JPH02255706A - Method for solventless polymerization of olefin - Google Patents

Abstract

PURPOSE:To efficiently obtain a powdery olefinic polymer with excellent fluidity and rare formation of sticking solid substances by polymerizing an olefin without a solvent in the presence of a catalyst system consisting of a specific solid component, organoaluminum compound and specified alkoxy group-containing aromatic compound. CONSTITUTION:An olefin is polymerized in the presence of a catalyst system consisting of (A) a solid component, composed of (i) a crystalline polyolefin and (ii) a solid catalyst component consisting of Mg, Ti, a halogen and an electron donor and combined with (B) an organoaluminum compound and (C) an alkoxy group-containing aromatic compound expressed by the formula [R<1> is 1-20C alkyl; R<2> is 1-10C hydrocarbon, OH, etc.; m is 1-6; n is 0 or 1 to (6-m)] without a solvent to afford an olefinic polymer with >=30wt.% content of a portion soluble in boiling heptane. Furthermore, o-dimethoxybenzene, etc., are preferred as the compound expressed by the formula. The reaction temperature is preferably 40-80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improvement in a solventless polymerization method for olefins. More specifically, the present invention utilizes olefin polymers such as soft polypropylene and olefinic thermoplastic elastomers, which have good powder fluidity, by a gas phase polymerization method, without problems such as the formation of adhesive solidified products, and with high efficiency. It relates to a method of manufacturing well.

[Prior Art J Conventionally, σ-olefin polymers have been produced using highly active catalyst systems for the purpose of improving the stereoregularity of the produced polymers. Chic polypropylene has an extremely low molecular weight and is of little practical value.

Therefore, the present inventors first used a new catalyst system to
Discovered a method for producing industrially useful high molecular weight atactic polyolefins (Japanese Patent Application Laid-open No. 63-24310
Publication No. 6, 63-. 243107). However, in these methods, when the gas phase polymerization of olefin is carried out using the catalyst, there are problems such as poor fluidity of the resulting polymer powder or the formation of adhesive solidified materials.

[Problems to be Solved by the Invention] The present invention solves the problems in the conventional method for producing high molecular weight atactic polyolefins, and solves the problems in the conventional method for producing high molecular weight atactic polyolefins. A method for efficiently producing an olefin polymer such as a plastic elastomer by a solvent-free polymerization method, especially a powdered olefin polymer that generates very little adhesive solidified matter and has good powder fluidity, by a gas phase polymerization method. It was made with the purpose of providing.

[Means for Solving the Problem] As a result of extensive research to achieve the above object, the present inventors found that a solid component consisting of a crystalline polyolefin and a specific solid catalyst component, an organoaluminum compound, and a specific alkoxy The inventors have discovered that the objective can be achieved by using a catalyst system consisting of a combination of group-containing aromatic compounds, and have completed the present invention based on this knowledge.

That is, the present invention provides a solid component consisting of (A) (a) a crystalline polyolefin and (b) a solid catalyst component consisting of magnesium, titanium, a halogen atom, and an electron donor, (B) an organoaluminum compound, and ( C) General formula (in the formula, R1 is an alkyl group having 1 to 20 carbon atoms, R2 is a hydrocarbon group, hydroxyl group, or nitro group having 1 to 10 carbon atoms, m is an integer of 1 to 6, and n is O or 1 to An olefin having a boiling hebutane soluble content of 30% by weight or more is produced by polymerizing an olefin in the presence of a catalyst system consisting of a combination of aromatic compounds containing alkoxy groups represented by The present invention provides a method for the solvent-free polymerization of olefins, which is characterized by producing a polymer.

The present invention will be explained in detail below.

In the method of the present invention, (A) fil, min, of the catalyst system;
That is, the solid component used is (a) a solid catalyst component consisting of crystalline polyolefin (b) magnesium, titanium, a halogen atom, and an electron donor.

As a method for preparing this solid component (A), for example, the above-mentioned (
(b) A method of prepolymerizing an olefin in the presence of a combination of a solid catalyst component, an organoaluminium compound, and an electron-donating compound used as necessary; (2)
A method of dispersing the solid catalyst component (b) and an organoaluminum compound and an electron-donating compound (melting point of 100°C or higher) used as necessary in a crystalline powder such as crystalline polypropylene or polyethylene with uniform particle size. ,(3
) A method that combines method (l,) and method (2) can be used.

In the method (1) of the method for preparing a solid component (A), the olefin is, for example, an a-olefin having 2 to 10 carbon atoms such as ethylene, propylene, butene-1,4-methylpentene-1, etc. used, usually 30-80℃
Prepolymerization is carried out at a temperature, preferably in the range of 55 to 70°C, to form a crystalline polyolefin, preferably with a melting point of 100°C or higher. At this time, the aluminum/titanium atomic ratio of the catalyst system is usually 0.1 to 100, preferably 0.
．． The electron donating compound/titanium molar ratio is selected within the range of 0 to 50, preferably 0.1 to 2.

Further, as the organoaluminum compound used in this prepolymerization, those exemplified later as the organoaluminum compound of component (B) can be used. Further, electron-donating compounds to be used as necessary include those that basically have the ability to improve regularity during propylene polymerization, such as diphenyldimethoxysilane, diphenyljethoxysilane, dibenzyldimethoxysilane,
Organosilicon compounds such as tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, benzyltrimethoxysilane, n-butyl heptalate ,7
Aromatic dicarboxylic acid esters such as diisobutyl tarate, alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, isopropyl methyl ether, isopropyl Ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl-n-
Globyl ether, t-butyl-n-butyl ether,
Asymmetric ethers such as t-amyl methyl ether, t-7 methyl ethyl ether, 2.2'-azobis(2-methylpropane), 2.2°-azobis(2-ethylpropane), 2.2'-azobis( 2-methylpentane).

, σ'-azobisisobutyronitrile, 1.1'azobis(1-cyclohexanecarboxylic acid), (1-phenylmethyl)-azodiphenylmethane, 2-7enylazo 2.4-dimethyl-4-tricypencune Examples include azo compounds in which a sterically hindered Wt substituent is bonded to an azo bond such as nitrile, and one type of these may be used, or two or more types may be used in combination.

The solid catalyst component used in the (A) solid component has magnesium, titanium, a halogen atom, and an electron donor as essential components, and the magnesium compound, the titanium compound, and the electron donor are brought into contact with each other. It can be prepared by:

Examples of the magnesium compound include magnesium cybaride such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium such as jetoxymagnesium, allyloxymagnesium,
Examples include alkylmagnesium halides, alkylmagnesium halides such as alkoxymagnesium halides, allyloxymagnesium halides, and ethylbutylmagnesium, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. However, among these, magnesium halides, alkoxymagnesiums, alkylmagnesiums, and alkylmagnesium halides are preferred. Further, these magnesium compounds may be used alone or in combination of two or more.

Further, examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-
Tetraalkoxytitanium such as butoxytitanium, tetrainebutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, tetrahalogenated titanium such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-
Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium (ribromide), dihalogenated dichloride such as jetoxytitanium dichloride, jetoxytitanium dichloride, dibroboxytitanium dichloride, di-n-propoxytitanium dichloride, jetoxytitanium dichloride, etc. Examples include monohalogenated trialkoxytitanium such as alkoxytitanium, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride. Titanium chloride is preferred.These titanium compounds may be used alone or in combination of two or more.

Furthermore, organic compounds containing oxygen, nitrogen, phosphorus, sulfur, etc. can be used as the electron donor.

Such electron donors include, for example, esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid rides, acid amides, and aldehydes. , organic acids, etc.

Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl 7-thalate, methyl ethyl phthalate, methyl ethyl phthalate, methyl isobutyl 7-thalate, ethylpropyl phthalate,
Ethyl isobutyl 7-thaleate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl tere-7thaleate, dipropyl tere-7thaleate, methyl ethyl terephthalate, methylpropyl terephthalate, methyl isobutyl terephthalate, ethylpropyl tere 7-thaleate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl Aromatic dicarboxylic acids such as isophthalate, diethyl isophthalate, dipropylisoheptalate, diisobutyl isophthalate, methylethyl isophthalate, methylpropylisophthalate, methylisobutyl isophthalate, ethylpropylisophthalate, ethylisobutyl isophthalate and propylisobutyl isophthalate Diesters, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate , dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, aminotoluate, ethyl anisate, Ethyl ethoxybenzoate, p
- Monoesters such as ethyl butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, esters having 2 to 18 carbon atoms such as r-valerolactone, coumarin, phthalide, ethylene carbonate, benzoic acid, p-oxybenzoate Acids such as acids, cono-phosphoric anhydride, benzoic anhydride,
Acid anhydrides such as p-)ruyl anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone with 3 or more carbon atoms
15 ketones, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde, acids with 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride, etc. halides,
Ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide. Examples include amines such as tributylamine, N,N-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as acetonitrile, benzonitrile, and tolnitrile.

Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl phthalate,
Suitable examples include aromatic dicarboxylic acid diesters such as diisobutyl phthalate, and alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

(b) The solid catalyst component can be prepared by a known method (Japanese Unexamined Patent Publication No. 53-4
3094, JP 55-135102, JP 55-135103, JP 56-1860
For example, (1) a magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence of an electron donor and a grinding aid used as desired, and then reacted with a titanium compound. (2) reacting a liquid magnesium compound that does not have reducing ability with a liquid titanium compound in the presence of an electron donor,
A method for precipitating a solid titanium composite, (3) the above (
(1) A method of reacting a titanium compound with the material obtained in (1) or (2), (4) A method of reacting the material obtained in (1) or (2) with an electron donor and a titanium compound, ( 5) A method in which a magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence of an electron donor, a titanium compound, a grinding aid used as desired, and the like, and then treated with a halogen or a halogen compound. , (6) The compound obtained in (1) to (4) above can be prepared by a method of treating the compound with a halogen or a halogen compound.

Furthermore, methods other than these (Japanese Unexamined Patent Publication No. 56-166205
No. 1, JP-A-57-63309, JP-A-57-
190004, JP-A-57-300407, JP-A-58-47003), the solid catalyst component (a) can also be prepared.

In addition, oxides of elements belonging to groups ■ to ■ of the periodic table, for example,
A composite oxide containing at least one oxide of an oxide such as silicon oxide, magnesium oxide, or aluminum oxide or an oxide of an element belonging to groups ■ to ■ of the periodic table, such as a solid material in which the magnesium compound is supported on silica alumina or the like. , an electron donor, and a titanium compound in a solvent at a concentration of 0 to 20
The solid catalyst component can be prepared by contacting for 2 minutes to 24 hours at a temperature preferably in the range of 10 to 150°C.

In preparing the solid catalyst component, an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene, is used as a solvent. It is possible to use halogenated hydrocarbons such as mono- and polyhalogen compounds of the group hydrocarbons or saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms.

The composition of the solid catalyst component prepared in this way usually has a magnesium/titanium atomic ratio of 2 to 10.
0, the halogen/titanium atomic ratio is in the range of 5 to 200, and the electron donor/titanium molar ratio is in the range of 0.1 to 10.

Regarding the ratio of the crystalline polyolefin (a) to the solid catalyst component (b) in the solid component (A), the weight ratio of the component (a) to the component (b) is usually 1/30 to 1/30.
200. It is preferably selected to be in the range of 1/10 to 50.

The component (B) of the catalyst system in the present invention, that is, the organoaluminum compound, has the general formula % (in the formula, R3 is an alkyl group having 1 to 1 o carbon atoms, X is a halogen atom such as chlorine or bromine, p is a number from 1 to 3) A compound represented by these can be used. Examples of such aluminum compounds include trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum. Dialkyl aluminum monohalides such as monochloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be suitably used. One type of these aluminum compounds may be used, or two or more types may be used in combination.

In addition, the alkoxy group-containing aromatic compound of component (C) is
A compound represented by the general formula (R', R2, m and n in the formula have the same meanings as above), such as m-methoxytoluene, 0-methoxyphenol,
m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, 1)-(1--10benyl)anisole, p-allylanisole, 1,3-bis(p-methoxyphenyl)-1-pentene, Monoalkoxy compounds such as 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenethol, O-dimethoxybenzene, m -dimethoxybenzene, p-dimethoxybenzene, 3.4-dimethoxytoluene, 2.6-simethoxyphenol, 1-allyl-3,
Dialkoxy compounds such as 4-dimethoxybenzene and 1.3.5-trimethoxybenzene, 5-allyl-1,
2,3-trimethoxybenzene, 5-allyl-X, 2
．． 4-trimethoxybenzene, 1,2.3-trimethoxy-5-(l-propenyl)benzene, 1.2.4-trimethoxy-5-(1-propenyl)benzene, 1.2
．． Examples include trialkoxy compounds such as 3-trimethoxybenzene and 1,2.4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferred.

These aromatic alkoxy group-containing compounds may be used alone or in combination of two or more.

Regarding the usage amount of each component of the catalyst system in the present invention, (
The solid component of component A) is usually 0.0005 to 1 m+aol per reaction volume IC in terms of titanium atoms. An amount is used that falls within the range of . I: The organoaluminum compound of component (B) is used in such an amount that the aluminum/titanium atomic ratio is usually 1 to 3,000, preferably 40 to 800. If this amount deviates from the above range, the catalytic activity may decrease. There is a risk that it will be insufficient. Furthermore, the alkoxy group-containing aromatic compound as component (C) has a molar ratio of usually 0.01 to SOO,
It is preferably used in a ratio of 1 to 300. If the amount is less than 0.01, the physical properties of the resulting polymer may deteriorate, while if it exceeds 500, the catalytic activity tends to decrease.

In the method of the present invention, a solid component of component (A) and (B)
A σ-olefin homopolymer or copolymer is produced by polymerizing at least one α-olefin in the presence of a catalyst system consisting of a combination of an organoaluminum compound as a component and an alkoxy group-containing aromatic compound as a component (C). A polymer is produced, and at this time, the (A) component, the CB) component, and the (C)
After mixing the components in a predetermined ratio and bringing them into contact, the olefin may be introduced immediately to initiate polymerization, or the olefin may be introduced after aging for about 0.2 to 3 hours after contact. Additionally, this catalyst component can be supplied suspended in an inert solvent, olefin, or the like.

In the method of the present invention, solventless polymerization methods such as gas phase polymerization and bulk polymerization are used as the polymerization format, and regarding the reaction conditions, the olefin pressure is usually 1 to 50 kg/
The C1''Gs reaction temperature is normally selected as appropriate within the range of 20 to 200°C, preferably 40 to 80''O. The molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. The reaction time depends on the type of olefin used as a raw material and the reaction temperature and cannot be determined generally, but about 5 minutes to 10 hours is sufficient.

In the method of the present invention, the σ-olefin used as a raw material preferably has 2 to 10 carbon atoms, such as ethylene, propylene, butene-11 pentene-1,
4-methylpentene-1, hexene-1, heptene-1
Examples include 1-octene-11-nonene-1, decene-1, etc., and each of these may be used alone or in combination of two or more types, or may be used in combination with a non-conjugated diene compound. . Examples of the non-conjugated diene compound include ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, 4-methyl-1,4
-hexadiene, 5-methyl-1,4-hexadiene, etc. are used.

Particularly preferred σ-olefins include propylene in the case of homopolymerization, and combinations of ethylene and σ-olefins having 3 to 10 carbon atoms, particularly propylene, in the case of copolymerization. In this copolymerization, the molar ratio of the α-olefin to ethylene is 0.2 to 2.
A range of 0 is preferred.

In the present invention, post-treatment after polymerization can be carried out by conventional methods. That is, in the gas phase polymerization method, after polymerization, a nitrogen stream or the like may be passed through the polymer powder drawn out from the polymerization vessel in order to remove olefins and the like contained therein. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

In addition, in the bulk polymerization method, after polymerization, after completely separating the seven polymers from the polymer derived from the polymerization vessel,
Can be pelletized.

FIG. 1 shows a flowchart of an example of an embodiment of the present invention.

The olefin polymer thus obtained contains 30% by weight or more of boiling hebutane soluble content,
It has excellent properties as a soft olefin polymer. Therefore, according to the method of the present invention, soft polypropylene and olefinic thermoplastic elastomer can be easily obtained.

Also, when the present invention is applied to a gas phase polymerization method, the bulk density is 0.
．． A powdered olefin polymer with good powder fluidity of 25 g/cs+' or more can be easily obtained, and almost no adhesive solidified matter is produced.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example 1 (1) Preparation of solid catalyst component (b) Into a glass Mitsulo flask with an internal volume of 500 mA that was sufficiently purged with nitrogen, 20 ml of purified hebutane was added (OE
t) Add s49 and 1.2 g of di-n-butyl phthalate, keep the system at 90°C, and stir without stirring.
, 4 ml, and then add j::T f(, l, 1
11+xl was added, the temperature was raised to 110°C, the reaction was continued for 2 hours, and then the mixture was washed with purified butane at 80°C. Next, 115 ml of T i C114 was added to the obtained solid phase part.
was added, and the reaction was continued at 110°C for an additional 2 hours. After the reaction was completed, the product was washed several times with 100*ffi of purified hemobutane to obtain a solid catalyst component (b).

(2) Preparation of solid acid (A) In a pressure-resistant glass three-tube flask with an internal volume of 2.51 and sufficiently purged with nitrogen, 1.7 Q of purified hebutane and AIE t were added.
@0.07 mol, diphenyldimethoxysilane (
0.05 mol of DMDPS) and 120 g of the solid catalyst component obtained in (1) above were added. Keep the inside of the system at 30℃,
Continuously supply propylene while stirring, and reduce the internal pressure to 0.
, 5 kg/cm". After continuing this reaction for 1 hour, the solid component (A
) [m of (a), p165°C] was obtained.

(3) Polymerization of propylene A#Et3 was placed in a 5M stainless steel pressure autoclave containing polypropylene powder 209.
4. Om mon, 1-allyl-3,4-dimethoxybenzene 2, 0 m moffi and solid component 13Q#19 obtained in (2) above (0.68 m in terms of titanium atom)
Add 20 I of heptane solution containing aol);
After evacuating the system for 5 minutes, the temperature was 55°C and the ultimate pressure was 20 ky/
Polymerization of propylene was carried out for 2 hours under the conditions of "cta". The results are shown in Table 1.

Examples 2 to 4 Same as Example 1 except that the reaction time in preparing the solid component (A) in (2) in Example 1 was changed and the molar ratio of component (A)/(B) was changed. carried out. The results are shown in Table 1.

Comparative Example 1 In the polymerization of propylene (3) in Example 1,
The same procedure as in Example 1 was carried out except that the solid catalyst component (B) was used instead of the solid component (A). The results are shown in Table 1.

Example 5 The same procedure as in Example 1 was carried out except that the method for preparing the solid component (A) in (2) in Example 1 was changed as follows. The results are shown in Table 1.

That is, 400 ml of heptane, 90 g of polyglopylene powder (A), and AffiE t 0.01 were placed in a three-necked 7-tube fusco with an internal volume of 500 g + 1 that was sufficiently purged with nitrogen.
191, diphenyldimethoxysilane 0.005m@1
and 30 g of solid catalyst component (b) were added under stirring,
After stirring for a minute, the supernatant was removed and vacuum dried to prepare solid component (A) [m, p of (a) 165°C].

Example 6 In the preparation of solid component (A) in (2) in Example 1, 4-methylpentene-1 was used instead of propylene to prepare solid component (A) [m, p of (a) at 240°C]. It was carried out in the same manner as in Example 1 except for the preparation. The results are shown in Table 1.

[Effects of the Invention] According to the method of the present invention, the content of boiling hebutane soluble matter is reduced to 30% by weight by a solventless polymerization method using a specific catalyst system.
Industrially useful olefin polymers such as the above-mentioned soft polypropylene and olefin thermoplastic elastomer can be efficiently produced. Particularly, by the gas phase polymerization method, a powdery olefin polymer having a bulk density of 0.25 g/cm' or more and good powder fluidity can be easily produced without the problem of forming an adhesive solidified product.

[Brief explanation of drawings]

FIG. 1 is a flow chart showing one example of an embodiment of the present invention.

Claims (1)

[Scope of Claims] 1 (A) A solid component consisting of (a) a crystalline polyolefin and (b) a solid catalyst component consisting of magnesium, titanium, a halogen atom, and an electron donor, (B) an organoaluminum compound, and (C) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula is an alkyl group with 1 to 20 carbon atoms, R^2
is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group,
(m is an integer of 1 to 6, n is an integer of 0 or 1 to (6-m)) The olefin is polymerized in the presence of a catalyst system consisting of a combination of alkoxy group-containing aromatic compounds represented by A method for the solvent-free polymerization of olefins, characterized by producing an olefin polymer having a heptane-soluble content of 30% by weight or more. 2. Claim 1: A powdery olefin polymer having a bulk density of 0.25 g/cm^3 or more is produced by a gas phase polymerization method.
A method for the solvent-free polymerization of olefins as described.