JPH0774247B2 - Method for producing α-olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an α-olefin polymer, and more specifically, an α-olefin having a high crystallinity and a good particle shape, using a specific catalyst. It relates to a method for producing a polymer in high yield.

[Conventional technology and its problems]

The α-olefin is composed of a transition metal compound of groups IV to VI of the periodic table and an organometallic compound of a metal of groups I to III, and includes a so-called Ziegler-Natta including those modified by adding an electron donor and the like. Polymerization by a catalyst is well known. Among them, titanium trichloride is most widely used as a transition metal compound component in order to obtain a highly crystalline polymer such as propylene and butene-1. The titanium trichloride is classified into the following three types depending on the manufacturing method.

After reducing titanium tetrachloride with hydrogen, it was pulverized and activated with a ball mill (titanium trichloride (HA)).

General formula activated by ball milling after reducing titanium tetrachloride with metallic aluminum A compound represented by (so-called titanium trichloride (AA)).

Heat treated after reduction of titanium tetrachloride with an organoaluminum compound.

However, none of these titanium trichlorides is sufficiently satisfactory, so improvements have been attempted. Above all, various methods have been considered for the above types because the shape of the obtained polymer is good. As one of the methods, titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound is treated with an electron donor and titanium tetrachloride to increase the catalytic activity and to form an amorphous polymer. A method of reducing the number has been proposed (for example, Japanese Patent Publication No. 53-3356). However, even by this method, the improvement of polymerization activity and crystallinity was insufficient.

On the other hand, as a method for improving the above-mentioned production method, the present applicant has proposed that a reaction product of an organoaluminum compound and an electron donor and a solid obtained by reacting titanium tetrachloride with an electron donor A method for producing an α-olefin polymer by polymerizing an α-olefin in the presence of a catalyst in which a solid product obtained by reacting with an electron acceptor is combined with an organoaluminum compound (JP-A-56-110707). Obtained by reacting an electron donor with an electron acceptor after polymerizing a solid obtained by reacting a reaction product of an organoaluminum compound and an electron donor with titanium tetrachloride with an α-olefin. A method for producing an α-olefin polymer by polymerizing an α-olefin in the presence of a catalyst in which a solid product is combined with an organoaluminum compound (JP-A-58-17104) has been filed.

According to these two methods (sometimes referred to as the previous invention), a significant improvement in storage stability, polymerization activity, crystallinity and the like of the catalyst used was recognized as compared with the conventional method. , Further improvement is desired.

Also, completely different from the above-mentioned titanium trichloride composition, mainly titanium compound supported titanium tetrachloride,
A method of obtaining a crystalline polymer such as propylene by a so-called supported Ziegler catalyst is also known.

These supported Ziegler catalysts have higher polymerization activity per titanium as compared with the method using the titanium trichloride composition, but in terms of crystallinity, they are practically insufficient,
Improvements are also being attempted in this field. For example, a method in which a titanium compound is supported on a carrier mainly composed of magnesium halide and a catalyst obtained by combining a solid catalyst component and an organoaluminum compound is further used with an organosilicon compound (Japanese Patent Publication No. 58-21921, JP-A-572191). -63312, JP-A-58-
83006), but the crystallinity is still insufficient for practical use. In addition, these supported Ziegler catalysts have poor poisoning resistance to polymerization inhibitors and must use high-purity α-olefin, which is an industrial disadvantage.

Therefore, there has been a demand for improvement of the prior art using a titanium trichloride composition which does not require a highly pure α-olefin and which is excellent in poisoning resistance to a polymerization inhibitor.

The inventors of the present invention have made diligent studies on the improvement of the prior art using a titanium trichloride composition, particularly as a result of combining a novel catalyst component, and as a result, the polymerization activity and crystallinity are improved, and particularly the polymerization activity is significantly increased. The present invention has been found to be improved, and the present invention has been achieved.

An object of the present invention is to further enhance the polymerization activity and crystallinity when producing an α-olefin polymer having an excellent shape with uniform particle size.

[Means for solving problems]

 The present invention has the following configurations.

(1) A reaction product (I) of an organoaluminum compound and an electron donor is reacted with titanium tetrachloride to obtain a solid product (II), and an electron donor and an electron acceptor are further reacted. The α-olefin is polymerized in the presence of a catalyst in which the titanium trichloride composition thus obtained, (2) an organoaluminum compound, and (3) an organosilicon compound having a Si—N bond are combined. -A method for producing an olefin polymer.

The titanium trichloride composition used in the present invention is a solid product obtained by reducing titanium tetrachloride using a reaction product of at least an organoaluminum compound and an electron donor, and further an electron donor and an electron acceptor. The titanium trichloride composition of the type obtained by reacting with can be used including those which are subjected to various modifications during or after the reduction. The titanium trichloride composition used in the above invention is preferable. The details are as follows although detailed in the specification of the above invention.

A solid product (II) obtained by reacting a reaction product (I) of an organoaluminum compound with an electron donor and titanium tetrachloride is not polymerized with α-olefin, or α
A solid product (III) or (I obtained by polymerizing with an olefin, and further reacting an electron donor and an electron acceptor.
V) is used as a titanium trichloride composition.

The reaction between the organoaluminum compound (A ₁ ) and the electron donor (B ₁ ) is carried out in the solvent (D) at −20 ° C. to 200 ° C., preferably −1.
It is carried out at 0 ° C to 100 ° C for 30 seconds to 5 hours. (A ₁ ), (B ₁ ),
The order of addition of (D) is not limited, and the amount ratio to be used is 0.1 to 8 mol, preferably 1 to 4 mol of electron donor, and 0.5 to 5 solvent, preferably 0.5 to 2 mol of electron donor per mol of organoaluminum.
Is appropriate. Aliphatic hydrocarbons are preferred as the solvent. Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state as it is after completion of the reaction (sometimes referred to as reaction product solution (I)) without separation.

The reaction between the reaction product liquid (I) and titanium tetrachloride (C) is 0
~ 200 ° C, preferably 10-90 ° C for 5 minutes to 8 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (I), (C) and the solvent may be carried out in any order, and the mixing of all the amounts is preferably completed within 5 hours. The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the reaction product liquid (I) is the ratio of the number of Al atoms in (I) to the number of Ti atoms in titanium tetrachloride ( Al / Ti) 0.05 to 10, preferably 0.06
~ 0.2. After the completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and the solid product (II) thus obtained is subjected to the next step while being suspended in the solvent after repeating washing with a solvent. It may be used, or may be dried and taken out as a solid to be used.

It is also possible to polymerize the solid product (II) obtained by reacting this reaction product liquid (I) with titanium tetrachloride with α-olefin and use it for the next reaction.

In the present invention, "polymerizing" means that a small amount of α-olefin is brought into contact with the solid product (II) to polymerize the α-olefin. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer.

The method of polymerizing with an α-olefin includes (1) a method of polymerizing a solid product (II) by adding an α-olefin in any process of the reaction between the reaction product liquid (I) and titanium tetrachloride, (2) A method of polymerizing the solid product (II) by adding α-olefin after the reaction between the reaction product liquid (I) and titanium tetrachloride, (3) the reaction product liquid (I) and tetrachloride After completion of the reaction with titanium, the liquid part is separated and removed by filtration or decantation, the obtained solid product (II) is suspended in a solvent, and an organoaluminum compound and α-olefin are added to carry out polymerization. There is a way to handle.

When an α-olefin is added at any stage of the reaction between the reaction product liquid (I) and titanium tetrachloride, and the reaction product liquid (I)
When the α-olefin is added after the reaction of the α-olefin with titanium tetrachloride, the reaction temperature is 30 to 90 ° C. for 5 minutes to 10 hours, and the α-olefin is passed at atmospheric pressure or at a pressure of 10 kg / cm ² G or less. To be added. The amount of α-olefin added is preferably 0.05 g to 1,000 g, using 10 to 5,000 g of α-olefin based on 100 g of the solid product (II).

After the reaction of the reaction product liquid (I) with titanium tetrachloride is completed by a polymerization treatment with α-olefin, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is used as a solvent. When the suspension is carried out, 100 ml to 2,000 ml of a solvent and 5 g to 500 g of an organoaluminum compound are added to 100 g of the solid product (II), and the reaction temperature is 30 to 90 ° C. for 5 minutes to 10 hours. 10 to 5,000 at 0 to 10 kg / cm ² G
It is desirable to add g and polymerize 0.05 to 1,000 g. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as or different from the one used in the reaction product liquid (I). After the completion of the reaction, the liquid portion was separated by filtration or decantation, and after further washing with a solvent, the obtained solid product (II) subjected to the polymerization treatment (hereinafter referred to as solid product (II-A )) May be used in the next step in the state of being suspended in the solvent, or may be dried and taken out as a solid to be used.

The solid product (II) or (II-A) is then reacted with an electron donating pair (B ₂ ) and an electron acceptor (E). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results. The amount used is 100 g of the solid product (II) or (II-A),
(B ₂ ) 10 g / 1,000 g, preferably 50 g-200 g, (E) 10 g-
The amount is 1,000 g, preferably 20 g to 500 g, and the solvent is 0 to 3,000 ml, preferably 100 to 1,000 ml. It is desirable that these 3 or 4 substances are mixed at -10 ° C to 40 ° C for 30 seconds to 60 minutes and reacted at 40 ° C to 200 ° C, preferably 50 ° C to 100 ° C for 30 seconds to 5 hours. The solid product (II) or (II-A), (B 2),
There is no limitation on the mixing order of (E) and the solvent. (B ₂ ) and (E) may be reacted with each other in advance before mixing with the solid product (II) or (II-A). In this case, (B ₂ ) and (E) Is reacted at 10 to 100 ° C. for 30 minutes to 2 hours and then cooled to 40 ° C. or lower. After completion of the reaction of the solid products (II) or (II-A), (B ₂ ) and (E), the liquid portion is separated and removed by filtration or decantation, and the solid product is repeatedly washed with a solvent. (II
I) or (IV) is obtained.

The solid product (III) or (IV) thus obtained is used as a titanium trichloride composition.

The titanium trichloride composition thus obtained, the organoaluminum compound and the organosilicon compound having a Si—N bond are combined to form a catalyst for use in the present invention. Further, it is a further preferable aspect of the present invention to use the catalyst after pre-activating it by reacting the catalyst with α-olefin.

The organoaluminum compound used in the present invention has the general formula AlR _{n
R 'n X 3- (n +} n') ( wherein R, R 'is an alkyl group, an aryl group, an alkaryl group, a hydrocarbon group or an alkoxy group such as a cycloalkyl group, X is fluorine, chlorine, Represents halogen of bromine and iodine, and n and n'are 0 <n + n'3
Of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri i-hexyl aluminum,
Trialkylaluminums such as tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluor. Dialkyl aluminum monohalides such as diethyl aluminum monobromide and diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride and ethyl aluminum sesquichloride, ethyl aluminum dichloride , I-Butyl aluminum dichloride, etc. Um di halides and the like, other monoethoxy diethylaluminum, can also be used alkoxyalkyl aluminum such as diethoxy monoethyl aluminum. Two or more kinds of these organoaluminums can be mixed and used. Each of the organoaluminum compound (A ₁ ) for obtaining the reaction product (I), the solid product (III), (IV) and the combination (A ₂ ) with (V) may be the same or different. Good.

As the electron donor used in the present invention, various ones shown below are shown. As (B ₁ ) and (B ₂ ), ethers are mainly used, and other electron donors are shared with ethers. Is preferred. What is used as an electron donor is an organic compound having any atom of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles,
Amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites,
Examples include phosphinites, hydrogen sulfide, thioethers, thioalcohols, and the like. Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether,
Di n-hexyl ether, di i-hexyl ether, di n-octyl ether, di i-octyl ether, di n
-Ethers such as dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol,
Alcohols such as butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl butyrate, ethyl benzoate, propyl benzoate. Butyl benzoate, octyl benzoate, benzoic acid 2-
Ethylhexyl, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate,
Ethyl anisate, propyl anisate, ethyl cinnamate,
Methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid,
Acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, aromatic acids such as maleic acid, aromatic acids such as benzoic acid, methyl ethyl ketone, methyl isobutyl ketone, ketones such as benzophenone, nitrile acid such as acetonitrile, methyl Amine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline,
Amine such as 2,4,6-trimethylpyridine, N, N, N ′, N′-tetramethylhexaneethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′ , N "-pentamethyl-N '
-Β-Dimethylaminomethylphosphoric triamide, amides such as octamethylpyrophosphoramide, N, N, N ′, N ′
-Ureas such as tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate,
Azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine and triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphine Fight, tri-n-butylphosphite,
Phosphites such as triphenylphosphite, phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite, and phenyldiphenylphosphinite, thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, and propylene sulfide. Kind,
Ethyl thio alcohol, n-propyl thio alcohol,
Thioalcohols such as thiophenol can also be mentioned. These electron donors can also be used as a mixture. The electron donor (B ₁ ) for obtaining the reaction product (I) and (B ₂ ) reacted with the solid product (II) may be the same or different.

The electron acceptor (E) used in the present invention has the general formula TiX ₄ or
It is represented by a halide represented by SiX ₄ (X is a halogen). Specific examples thereof include silicon tetrachloride and titanium tetrachloride, which can be mixed and used.
Most preferred is titanium tetrachloride.

The following solvents are used. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, i-octane and the like, and carbon tetrachloride, chloroform instead of or together with the aliphatic hydrocarbon. It is also possible to use halogenated hydrocarbons such as dichloroethane, trichloroethylene, and tetrachloroethylene. As aromatic compounds, aromatic hydrocarbons such as naphthalene, and mesitylene which is a derivative thereof,
Durene, ethylbenzene, isopropylbenzene, 2
Alkyl-substituted compounds such as -ethylnaphthalene and 1-phenylnaphthalene, and halides such as monochlorobenzene, chlorotoluene, chlorxylene, chloroethylbenzene, dichlorobenzene and bromobenzene are shown.

As the α-olefin used in the polymerization treatment, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1, 4-methyl-pentene-1,2-methyl- Penten-1, 3-
Examples are branched chain monoolefins such as methyl-butene-1 and styrene. These α-olefins may be the same as or different from the α-olefin to be pre-activated or polymerized, or two or more α-olefins may be mixed and used.

The titanium trichloride composition thus obtained is then used, in combination with an organoaluminum compound and an organosilicon compound having a Si--N bond, as a catalyst for the polymerization of α-olefins by a conventional method, or more preferably α-olefin. It is used as a catalyst pre-activated by reacting an olefin.

As the organoaluminum compound used for the polymerization of the α-olefin of the present invention, the same organoaluminum compound as that used when the above-mentioned titanium trichloride composition is prepared can be used. The organoaluminum compound may be the same as or different from the one used in preparing the titanium trichloride composition.

Specific examples of the organosilicon compound having a Si—N bond used for the polymerization of the α-olefin of the present invention include the compounds shown below. That is, tris (dimethylamine) silane, tris (dimethylethylamine), methyltris (dimethylamino) silane, tetrakis (dimethylamino) silane, tetrakis (diethylamino) silane, phenyltris (dimethylamino) silane, bis (dimethylamino) Methylsilane, bis (dimethylamino) methylvinylsilane, tris (dimethylamino) methylsilane, dimethylaminodimethylsilane, diethylaminodimethylsilane, bis (dimethylamino) dimethylsilane, bis (ethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, bis (Butylamino) dimethylsilane, dianilinodimethylsilane, N, N
-Dimethylaminotrimethylsilane, N, N-diethylaminotrimethylsilane, allylaminotrimethylsilane, anilinotrimethylsilane, piperidinotrimethylsilane, dianilinodiphenylsilane, bis (dimethylamino) diphenylsilane, methyltripiperidinosilane, methyltris (Cyclohexylamino) silane, 1
-Trimethylsilyl-1,2,4-triazole, 2-trimethylsilyl-1,2,3-triazole, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidine, 1,
1,3,3, -tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, 1,3-divinyl-1,1,
3,3'-tetramethyldisilazane, nonamethyltrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5,7,7-octa It is an organosilicon compound having at least one Si—N bond in the molecule such as methylcyclotetrasilazane, triethylazidosilane, and trimethylsilylazidotris (dimethylamino) azidosilane.

The use ratio of each catalyst component is 0.1 to 500 mol of an organoaluminum compound, 0.05 to 50 mol of an organosilicon compound having a Si—N bond, and 1 mol of an organoaluminum compound with respect to 1 mol of titanium in the titanium trichloride composition. On the other hand, 0.005 to 5 mol of an organosilicon compound having a Si-N bond is used.

Further, the above-mentioned three components may be mixed without using an inert solvent, but it is preferable to use them, and the order of mixing is arbitrary. They may be mixed before being supplied to the polymerization vessel, or may be separately supplied to the polymerization vessel and contacted in the polymerization vessel. When the catalyst is used by pre-activating it by reacting an α-olefin, an organosilicon compound having a Si—N bond may be added before the pre-activating, or the pre-activating is completed. You may make it contact later.

A catalyst combining a titanium trichloride composition, an organoaluminum compound and an organosilicon compound having a Si—N bond is sufficiently effective for slurry polymerization or bulk polymerization, but in the case of gas phase polymerization, α-olefin is used. Those which have been reacted and pre-activated are preferable. When performing gas phase polymerization subsequent to slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, at the time of gas phase polymerization, the reaction of α-olefin has already been performed, the latter catalyst The same effect can be obtained.

Pre-activation is 1 g of titanium trichloride composition, 0.1 g to 500 g of organic aluminum, 0 to 50 solvent, 0 to 1,000 m hydrogen.
l, and α-olefin 0.05 g to 5,000 g, preferably 0.05 g
Use ~ 3,000g. At this time, an organosilicon compound having a Si—N bond may or may not be used.

It is desirable to react the α-olefin at a temperature of 0 ° C. to 100 ° C. for 1 minute to 20 hours and to react 0.01 to 2,000 g, preferably 0.05 to 200 g of the α-olefin per 1 g of the titanium trichloride composition.

Pre-activation can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, benzene and toluene, and is also a gas in liquefied α-olefins such as liquefied propylene and liquefied butene-1. Can be carried out in ethylene or propylene, and hydrogen may be allowed to coexist during the preliminary activation.

Polymer particles obtained by slurry polymerization, bulk polymerization or gas phase polymerization in advance may be allowed to coexist during the preliminary activation. The polymer may be the same as or different from the α-olefin polymer to be polymerized. The polymer particles that can coexist are in the range of 0 to 5,000 g per 1 g of the titanium trichloride composition.

The solvent or α-olefin used in the pre-activation can be removed during the pre-activation or after completion of the pre-activation by distillation under reduced pressure, filtration or the like, or the solid product
Solvents can also be added to suspend them in amounts not exceeding 80 per gram.

There are various modes of the preliminary activation method. For example, (1) a slurry reaction is performed by contacting an α-olefin with a catalyst in which a titanium trichloride composition and an organoaluminum are combined.
Bulk reaction or gas phase reaction, (2) combination of solid product (III) and organoaluminum in the presence of α-olefin, (3) α-olefin polymer by the methods of (1) and (2) There are a method of coexisting the coalescence, a method of (4) (1), (2) and (3) coexisting with hydrogen.

There is essentially no difference between making the catalyst in the slurry state or making it into a granular material.

As described above, a catalyst composed of a titanium trichloride composition, an organoaluminum compound and an organosilicon compound having a Si—N bond combined with each other, or a catalyst pre-activated with an α-olefin is an α-olefin polymer. Used in the manufacture of.

In the method of the present invention, the polymerization method for polymerizing the α-olefin includes slurry polymerization carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, liquefied propylene and liquefaction. Parc polymerization conducted in a liquefied α-olefin monomer such as butene-1, α-of ethylene, propylene, etc.
There is a gas phase polymerization in which an olefin is polymerized in a gas phase, or a method of stepwise combining two or more of the above.
In either case, the polymerization temperature is room temperature (20 ° C) to 200 ° C, the polymerization pressure is normal pressure (0 kg / cm ² G) to 50 kg / cm ² G, and usually 5 minutes to 20 minutes.
It is carried out for about an hour.

At the time of polymerization, addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as in the conventional polymerization method. The method of the present invention is also used for multi-stage polymerization of α-olefins, gas phase polymerization,
It is also possible to connect 2 to 10 reactors in series by slurry polymerization or bulk polymerization, change the polymerization phase in each reactor, and change the amount of the catalyst, α-olefin and hydrogen to be fed.

The α-olefin used for the polymerization in the method of the present invention is ethylene, propylene, butene-1, hexene-
1, linear monoolefins such as octene-1, 4-
Methylpentene-1,2-methyl-pentene-1,3-
Branched chain mono-olefins such as methyl-butene-1, di-olefins such as butadiene, isoprene and chloroprene, styrene and the like. In the method of the present invention, not only homopolymerization of each of these but also mutual olefins In combination with, for example, propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or three components such as propylene, ethylene and butene-1 can be used for copolymerization. Also, block copolymerization can be carried out by changing the type of α-olefin fed in the multistage polymerization.

[Effect of the Invention] The main effect of the present invention is that a high crystalline polymer having a good powder shape can be obtained with a high polymer yield.

The effects of the present invention will be described more specifically.

The first effect of the present invention is that the activity of the obtained catalyst is very high, for example, when it is combined with the titanium trichloride composition obtained by the method of the previous invention, the polymer yield per 1 g of the titanium trichloride composition is high. Is 9210-14680 (Examples 1-18), and Si-
This is 1.7 to 2.5 times that of the above-mentioned invention (Comparative Examples 1, 3 to 19) which does not use an N-bonded organosilicon compound catalyst component.

The second effect of the present invention is that the production rate of the amorphous polymer is reduced during the production of the α-olefin polymer and a highly crystalline polymer is obtained. For example, in the production of propylene polymer, isotactic polypropylene as an n-hexane (boiling) insoluble matter has an isotactic index of 96.3 to 97.3 (Examples 1 to 18), and Si-N
That is, the crystallinity is higher than that of the above-mentioned inventions (Comparative Examples 1, 3 to 19) in which an organosilicon compound catalyst component having a bond is not used. Therefore, even if the atactic polymer is not removed, the disadvantages such as deterioration of the physical properties of the polymer, such as rigidity and thermal stability, are eliminated, and the atactic polymer removal step can be omitted, and the polymer production process can be omitted. It can be simplified. The third effect of the present invention is that polymer particles having a good shape can be obtained. The particles are close to spheres, the bulk specific gravity (BD) of the polymer is in the range of 0.45 to 0.50, the volume of the storage tank per weight of the polymer is small, and the polymer production plant can be compact.
The trouble of line clogging due to the aggregation of polymer particles and the trouble of transportation due to fine powder particles are eliminated, and stable operation can be performed for a long time even by the gas phase polymerization method.

〔Example〕

 Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

The polymer yield used in Examples and Comparative Examples is the amount (g) of the α-olefin polymer obtained per 1 g of the titanium trichloride composition, and indicates the polymerization activity. II is an isotactic index, which indicates crystallinity, according to the following formula.

In the case of slurry polymerization and bulk polymerization, the solvent-soluble polymer is also evaporated by heating the solvent to recover the polymer,
It was added to the total amount of α-olefin polymer.

BD indicates the bulk specific gravity of the polymer powder (g / ml), MFR is A
Flowability according to STMD-1238 (L).

Example 1 (1) Preparation of titanium trichloride composition n-hexane 60 ml, diethyl aluminum monochloride (DEAC) 0.05 mol, diisoamyl ether 0.12 mol 25
The mixture was mixed at 1 ° C for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4). 0.4 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C., and the whole amount of the above reaction product liquid (I) was added dropwise thereto over 30 minutes. The temperature was raised and the reaction was continued for another 1 hour, the mixture was cooled to room temperature, the supernatant was removed, 400 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain a solid product (II) 19
got g.

With the total amount of this (II) suspended in 300 ml of n-hexane, 16 g of diisoamyl ether and 35 g of titanium tetrachloride were added at 20 ° C. at room temperature for about 1 minute and the mixture was reacted at 65 ° C. for 1 hour. After the reaction was completed, the mixture was cooled to room temperature (20 ° C), the supernatant was removed by decantation, 400 ml of n-hexane was added, and the mixture was stirred for 10 minutes and allowed to stand, and the operation of removing the supernatant was repeated 5 times. After that, it was dried under reduced pressure to obtain a titanium trichloride composition. The content of titanium atoms in 1 g of the titanium trichloride composition is
It was 252 mg.

(2) Preparation of pre-activated catalyst After replacing the stainless reactor with an inclined blade with an internal volume of 2 with nitrogen gas, 20 ml of n-hexane, 280 mg of diethylaluminum monochloride, 30 mg of titanium trichloride composition, and phenyltris ( Dimethylamino) silane (36 mg) was added at room temperature, then hydrogen (150 ml) was added, and the propylene partial pressure was 5 kg / cm ²
React with G for 5 minutes, unreacted propylene, hydrogen and n-
Hexane was removed under reduced pressure to obtain a preactivated catalyst in the form of powder (110 g of propylene reaction per 1 g of the titanium trichloride composition).

(3) Polymerization of propylene Hydrogen was added to the reactor containing the catalyst which had been pre-activated.
0 ml was added, and vapor phase polymerization was carried out at a propylene partial pressure of 25 kg / cm ² G and a polymerization temperature of 70 ° C. for 2 hours. After the completion of the reaction, 5 g of methanol was added thereto, the kill reaction was carried out at 70 ° C. for 30 minutes, and the polymer was cooled to room temperature and dried to obtain 387.3 g of a polymer. The polymer yield per 1 g of titanium trichloride composition is
12910g, 97.3 polymer with isotactic index
The BD was 0.50 and the polymer particles were close to spherical.

Comparative Example 1 Propylene gas phase polymerization was carried out in the same manner as in Example 1 except that phenyltris (dimethylamino) silane was not used in (2) of Example 1. The results are shown in Table 1.

Comparative Example 2 Propylene was vapor-phase polymerized in the same manner as in Example 1 (2) except that 25 mg of silicon tetrachloride was used instead of phenyltris (dimethylamino) silane. The results are shown in Table 1.

Example 2 (1) Preparation of titanium trichloride composition n-heptane 40 ml, diethyl aluminum monochloride
The reaction solution obtained by reacting 0.05 mol, 0.09 mol of diisoamyl ether and 0.05 mol of di-n-butyl ether at 18 ° C for 30 minutes was added dropwise to 0.275 mol of titanium tetrachloride at 40 ° C over 300 minutes, and then at the same temperature. After reacting for 1.5 hours,
The temperature was raised to ℃ and the reaction was carried out for 1 hour. The operation of removing the supernatant liquid, adding 200 ml of n-hexane and removing by decantation was repeated 6 times, and 18 g of the obtained solid product (II) was added to n-hexane 5
Suspend in 00 ml and diethylaluminium monochloride
2 g was added, and 10 g of propylene was added at 60 ° C. and the reaction was carried out for 1 hour to obtain a solid product (II) subjected to a polymerization treatment (propylene reaction amount 5.0 g). After the reaction, the supernatant liquid was removed, 300 ml of n-hexane was added, and the operation of removing by decantation was repeated twice, and the solid product (II) subjected to the above-mentioned polymerization treatment
(23 g) was suspended in 40 ml of n-hexane, 18 g of titanium tetrachloride and 18 g of n-butyl ether were added, and the mixture was reacted at 60 ° C for 3 hours. After completion of the reaction, the supernatant was removed by decantation, 200 ml of n-hexane was added, the mixture was stirred for 5 minutes and allowed to stand, and the operation of removing the supernatant was repeated 3 times, followed by drying under reduced pressure and trichloride. A titanium composition was obtained. Titanium trichloride composition 1g
The content of titanium atoms therein was 200 mg.

(2) Preparation of pre-activated catalyst After replacing a stainless reactor with an inclined blade with an internal volume of 2 with nitrogen gas, 20 ml of n-hexane, 270 mg of diethylaluminum monochloride, 28 mg of titanium trichloride composition, 1
After adding 56 mg of trimethylsilylpyrrole at room temperature, the mixture was reacted at a propylene partial pressure of 2 kg / cm ² G for 10 minutes at 40 ° C. (24.3 g reaction of propylene per 1 g of titanium trichloride composition), and unreacted propylene and n-hexane were added. Removal under reduced pressure gave a preactivated catalyst.

(3) Polymerization of Propylene Gas phase polymerization of propylene was carried out in the same manner as in (3) of Example 1 except that the above-mentioned catalyst which had been pre-activated was used.
The results are shown in Table 1.

Comparative Example 3 Gas phase polymerization of propylene was carried out in the same manner as in Example 2 except that 1-trimethylsilylpyrrole in (2) of Example 2 was not used. The results are shown in Table 1.

Example 3 In Example 1 (2), preactivation was performed without using phenyltris (dimethylamino) silane. Next, after purging unreacted propylene and hydrogen, 1000 ml of n-hexane,
Add 16 mg of piperidinotrimethylsilane and add 150 ml of hydrogen.
Was added, and then a slurry polymerization reaction was carried out at 70 ° C. for 2.5 hours at a propylene partial pressure of 12 kg / cm ² G, and then n-hexane was removed by stripping with steam to obtain a polymer. The results are shown in Table 1.

Comparative Example 4 Slurry polymerization of propylene was carried out in the same manner as in Example 3 except that piperidinotrimethylsilane was not used. The results are shown in Table 1.

Example 4 1,000 ml of n-hexane, 300 mg of diethylaluminum monochloride, and 20 mg of the titanium trichloride composition obtained in Example 2 were added, and propylene was reacted at a partial pressure of propylene of 1.2 kg / cm ² G at 20 ° C. for 10 minutes. Pre-activation was performed (0.9 g reaction per 1 g of titanium trichloride composition). Purge unreacted propylene,
30 mg of methyltripiperidinosilane and 120 ml of hydrogen were added, slurry polymerization was carried out at a propylene partial pressure of 10 kg / cm ² G and 70 ° C. for 2.5 hours, and n-hexane was removed by steam stripping to obtain a polymer. The results are shown in Table 1.

Comparative Example 5 Slurry polymerization of propylene was carried out in the same manner as in Example 4 except that methyltripiperidinosilane was not used. The results are shown in Table 1.

Example 5 After obtaining a catalyst in the same manner as in Example 3 except that 33 mg of anilinotrimethylsilane was used instead of piperidinotrimethylsilane, 300 ml of hydrogen was added, 600 g of propylene was added, and the propylene partial pressure at 70 ° C. Bulk polymerization was carried out at 31 kg / cm ² G for 1 hour. After completion of the reaction, unreacted propylene was purged and post-treatment was carried out in the same manner as in Example 1 to obtain a polymer. The results are shown in Table 1.

Comparative Example 6 Bulk polymerization of propylene was carried out in the same manner as in Example 5 except that anilinotrimethylsilane was not used. The results are shown in Table 1.

Example 6 After obtaining a catalyst in the same manner as in Example 4 except that 37 mg of dianilinodiphenylsilane was used instead of methyltripiperidinosilane, 300 ml of hydrogen was added and 600 g of propylene was added.
Was charged, and bulk polymerization was carried out at 70 ° C. at a propylene partial pressure of 31 kg / cm ² G for 1 hour. After completion of the reaction, unreacted propylene was purged and post-treatment was carried out in the same manner as in Example 2 to obtain a polymer.
The results are shown in Table 1.

Comparative Example 7 Bulk polymerization of propylene was carried out in the same manner as in Example 6 except that dianilinodiphenylsilane was not used. The results are shown in Table 1.

Example 7 In Example 1, 250 ml of hydrogen was used and the propylene partial pressure was 21 kg / cm.
After propylene was vapor-phase polymerized in the same manner except that the amount was ² G, unreacted propylene and hydrogen were purged. Subsequently, the hydrogen partial pressure was 8 kg / cm ² G and the ethylene partial pressure was 12 kg / cm ² G.
Ethylene polymerization was carried out at ℃ for 2 hours. After that, Example 1
Post-treatment was carried out in the same manner as above to obtain a propylene-ethylene glob block copolymer. The results are shown in Table 2.

Comparative Example 8 A propylene-ethylene block copolymer was obtained in the same manner as in Example 7, except that the preactivated catalyst was used without using phenyltris (dimethylamino) silane. The results are shown in Table 2.

Example 8 In Example 2, 250 ml of hydrogen was used and the propylene partial pressure was 21 kg / cm.
After propylene was vapor-phase polymerized in the same manner except that the amount was ² G, unreacted propylene and hydrogen were purged. Subsequently, 65 with hydrogen partial pressure of 10 kg / cm ² G and ethylene partial pressure of 10 kg / cm ² G.
Ethylene polymerization was carried out at ℃ for 2 hours. After that, Example 2
Post-treatment was carried out in the same manner as above to obtain a propylene-ethylene block copolymer. The results are shown in Table 2.

Comparative Example 9 A propylene-ethylene block copolymer was obtained in the same manner as in Example 8 except that the preactivated catalyst was used without using 1-trimethylsilylpyrrole. The results are shown in Table 2.

Example 9 120 ml of hydrogen and a partial pressure of propylene of 10 kg / cm 2 were used by using the catalyst which was not pre-activated by propylene in Example 3.
After slurry polymerization of propylene in the same manner as in Example 3 except that ² G was used, unreacted propylene and hydrogen were purged, and n-
Hexane was distilled off under reduced pressure until the content of hexane in the polymer was 30%. Polymer containing this solvent is 20 cm in diameter and 20 in volume.
Was placed in a fluidized bed equipped with a stirring blade. Subsequently, 450 ml of hydrogen
Then, propylene was circulated at a reaction temperature of 70 ° C. and a propylene partial pressure of 21 kg / cm ² G at a flow rate of 5 cm / sec to carry out a gas phase polymerization reaction for 2 hours while fluidizing the polymer. After that, post-treatment was carried out in the same manner as in Example 1 to obtain a polymer. The results are shown in Table 2.

Comparative Example 10 A slurry was polymerized in the same manner as in Example 9 except that piperidinotrimethylsilane was not used, and then gas phase polymerization was carried out to obtain a polymer. The results are shown in Table 2.

Example 10 In Example 9, diethyl aluminum monochloride
300 mg, bis (dimethylamino) diphenylsilane 27 mg
And, slurry polymerization was carried out in the same manner except that 20 mg of the titanium trichloride composition obtained in Example 2 was used, and then gas phase polymerization was subsequently carried out. The results are shown in Table 2.

Comparative Example 11 A slurry was polymerized in the same manner as in Example 10 except that bis (dimethylamino) diphenylsilane was not used, and then gas phase polymerization was carried out to obtain a polymer. The results are shown in Table 2.

Example 11 In the same manner as in (1) and (2) of Example 1, a pre-activated catalyst was obtained in the form of powdery particles in a reactor, and 300 ml of hydrogen, 200 g of propylene, and 30 g of butene-1 were added, and propylene was added. Partial pressure 2
Bulk polymerization was carried out at 60 ° C. for 30 minutes under 6 kg / cm ² G to polymerize 38 g, and then the slurry containing unreacted propylene was flushed to the fluidized bed with stirring blade used in Example 9. Subsequently, gas phase polymerization was carried out in the same manner as in Example 9 to obtain a polymer. The results are shown in Table 2.

Comparative Example 12 In Example 11, phenyltris (dimethylamino)
After bulk polymerization was performed in the same manner except that silane was not used, vapor phase polymerization was carried out to obtain a polymer. The results are shown in Table 2.

Example 12 As in Example 11, except that the pre-activated catalyst obtained in the same manner as in (1) and (2) of Example 2 was used as the catalyst, the bulk phase polymerization followed by the gas phase polymerization was carried out. , A polymer was obtained. The results are shown in Table 2.

Comparative Example 13 A polymer was obtained by performing vapor phase polymerization after bulk polymerization in the same manner as in Example 12 except that 1-trimethylsilylpyrrole was not used. The results are shown in Table 2.

Example 13 (1) Preparation of titanium trichloride composition 80 ml of n-heptane, 0.16 mol of di-n-butylaluminum monochloride and 0.10 mol of di-n-butyl ether were mixed at 30 ° C. for 3 minutes and reacted for 20 minutes to react. A product liquid (I) was obtained. The total amount of this reaction product liquid (I) was added to a solution consisting of 50 ml of toluene and 0.64 mol of titanium tetrachloride kept at 45 ° C.
After dripping in minutes, the temperature was raised to 85 ° C and the reaction was continued for another 2 hours. Then, the mixture was cooled to room temperature, the supernatant was removed, and 300 ml of n-heptane was added.
Was added and the operation of removing the supernatant liquid by decantation was repeated twice to obtain 49 g of a solid product (II) obtained. This (I
The entire amount of I) was suspended in 300 ml of n-heptane, 20 g of di-n-butyl ether and 150 g of titanium tetrachloride were added at room temperature for about 2 minutes, and the mixture was reacted at 90 ° C. for 2 hours, cooled, and then decanted n-. Heptane washing and drying were performed to obtain a titanium trichloride composition. The content of titanium atoms in 1 g of the titanium trichloride composition was 255 mg.

(2) Preparation of pre-activated catalyst In the reactor of (2) of Example 1, 4 ml of n-pentane, 160 mg of diethylaluminum monochloride, 39 mg of allylaminotrimethylsilane, 20 mg of the titanium trichloride composition obtained in (1) above. And 5 g of polypropylene powder were mixed and mixed, then n-pentane was removed under reduced pressure, and the reaction was conducted in the gas phase while fluidizing the catalyst with propylene gas for 20 minutes at a propylene partial pressure of 0.8 kg / cm ² G at 30 ° C. After that, unreacted propylene was removed to obtain a pre-activated catalyst (2.6 g reaction of propylene per 1 g of titanium trichloride composition).

(3) Polymerization of propylene Using the pre-activated catalyst obtained in (2), vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1. The results are shown in Table 3.

Comparative Example 14 Propylene gas-phase polymerization was carried out in the same manner as in Example 13 except that allylaminotrimethylsilane was not used in (2) of Example 13. The results are shown in Table 3.

Example 14 (1) Preparation of titanium trichloride composition 80 ml of n-octane, 0.05 mol of diisopropylaluminum monochloride, and 0.11 mol of di-n-octyl ether were added.
The reaction mixture obtained by reacting at ℃ for 4 hours was added dropwise to 0.25 mol of titanium tetrachloride at 31 ℃ for 120 minutes, then reacted at 40 ℃ for 30 minutes, then heated to 50 ℃ and reacted for 30 minutes. After that, 10 g of propylene was added at the same temperature and reacted for 50 minutes, the liquid was removed by filtration, 300 ml of n-octane was added and stirred for 5 minutes, and the operation of filtering off was repeated twice to give a polymerized solid. The product (II) was obtained (solid product (II) 17.5 g, propylene reaction amount 4.5 g). 40 ml of n-octane, 22 g of diisoamyl ether, and 14 g of titanium tetrachloride were added to the solid product subjected to this polymerization treatment, and the mixture was reacted at 85 ° C for 30 minutes, then filtered and added with 100 ml of n-pentane for 10 minutes. The operation of stirring and filtering was repeated 4 times, and then dried to obtain a titanium trichloride composition. The content of titanium atoms in 1 g of the titanium trichloride composition was 205 mg.

(2) Preparation of preactivated catalyst 20 mg of the titanium trichloride composition obtained in (1) above as the titanium trichloride composition in (2) of Example 13 and 28 mg of 1-trimethylsilylpyrrolidine instead of allylaminotrimethylsilane A preactivated catalyst was obtained in the same manner except that it was used.

(3) Polymerization of propylene Using the preactivated catalyst obtained in (2), vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 13. The results are shown in Table 3.

Comparative Example 15 Gas phase polymerization of propylene was carried out in the same manner as in Example 14 except that 1-trimethylsilylpyrrolidine was not used in (2) of Example 14. The results are shown in Table 3.

Example 15 (1) Preparation of titanium trichloride composition In (1) of Example 1, instead of reacting the solid product (II) with diisoamyl ether and titanium tetrachloride,
-In 200 ml of hexane, 38 g of diisoamyl ether, 12 g of silicon tetrachloride and 17 g of titanium tetrachloride were added at room temperature (20 ° C) for about 1 minute, and then 19 g of the solid product (II) was added,
The reaction was carried out at 0 ° C for 2 hours. After completion of the reaction, the product was washed with n-hexane and dried to obtain a titanium trichloride composition. The titanium atom content in 1 g of the titanium trichloride composition was 254 mg.

(2) Polymerization of Propylene In the reactor used in (2) and (3) of Example 1, 1000 ml of n-hexane and 260 m of diisopropylaluminum chloride.
g, bis (dimethylamino) methylvinylsilane 16 mg, and 20 mg of the titanium trichloride composition obtained in the above (1) were added.
Slurry polymerization of propylene was carried out in the same manner as in Example 3 except that the preliminary activation treatment was not performed. The results are shown in Table 3.

Comparative Example 16 Propylene slurry polymerization was carried out in the same manner as in Example 15 (2) except that bis (dimethylamino) methylvinylsilane was not used. The results are shown in Table 3.

Example 16 (1) Preparation of Titanium Trichloride Composition 19.5 g (butene) of a solid product (II) polymerized by using 10 g of butene-1 instead of 10 g of propylene in (1) of Example 2 A titanium trichloride composition was obtained in the same manner except that -1 reaction amount of 1.5 g) was obtained.

(2) Polymerization of Propylene In the same manner as in Example 15, except that 20 mg of the titanium trichloride composition obtained in (1) above was used as the titanium trichloride composition in (2) of Example 15, pre-activation was performed. Slurry polymerization of propylene was carried out without chemical treatment. The results are shown in Table 3.

Comparative Example 17 A slurry polymerization of propylene was carried out in the same manner as in Example 16 (2) except that bis (dimethylamino) methylvinylsilane was not used. The results are shown in Table 3.

Example 17 When preactivating in Example 1, 70 m of nonamethyltrisilazane was used instead of phenyltris (dimethylamino) silane.
g, or butene-1 instead of propylene,
Butene-1 partial pressure 0.5 kg / cm ³ G for 10 minutes, butene-1 at 35 ℃
(Butene-1 of 1 g of solid product (III))
Example 1 was repeated except for (0.3 g reaction). The results are shown in Table 3.

Comparative Example 18 A preactivated catalyst was obtained in the same manner as in Example 17 except that nonamethyltrisilazane was not used, and Example 17 was repeated.
The results are shown in Table 3.

Example 18 Instead of using 280 mg of diethyl aluminum monochloride in (2) of Example 2, triethyl aluminum 2
Using 20 mg, pre-activation was carried out in the same manner as in (2) of Example 2, hydrogen partial pressure 12 kg / cm ³ G, ethylene partial pressure 12 kg / cm.
^A polymer was obtained in the same manner as in Example 2 (3) except that ethylene was polymerized at ³ G and 85 ° C. The results are shown in Table 3.

Comparative Example 19 Polymerization of ethylene was carried out in the same manner as in Example 18 except that the catalyst pre-activated without using 1-trimethylsilylpyrrole was used. The results are shown in Table 3.

Example 19 Propylene slurry polymerization was carried out in the same manner as in Example 3 except that the titanium trichloride composition obtained by the method described in JP-B-53-3356 was used as the titanium trichloride composition.
A polymer was obtained. The results are shown in Table 3.

Comparative Example 20 A preactivated catalyst was obtained without using piperidinotrimethylsilane in Example 20, and propylene slurry polymerization was carried out in the same manner as in Example 20 to obtain a polymer. The results are shown in Table 3.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow sheet illustrating the method of the present invention.

Continuation of front page (56) Reference JP-A-49-53190 (JP, A) JP-A-50-90684 (JP, A) JP-A-58-17104 (JP, A) JP-A-56-110707 (JP , A) Japanese Patent Publication Sho 41-19993 (JP, B1)

Claims (6)

[Claims] 1. A solid product (II) obtained by reacting (1) a reaction product (I) of an organoaluminum compound and ethers with titanium tetrachloride, further comprising ethers and a general formula:
Titanium trichloride composition obtained by reacting with a compound represented by TiX ₄ or SiX ₄ (X represents a halogen atom), (2) organoaluminum compound, and (3) organosilicon compound having Si—N bond A method for producing an α-olefin polymer, which comprises polymerizing an α-olefin in the presence of a catalyst combined with 2. A solid product (II) obtained by reacting a reaction product (I) of an organoaluminum compound and ethers with titanium tetrachloride as a titanium trichloride composition is α-.
Polymerized with olefins, then with ethers and general formula TiX ₄
Alternatively, the production method according to claim 1, wherein a solid product (III) obtained by reacting with a compound represented by SiX ₄ (X represents a halogen atom) is used. 3. The production method according to claim 1, wherein the catalyst is used after being preactivated by reacting an α-olefin. 4. The production method according to claim 1, wherein the α-olefin is vapor-phase polymerized. 5. The method according to claim 1, wherein the α-olefin is slurry-polymerized. 6. The production method according to claim 1 or 3, wherein bulk polymerization of α-olefin is carried out.