogen. n usually represents an integer from 1 to 1000). Examples of such linear polysiloxanes include dimethylsiloxane, methylphenylsiloxane, methylhydrodienesiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, tetracosamethylundicasiloxane, and 3-hydroheptamethyltrisiloxane. , 3,5-dihydrooctamethyltetrasiloxane, 3,5,7-trihydrononamethylbentasiloxane, tetramethyl-1,3-
Diphenyldisiloxane, bentamethyl-1,3,5-
Examples include triphenyltrisiloxane, heptaphenyldisiloxane, and octaphenyltrisiloxane. 'ii} Cyclic (cyclo)polysiloxane represented by the general formula (Q'2Si○)p (where Q' is hydrogen, an alkyl group containing for example 1 to 4 carbon atoms, for example 3 to 8 carbon atoms) a cycloalkyl group containing, for example, 6 or 8 carbon atoms, an alkoxy group or phenoxy group containing, for example, 1 or 12 carbon atoms, and a plurality of Q' may be the same or different. You can leave it there.

However, this excludes the case where all Q' are hydrogen. p usually represents an integer of 1 or 10). Examples of such cyclopolysiloxanes include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethyl Examples include cyclobentanerosiloxane, dodecamethylcyclohexasiloxane, triphenyl-1,3,5-trimethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane. Stiffness Various modifications such as HOOCC2day 4Si
(CH3)20(CH3)2SIC2days4COOdays,(CH3)3SiOSi*(CH2)buiCQ
COOH, [(CH3)3Sj○]2Si (C ratio) (C
H2) Acid-modified siloxane, such as 30S03, [(C
Q)3Si0]3Si(CH2)3NH(CH2)2N
Examples include amine-modified siloxanes such as H2 and oxyalkylene-modified siloxanes.

In the above example, 1, m, q, x are, for example, ISxmi500, OSIS500, OSmS500, 1≦q≦5
Indicates the number of 00. Moreover, two or more types of siloxanes can be used in combination if they are compatible with each other. The concentration of the magnesium halide/active hydrogen compound complex in the organic liquid medium A is, for example, about 0.05 to about 2 mol.
/1, particularly about 0.1, preferably about 1 mol'1.

In the present invention, a suspension containing the key particles in a molten state is formed by emulsifying and suspending the upper twill body in a molten state in an organic liquid medium A containing siloxane. do.

The suspension may be formed by, for example, making siloxane present at a temperature equal to or higher than the melting temperature of the collar body, and selecting and employing an appropriate emulsifying and suspending means that is commonly used. Examples of such methods include the shaking method, the Azusa method, the leakage method, the injection method, the Jm trout n-yama hman method, the ultrasonic method, the colloid mill method, the high pressure injection method, or a combination thereof. I can do it. The flange particles in the emulsified suspension state are usually spherical with a particle size of about 0.1 mm to about 200 mm, preferably about 1 mm to about 100 mm, so they are rapidly cooled. It can be solidified to form a spherical carrier. As the rapid solidification means, any means can be employed as long as the suspended particles do not coalesce or deform and substantially lose their desired spherical shape. A preferred embodiment is one in which the suspension is brought into immediate contact with the organic liquid medium B, which has been cooled to a temperature low enough to solidify the suspended rust particles. For example, the suspension is introduced into the organic liquid medium B, preferably under Nada framework conditions. Conversely, the medium B can also be introduced into the suspension. The organic liquid medium B does not need to be the same as the organic liquid medium A, but may be the same, and is preferably selected as appropriate from among those exemplified above as the organic liquid medium A. Moreover, the above-mentioned siloxane can also be added to the organic liquid medium B. In this embodiment, it is desirable to maintain the temperature of organic liquid medium B at about 10 degrees or more below the melting temperature of the complex. Alternatively, the complex particles can be solidified by blowing a cooling gas such as liquefied gas into the suspension. The solidified complex particles can be separated and collected by means such as filtration or centrifugation.

The olefin polymerization catalyst carrier obtained by such a method is hard, exhibits satisfactory collapse resistance during subsequent operations and handling, has a narrow particle size distribution, and has a good spherical shape. A transition metal compound catalyst component for olefin polymerization in which a transition metal compound component is supported on such a carrier by any means that does not substantially involve crushing maintains the same characteristics of being hard and difficult to disintegrate. Of course, when supporting the transition metal compound component, classification may be performed in advance in order to make the particle size distribution even narrower. Various methods can be employed to support the transition metal compound component on the olefin polymerization catalyst carrier obtained by the method of the present invention.

For example, Japanese Patent Publication No. 46-34092, Japanese Patent Application No. 43-96
A method of directly reacting a transition metal compound with the carrier as in No. 49;
21093, a method in which the support is reacted with an organometallic compound of a metal from Group 1 to Group 3 of the periodic table and then reacted with a transition metal compound; JP-A-49-72383;
JP-A-49-88983, a method in which the carrier is reacted with a silicon or tin halide compound or an organic compound and a transition metal compound sequentially or simultaneously;
1-28189, a method in which the carrier is reacted with an organic acid ester and an organometallic compound of a metal from Group 1 to Group 3 of the periodic table, and then reacted with a transition metal compound;
A method in which the carrier is reacted with an organic acid ester and a halogen compound or an organic compound of silicon or tin, and then a transition metal compound is reacted, as in JP-A-51-92885; as shown in JP-A-51-127185. A method in which the transition metal compound catalyst component obtained by each of the above methods is further reacted with an organometallic compound of a metal from Group 1 to Group 3 of the periodic table; as in Tsubaki Kaisho No. 52-30888. Alternatively, a method of reacting the transition metal compound component obtained by each of the above methods with an electron donor and a transition metal compound can be adopted. Examples of the transition metal compound supported on the olefin polymerization catalyst carrier obtained by the method of the present invention include compounds such as titanium, vanadium, and chromium.

Particularly preferred are titanium compounds. The supporting reaction can be carried out by pre-treating the carrier as exemplified above or without pre-treating it, suspending the carrier in a transition metal compound which forms a liquid phase under the supporting reaction conditions, or subjecting the carrier to pre-treating as exemplified above. This can be carried out by suspending the transition metal compound in an inert solvent in which the transition metal compound has been dissolved, or after pretreatment. For example, the sustained reaction may be carried out at a temperature of about 0 to about 200°C,
Preferably, it can be carried out at about 30 to about 150 oo. The support reaction is also preferably conducted in the presence of an excess of transition metal compound, such as from about 0.1 to about 100 moles, more preferably from about 1 to about 50 moles, of transition metal compound per gram atom of Mg in the support. It is appropriate to have it present in molar amounts. The loading reaction can be carried out in two or more stages. The transition metal compounds used in the support reaction include:
In the case where a solvent is used in the supporting reaction, it is preferable that the material is in a liquid state under the supporting reaction conditions or is soluble in the solvent. Specifically, the formula Ti(OR)nX4 core (wherein R
is a hydrocarbon group, X is a halogen, a titanium compound represented by 0≦n≦4), VX4, V0(OR)mX3-m(R,
x has the same definition as above, and vanadium compounds represented by 0≦n≦3) can be exemplified. Examples of the above R include C2 to C,
Examples include a C5-C8 alkyl group, a C5-C8 cycloalkyl group, an allyl group, and a C6-C,5 aryl group.
Examples of the above-mentioned x include chlorine, bromine, and iodine. Preferred are titanium compounds, with titanium tetrahalide being the most preferred. Details of the method of pre-treating the carrier with an electron donor, an organometallic compound of Groups 1 to 3 of the periodic table, a halogen compound of silicon or tin, or an organic compound prior to supporting a transition metal compound are described above. As stated in each example publication,
For example, the treatment can be carried out at a temperature of about 150 qo below about 0° C. while suspending the carrier in an inert solvent.

In a preferred embodiment of the catalyst component in which a transition metal compound is supported on an olefin polymerization catalyst carrier obtained by the method of the present invention, the amount of transition metal per catalyst component is about 3 to about 120 9,
Preferably it contains about 5% to about 60%.

Further, the halogen/transition metal (atomic ratio) is preferably about 8
More preferably, it is in the range of about 10 to about 50. The above-mentioned catalyst component contains magnesium, halogen, and transition metal as essential components, and may also contain an electron donor such as an organic acid ester depending on the case.
The supported transition metal catalyst component obtained as above is
By roughly combining it with an organometallic compound of a metal from Group 1 to Group 3 of the Periodic Table, it can be used for the polymerization or copolymerization of olefins, olefins, and other comonomers.

As the organometallic compound, organoaluminum compounds are particularly preferred, and among them, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquiride, alkylaluminum/, fido, or mixtures thereof are preferably used. Examples of olefins used in the polymerization are C2-C, such as ethylene, propylene, 1-butene, 4-methyl-1-bentene, 1-octene, and the like.

olefins can be given. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. For copolymerization, polyunsaturated compounds such as conjugated or non-conjugated compounds can be selected as polymerization components. For example, when copolymerizing propylene, the propylene is polymerized to obtain an amount of homopolymer equal to about 60 to about 9 percent by weight of the total composition, followed by polymerization of the propylene-ethylene mixture or ethylene. You can find a way. Alternatively, a mixture of propylene and ethylene can be polymerized to obtain a copolymer containing up to about 10 mole percent ethylene. Polymerization can be carried out in either liquid phase or gas phase.

When carrying out liquid phase polymerization, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium. When carrying out liquid phase polymerization, the amount of the supported transition metal compound component is approximately 0.0001 mmol to approximately 1 mmol in terms of transition metal atoms per liquid phase 11, and the organic metal compound component is Preferably, the amount of metal atoms therein is from about 1 to about 1000 moles, preferably from about 5 to about 500 moles. In addition, when performing gas phase polymerization, a method using a fluidized bed, an azure fluidized bed, etc. can be adopted, and the supported transition metal compound component as a catalyst component can be a solid such as polyethylene, polypropylene, glass beads, silica, or hexane. The organometallic compound component is diluted with hexane, olefin, etc., or added to the polymerization vessel as it is without dilution, while in some cases hydrogen, etc., is added in a gaseous state to the polymerization vessel. Polymerization can be carried out by supplying The proportions of catalysts, etc. used are the same as in the case of liquid phase polymerization. The polymerization temperature of olefin is
Generally about 20 to about 20,000, preferably about 20
The temperature is preferably from about 40°C to about 120°C below the melting point of the resulting polyolefin.

The polymerization can then be carried out at atmospheric pressure to about 100 k9/c fin G, particularly under pressurized conditions, from about 2 to about 50 kg/g.
It is preferable to carry out the process under moderate conditions. When polymerizing Q-olefin, the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, but it is effective to add hydrogen into the polymerization system.

Furthermore, in the polymerization of Q-olefins having 3 or more carbon atoms,
In order to control stereoregularity, an electron donor such as alcohol, ether/ester, amine, acid anhydride, ketone, carboxylic acid, amide, phosphorus compound, or polysiloxane may be present. They can also be used in the form of organometallic components or addition compounds with Lewis acids, such as AIX3. The advantage of using a supported catalyst component using the support obtained by the method of the present invention is that, in addition to the advantages already mentioned, the amount of transition metal is extremely small compared to the amount of polypropylene produced by polymerization of propylene, for example. Since spherical polypropylene with a small amount and a narrow particle size distribution and high specific gravity can be obtained, post-treatment of the polymer after polymerization is extremely simplified or, in many cases, is not necessary at all.

Therefore, in gas phase polymerization that does not use any solvent, there are problems in the polymerization process, such as uniformity of the fluid state, or
This method significantly improves the process constraints caused by the finely divided polymer component and the transportation of the polymer powder within the process, making it possible to obtain polymers that can be used directly as products through solvent-free polymerization. Example 1 [1] Synthesis of spherical MgC12/Himenohi After a high-speed Kenyoso layer (manufactured by Tokushu Kika Kogyo) with an internal volume of 21 was sufficiently replaced with N2, refined kerosene 700%, commercially available MgC1210, and ethanol 24% were added. 2 hours and 2.7 hours of product name YF-3860 (manufactured by Toshiba Silicone Co., Ltd., polyoxyalkylene-modified siloxane) were added, the temperature of the system was raised to 12,000 degrees Celsius, and the system was heated at 800 degrees pm for 10 minutes.

Using a Teflon tube with an inner diameter of 5 willow,
The liquid was transferred to a 21 glass flask (equipped with a Hashimoto machine) filled with refined kerosene 11 that had been previously cooled to -100C. The produced solid was collected in a furnace, thoroughly washed with hexane, and then dried for 4 hours at 35:00. The solid obtained in this way was found to be perfectly spherical by microscopic observation, and the particle size was 10 to 8.
It was 0 Buddha. [B] Preparation of Ti-containing catalyst component 30
Into a glass flask with 0 solids (MgC
1239. After adding ethyl benzoate 1.1 at 0°C, TIC1422.5 was slowly added dropwise at 0°C.

After dropping, incubate at 20qC for 1 hour, and further incubate at TIC14.
After adding 100°C and contacting it at 100o○ for 2 hours,
The solid portion was collected by filtration. Further, TIC 14200 I was added to the solid transferred to the glass flask above No. 300, and after contacting for 2 hours at 100 oo of water, the solid portion was passed through a heat oven, washed with hot kerosene and hexane, and dried.

The components of the Ti-containing catalyst thus obtained are Tj in terms of atoms.
5.7wt%, CI55. Skin t%, Mg15. skin t%,
Ethyl benzoate9. It was shoei%. Also, the specific surface area is 1
The average particle size was 38 particles. [m]
0.79 m of hexane was charged into the autoclave of Polymerization 21, and 3.75 m of triethylaluminum was charged under a propylene atmosphere.
1.25 mmol of methyl p-tolylate and 0.0225 9-atoms in terms of Ti atom of the Ti-containing solid catalyst were charged.

After adding 2,400 Nml of the system, the temperature of the system was raised to 6,000 ml, and the temperature was raised to (G) with a total pressure of 7.0 k9/m with propylene, and polymerization was carried out for 4 hours while maintaining the propylene pressure. After the polymerization was completed, the slurry containing the polymer was filtered to obtain a white powdery polymer of 108%. M. 1. was 1.2.

In addition, the average particle size of the polymer is 530 French, and the particle size distribution is 0.1
~1. The content was 97 wt% in the ribs, and the shape was spherical.
Further, by concentrating the solvent portion, 3.0% of a solvent-soluble polymer was obtained. Therefore, the average polymerization specific activity of the Ti-containing catalyst is 4
It was 900 terPP/mmol-Ti. Example 2 In the synthesis of spherical M&12・fertility tOH in Example 1, M
When the complex of gC12 and ethanol was melted in refined kerosene, the amount of YF-3860 was 4.0', and YF-
When the carrier was synthesized in the same manner as in Example 1 except that 3860 was added to 3.0', the particle size was 5 to 30.
A perfectly spherical solid was obtained.

The components of a Ti-containing catalyst prepared using the solid in the same manner as in Example 1 were as follows: Ti5.5wt%, CI5
7. Skin t%, Mg17. Skin t%, ethyl benzoate 8.4
wt%, and its average particle size was 14 F.

Furthermore, when propylene polymerization was carried out in the same manner as in Example 1, a white powdery polymer of 120% was obtained, with a boiling n-hebutane extraction residue of 95.2% and an apparent density of 0.41%. Shout M. 1. was 1.3. The average particle diameter of the polymer was 270 mm, the particle size distribution was 0.1 to 1.0 9%, and the shape was spherical. Further, 3.8% of a solvent-soluble polymer was obtained by concentrating the solvent portion. Therefore, the average specific polymerization activity of the Ti-containing catalyst is 5500 terPP/mmol-T.
It was j. Comparative Example 1 In the synthesis of spherical M history 12 and fertilizer tOH of Example 1, Y
When constant synthesis was carried out in the same manner as in Example 1 except that E-3860 was not used, almost no spherical carrier was obtained.

Ti prepared using the carrier in the same manner as in Example 1
The components of the catalyst contained are Ti4.1wt%, CI
63. % of enemy, Mg18. 9% ethyl benzoate 8.
It was 9wt%.

Furthermore, when propylene polymerization was carried out in the same manner as in Example 1, a white powdery polymer of 193% was obtained, the residual rate of which was extracted with heptane was 94.2%, and the M.I. 1. was 4.7, but the apparent specific gravity was as low as 0.30 evening/fence.

The particle size distribution of the polymer is also wide, ranging from 0.1 to 1. Enemy skin 5
It was 9%. By concentrating the solvent portion, 7.0 g of a solvent-soluble polymer was obtained. Example 3 [1] Synthesis of spherical MgC12.n (n-BuOH) Into a high-speed shipbuilding layer with an inner volume of 21 which was sufficiently replaced with N2, 600 tons of refined kerosene, commercially available M&1210, and n-butanol were added.
3.4 and trade name TSF-451 (manufactured by Toshiba Silicone Co., Ltd., dimethylpolysiloxane, 20 ratio.s.) 5.3
Put him in, raise the temperature of the system to 800 at 13000.
I worshiped the lights for 2 minutes at the enemy PM.

High-speed fly Azusa, teff with an inner diameter of 5 skin. using a tube made of
The liquid was transferred to a 21 glass flask (equipped with a cylindrical flask) filled with refined kerosene 11 previously cooled to -100C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

The solid seen by microscopic observation is perfectly spherical, and the particle size is 5 to 5.
It was 90 mu. [0] Preparation of Tj-containing catalyst component 5
In a glass flask above 00, 15.5 liters of solid [1] (containing M and 1248.9 hmol) was mixed with 300 ml of refined kerosene.
Add ethyl benzoate 2.1% to 25oC.
I worshiped the lanterns at o for an hour.

Diethyl aluminum monochloride 10.5' to 0
The mixture was added dropwise at 1 hour at 25 DEG C. After contacting at 25 DEG C. for 1 hour, the solid portion was collected by filtration, thoroughly washed with hexane, and dried. Add TIC1 to the solid transferred to a glass flask.
4100' of TIC1 was added, left to stand at 80°C for 2 hours, the supernatant was removed by decantation, and TIC1
4100' was added. After heating at 80 qC for 2 hours, the solid portion collected by thermal furnace filtration was washed with hot kerosene and hexane and dried to obtain a Ti-containing catalyst.

The component is Ti3. Fear%, CI59. Book t
%, Mg16. Skin t%, ethyl benzoate 14.5wt%
The average particle size was 40. [m] Polymerization Example 1
When propylene polymerization was carried out in the same manner as in the above, a white powdery polymer 145 was obtained, the residual rate of which was extracted with n-hebutane was 95.8%, the specific gravity was 0.39 units/ground, and the M.I. 1. is 4
．． It was 4.

In addition, the average particle size of the polymer is 730 French, and the particle size distribution is 0.1
It was 96% on the ~1.0 side, and the shape was spherical. Further, by concentrating the solvent portion, 3.9 g of a solvent-soluble polymer was obtained.
Therefore, the average polymerization specific activity of the Ti-containing catalyst is 660
0 terPP/mmol-Ti. Example 4 [1] Synthesis of spherical MgCl2/Himenohi After an autoclave with an internal volume of 31 was sufficiently replaced with N2, refined kerosene 1.
9. Add 15 pieces of commercially available MgC1275, Airnol 109 and trade name TSF-433 (manufactured by Toshiba Sireen Corporation, methylphenyl polysiloxane, 35 ratio.S.), raise the temperature of the system to 125 60pm at 2
I prayed for 0 minutes.

The system internal pressure was set to 10 kg/(G) with N2, the cock of the 3-rib SUS tube that was directly connected to the autoclave and kept at 125 oo was opened, and refined kerosene 3 pre-cooled to -15 qo was charged. 2 liquids were transferred to a 51 glass flask (equipped with a Kaede Azusa machine). The amount of liquid transferred was 11, and the required time was approximately 0 seconds. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. When observed under a microscope, the solid was perfectly spherical and had a particle size of 5 to 60 particles. 3 [B]
Preparation of Ti-containing catalyst component Into a 300 ml glass flask was added 8.0 ml of solid [1] (1234.3 hmol of MgC).
) and 100% refined kerosene, and heated to 5°C under the fly frame.
After dropping triethyl aluminum 14.1 base,
I prayed for 1 hour at 25 o○, and then worshiped the lantern for another 3 hours at 80 o'clock.

The solid portion was collected by filtration, thoroughly washed with hexane, and then dried. Refined kerosene 100, suspending the generated solids in the ground,
Dry air was blown into the Nada drop for 2 hours at room temperature. The solid portion was collected by filtration and thoroughly washed with hexane. After suspending the resulting solid in 100 g of refined kerosene, 2.2 g of ethyl benzoate was added, and after stirring for 1 hour at 25 o
I prayed for 2 hours at 000. The solid part is collected by filtration,
After thorough washing with hexane, it was dried. TIC14100' was added to the solid transferred to a 200°C glass flask and heated at 9,000°C for 2 hours, the supernatant was removed by decantation, TIC14100' was further added and heated at 9,000°C for 2 hours.

The solid portion collected by thermal furnace filtration was thoroughly washed with hot kerosene and hexane and then dried to obtain a Ti-containing catalyst. The component is Ti2. Sakaki t%, Cl63. skin t%,
Mg20. The skin content was t%, and the ethyl benzoate content was 9.8wt%.

The specific surface area was 320 m/m, and the average particle size was 38 m/m. [m] When propylene polymerization was carried out in the same manner as in Polymerization Example 1, a white powdery polymer 212 was obtained, the residual rate of n-hebutane extraction was 96.0%, and the apparent specific gravity was 0.39. ta'no', M
．． 1. was 3.0.

Claims (1)

[Scope of Claims] 1. A suspension containing molten complex particles of magnesium halide and an active hydrogen compound in an organic liquid medium A containing about 0.1 to about 40% by weight of siloxane,
A method for producing a carrier for an olefin polymerization catalyst, which comprises solidifying the complex particles by rapid cooling. 2. The method according to claim 1, wherein the quenching is carried out by immediately bringing the suspension into contact with an organic liquid medium B maintained at a low enough temperature to solidify the complex particles. 3 Magnesium halide is magnesium chloride cm^
2. The method according to claim 1. 4. The method according to claim 1, wherein the active hydrogen compound is an alcohol. 5. The method according to claim 1, wherein the siloxane is at least one type of siloxane selected from the group consisting of methylsiloxane, methylphenylsiloxane, and oxyalkylene-modified siloxane. 6. The method according to claim 1, wherein the organic liquid medium A is a hydrocarbon. 7. The method according to claim 2, wherein the organic liquid medium B is a hydrocarbon.