JPS59145203A - Production of catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To produce the titled catalyst component capable of providing a stereoregular polymer of a high bulk density and a sharp particle diameter distribution, by contacting a specified solid composition with a liquid crosslinking agent in a dispersing medium, and contacting the product with a halogen-containing titanium compound. CONSTITUTION:A solid composition is obtained by contacting a Mg compound (e.g., MgCl2), alone or together with an electron donor (e.g., diethyl ether), with at least one medium selected from halogen-containing compounds (e.g., thionyl chloride). 1g of this solid composition is dispersed in a dispersing medium (e.g., hexane), 0.001-10ml of a liquid crosslinking agent (e.g., 1-propanol) is added to the dispersion, and the mixture is agitated at -10-50 deg.C for 1min-10hr. The product resulting from this agitation treatment is contacted with a halogen-containing titanium compound (e.g., TiCl4) in the presence (absence) of an electron donor for 10min-100hr to obtain a catalyst component for olefin polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a high-performance catalyst component that exhibits high activity when subjected to the polymerization of olefins and is capable of obtaining a stereoregular polymer in high yield. More specifically, the purpose of the present invention is to provide a method for producing a catalyst component suitable for producing a polymer having a high bulk density, a narrow particle size distribution, and a well-ordered particle shape. A solid composition obtained by bringing a magnesium compound into contact with at least one selected from an electron donor and a no)rogne-containing compound (hereinafter may be simply referred to as a "solid composition").

) is subjected to a stirring treatment together with a liquid crosslinking agent in a dispersant, and then brought into contact with a helogne-containing titanium compound in the presence or absence of an electron donor. The present invention relates to a manufacturing method.

Conventionally, many proposals have been made regarding methods for producing solid catalyst components containing magnesium, titanium, 710rn, and the like.

In many of these, transition metal compounds such as titanium helogonide are supported on magnesium 710gnide, and when used in the polymerization of olefins, it is said that the polymerization activity of titanium in the catalyst component was dramatically increased. However, problems remain in that the shape of the particles of the produced polymer is not constant, the particle size distribution is wide, and the bulk density is not sufficiently high.

Proposals have also been made regarding methods to solve such problems. For example, JP-A-49-65999 discloses a method for obtaining substantially uniform particles by spraying an aqueous solution of magnesium herogonide or molten magnesium halide (MgX2.6H2o). However, this method requires a special device called a spray granulator to spray at high pressure, and also requires a heated granulator to melt the mixture.
There remains the problem that when an aqueous solution is used, it requires additional steps such as drying. Moreover, JP-A-55-1
No. 35102 discloses a method in which a suspension containing complex particles of magnesium herodanide and an active hydrogen compound in a molten state is dispersed in an organic liquid medium in the coexistence of a surfactant or a polysiloxane, and then rapidly cooled and solidified. ing.

However, this method has the disadvantage that the process becomes complicated because it requires heating to a high temperature and immediately quenching in order to solidify uniformly.

As a result of intensive research to solve the problems remaining in the prior art, the present inventors have developed a catalyst component that is extremely easy to operate and can achieve the desired purpose without using special equipment. He discovered a manufacturing method and proposed it to the ox.

That is, the present invention is characterized by the above-mentioned solid.

After the composition is stirred in a dispersant together with a liquid crosslinking agent to obtain a stirred product, the composition is brought into contact with a heroxane-containing titanium compound in the presence or absence of an electron donor to form a catalyst. The process for obtaining the ingredients is simple and the operation is extremely simple.

When the catalyst component obtained according to the present invention is used in the polymerization of olefins, the resulting polymer has the advantage of having a uniform particle shape, a narrow particle size distribution, and a high bulk density. Of course, the polymerization characteristic values of the catalyst components, the sieving polymerization activity, and the yield of stereoregular polymers are also comparable to those of conventionally known products.

To further comment on the features of the present invention, the solid composition and the liquid crosslinking agent are made to coexist in a dispersing agent that does not dissolve the solid composition, and after stirring and treatment, the solid composition and the liquid crosslinking agent are mixed in the presence or absence of an electron donor. The catalyst component is produced by a novel method in which the catalyst component is brought into contact with a helocene-containing titanium compound.

Although the mechanism by which such a simple method achieves the above-mentioned effects is not clear, the particles of the solid composition are taken into the droplets of the liquid crosslinking agent dispersed in the dispersant, and the liquid The solids in the liquid droplets are coagulated by the action of the crosslinking agent, and the particles in the droplets are tightly agglomerated due to collisions between the particles during the stirring process and interaction between the particles and the inner wall of the device. It is considered that the particles gradually become more tidy due to the repeated action of incorporating fatty substances. By then contacting this product with a heloquine-containing titanium compound in the presence or absence of an electron donor, a catalyst component for polymerizing olefins that can achieve the objects of the present invention can be produced.

The effects of the present invention have been described above, but a more detailed explanation will be given below.

(1) Olefin polymers obtained using the catalyst component' obtained in the present invention exhibit high bulk density. Therefore, especially in the case of slurry polymerization, the burden of drying the produced polymer is reduced.
Furthermore, it is possible to increase the slurry concentration and increase the production volume of the equipment.

can.

(2) The resulting polymer has a narrow particle size distribution and a well-defined particle shape. Furthermore, since the amount of fine powder is reduced, the danger of dust explosions can be avoided.

(3) Since the resulting polymer has good fluidity, handling such as transportation and storage becomes easier.

(4) It is also possible to control the particle size of the catalyst component by selecting the conditions during the stirring treatment.

As a result, it is possible to produce an olefin polymer in which a pelletizing step can be omitted depending on the type of polymer resin in an industrial olefin polymer production process.

The magnesium compound used in the present invention is Hero
magnesium chloride, magnesium alkoxyhalodide, magnesium allyloxyhalide, dialkoxymagnesium, diallyloxymagnesium, fatty acid magnesium, inorganic magnesium, etc. More specifically, magnesium chloride, magnesium bromide, magnesium iodide, etc. , methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, methoxymagnesium bromide, ethoxymagnesium bromide, impropoxymagnesium bromide, phenoxymagnesium chloride, methylphenoxymagnesium chloride, phenoxymagnesium bromide, methylphenoxymagnesium magnesium chloride, jetoxymagnesium, diisozolopoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, magnesium stearate,
Magnesium octoate, magnesium laurate, magnesium caproate, magnesium oxalate, magnesium oxide, magnesium hydroxide, magnesium carbonate,
Examples include magnesium sulfate, a double oxide of magnesium and aluminum, and a double oxide of magnesium and silicon. Furthermore, it is also possible to use two or more of these compounds.

Examples of the heloquinone-containing compound used in the present invention include hydrogen chloride, sulfur herodane compounds such as thionyl chloride, or boron, aluminum, and silicon.

Halides such as dalmanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, or general formula Ti
(OR)nX4-n (wherein R is a hydrocarbon group,
n is O or an integer from 1 to 3. ) and the like are halogen-containing titanium compounds.

The electron donor used in the present invention is an organic compound containing at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus in its molecule, such as ether, ester, ketone, and phosphinamide. etc. can be mentioned. More specifically, aliphatic ethers such as diethyl ether, aromatic ethers such as anisole, aliphatic carboxylic acid esters such as ethyl acetate and methyl methacrylate, ethyl toluate, ethyl anisate, ethyl benzoate, etc. Examples include aromatic carboxylic acid esters, ketones such as acetone, and phosphine amides such as triphenylphosphine, but among these, aromatic carboxylic acid esters are preferred, and ethyl benzoate is particularly preferred. , p-ethyl anisate, p-)ethyltheal ruylate.

The titanium compound containing No.10g used in the present invention has the general formula Ti(OR)nX4-n (wherein R is a hydrocarbon group, X is a halogen, and n is O or an integer from 1 to 3). The indicated titanium compound, specifically Ti
C44, TiBr4# TiI4# Ti (OCH3)
C63゜Ti(OC2H5)Ct31Ti(0-n-C
4H7)Ct31Ti(OC2H5)Br31Ti(O
CH3)2C62,Ti(OC2H5)2Ct21Ti
(OC2H5)2Br21Ti(OCH3)6C4lT
i(OC2H6), Ct, Ti(OC2H5)5Br, etc., among which T i C44 is preferred.

The dispersant used in the present invention is an aliphatic hydrocarbon, an aromatic hydrocarbon, which does not dissolve the solid composition,
Examples include alicyclic hydrocarbons, aliphatic halodanated hydrocarbons, aromatic halogenated hydrocarbons, and alicyclic halogenated hydrocarbons. More specifically, they include hexane, hegetane, benzene, l-toluene, xylene, methylcyclohexane, methylene chloride #L2-dichloroethane, benzene tetrahydride, and the like.

The liquid crosslinking agent used in the present invention includes oxygen-containing organic compounds such as alcohols and esters that have affinity with the solid composition, nitrogen-containing organic compounds such as amines and amides, phosphines, and phosphates. Sulfur-containing organic compounds such as sulfides, sulfoxides, etc. are organic compounds that have the property of being difficult to dissolve in dispersants. More specific examples include ethanol, 1-prono, nor, 1-butanol, benzyl alcohol/L
/, 1 f-lene glycol, diethylene glycol diethylamine, triethylamine, dimethylamine, ethanolamine, jetanolamine NN-dimethylformamide, N,N''-dimethylacetamide, diethylphosphine, triethylphosphine, diphenylphosphine, triethylphosphate, Examples include dimethyl sulfoxide, dimethyl sulfide, diethyl sulfide, and the like.

Further, it is not prohibited to use two or more of these liquid crosslinking agents in combination.

As the stirring treatment method in the present invention, any method can be selected as long as each component used can be sufficiently stirred and the object of the present invention can be achieved.

Although the order of addition of each component in the present invention is not particularly limited, the following method may be cited as an example thereof.

(1) A method in which the solid composition is suspended in a dispersant, and then a liquid crosslinking agent is added and stirred.

(2) A method in which the solid composition is charged and stirred while a liquid crosslinking agent is added to a dispersant and dispersed.

(3) A method in which a liquid crosslinking agent and the solid composition are simultaneously added to a dispersant and then stirred.

etc. can be exemplified.

The proportions of the dispersant, liquid crosslinking agent and the solid composition used in the stirring process of the present invention may be arbitrary as long as the purpose of the present invention can be achieved. Although it varies depending on the composition and components of the solid composition, usually for 1 g of a solid composition containing magnesium,
The liquid crosslinking agent is added in an amount of 0.001 to 10rn11, preferably 0.001 to 10rn11.
01~'5 m11 dispersant is 5 ml for 1 ml of liquid crosslinking agent.
It is used in a range of m1 or more, preferably 19 m1 or more.

The treatment temperature in the present invention is lower than the boiling point of the dispersant, and is within a temperature range at which the liquid crosslinking agent does not crystallize or solidify in the dispersant, and is usually in the range of -1.0 to 50°C.

The stirring treatment time in the present invention is also not particularly limited, but is 1 minute to 10 hours, preferably 10 minutes to 5 hours.
It is a range of time.

To the product obtained by the stirring treatment in the present invention: 1. The method of contacting with the rhodan-containing titanium compound is not particularly limited. Examples include a method of contacting the titanium compound at a temperature up to the boiling point of the halogen-containing titanium compound for 10 minutes to 100 hours.

In addition, at this time, inert carbonization and hydrogen solvent were allowed to coexist during the treatment, and contact with the halogen-containing titanium compound was not yet carried out.
There is no hindrance to doing this more than once.

It is also possible to contact the stirred product with a halogen-containing titanium compound in the presence or absence of an electron donor and then wash it with an inert hydrocarbon solvent.

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for polymerizing olefins. The organoaluminum compound used is used in a molar ratio of 9 to 9 moles of titanium atoms in the catalyst component, preferably in the range of 1 to 1000, preferably 1 to 300. It is also possible to add and use a third component such as an electron-donating substance during trench polymerization.

Polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. The polymerization temperature is 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 kl? /CW12・G or less, preferably 50k
g/d-G or less.

Olefins that can be homopolymerized or copolymerized using the catalyst component produced by the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-1-pentene, and the like.

The present invention will be specifically explained below using Examples and Comparative Examples.

The physical property values in the examples were measured by the following methods. The bulk density of the solid polymer was measured according to JIS K6721. The particle size distribution of the solid polymer was measured using a rotary tube sieve shaker equipped with a JIS standard sieve. The integrated particle size 84% particle size index indicating the width of the particle size distribution is p, s, skin value = 10 gla, 16% a@
It was calculated by -.

The closer this value is to O, the narrower the particle size distribution is.

Example 1 (Preparation of solid composition) Volume M5 sufficiently purged with nitrogen gas and equipped with a stirrer
40 g of magnesium stearate, ethyl benzoate f3rnl, and TlC44 in a 00 ml round bottom flask.
200 ml was charged and stirred at room temperature for 30 minutes.

Subsequently, the temperature was raised to 65° C. and maintained at that temperature for 2 hours. Separately, 400 ml of n-heptane was charged into a 10,100 O three-necked flask equipped with a stirrer under a nitrogen atmosphere. After the above-mentioned product was pumped into this, it was allowed to stand, and the supernatant liquid was extracted by decantation. Next, n-hebutane 4
A solid composition was obtained by washing 10 times with 00ml.

(Harmonization of catalyst components) 400 ml of n-heptane was placed in a cylindrical flask (internal volume: 500 i7I) with an inner diameter of 85 wnφ, which was sufficiently purged with nitrogen gas and equipped with a stirrer and a stirring blade of 30 mm. 9 g of the above solid composition was charged. Next, add 1.35 ml of ethanol while stirring, keep at room temperature, and incubate at 2000 rpm.
The mixture was stirred for 1 hour at a stirring speed of pm.

Further, the mixture was washed three times with n-hebutane to obtain a stirred product.

8g1 of the above stirring treatment product and 4100ml TICZ
The mixture was placed in a 200 ml three-necked flask under a nitrogen atmosphere, heated to 65°C, and stirred at that temperature for 2 hours. After standing still, the supernatant liquid was removed by decantation and washed with n-hebutane to obtain a catalyst component.

(Polymerization of propylene) Internal volume completely replaced with nitrogen gas 1.5! 700 ml of n-hebutane was charged into an autoclave equipped with a stirring device,
While maintaining a nitrogen gas atmosphere, triethylaluminum 3
001n9. 137 g of ethyl p-)ruylate and 0.91 n9 of the above catalyst components as titanium atoms were charged. Thereafter, 100 ml of hydrogen was added, the temperature was raised to 60°C, and glopyrene gas was introduced.

Propylene pressure to 6! Maintain l/1yn2・G and 2
Time polymerization was performed. The amount of solid polymer is 227. ! 9, and the n-heptane extraction residue was 95.5%. At this time, the polymerization activity of 1 gram of fine Ti is 251 kg.
-pp/g-Ti.

However, the bulk density of the solid polymer was 0.43.9/CC, and the P, S, and D values were 0.48.

Comparative Example 1 Volume fx sufficiently purged with nitrogen gas and equipped with a stirrer
In a 500 ml round bottom flask 40 g magnesium stearate 1 8 ml ethyl benzoate and TiCt420
(1 liter) and stirred at room temperature for 30 minutes.
and held at that temperature for 2 hours.

Separately, 400 ml of n-hebutane was charged into a 1,000 ml three-necked flask equipped with a stirrer under a nitrogen atmosphere. After the above product was pumped into this, it was allowed to stand still, and the supernatant liquid was extracted by decantation. Next, n-hebutane 4
The catalyst component was obtained by washing 10 times with 0IOInl.

Further, as a result of carrying out propylene polymerization in the same manner as in Example 1, the amount of solid polymer and the extraction residual rate of n-hegetane were 18 A- and 95.1%, respectively.

At this time, the polymerization activity of 1 gram of Ti is 220 kg.
-pp/g-Ti. The bulk density of the solid polymer was... Example 2 A catalyst component was prepared in the same manner as in Example 1 except that triethylamine was used in place of ethanol.

Further, propylene polymerization was carried out in the same manner as in Example 1. As a result, the amount of solid polymer and the n-heptane extraction residue were 200.9 and 94.8, respectively. At this time, the polymerization activity per gram of Ti was 225 kg.
-pp/g-Ti.

Further, the bulk density of the solid polymer was 0.45 g/cr-, and the values of P, S, and D were 0.38.

Example 3 (Preparation of solid composition) ゛Capacity 2 fully purged with nitrogen gas and equipped with a stirrer
Magnesium stearate 5I in a 00 ml round bottom flask! “, jetoxymagnesium 5I!, ethyl benzoate 2.5M and 1,2-dichloroethane 59m/!
was added to form a suspension, and the mixture was stirred under reflux for 2 hours. Next, this suspension A was pumped into 11,044,200 ml of a 5QQmJ round bottom flask at 0°C equipped with a stirrer, heated to 90°C, and reacted with stirring for 2 hours. After the reaction is complete, cool to 40°C, then add 200ml of n-heptane.
1 was washed 10 times to obtain a solid composition.

(Preparation of catalyst component) Example 1 sufficiently purged with nitrogen gas and equipped with a stirrer
In a cylindrical flask with the same specifications, add 4 ooml of n-heptane.
, and 1 ml of ethanol were added and stirred. Next, 4.5 g of the above solid composition was added and stirred 2 times at room temperature.
The mixture was stirred at 0.00 rpm for 1 hour.

Further washing was performed with 206 rnl of n-heptane to obtain a stirred product.

The above stirring treatment product 41! , and TiC24200m
1 was placed in a 500 rnl three-neck flask under a nitrogen atmosphere, heated to 90°C, and stirred for 2 hours.

Then, the mixture was cooled to 40°C and the supernatant liquid was removed. Further n
- repeated washing with 200 ml heptane;
When chlorine was no longer detected in the amount of cleaning liquid, cleaning was completed and a catalyst component was obtained.

(Polymerization of Zoropylene) Propylene polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 70°C. As a result, the amount of solid polymer and the n-heptane extraction residue were 260 g and 964 g, respectively. The polymerization activity per gram of Ti at this time was 30 okg-pp/g-Ti.

In addition, the bulk density of the solid polymer is 0.40 g/CC,
The P, S, and D values were 0.56.

Comparative Example 2 The same operation as in Example 3 was performed except that the stirring treatment with ethanol was not performed. Fist・Fist・・Fight 1・・
・・・・・・・・・・・・・Cloudy・Also, propylene polymerization,
The procedure was carried out in the same manner as in Example 1 except that the amount of the catalyst component was 0.5 cm in terms of titanium atoms. As a result, the amount of solid polymer and the yield of crystalline polymer are each 1
7'OI and 95.0%. Ti at this time
The polymerization activity per gram is a 50 kg-pp/
It was g-Ti.

Moreover, the bulk density of the solid polymer was 0.32.9/CC, and the P, S, and D values were 0.94. me...
......O...-Fist... Example 4 A catalyst component was prepared in the same manner as in Example 3 except that ethylene glycol was used instead of ethanol. Further, dipropylene polymerization was carried out in the same manner as in Example 1. As a result, the amount of solid polymer and the n-hebutane extraction residue were 237 g and 95.5%, respectively. At this time, the polymerization activity of 1 gram of ΩTi is 29.2
kg-pp/g-Ti.

In addition, the bulk density of the solid polymer is 0.43 g/CC,
The P, S, and D values were 0.60.

Asahi

Claims (3)

[Claims] (1) A solid composition obtained by contacting a magnesium compound or the magnesium compound with at least one selected from an electron donor and a heron-containing compound,
1. A method for producing a catalyst component for polymerizing olefins, which comprises carrying out a stirring treatment together with a liquid crosslinking agent in a dispersant to obtain a stirred product, and then contacting the product with a herokane-containing titanium compound. (2) The method according to claim 1, wherein the solid composition contains an electron donor. (3) The method according to claim 1 or 2, wherein the stirred product is brought into contact with a halodane-containing titanium compound in the presence of an electron donor.