JPH0784489B2 - Method for producing titanium trichloride composition for α-olefin polymerization - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a titanium trichloride composition for α-olefin polymerization. More specifically, the present invention relates to a method for producing a titanium trichloride composition for α-olefin polymerization, which is suitable as a transition metal compound catalyst component for producing a highly crystalline polyolefin having excellent transparency.

[Conventional technology and its problems]

A crystalline α-olefin polymer such as crystalline polypropylene is an α-olefin produced by a so-called Ziegler-Natta catalyst composed of a transition metal compound of IV-VI group of the periodic table and an organometallic compound of a metal of I-III group. It is well known that it can be obtained by polymerizing
Various titanium trichloride compositions have been widely used as transition metal compound catalyst components.

Of these titanium trichloride compositions, those obtained by reducing titanium tetrachloride with an organoaluminum compound and then heat-treating it, many improved production methods have been investigated because the shape of the obtained polymer is good. There is. For example, 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 reduce the production of an amorphous polymer ( Japanese Patent Publication No. 53-3356).

The present applicant has already made many proposals in this field. Among them, a solid obtained by reacting titanium tetrachloride with a reaction product of an organoaluminum compound and an electron donor is an electron donor and an electron acceptor. And a method for producing an α-olefin polymer using the titanium trichloride composition obtained by reacting with an organic aluminum compound and an electron donor as a reaction product with tetrachloride. A solid obtained by reacting titanium is subjected to a polymerization treatment with α-olefin, and then a titanium trichloride composition obtained by reacting an electron donor and an electron acceptor is used to produce an α-olefin polymer. Method (Japanese Patent Laid-Open No. 58-17104), the storage stability of the titanium trichloride composition, the polymerization activity, and the crystallinity of the obtained α-olefin polymer are greatly improved as compared with the conventional method. It has carried out a proposal that was.

However, although these improved methods have the advantages as described above, the obtained α-olefin polymer is translucent, which may impair the commercial value in the field of use, resulting in improved transparency. Was wanted.

On the other hand, attempts have been made to improve the transparency of α-olefin polymers, for example, aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22740). However, when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. ,
Also, when a benzylidene sorbitol derivative is used, although a certain improvement in transparency is observed,
There were problems such as strong odor during processing and bleeding of additives (embossing).

In order to improve the above-mentioned problems when the nucleating agent is added, a method for carrying out polymerization of styrenes and propylene in multiple stages and a composition thereof (JP-A-62-1738 and JP-A-62-122)
7,911, JP 63-15,803, JP 63-68,
No. 648) has been proposed, the inventors of the present invention, according to the method of the proposal, when producing polypropylene, not only the polymerization activity of propylene is reduced in any of the methods, bulk polymer Since it is produced, it is a method that cannot be adopted in an industrial long-term continuous polymerization method, particularly in a gas phase polymerization method in which the polymerization of α-olefin is carried out in a gas phase. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

As a similar technique, a method of polymerizing propylene using the catalyst component obtained by adding a polymer of styrenes during the production of a transition metal catalyst component for propylene polymerization (Japanese Patent Laid-Open No. 63-69,809). However, since the proposed method requires a separate step for producing a polymer of styrenes, it is not only accompanied by industrial disadvantages, but also a film similar to the above-mentioned prior art is produced. It had a problem of void generation.

The inventors of the present invention, when producing an α-olefin polymer with improved transparency, have a void in the film due to generation of a bulk polymer or poor dispersion, which is a problem of the prior art using a polymer of styrenes. We have studied earnestly how to solve problems such as occurrence.

As a result, a method for producing a titanium trichloride composition containing a polymer of styrenes was found by a specific method, and when a catalyst obtained by combining the titanium trichloride composition with an organoaluminum compound was used, it was as described above. Prior art α-
Not only is it possible to obtain an α-olefin polymer having excellent transparency and crystallinity, which has excellent dispersibility, extremely few voids, and which solves the problems in the production of the olefin polymer. The present invention was accomplished by knowing that there is a remarkable effect also on the storage stability of the composition at a high temperature of 35 ° C. or higher, and on the attrition resistance in the production apparatus during the large-scale production of the titanium trichloride composition. .

The present invention provides a method for producing a titanium trichloride composition for α-olefin polymerization, which is capable of producing an α-olefin polymer having extremely high transparency and extremely high crystallinity with extremely low productivity and extremely few voids. That is the purpose.

[Means for Solving Problems and Action of Invention]

 The present invention has the following configurations.

(1) Solid product (II) obtained by reacting an organoaluminum compound or a reaction product (I) of an organoaluminum compound and an electron donor (B ₁ ) with titanium tetrachloride.
Is polymerized with at least one monomer selected from o-methylstyrene, p-t-butylstyrene, and 1-vinylnaphthalene, and the electron donor (B ₂ ) and the electron acceptor are reacted with each other. A polymer of one or more monomers selected from o-methylstyrene, pt-butylstyrene, and 1-vinylnaphthalene, characterized by being obtained by
Alternatively, a method for producing a titanium trichloride composition for α-olefin polymerization, containing 0.01% by weight to 99% by weight of a copolymer.

(2) As the organoaluminum compound, the general formula is AlR ¹ _m R
² _{m ′} X _{3- (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group or an alkoxy group such as an alkyl group, a cycloalkyl group, an aryl group, etc., X represents a halogen, and m,
m ′ represents an arbitrary number of 0 <m + m ′ ≦ 3. The manufacturing method of said 1st item using the organoaluminum compound represented by these.

The method for producing the titanium trichloride composition for α-olefin polymerization of the present invention is carried out according to a specific method.
Titanium trichloride composition containing a polymer or a copolymer of one or more kinds of monomers selected from -t-butylstyrene and 1-vinylnaphthalene (hereinafter simply referred to as styrene). The method for producing the product will be described in detail below.

The titanium trichloride composition is manufactured as follows. First,
A solid product (II) or organoaluminum obtained by reacting an organoaluminum compound with an electron donor (B ₁ ) to obtain a reaction product (I), and reacting this (I) with titanium tetrachloride. A solid product (II) obtained by reacting a compound with titanium tetrachloride is subjected to a polymerization treatment with styrenes, and then an electron donor (B ₂ ) and an electron acceptor are further reacted to give a titanium trichloride composition. To get

In the present invention, "polymerizing" means that the styrenes are polymerized by bringing them into contact with the solid product (II) under the condition that the styrenes can be polymerized. By this polymerization treatment, the solid product (II) is in a state of being covered with the polymer.

The reaction between the above-mentioned organoaluminum compound 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. The order of addition of the organoaluminum compound, (B ₁ ) and (D) is not limited, and the amount ratio used is 0.1 mol to 8 mol, preferably 1 to 4 mol of the electron donor (B ₁ ) per 1 mol of the organoaluminum compound. Mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L.

Thus, the reaction product (I) is obtained. The reaction product (I) can be used for the next reaction in a liquid state as it is after completion of the reaction (sometimes referred to as the reaction product liquid (I)) without separation.

As a method of polymerizing the reaction product (I) with titanium tetrachloride or the solid product (II) obtained by reacting an organoaluminum compound with titanium tetrachloride with styrene, the reaction product ( I) or a method of polymerizing the solid product (II) by adding styrenes at any stage of the reaction between the organoaluminum compound and titanium tetrachloride, the reaction product (I), or the organoaluminum compound and tetrachloride. After completion of the reaction with titanium chloride, a method of polymerizing the solid product (II) by adding styrene, and after completion of the reaction between the reaction product (I) or the organoaluminum compound and titanium tetrachloride, filtration is performed. Alternatively, after separating and removing the liquid portion by decantation, the obtained solid product (II) is suspended in a solvent, and an organoaluminum compound and styrenes are added, There is a method of case processing.

The reaction of the reaction product (I) or the organoaluminum compound with titanium tetrachloride is -10 ° C to 200 ° C, preferably 0 ° C to irrespective of whether styrene is added in any step of the reaction. Perform at 100 ° C for 5 minutes to 10 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (I) or the organoaluminum compound, titanium tetrachloride, and the solvent may be performed in any order, and the styrenes may be added at any stage. It is preferable that the mixing of (I) or the organoaluminum compound, titanium tetrachloride, and the solvent is completed within 5 hours, and the reaction is performed during the mixing.

It is preferable to continue the reaction within 5 hours after mixing the whole amount. The amount of each used in the reaction is titanium tetrachloride 1
The solvent is 0 to 3,000 ml, and the ratio of the number of Al atoms in the reaction product (I) or the organoaluminum compound to the number of Ti atoms in titanium tetrachloride (Al / Ti) is 0.05 to 10, preferably 0.06. ~ 0.3.

The polymerization treatment with styrene is carried out by adding styrene in any step of the reaction between the reaction product (I) or the organoaluminum compound and titanium tetrachloride, and the reaction product (I) or the organoaluminum compound and the titanium tetrachloride. When styrene is added after completion of the reaction, the reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10 kg.
0.01 g per 100 g of solid product (II) under the condition of f / cm ² G
Polymerization is carried out by using ~ 100 kg of styrene so that the content of the styrene polymer in the final titanium trichloride composition is 0.01% by weight to 99% by weight. The content of the styrene polymer is
The effect of improving transparency and crystallinity of the α-olefin polymer produced by using the titanium trichloride composition obtained is less than 0.01% by weight, and the improvement effect is more than 99% by weight. Is not noticeable and becomes economically disadvantageous.

After the completion of the reaction of the reaction product (I) or the organoaluminum compound with titanium tetrachloride in the polymerization treatment with styrenes, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is obtained. In the case of carrying out after suspending in a solvent, to 100 g of the solid product (II),
Solvent 100 ml ~ 5,000 ml, organoaluminum compound 0.5 g ~ 5,
000 g was added, the reaction temperature was 0 ° C to 90 ° C for 1 minute to 10 hours, and the reaction pressure was atmospheric pressure to 10 kgf / cm ² G.
I) Using 0.01 g to 100 kg of styrene per 100 g, the content of styrene polymer in the final titanium trichloride composition is
Polymerization is performed so that the content is 0.01% by weight to 99% by weight. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound was used for obtaining the reaction product (I) or used for the reaction with titanium tetrachloride directly without reacting with the electron donor (B ₁ ). It may be the same as or different from the one.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further washing with a solvent,
The obtained solid product subjected to the polymerization treatment (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step as it is in a state of being suspended in a solvent, and further dried to give a solid. You may take it out and use it.

The solid product (II-A) is then reacted with an electron donor (B ₂ ) and an electron acceptor (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results. The amount of (B ₂ ) 0.1 g to 1, based on 100 g of the solid product (II-A).
000 g, preferably 0.5 g to 200 g, (F) 0.1 g to 1,000 g, preferably 0.2 g to 500 g, solvent 0 to 3,000 ml, preferably 100
~ 1,000 ml.

As a reaction method, a solid product (II-A) is reacted with an electron donor (B ₂ ) and an electron acceptor (F) at the same time, and after (II-A) is reacted with (F), ( a method of reacting B _2), was reacted with (B ₂₎ to (II-a),
There are a method of reacting (F) and a method of reacting (B ₂ ) with (F) and then reacting with (II-A), but any method may be used.

The reaction conditions are 40 ° C. to 20 ° C. in the above method.
It is desirable to carry out the reaction at 0 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 hours, and in the method of (II-A) and (B ₂ ) the reaction is performed at 0 ° C. to 50 ° C. for 1 minute to 3 hours. After the reaction, (F) is reacted under the same conditions as described above. In the other method, (B ₂ ) and (F) are heated at 10 ° C to 10 ° C.
After reacting at 0 ℃ for 30 minutes to 2 hours, cool to 40 ℃ or below,
After adding (II-A), the reaction is carried out under the same conditions as above.

After the reaction of the solid products (II-A), (B ₂ ) and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated to remove the weight of the target styrenes. A titanium trichloride composition for polymerizing α-olefins containing the coalesced product is obtained.

The titanium trichloride composition thus obtained contains a polymer of styrenes in an amount of 0.01% by weight to 99% by weight, and as a transition metal compound catalyst component for α-olefin polymerization, α-in combination with at least an organoaluminum compound. Used in the polymerization of olefins.

The organoaluminum compound used in the production of the titanium trichloride composition of the present invention has a general formula of AlR ¹ _m R ² _{m ′} X
_{3- (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group or an alkoxy group such as an alkyl group, a cycloalkyl group and an aryl group, X represents a halogen, and m and m ′ are 0 <m.
+ M'≤3. ), And specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, and tri i-hexyl aluminum. 2-Methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and other trialkylaluminums, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminum monochloride, diethylaluminum monofluoride. ,
Diethyl aluminum monobromide, dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride,
Examples thereof include monoalkylaluminum dihalides such as ethylaluminum dichloride and i-butylaluminum dichloride, and other alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum.
Two or more kinds of these organoaluminums can be mixed and used.

As (B ₁ ) and (B ₂ ) used in the present invention, ethers are mainly used, and other electron donors can be shared with the ethers. The one used as an electron donor is oxygen,
An organic compound having an atom of nitrogen, sulfur or phosphorus,
That is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites , Hydrogen sulfide or 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-hexyl ether, di-n-
Ethers such as octyl ether, di-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol,
Alcohols such as phenol, cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate,
Amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, anise. Esters such as ethyl acidate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, Formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, fatty acids such as maleic acid,
Aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone and benzophenone, nitrile acids such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β
(N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, N,
Amines such as N, N ′, N′-tetramethylethylenediamine, aniline and dimethylaniline, formamide,
Hexamethylphosphoric acid triamide, N, N, N ′, N ′, N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric acid triamide, octamethylpyrophosphoramide and other amides, N, N, N ′ , N′-tetramethylurea and other ureas, phenyl isocyanate, toluyl isocyanate and other isocyanates, azobenzene and other azo compounds, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, Phosphines such as triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, tri-n-butylphosphite, phosphites such as triphenylphosphite, ethyldiethylphosphinite, ethylbutylphosphite Finite, Fe Phosphinite such as Le diphenyl phosphinite, diethyl thioether, diphenyl thioether, methyl phenyl thioether,
Other examples include thioethers such as ethylene sulfide and propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol. 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-A) may be the same or different.

The electron acceptor (F) used in the present invention is a compound of Periodic Table III.
~ Represented by halides of Group VI elements. Specific examples thereof include silicon tetrachloride and titanium tetrachloride, and these may be used in combination. 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. A halogenated hydrocarbon such as dichloroethane, trichloroethylene, or tetrachloroethylene can also be used. 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 described above, the monomer used for the polymerization treatment is at least one monomer selected from o-methylstyrene, pt-butylstyrene, and 1-vinylnaphthalene.

As described above, the titanium trichloride composition obtained by the production method of the present invention is used in combination with at least an organoaluminum compound as a catalyst according to a conventional method for polymerization of α-olefin, or more preferably α-olefin. It is used for the polymerization of α-olefin as a catalyst that is pre-activated by reacting olefin. As the organoaluminum compound used for the polymerization of α-olefin, the same organoaluminum compound as that used when the titanium trichloride composition of the present invention described above is produced can be used. The organoaluminum compound may be the same as or different from the one used in producing the titanium trichloride composition. Further, as the α-olefin used for the preliminary activation, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1, 4-methyl-pentene-1, 2, -Methyl-pentene-1 and other branched chain monoolefins.

These α-olefins may be the same as or different from the α-olefin to be polymerized, or two or more α-olefins may be mixed and used.

The olefin polymerization method using the above catalyst is not limited, and in addition to liquid phase polymerization such as slurry polymerization and bulk polymerization,
It can also be suitably carried out by gas phase polymerization.

A catalyst obtained by combining a titanium trichloride composition and an organoaluminum compound is sufficiently effective for slurry polymerization or bulk polymerization, but in the case of gas phase polymerization, a catalyst pre-activated by reacting an α-olefin is preferable. When performing gas phase polymerization following slurry polymerization or bulk polymerization,
Even if the catalyst initially used is the former, since the reaction of the α-olefin has already been carried out during the gas phase polymerization, it becomes the same as the latter catalyst and an excellent effect can be obtained.

Pre-activation is based on 1 g of titanium trichloride composition, 0.005 g to 500 g of organoaluminum compound, 0 to 50 solvent, 0 to hydrogen.
1,000 ml and α-olefin 0.05 g to 5,000 g, preferably
Use 0.05g to 3,000g. Temperature is 0 ℃ to 100 ℃, 1 minute to 20
Titanium trichloride composition by reacting α-olefin for a period of time
It is desirable to react 0.01-2,000 g, preferably 0.05-200 g of α-olefin per 1 g.

The 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 even in liquefied α-olefins such as liquefied propylene and liquefied butene-1, It can be carried out in gaseous 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 embodiments of the pre-activation method, for example, a method in which an α-olefin is brought into contact with a catalyst in which a titanium trichloride composition and an organoaluminum are combined to carry out a slurry reaction, a bulk reaction or a gas phase reaction, an α-olefin. The method of combining the titanium trichloride composition with organoaluminum in the presence of, the method of coexisting the α-olefin polymer with the method of, and the coexistence of hydrogen with the method of. There is essentially no difference between making the catalyst in the slurry state or making it into a granular material.

As described above, the catalyst comprising the combined titanium trichloride composition and the organoaluminum compound, or the catalyst pre-activated with α-olefin is used for the production of α-olefin polymer. Similar to the olefin polymerization, it is possible to further add an electron donor as a third component of the catalyst for the purpose of improving stereoregularity and use it for the polymerization.

The amount of each catalyst component used is the same as in ordinary α-olefin polymerization, but specifically, to 1 g of the titanium trichloride composition,
Organoaluminum compound 0.05g-500g, electron donor 0-2
Use 00g.

Examples of the polymerization method for polymerizing the α-olefin include slurry polymerization carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, liquefied propylene and liquefied butene as described above. There are a bulk polymerization carried out in a liquefied α-olefin monomer such as −1, a gas phase polymerization in which an α-olefin such as ethylene and propylene 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 the polymerization is usually performed for about 5 minutes to 20 hours.

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 α-olefin used for the polymerization includes linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 4-methylpentene-1, 2,
-Branched monoolefins such as -methyl-pentene-1,
Diolefins such as butadiene, isoprene, chloroprene, etc., and not only homopolymerization of each of these, but also in combination with each other α-olefin, for example, propylene and ethylene, butene-1 and ethylene, Copolymerization can be carried out by combining propylene and butyne-1 or by combining three components such as propylene, ethylene and butene-1, and α-feeding by multistage polymerization.
It is also possible to carry out block copolymerization by changing the type of olefin.

〔The invention's effect〕

The main effect of the present invention is that when the titanium trichloride composition obtained by the method of the present invention is used as a transition metal compound catalyst component for α-olefin polymerization in the polymerization of α-olefin, the voids are remarkably high in productivity. That is, it is possible to produce an α-olefin polymer having extremely low transparency and extremely high crystallinity.

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

The first effect of the present invention is that when it is used for the polymerization of α-olefins, both transparency and crystallinity of the obtained α-olefin polymer are improved and the number of voids is extremely small.

As will be apparent from the examples shown below, the internal haze of the press film of the α-olefin polymer polymerized using the titanium trichloride composition obtained by the method of the present invention was not subjected to polymerization treatment with styrenes. Compared with the α-olefin polymer polymerized by using the obtained titanium trichloride composition, the ratio is about 1/4 to 1/2, which is remarkably high transparency. Further, the crystallization temperature is increased by about 5 ° C to 9 ° C, the crystallinity is remarkably improved, and the flexural modulus is also remarkably increased (see Examples 1 to 9 and Comparative Examples 1 and 5 to 10). .

Further, it is clear that the number of voids generated is significantly smaller than that of the α-olefin polymer introduced with the styrene polymer by the method other than the present invention (Examples 1 to 1).
9, see Comparative Examples 2 and 3).

The second effect of the present invention is an extremely high polymerization activity,
That is, an α-olefin polymer having a good particle shape and high stereoregularity can be obtained. Therefore, the catalyst removing step and the atactic polymer removing step can be omitted, and the α-olefin polymer can be produced by a simpler process such as a gas phase polymerization method, which is extremely advantageous in industrial production.

The third effect of the present invention is that the titanium trichloride composition for α-olefin polymerization of the present invention is excellent in storage stability and thermal stability. It is extremely important industrially to be able to store stably for a long period of time regardless of whether the outside temperature is high or low. The storage can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Further, the fourth effect of the present invention is that the titanium trichloride composition for α-olefin polymerization of the present invention is excellent in abrasion resistance. The titanium trichloride composition is not susceptible to grinding during use, that is, not only in the α-olefin polymer production process but also in the catalyst production process. This means preventing the formation of finely divided catalyst and thus the formation of finely divided α-olefin polymer.

As a result, it is extremely effective in preventing line blockage troubles in the gas phase polymerization process, and preventing compressor troubles due to mixing of the fine powder α-olefin polymer into the circulating gas.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. The definitions of terms used in Examples and Comparative Examples and the measuring methods are as follows.

(1) TY: indicates polymerization activity, polymer yield per gram atom of titanium (unit: kg / gram atom) (2) II: indicates stereoregularity, 20 ° C n-hexane extraction residual amount (unit: weight) %) (3) BD: Bulk specific gravity (unit: g / ml) (4) MFR: Melt flow index ASTM D-1238
According to (L). (Unit: g / 10 minutes) (5) Internal haze: The internal haze excluding the effect of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg.
The α-olefin polymer was formed into a film having a thickness of 150 μm under the condition of / cm ² G, liquid paraffin was applied to both surfaces of the film, and then the haze was measured according to JIS K 7105. (unit:
%) (6) Crystallization temperature: measured with a differential scanning calorimeter at a temperature decreasing rate of 10 ° C./min. (Unit: ° C.) (7) Flexural modulus: Tetrakis [methylene-3- (3 '-, 5'-di-t-butyl-4'-hydroxyphenyl) based on 100 parts by weight of α-olefin polymer. Propionate] 0.1 parts by weight of methane and 0.1 parts by weight of calcium stearate are mixed, and the mixture is mixed with a screw bore of 40 mm.
It granulated using the extrusion granulator of. Then, the granulated product was made into an injection molding machine at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. to prepare a JIS type test piece, and the test piece had a wet temperature of 50 ° C.
%, After being left for 72 hours in a room at room temperature of 23 ° C., the flexural modulus was measured according to JIS K7203. (Unit: kgf / cm ² ) (8) Void: The α-olefin polymer was granulated in the same manner as in the above item, and the obtained granulated product was melted at a molten resin temperature of 250 using a T-die type film forming machine. It was extruded at a temperature of 20 ° C., and a sheet having a thickness of 1 mm was prepared with a cooling roll at a temperature of 20 ° C. The sheet with hot air at 150 ° C
It was heated for 70 seconds and stretched 7 times in both longitudinal and transverse directions using a biaxial stretching machine to obtain a biaxially stretched film having a thickness of 20μ. The film was observed with an optical microscope and the number of voids having a diameter of 10 μm or more was measured. Less than 20 per 1 cm ² was indicated by ◯, 20 or more and less than 50 by Δ, and 50 or more by X.

Example 1 (1) Production of titanium trichloride composition n-hexane 6 diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12.0 mol 25
℃ mixed for 1 minute, reacted at the same temperature for 5 minutes, reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4)
Got 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C., and the whole amount of the reaction product solution (I) was added dropwise thereto for 180 minutes, and then added to the same temperature for 60 minutes, Maintain the same temperature for 60 minutes, raise the temperature to 80 ° C and react for another hour, cool to room temperature, remove the supernatant, and add 20 ml of n-hexane.
Was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (II). The entire amount of this (II) was suspended in n-hexane 30, 400 g of diethylaluminum monochloride was added, 9.5 kg of 1-vinylnaphthalene was added at 40 ° C, and polymerization treatment was carried out at 40 ° C for 2 hours. After the treatment, the temperature was raised to 50 ° C., the supernatant was removed, n-hexane 30 was added, and the operation of removing the supernatant by decantation was repeated 4 times, and the solid product (II-A) was polymerized. Got With the total amount of this solid product suspended in n-hexane 9, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes and reacted at 80 ° C for 30 minutes, and then diisoamyl ether was added. 1.6 kg was added and reacted at 80 ° C. for 1 hour. After the reaction was completed, the supernatant was removed by decantation.
N-Hexane was added, and the mixture was stirred for 10 minutes, allowed to stand, and the procedure of removing the supernatant was repeated 5 times and then dried under reduced pressure to obtain a titanium trichloride composition. The titanium trichloride composition obtained had a poly-1-vinylnaphthalene content of 50.0% by weight and a titanium content of 12.6% by weight.

(2) Preparation of pre-activated catalyst Titanium trichloride obtained in (1) after n-hexane 40 and diethyl aluminum monochloride 28.5 g were replaced with nitrogen gas in a stainless steel reactor with an inclined blade and having an inclined blade. After adding 450 g of the composition at room temperature, 0.9 Nm ^{3 of} ethylene was fed at 30 ° C. for 2 hours to cause a reaction (reaction of 2.0 g of ethylene per 1 g of the titanium trichloride composition), and then unreacted ethylene was removed. After washing with n-hexane and drying, a preactivated catalyst was obtained.

(3) Polymerization of α-olefin After 20 kg of polypropylene powder of MFR2.0 was put into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer with an internal volume of 80 and nitrogen substitution, the preliminary obtained in (2) above. After n-hexane was added to the activated catalyst to prepare a 4.0 wt% n-hexane suspension, the suspension was converted into titanium atoms at 6.41 mg / hr and diethylaluminum monochloride at 3.8 g / hr. It was continuously supplied from the same pipe.

Also, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G, and the gas phase polymerization of propylene was performed at 70 ° C for 120 hours. It went continuously. During the polymerization period, the polymer was continuously withdrawn from the polymerization vessel at 10 kg / hr so that the retained level of the polymer in the polymerization vessel was 50% by volume. The polymer extracted was subsequently obtained as a product powder after being contact-treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 15 minutes.

(4) Thermal stability test A titanium trichloride composition obtained in the same manner as in (1) above was tested at 40 ° C.
After being stored for 4 months in (4), propylene was polymerized in the same manner as (2) and (3).

(5) Attrition resistance test After connecting a circulation line equipped with a circulation pump to the reactor used in (2), n-hexane 20 was obtained in a nitrogen atmosphere and in the same manner as in (1) above. 450 g of titanium trichloride composition was added. Then, the circulation pump was operated, and the suspension in the reactor was flowed at a flow rate of 10 / min using the circulation line.
After circulating for 4 hours at a temperature of 25 ° C, (2),
Polymerization of propylene was carried out in the same manner as in (3).

Comparative Example 1 (1) The solid product (II) was added to 1 in (1) of Example 1.
A titanium trichloride composition was obtained in the same manner except that the fixed product (II-A) was used as the equivalent product without polymerizing with vinylnaphthalene.

(2) A preactivated catalyst was prepared in the same manner as in (2) of Example 1 except that the titanium trichloride composition obtained in (1) above was used as the titanium trichloride composition.

(3) Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the preliminary activation catalyst obtained in the above (2) was used as the preliminary activation catalyst.

(4) Polymerization of propylene was carried out in the same manner as in (4) of Example 1 except that the titanium trichloride composition obtained in the same manner as in (1) above was used as the titanium trichloride composition.

(5) Polymerization of propylene was carried out in the same manner as in Example 1 (5) except that the titanium trichloride composition obtained in the same manner as in (1) above was used as the titanium trichloride composition.

Comparative Example 2 (1) A titanium trichloride composition was obtained in the same manner as in (1) of Comparative Example 1.

(2) After adding n-hexane 20, 30 g of diethylaluminum monochloride and 180 g of the titanium trichloride composition obtained in (1) above to the reactor used in (2) of Example 1 at room temperature, 1- 720 g of vinylnaphthalene was added and reacted at 40 ° C. for 2 hours. (Per 1 g of titanium trichloride composition, 1-
After the reaction was completed, 1.0 g of vinylnaphthalene was reacted. After completion of the reaction, the catalyst was washed with n-hexane, filtered and dried to obtain a catalyst preactivated with 1-vinylnaphthalene.

(3) Propylene was polymerized in the same manner as in Example 1 (3) except that the catalyst pre-activated with 1-vinylnaphthalene obtained in (2) above was used as the pre-activated catalyst. Since the lumped polymer that had been formed had taken out and clogged the piping, it was necessary to stop the production within 10 hours after starting the polymerization.

Comparative Example 3 (1) In (1) of Comparative Example 1, when the reaction product (I) is reacted with titanium tetrachloride, (1) of Comparative Example 1 is separately prepared.
Using 500 g of a titanium trichloride composition and 120 g of diethylaluminum monochloride obtained in the same manner as
-Polyvinyl-1-naphthalene obtained by polymerizing 1-vinylnaphthalene added with 5.3 kg in hexane 100 at 60 ° C for 2 hours, washed with methanol and dried was placed in a vibrating mill having a capacity of 10. After pulverizing at room temperature for 5 hours, a titanium trichloride composition containing 50% by weight of poly-1-vinylnaphthalene was obtained in the same manner except that it was suspended in titanium tetrachloride.

(2) A preactivated catalyst was obtained in the same manner as in (2) of Example 1 except that the titanium trichloride composition obtained in (1) above was used as the titanium trichloride composition.

(3) Propylene was prepared in the same manner as in Example 1 (3) except that the preactivated catalyst obtained in (2) above was fed as the preactivated catalyst so that the total pressure was maintained at 23 kg / cm ² G. Polymerization was performed to obtain polypropylene.

Comparative Example 4 and Examples 2 and 3 By changing the amount of 1-vinylnaphthalene used in the polymerization treatment in (1) of Example 1, the poly-1-vinylnaphthalene contents were 0.001% by weight and 4.8% by weight, respectively. , 33.3
A weight percent titanium trichloride composition was obtained. Thereafter, polypropylene was obtained in the same manner as in (2) and (3) of Example 1.

Example 4 n-heptane 4, diethylaluminum monochloride
The reaction solution obtained by reacting 5.0 mol, 9.0 mol of diisoamyl ether and 5.0 mol of di-n-butyl ether at 18 ° C for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C over 300 minutes, and then the same. After keeping the temperature for 1.5 hours and reacting, 65 ℃
The temperature was raised to 1, the mixture was reacted for 1 hour, the operation of removing the supernatant liquid, adding n-hexane 20 and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to n-hexane 4
Suspended in 0, 500 g of diethylaluminum monochloride was added, 10 kg of 1-vinylnaphthalene was added at 50 ° C., and the mixture was reacted for 1 hour to obtain a polymerized solid product (II-
A) was obtained.

After the reaction, the supernatant was removed, and then n-hexane 20 was added,
The operation of removing by decantation was repeated twice, and the solid product (II-A) subjected to the above-mentioned polymerization treatment was added to n-hexane 7
The mixture was suspended in the mixture, 1.8 kg of titanium tetrachloride and 1.8 kg 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, and then 20 n-
Hexane was added, and the mixture was stirred for 5 minutes and allowed to stand, and the operation of removing the supernatant was repeated 3 times, and then dried under reduced pressure to obtain a titanium trichloride composition, which was used as (2) and (3) in Example 1. Polymerization of propylene was carried out in the same manner.

Comparative Example 5 The solid product (II) in Example 4 was subjected to no polymerization treatment with 1-vinylnaphthalene to give the solid product (II-
A titanium trichloride composition was obtained in the same manner except that it was the equivalent of A), and then propylene was polymerized in the same manner as in Example 4.

Example 7 Instead of titanium tetrachloride in (1) of Example 1, a mixed solution of 1.8 kg of silicon tetrachloride and 2.0 kg of titanium tetrachloride was used.
Further, a titanium trichloride composition was obtained in the same manner except that the amount of diisoamyl ether used was 2.2 kg and the solid product (II-A) was reacted.

Subsequently, n-hexane was added to the above titanium trichloride composition in a polymerization vessel with a stirrer equipped with a two-stage turbine blade having an internal volume of 200 to prepare a 4.0 wt% n-hexane suspension, and then the suspension was prepared. From the same pipe at 10.0 mg atom / hr in terms of titanium atom, and 6.0 g / hr of diethyl aluminum monochloride.
Further, n-hexane was continuously supplied at 21 kg / hr from another pipe. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was kept at 1.5% by volume, and propylene was supplied so that the total pressure was kept at 10 kg / cm ² G.
At 120 hours continuously. During the polymerization period, the slurry was continuously withdrawn from the polymerization vessel into a flash tank having an internal volume of 50 so that the retained level of the slurry in the polymerization vessel was 75% by volume. Unreacted propylene is removed by depressurization in the flash tank, while methanol is 1 kg / hr.
And contact-treated at 70 ° C. Subsequently, the slurry was separated from the solvent by a centrifuge and then dried to obtain a product powder at 10 kg / hr.

Comparative Example 6 Titanium trichloride composition obtained in the same manner as in Example 5 except that the solid product (II) was used as the solid product (II-A) equivalent without the polymerization treatment with 1-vinylnaphthalene. The slurry was used to carry out slurry polymerization of propylene in the same manner as in Example 6.

Example 6 27.0 mol of titanium tetrachloride was added to n-hexane 12 and the temperature was 1 ° C.
After cooling to 1, the n-hexane 12.5 containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C. over 4 hours. After completion of the dropping, the reaction was maintained at the same temperature for 15 minutes, followed by raising the temperature to 65 ° C. over 1 hour, and further reacting at the same temperature for 1 hour. Next, the supernatant was removed and n-hexane 10
Repeat 5 times by adding and removing by decantation.
Of 5.7 kg of the obtained solid product (II), 1.8 kg was suspended in n-hexane 50, 350 g of diethyl aluminum monochloride was added, and pt-butyl styrene was added at 40 ° C.
After further adding 3.8 kg, polymerization treatment was carried out at 40 ° C. for 2 hours.

After the polymerization treatment, the operation of removing the supernatant liquid and adding n-hexane 30 and removing by decantation was repeated twice, and the total amount of the obtained solid product (II-A) subjected to the polymerization treatment was added to n-hexane 11 Suspended in diisoamyl ether 1.6
Was added. This suspension was stirred at 35 ° C for 1 hour and then n-
It was washed 5 times with hexane 3 to obtain a treated solid. The treated solid obtained was treated with 40% by volume of titanium tetrachloride in n-hexane 6
Suspended in.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, n-hexane 20 was used once and 3
The solid obtained was washed and then dried under reduced pressure to obtain a titanium trichloride composition.

Using the resulting titanium trichloride composition, slurry polymerization of propylene was then performed in the same manner as in Example 5.

Comparative Example 7 Trichloride obtained in the same manner as in Example 6 except that the solid product (II) was replaced with the solid product (II-A) without the polymerization treatment with pt-butylstyrene. Using the titanium composition, slurry polymerization of propylene was then performed in the same manner as in Example 7.

Example 7 Using 2.5 kg of o-methylstyrene instead of 1-vinylnaphthalene in (1) of Example 1, a polymerized solid product (II-A) was obtained, followed by n-heptane 10
After adding 3.0 kg of titanium tetrachloride, the whole amount of the solid product (II-A) was added and reacted at 80 ° C. for 30 minutes. After the reaction, add 2.8 kg of di-n-pentyl ether, and add 80
The reaction was carried out at 0 ° C. for 1 hour to obtain a titanium trichloride composition.

Using the titanium trichloride composition thus obtained, propylene vapor-phase polymerization was then carried out in the same manner as in (2) and (3) of Example 1.

Comparative Example 8 Titanium trichloride composition obtained in the same manner as in Example 7 except that the solid product (II) was used as the solid product (II-A) equivalent without the polymerization treatment with o-methylstyrene. Using the product, propylene was polymerized in the same manner as in Example 8.

Example 9 In Example 6, the amount of 1-vinylnaphthalene used in obtaining the titanium trichloride composition was 7.6 kg, and ethylene was further added so that the concentration in the gas phase of the polymerization vessel was 0.2% by volume during propylene polymerization. Propylene-ethylene copolymerization was performed in the same manner as in Example 6 except that the supply was performed.

Comparative Example 10 Titanium trichloride composition obtained in the same manner as in Example 9 except that the solid product (II) was used as the solid product (II-A) equivalent without the polymerization treatment with 1-vinylnaphthalene. Using the product, propylene-ethylene copolymerization was performed in the same manner as in Example 9.

[Brief description of drawings]

FIG. 1 is a flow sheet illustrating the method of the present invention.

Claims (2)

[Claims] 1. A solid product (II) obtained by reacting an organoaluminum compound, or a reaction product (I) of an organoaluminum compound and an ether (B ₁ ) with titanium tetrachloride is treated with o-methyl. Polymerized with at least one monomer selected from styrene, pt-butylstyrene and 1-vinylnaphthalene, and further treated with ethers (B ₂ ) and halides of elements of groups III to VI of the periodic table. And o-methylstyrene, p-t, which are obtained by reacting
A method for producing a titanium trichloride composition for α-olefin polymerization, containing 0.01% by weight to 99% by weight of one or more kinds of monomers or copolymers selected from butylstyrene and 1-vinylnaphthalene. 2. An organoaluminum compound having the general formula
AlR ¹ _m R ² _{m ′} X _{3- (m + m ′)} (In the formula, R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; The production method according to claim 1, wherein the organoaluminum compound represented by m and m ′ represents an arbitrary number of 0 <m + m ′ ≦ 3).